CN103303872B - System device and method for recycling sulfur dioxide from fume to prepare sulfur - Google Patents

System device and method for recycling sulfur dioxide from fume to prepare sulfur Download PDF

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Publication number
CN103303872B
CN103303872B CN201310277794.1A CN201310277794A CN103303872B CN 103303872 B CN103303872 B CN 103303872B CN 201310277794 A CN201310277794 A CN 201310277794A CN 103303872 B CN103303872 B CN 103303872B
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gas
sulphur
pipeline
absorption
boiler
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CN201310277794.1A
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CN103303872A (en
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李蒙
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陕西智惠环保科技有限公司
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The invention discloses a system device and a method for recycling sulfur dioxide from fume to prepare sulfur. The device comprises three units of an absorption and pyrolysis unit, a reduction unit and a krauss unit, wherein the absorption and pyrolysis unit mainly consists of a cooling tower, an absorbing tower, a purifier, a circulation pump, a regeneration pyrolysis tank and a rich and lean liquid heat exchanger; the reduction unit mainly consists of a mixed gas generation system, a reduction reactor and a sulfur condenser; the krauss unit mainly consists of a krauss reactor and a sulfur condenser. The method comprises the steps that the absorption and pyrolysis unit absorbs and pyrolyzes the fume so as to obtain a pure sulfur dioxide gas, and the reduction unit converts the sulfur dioxide into elementary sulfur through catalysis reaction, wherein the conversion per pass is not less than 95%, and the total conversion is greater than 99.5%. The sulfur dioxide content that the fume is completely discharged is not greater than 50 milligrams per normal cubic meter. The sulfur dioxide is converted into national best grade sulfur products which are stable in property and convenient to store and transport, with high efficiency and low cost, the desulfuration operation cost is lower than the value of a recycled product, and the products can be widely applied to chemistry and thermal power industry.

Description

From flue gas, reclaim sulfurous gas and produce system and device and the method for sulphur

Technical field

The present invention relates to the industry equipment such as chemical industry and thermoelectricity, be specifically related to reclaim system and device and the method that sulfurous gas is produced sulphur from flue gas.

Background technology

Sulphur pollution situation and reason

China is maximum sulphur pollution source place, the whole world, and sulphur dioxide emission surpass 2,000 ten thousand tons and sustainable growths for years, wherein the sulfurous gas of power plant emission account for total amount half, acid rain control district and sulfur dioxide control district sulphur emissions amount account for 60% of total amount.The urban population in the whole nation 1/3 is being breathed the air of severe contamination, and 1/3 territory is corroded by acid rain.

The sulfurous gas in the whole nation 90% is by coal fire discharged, and boiler smoke sulfur-bearing is sulphur pollution the largest source.Although power plant all has boiler flue gas desulfurization device to remove most of sulfurous gas, flue gas remaining sulfur dioxide enters atmospheric layer with " legal discharge up to standard " form, and along with coal consumption amount increases severely, topsoil is day by day serious.

The sulfurous gas of " legal discharge up to standard " is more and more, is that basic reason is that existing desulfurization technology is difficult to reach higher standard because emission standard is slowly difficult to improve.Because of the flue gas desulfurization technique overwhelming majority in use, be also retirement method, sulphur resource cannot reclaim, and operation desulfurizer equals to burn money, arranges steathily phenomenon and is difficult to radical cure.

The overwhelming majority of retirement method is calcium method, and with gypsum form " fixedly sulphur " discarded, annual 20000000 tons of sulphur do not obtain resource utilization and reclaim, and the up to ten million ton of import sulphur meets the industry needs such as chemical fertilizer, rubber again simultaneously.

Domestic Boiler Flue Gas Desulphurization Technology situation

Chinese large-sized coal burning boiler of power station flue gas desulfurization technique has experienced the development of more than 30 year, and the flue gas desulfurization technique that successively drops into application has tens kinds.The nineties rise to application in the world more widely sulfur removal technology carry out engineering demonstration and progressively promote, become the mainstream technology of present domestic power plant desulfurization.These sulfur removal technologies are mainly:

1, Wingdale-gypsum wet flue gas desulfurizing technique;

2, simple and easy Wingdale-gypsum wet flue gas desulfurizing technique;

3, the rotary spray semi-dry flue gas desulphurization (LSD method);

4, flue gas desulfurization with seawater technique;

5, in-furnace calcium spraying adds afterbody humidification activation technique (LIFAC method);

6, electron beam flue gas desulfurization technique (EBA);

7, ciculation fluidized catalyst bed boiler desulfurization technique (boiler CFB);

Above technology all belongs to the disposable method of abandoning, and the overwhelming majority be take lime as sulphur-fixing agent.

The background of the technology the present invention relates to

The alkali liquor absorption technology the present invention relates to

Prior art alkali absorption method is called Weir Man-Luo Defa (W-L method), than existing calcium law technology, can reduce sulfur dioxide emissions.But absorbing the product obtaining is hypertoxic sulfur dioxide gas, be not easy to transportation, its utilization is very limited, and the system complex of sulfurous gas absorption and regeneration of absorption solution and sulfurous gas utilization, investment is higher with working cost, can not get for a long time widespread use.

W-L sources of law reclaim the technique of sulfurous gas from tail gas in vitriol works.Comprise SO 2absorption, pyrolysis regeneration and SO 2gas recovery such as processes again at several unit.Its main processes is flue gas through Venturi scrubber pre-treatment, washes away 70%~80% flying dust and 90%~95% muriate.Pretreated flue gas passes into packed absorber, reversely contacts with sodium sulfite solution, and sodium sulfite solution reacts with sulfurous gas and generates sodium bisulfite and remove the sulfurous gas in flue gas, and solution refluxes piecemeal and is able to enrichment.Flue gas after purification is emptying from chimney.

The sulfurous gas that W-L method reclaims can sulfuric acid processed, and the vitriol oil with 98% is dried, through V 2o 5touch oxidation of coal and generate SO 3, with the vitriol oil, absorb and be diluted to industrial sulphuric acid.

The chlorine more than reclaiming is the same with gaseous sulfur dioxide, has the defect of severe toxicity, difficult transportation storage, and sulfuric acid product also exists when lacking user or fluctuation of price dull sale nearby defect that cannot mass storage, usually becomes insurmountable burden.

The reduction technique the present invention relates to

Wherein, mixed gas preparation adopts the skid suite of equipment of commercialization buying, and technology maturation is reliable.Hydrogen reduction sulfurous gas produces sulphur and hydrogen sulfide is also mature technology, but be only applied to the recovery of lower concentration sulphur tail gas, and pure sulfur dioxide gas is recovered as sulphur or blank.

The Crouse's technology the present invention relates to

The present invention also applies the hydrogen sulfide recovery sulphur of Sulfur Recovery Unit technical finesse reduction process output gas, but simplified classical Crouse's flow process, reduces equipment handled easily.Classical Sulfur Recovery Unit technology is as follows:

Crouse's technology is hydrogen sulfide to be changed into the commercial run of sulphur, three grades of classical claus process flow processs comprise partial oxidation, condensation divide sulphur, Process Gas again heat react again, enter the steps such as atmosphere after the burning of tail gas unreacted hydrogen sulfide.The liquid sulfur that Crouse's condensers at different levels are separated becomes solid sulfur product through moulding, the tail gas of isolating liquid sulfur contains a small amount of unreacted hydrogen sulfide, through incinerator, take excess air all burns unreacted hydrogen sulfide after sulfurous gas, to enter atmosphere, its content of sulfur dioxide of burning rear emission is higher, thereby the recovery of sulphur is not thorough.

Summary of the invention

In order to change the disposable present situation of abandoning the leading flue gas desulfurization industry of method of decades prevailing, with regenerating desulfurization agent, realizing low cost removes SO 2 from fume and is converted into the product that has utility value that is easy to storage, need to overcome the deficiency of prior art alkali liquor absorption technology, hydrogen reduction sulfurous gas technology, Crouse's technology, three is integrated into brand-new recovery system that can low cost movement.

One of object of the present invention is to provide a kind of system and device that sulfurous gas is produced sulphur that reclaims from flue gas.

Another object of the present invention is to provide a kind of method that sulfurous gas is produced sulphur that reclaims from flue gas.

Technical scheme of the present invention: the inventive system comprises boiler systems, its feature is to comprise absorption pyrolysis unit, reduction unit and Crouse unit, described unit and boiler systems are used in conjunction with, and wherein said absorption pyrolysis unit is comprised of wash cooling tower 7, absorption tower 8, cleaner 9, cycles of washing groove 21, cleaning circulation pump 22, regeneration pyrolysis groove 16, regenerative heater 11, absorbent recirculation pump 19, poor rich liquid heat exchanger 20, slush pump 18 and spiral desilt machine 17, described reduction unit is comprised of mixed gas generation systems 13, reduction reactor 10 and a sulfur condenser 12, described Crouse unit is comprised of claus reaction device 14 and No. two sulfur condensers 15, described boiler systems is comprised of boiler 1, air preheater 2, chimney 3, gas door 4, No. two gas doors 5 and No. three gas doors 6, and feature of the present invention is also by a gas door 4, to be connected with the gas approach of wash cooling tower 7 before No. three gas doors 6 from the flue of air preheater 2, described wash cooling tower 7 communicates with the exhaust gases passes on absorption tower 8, and the exhanst gas outlet on absorption tower 8 is connected with chimney 3 by pipeline and No. two gas doors 5, described cleaning circulation pump 22 entrance ends are connected with cycles of washing groove 21 by pipeline, described cleaning circulation pump 22 exit end are connected with the washings import of wash cooling tower 7 by pipeline, the washings outlet of described wash cooling tower 7 is connected with cycles of washing groove 21 by pipeline, slush pump 18 entrance ends are connected with cycles of washing groove 21 by pipeline, the exit end of slush pump 18 is connected with spiral desilt machine 17 by pipeline, the entrance end of absorbent recirculation pump 19 is connected with the lean solution outlet of regeneration pyrolysis groove 16 by pipeline, absorbent recirculation pump 19 exit end are connected with poor rich liquid heat exchanger 20 lean solution imports by pipeline, the lean solution outlet of described poor rich liquid heat exchanger 20 is connected with absorption tower 8 lean solution imports by pipeline, on the pipeline of the lean solution outlet connection absorption tower 8 lean solution imports of poor rich liquid heat exchanger 20, has valve to be connected with cleaner 9 with bypass duct, the sewage draining exit of described cleaner 9 is connected with cycles of washing groove 21 by pipeline, the rich solution outlet on described absorption tower 8 is connected by pipeline with the rich solution import of poor rich liquid heat exchanger 20, and the rich solution outlet of poor rich liquid heat exchanger 20 is connected by pipeline with the rich solution import of regeneration pyrolysis groove 16, the cold liquid import of regenerative heater 11 and hydrothermal solution outlet are connected with regeneration pyrolysis groove 16 by pipeline, the pneumatic outlet of described regeneration pyrolysis groove 16 is connected with reduction reactor 10 sulfurous gas imports by pipeline, the 13 mixed gas outlets of mixed gas generation systems are connected with reduction reactor 10 mixed gas imports by pipeline, reduction reactor 10 pneumatic outlets are connected with sulfur condenser 12 gas feeds by pipeline, sulfur condenser 12 tail gas outlets are connected with 14 gas feeds of claus reaction device by pipeline, the described shunting sulfurous gas device for cleaning pipeline from regeneration pyrolysis groove 16 crosses valve and a sulfur condenser 12 is connected with the pipeline between claus reaction device 14, described No. two sulfur condenser 15 gas feeds are connected with claus reaction device 14 by pipeline, the tail gas outlet of No. two sulfur condensers 15 is connected with air preheater 2 to the hot-air duct between boiler 1 by pipeline,

Reduction reactor of the present invention is by shell, a transformation catalyst bed, two reducing catalyst beds and gas distributor and an a set of waste heat boiler module composition for Quench and sulfurous gas mixing.Gas distributor can make it to be applicable to carrying out the reaction that next catalyst bed is new by dispersed sulfur dioxide gas reduction reducing catalyst bed output gas temperature.Between one-level and second-stage reduction catalyst bed, arrange that a set of waste heat boiler conduit assembly makes it to be applicable to next stage reduction reaction for the output gas cooling to first step reducing catalyst bed.Concrete structure is that mixed gas import A is established in the upper end of described shell of reactor 35, pneumatic outlet E is established in lower end, middle part is established sulfurous gas import B and is connected by flange with the gas distributor 34 of inside reactor, and the first manhole 23, the second manhole 25, drum 26 and spigot discharge 30 are established in the side of described shell of reactor 35, described drum 26 is provided with byproduct steam outlet C and is connected 2-6 header group with oiler feed import D and by pipeline, described header group is comprised of a header 27-1 and another header 27-2, and the header of described header group is interconnected by waste heat boiler boiler tube 32 and is connected with shell of reactor 35 by flange, described catalyst bed is arranged from top to bottom at shell of reactor 35 inner chambers, the first layer grating plate 29-1 is connected with shell of reactor 35 on top, put porcelain ball two 31-1 on it, transformation catalyst 24 forms the first catalyst bed with porcelain ball one 33-1 of covering catalyst, second layer grating plate 29-2 is connected with shell of reactor 35 at middle part, put another porcelain ball two 31-2 on it, another porcelain ball one 33-2 of reducing catalyst 28-1 and covering catalyst forms the second catalyst bed, the 3rd layer of grating plate 29-3 is connected with shell of reactor 35 in bottom, put porcelain ball two 31-3 again on it, porcelain ball one 33-3 again of another transformation catalyst 28-2 and covering catalyst forms the 3rd catalyst bed.Described claus reaction device, because the high reaction temperature rising of sulfurous gas unstripped gas purity is large, adopts bilayer structure to avoid housing contacts high-temperature gas, and can utilize catalyst bed output gas in the heat exchange of down going channel and unstripped gas to unstripped gas preheating.Catalytic reaction catalyst berth is in reactor center cylinder, feeding gas enters reactor by bottom, through fold-line-shaped between the pipe of tubulation group rise again by central tube around annular space rise to headspace and enter catalyst bed under backward, in the pipe of output gas by tubulation group, drop to outlet at bottom and leave reactor, cold and hot gas is through the tube wall heat conduction heat-shift of tubulation group, device housings does not contact high temperature output gas, can use common iron manufacture.Central tube is only catalyzer pallet, contact high temperature but not by thin-wall stainless steel plate, made by thermal stresses, the tubulation that forms passage is whole by upper and lower two Tube-sheet Weldings, lower tubesheet and reactor lower part shell are welded and fixed, the welding of upper tubesheet and central tube and shell are not connected can unmanaged flexibility, the some longitudinal flaps of central tube outside suitable for reading welding keep central tube concentric with shell, and concrete structure is as follows:

The catalyzer 50 of described claus reaction device 14 is positioned at alumina ball 48 tops in the middle of inner core 47, inner core 47 is connected with the upper tubesheet 46 that is positioned at its below, upper tubesheet 46 is connected with the tubulation group 44 that is positioned at its below, tubulation group 44 is connected with the lower tubesheet 43 that is positioned at its below, the hypomere inner side of lower tubesheet 43 and hypomere urceolus 40 is connected, forms inside outer tube inner chamber the lower end internals that fixedly upper end can unmanaged flexibility and combines; The top cover of epimere urceolus 36 connects hand-hole 37, and stage casing cone cylinder 38 connects bearing 39, and hypomere urceolus 40 sides are established gas feed 41 bottom surfaces and established pneumatic outlet 42, between inner core 47 and epimere urceolus 36, are annular space; The gas feed 41 of hypomere urceolus 40 sides communicates with the suitable for reading of inner core 47 with the annular space between urceolus by space between the pipeline of tubulation group 44 and inner core 47, and the end opening of inner core 47 communicates with the pneumatic outlet 42 of hypomere urceolus 40 bottoms by space in the pipe of the tubulation group 44 of its below; Inner core 47 outside surroundings are connected with flap centralizer 49, connect a ring baffle plate 45-1 and another ring baffle plate 45-2 between the pipe of tubulation group 44;

A kind of method that sulfurous gas is produced sulphur that reclaims from flue gas of the present invention, carry out in the steps below:

1), the high-temperature flue gas from boiler 1 is cooled to 130 ℃~160 ℃ with the air that enters boiler 1 in air preheater 2 heat exchange, through gas door 4 of bypass flue, be admitted to wash cooling tower 7 cooling of giving a dinner of welcome, with 60-65 ℃, approach water saturated state and enter 8 bottoms, absorption tower, in absorption tower 8, fully contact with circulating absorption solution, sulfurous gas in flue gas and the S-WAT in the absorption liquid generation sodium bisulfite that reacts, the clean flue gas removing after sulfurous gas enters chimney 3 emptying by 8 tops, absorption tower through No. two gas doors 5 of bypass flue;

2), the washings of wash cooling tower 7 is saturated brine, washings delivers into through cleaning circulation pump 22 circulation the dust that 7 pairs of flue gases of wash cooling tower carry by cycles of washing groove 21 and carries out spray washing, the moisture evaporation of washings makes boiler flue gas cool-down and makes the crystallization of the concentrated generation of washings salt, together with the flue dust that the salt of washings crystallization carries with washings, form salt slurry and fall to cycles of washing groove 21 bottoms, through slush pump 18, send into 17 centrifugations of spiral desilt machine and remove, isolated clear liquid returns to cycles of washing groove 21 by spiral desilt machine 17 and recycles;

3), the circulating absorption solution on absorption tower 8 is divided into lean solution and rich solution according to the content of sodium bisulfite wherein, enter the lean solution on absorption tower 8 for containing more than 20% sodium sulfite aqueous solution of S-WAT, absorbent recirculation pump 19 is sent lean solution into 8 tops, absorption tower, under 60~65 ℃, gauge pressure 3kPa condition, carry out absorption reaction, absorbing the rich solution producing is the absorption liquid that is rich in sodium bisulfite; After heat is reclaimed in poor rich liquid heat exchanger 20 and the lean solution heat exchange of entering absorption tower 8, enter regenerative heat solution groove 16 regenerates under 90~130 ℃ of conditions, to the regeneration of rich solution, make sodium bisulfite decomposition wherein become S-WAT, the sulfur dioxide gas that rich solution regeneration produces is collected through regeneration pyrolysis groove 16 tops, and steam provides regeneration of absorption solution required heat by regenerative heater 11;

4) absorption liquid removes to avoid accumulating in absorption liquid from a small amount of chlorion and the cleaner 9 of sulfate ion through absorption liquid bypass duct of smoke absorption, and the sodium-chlor that cleaner 9 removes and sodium sulfate are usingd effluent brine form and drained into cycles of washing groove 21 as the part make up water of washings;

5) reduction reaction of sulfurous gas is completed through reduction reactor catalysis by mixed gas, and mixed gas contains H 211~15%, CO 24~30% and water vapor, mixed gas enters reduction reactor top the first catalyst bed by the gas inlet A of reduction reactor 10, and carbon monoxide reacts and generates hydrogen at catalyst bed with water vapor, and the volumetric molar concentration of hydrogen in mixed gas is reached more than 30% by 11~15%; Sulfurous gas from regeneration pyrolysis groove 16 splits into two-way, the 70-80% that wherein a road accounts for total amount is entered by the sulfurous gas import B of reduction reactor 10, hydrogen in the second catalyst bed and mixed gas and reaction of carbon monoxide, the sulfurous gas that enters reduction reactor 10 is partly reduced to sulphur, all the other are reduced to hydrogen sulfide, the output gas of reduction reactor 10 enters that a sulfur condenser 12 is cooling, and sulphur steam is condensed into Molten sulphur, and incoagulability tail gas is sent into claus reaction device 14;

6) the incoagulability tail gas of a described sulfur condenser 12 enters claus reaction device 14 after mixing with all the other 20-30% sulfurous gas of described shunting and carries out claus reaction, it is cooling that reaction output gas enters No. two sulfur condensers 15, sulphur steam is condensed into Molten sulphur, incoagulability tail gas is sent into the hot-air duct of air preheater 2 outlets of boiler systems through pipeline, after mixing with warm air, entering boiler 1 burns, the trace hydrogen sulfide containing in tail gas is oxidized to sulfurous gas in boiler 1, enters absorption tower 8 together with the sulfurous gas producing to reclaim with boiler combustion;

The special feature of aforesaid method also comprises:

The cleaner that absorption liquid is absorbed liquid bypass duct from a small amount of chlorion and the sulfate ion objectionable impurities of smoke absorption removes to avoid accumulating in absorption liquid, the sodium chloride salt that cleaner removes and sodium sulfate salt are usingd effluent brine form and are drained into cycles of washing groove as the make up water of washings, the salt of effluent brine is by the inspissated of flue gas in wash cooling tower and crystallization removes from washings with salt slurry form;

Described sulphur dioxide reduction, is reacted through the catalyst of described reduction reactor with described sulfurous gas by described mixed gas and generates sulphur and hydrogen sulfide.

The hydrogen sulfide that described reduction reaction generates reacts with the sulfurous gas of described shunting at claus reaction device and generates sulphur.

In the solidifying sulphur tail gas of described Crouse, residual hydrogen sulfide burns, do not need to arrange specially incinerator, incineration ashes sulfurous gas does not adopt Dilution air discharge yet, but send into boiler, burns and is again reclaimed by absorption tower, and the final transformation efficiency of sulfurous gas is reached more than 99.5%.

The described H that enters claus reaction device 2s and SO 2mol ratio can according to the catalyst activity of reduction reactor and reaction residual hydrogen sulfide content regulate, due to not directly discharge but again absorb and can guarantee that clean fume emission is up to standard through absorption tower of residual sulfur compound in the solidifying sulphur tail gas of Crouse, Crouse's per pass conversion is little on the content of sulfur dioxide impact of clean flue gas, so to H 2s and SO 2mol ratio control to require to be different from general Crouse's strict ratio, span of control is 1.90:1-2.10:1, possesses flexible operation condition.

Method of the present invention comprises Claus tail gases and sends into the flow process that boiler burns and again reclaimed by absorption tower, S-contained substance in Claus tail gases can be reclaimed and be returned to Crouse unit by cost effective method, final quantity discharged and Crouse's per pass conversion relation of sulphur are little, system and device does not rely on Crouse's per pass conversion to reclaiming the high conversion of sulfurous gas, therefore, the present invention adopts common Crouse to reclaim the remaining hydrogen sulfide of reduction sulphur processed unit, although per pass conversion is not high but satisfy the demand completely, therefore the Crouse unit of this technology adopts common Crouse's technology, flow process and equipment have also been simplified.

This technology reduces than the clean SO 2 from fume quantity discharged of existing calcium method desulfurization technology.This technology purifies and the improvement of regeneration link makes to absorb pyrolysis system and more simplifies effectively at alkali liquor absorption and absorption liquid, at sulfurous gas, utilize link to adopt mixed gas cheap and easy to get and dual catalyst multi-catalyst bed reduction reactor that sulfurous gas is made to sulphur, and utilize claus reaction further to process remaining hydrogen sulfide, make sulfurous gas high-efficiency and low-cost be converted into state's top grade sulfur product that stable performance is convenient to store transportation, make desulfurization operation cost lower than the value that reclaims product.

The present invention compared with prior art, have adopt regenerating desulfurization agent, flue gas sulphur content is lower, equipment simple, investment and the low feature of running cost, can be widely used in chemical industry and Thermal Power Generation Industry.

Accompanying drawing explanation

Fig. 1 is the formation schematic diagram of system and device of the present invention;

Fig. 2 is the reduction reactor structural representation of Fig. 1

Fig. 3 is the claus reaction device structural representation of Fig. 1

Sequence number explanation in Fig. 1: 1, boiler, 2, air preheater, 3, chimney, 4, a gas door, 5, No. two gas doors, 6, No. three gas doors, 7, wash cooling tower, 8, smoke absorption tower, 9, cleaner, 10, reduction reactor, 11, regenerative heater, l2, a sulfur condenser, 13, mixed gas generating unit, 14, claus reaction device, 15, No. two sulfur condensers, 16, regeneration pyrolysis groove, 17, spiral desilt machine, 18, slush pump, 19, absorbent recirculation pump, 20, poor rich liquid heat exchanger, 2l, cycles of washing groove, 22, cleaning circulation pump.

Sequence number explanation in Fig. 2: A mixed gas import, the import of B sulfurous gas, the outlet of C byproduct steam, D oiler feed import, E pneumatic outlet, 23, manhole one, 24, transformation catalyst bed, 25, manhole two, 26, drum, 27-1, one header, 27-2, another header, 28-1, one reducing catalyst bed, 28-2, another reducing catalyst bed, 29-1, grating plate, 29-1, another grating plate, 29-1, a grating plate again, 30, discharge opening, 31-1, porcelain ball two, 31-2, another porcelain ball two, 31-3, a porcelain ball two again, 32, waste heat boiler boiler tube group, 33-1, porcelain ball one, 33-2, another porcelain ball one, 33-3, porcelain ball one again, 34, gas distributor, 35, shell of reactor.

Sequence number explanation in Fig. 3: 36, epimere urceolus, 37, manhole, 38, middle cone cylinder, 39, bearing, 40, hypomere urceolus, 41, gas feed, 42, pneumatic outlet, 43, lower tubesheet, 44, tubulation group, 45, ring baffle plate, 46, upper tubesheet, 47, stainless steel inner core, 48, alumina ball, 49, flap centralizer, 50, catalyst bed.

Embodiment

Below by the description to design philosophy of the present invention, by reference to the accompanying drawings 1 to 3 and the invention will be further described by embodiment, but the present invention is not limited to these embodiment.

The present invention reclaims sulfurous gas from flue gas, and to produce the system and device of sulphur be to form by absorbing pyrolysis unit, reduction sulphur processed unit, Crouse sulphur processed unit and boiler systems; The present invention has entered to improve perfect to each monotechnics scheme, creatively be combined in system and device, make the process simplification of sulfurous gas absorption and regeneration of absorption solution, at sulfurous gas, utilize link to adopt hydrogen reduction technology that sulfurous gas is made to sulphur, in conjunction with the further recovery sulphur in Crouse unit of simplifying, make to absorb the sulfurous gas that pyrolysis obtains and be all recovered as state's top grade sulfur product that stable performance is convenient to store transportation.

Technology of the present invention utilizes link to adopt mixed gas reduction sulfurous gas at sulfurous gas, and coal gas preparation adopts ripe business procurement complexes.The hydrogen reduction sulfurous gas adopting is produced sulphur know-why:

Hydrogen, under catalyst action, can directly react and is reduced into elemental sulfur with sulfurous gas, H 2: SO 2=3,300 ℃ of temperature of reaction, sulfurous gas is at CO-MO/Al 2o 3on series catalysts by H 2be reduced into elemental sulfur.Reaction comprises two separate reaction process that occur at different activities center:

For the carbon monoxide in mixed gas being converted into hydrogen as much as possible before reduction, reduction reactor arranges transformation catalyst bed before reducing catalyst bed, improves the hydrogen richness of mixed gas by following reaction.

Within the present invention is integrated in a reactor by two kinds of catalyst beds.Exothermic effect due to above reaction, the temperature of transformationreation output gas is by the temperature needing higher than reduction reaction, sulfurous gas adopts cold conditions to enter the mode charging of reactor to conversion mixed gas Quench, the mixed gas temperature that makes to enter reducing catalyst bed more approaches the temperature that reduction reaction needs, and flow process and equipment simple.

Hydrogen reacts the process that is reduced into elemental sulfur with sulfurous gas, also have a large amount of hydrogen sulfide to produce.

The present invention also applies the further recovery sulphur of hydrogen sulfide of Sulfur Recovery Unit technical finesse reduction process output gas, comprises Claus tail gases is sent into the flow process that boiler burns and again reclaimed by absorption tower.The improved Crouse of the present invention has simplified technical process, more convenient operation in unit.

The present invention improves the technology that absorbs pyrolysis unit, reduction unit, Crouse unit and adopt, and it is creationaryly combined into a kind of system and device that sulfurous gas is produced sulphur that reclaims from flue gas, is unexistent at present.Adopt this system and device from flue gas, to reclaim sulfurous gas and produce the method for sulphur, by to sulfurous gas absorption, the removing of absorption liquid detrimental impurity, the improvement that sulfurous gas utilizes each link, with the method for cheap and simple comparatively, solved desulfurizer " too complicated economy is a uneconomical " difficult problem that adopts regenerating desulfurization agent, make desulfurization operation cost lower than the value that reclaims product, sulfurous gas is made to state's top grade sulfur product that stable performance is convenient to store transportation.This technology will be brought a revolution to flue gas desulfurization industry, be one and both be conducive to environment protection, have again the technology of great social profit and economic benefit, also can utilize the sulphur resource in coal, make China no longer rely on other country's sulphur resource.

Shown in Fig. 1, the present invention from flue gas, reclaim system and device that sulfurous gas produces sulphur by absorbing pyrolysis unit, reduction unit, Crouse unit forms and be used in conjunction with boiler systems, wherein said absorption pyrolysis unit is comprised of wash cooling tower 7, absorption tower 8, cleaner 9, cycles of washing groove 21, cleaning circulation pump 22, regeneration pyrolysis groove 16, regenerative heater 11, absorbent recirculation pump 19, poor rich liquid heat exchanger 20, slush pump 18, spiral desilt machine 17, described reduction unit is comprised of mixed gas generation systems 13, reduction reactor 10, a sulfur condenser 12, described Crouse unit is comprised of claus reaction device 14, No. two sulfur condensers 15, described boiler systems is comprised of boiler 1, air preheater 2, chimney 3, gas door 4, No. two gas doors 5, No. three gas doors 6, from the flue of air preheater 2, before No. three gas doors 6, by a gas door 4, is connected with the gas approach of wash cooling tower 7, described wash cooling tower 7 communicates with the exhaust gases passes on absorption tower 8, and the exhanst gas outlet on absorption tower 8 is connected with chimney 3 by pipeline and No. two gas doors 5, described cleaning circulation pump 22 entrance ends are connected with cycles of washing groove 21 by pipeline, described cleaning circulation pump 22 exit end are connected with the washings import of wash cooling tower 7 by pipeline, the washings outlet of described wash cooling tower 7 is connected with cycles of washing groove 21 by pipeline, slush pump 18 entrance ends are connected with cycles of washing groove 21 by pipeline, the exit end of slush pump 18 is connected with spiral desilt machine 17 by pipeline, the entrance end of absorbent recirculation pump 19 is connected with the lean solution outlet of regeneration pyrolysis groove 16 by pipeline, absorbent recirculation pump 19 exit end are connected with poor rich liquid heat exchanger 20 lean solution imports by pipeline, the lean solution outlet of described poor rich liquid heat exchanger 20 is connected with absorption tower 8 lean solution imports by pipeline, on the pipeline of the lean solution outlet connection absorption tower 8 lean solution imports of poor rich liquid heat exchanger 20, has valve to be connected cleaner 9 with bypass duct, the sewage draining exit of described cleaner 9 is connected with cycles of washing groove 21 by pipeline, the rich solution outlet on described absorption tower 8 is connected by pipeline with the rich solution import of poor rich liquid heat exchanger 20, and the rich solution outlet of poor rich liquid heat exchanger 20 is connected by pipeline with the rich solution import of regeneration pyrolysis groove 16, the cold liquid import of regenerative heater 11 and hydrothermal solution outlet are connected with regeneration pyrolysis groove 16 by pipeline, the pneumatic outlet of described regeneration pyrolysis groove 16 is connected with reduction reactor 10 sulfurous gas imports by pipeline, the 13 mixed gas outlets of mixed gas generation systems are connected with reduction reactor 10 mixed gas imports by pipeline, the pneumatic outlet of reduction reactor 10 is connected with sulfur condenser 12 gas feeds by pipeline, sulfur condenser 12 tail gas outlets are connected with 14 gas feeds of claus reaction device by pipeline, the described shunting sulfurous gas device for cleaning pipeline from regeneration pyrolysis groove 16 crosses valve and a sulfur condenser 12 is connected with the pipeline between claus reaction device 14, described No. two sulfur condenser 15 gas feeds are connected with claus reaction device 14 by pipeline, the tail gas outlet of No. two sulfur condensers 15 is connected with air preheater 2 to the hot-air duct between boiler 1 by pipeline,

As shown in Figure 2, described reduction reactor 10 is by shell of reactor, three catalyst beds, a gas distributor, a set of waste heat boiler module composition, described shell of reactor is Steel Vessel, there are two reacting gas inlets outside, pneumatic outlet and manhole, discharge opening, inner arrange have at least 3 series connection by grating plate, porcelain ball, the catalyst bed that catalyzer forms, described catalyzer has one deck to carry out for mixed gas carbon monoxide and water vapour the reducing catalyst that the transformation catalyst of transformationreation and the two-layer hydrogen for mixed gas and carbon monoxide and sulfurous gas carry out reduction reaction, mixed gas import A is established in the upper end of described shell of reactor 35, and output pneumatic outlet E is established in lower end, and middle part is established sulfur dioxide gas import B and is connected by flange with the gas distributor 34 of inside reactor, the first manhole 23, the second manhole 25, drum 26 and spigot discharge 30 are established in the side of described shell of reactor 35, described drum 26 is provided with byproduct steam outlet C and is connected 2-6 header group with oiler feed import D and by pipeline, described header group is comprised of a header 27-1 and another header 27-2, and the header of described header group is interconnected by waste heat boiler boiler tube 32 and is connected with shell of reactor 35 by flange, described catalyst bed is arranged from top to bottom at shell of reactor 13 inner chambers, the first layer grating plate 29-1 is connected with shell of reactor 35 on top, put porcelain ball two 31-1 on it, transformation catalyst 24 forms the first catalyst bed with porcelain ball one 33-1 of covering catalyst, second layer grating plate 29-2 is connected with shell of reactor 35 at middle part, put another porcelain ball two 31-2 on it, another porcelain ball one 33-2 of reducing catalyst 28-1 and covering catalyst forms the second catalyst bed, the 3rd layer of grating plate 29-3 is connected with shell of reactor 35 in bottom, put porcelain ball two 31-3 again on it, porcelain ball one 33-3 again of another transformation catalyst 28-2 and covering catalyst forms the 3rd catalyst bed.

Reduction reactor of the present invention inside is arranged from top to bottom one-level transformation catalyst bed and two-stage reductive catalyst bed is installed, and every layer of catalyzer covers and supported by grating plate by porcelain ball in bulk up and down.For Quench and and sulfurous gas mixes is a set of gas distributor, can dispersed sulfur dioxide gas reduce the first catalyst bed output gas temperature and make it to be applicable to carrying out the reaction that next catalyst bed is new.Between one-level and second-stage reduction catalyst bed, arrange a set of waste heat boiler conduit assembly, connect to form the Waste Heat System of reactor with external drum, for the output gas cooling to first step reducing catalyst bed, make it to be applicable to next stage reduction reaction.

As shown in Figure 3, claus reaction device 14 of the present invention is by epimere urceolus, manhole, stage casing cone cylinder, bearing, hypomere urceolus, inlet mouth, air outlet, lower tubesheet, tubulation group, ring baffle plate, upper tubesheet, stainless steel inner core, alumina ball, flap centralizer, catalyst bed forms, catalyst bed 50 is positioned at alumina ball 48 tops in the middle of stainless steel inner core 47, stainless steel inner core 47 is connected with the upper tubesheet 46 that is positioned at its below, upper tubesheet 46 is connected with the tubulation group 44 that is positioned at its below, tubulation group 44 is connected with the lower tubesheet 43 that is positioned at its below, lower tubesheet 43 is connected with the hypomere inner side of hypomere urceolus 40, forming lower end, one of the inside of the outer tube inner chamber internals that fixedly upper end can unmanaged flexibility combines.

The top cover of epimere urceolus 36 is connected with manhole 37, and stage casing cone cylinder 38 is connected with bearing 39, and hypomere urceolus 40 sides are established inlet mouth 41 bottom surfaces and set out gas port 42, between stainless steel inner core 47 and epimere urceolus 36, are annular space; The inlet mouth 41 that hypomere urceolus 40 sides connect communicates with the suitable for reading of catalyst bed 50 with the annular space between epimere urceolus 36 by space between the pipeline of tubulation group 44 and stainless steel inner core 47, and the end opening of catalyst bed 50 communicates with the pneumatic outlet 42 of hypomere urceolus 40 bottoms by space in the pipe of the tubulation group 44 of its below; Stainless steel inner core 47 outside surroundings are connected with flap centralizer 49, connect a ring baffle plate 45-1 and another ring baffle plate 45-2 between the pipe of tubulation group 44.

Claus reaction device of the present invention, because the high reaction temperature rising of sulfurous gas unstripped gas purity is large, adopts bilayer structure to avoid housing contacts high-temperature gas, and can utilize catalyst bed output gas in the heat exchange of down going channel and unstripped gas to unstripped gas preheating.Catalytic reaction catalyst berth is in reactor center cylinder, feeding gas enters reactor by bottom, through fold-line-shaped between the pipe of tubulation group rise again by central tube around annular space rise to headspace and enter catalyst bed under backward, in the pipe of output gas by tubulation group, drop to outlet at bottom and leave reactor, cold and hot gas is through the tube wall heat conduction heat-shift of tubulation group.Device housings does not contact high temperature output gas, can use common iron manufacture.Central tube is only catalyzer pallet, contacts high temperature but not by thin-wall stainless steel plate, made by thermal stresses.The tubulation that forms passage is whole by upper and lower two Tube-sheet Weldings, and lower tubesheet and reactor lower part shell are welded and fixed, and upper tubesheet is not connected with shell with central tube welding can unmanaged flexibility.The some longitudinal flaps of central tube outside suitable for reading welding keep central tube concentric with shell.

A kind of method that sulfurous gas is produced sulphur that reclaims from flue gas of the present invention, carry out in the steps below:

1), the high-temperature flue gas from boiler 1 is cooled to 130 ℃~160 ℃ with the air that enters boiler 1 in air preheater 2 heat exchange, through gas door 4 of bypass flue, be admitted to wash cooling tower 7 cooling of giving a dinner of welcome, with 60-65 ℃, approach water saturated state and enter 8 bottoms, absorption tower, in absorption tower 8, fully contact with circulating absorption solution, sulfurous gas in flue gas and the S-WAT in the absorption liquid generation sodium bisulfite that reacts, the clean flue gas removing after sulfurous gas enters chimney 3 emptying by 8 tops, absorption tower through No. two gas doors 5 of bypass flue;

2), the washings of wash cooling tower 7 is saturated brine, washings delivers into through cleaning circulation pump 22 circulation the dust that 7 pairs of flue gases of wash cooling tower carry by cycles of washing groove 21 and carries out spray washing, the moisture evaporation of washings makes boiler flue gas cool-down and makes the crystallization of the concentrated generation of washings salt, together with the flue dust that the salt of washings crystallization carries with washings, form salt slurry and fall to cycles of washing groove 21 bottoms, through slush pump 18, send into 17 centrifugations of spiral desilt machine and remove, clear liquid returns to cycles of washing groove 21 by spiral desilt machine 17 and recycles;

3), the circulating absorption solution on absorption tower 8 is divided into lean solution and rich solution according to bisulfite sodium content difference, enter the lean solution on absorption tower 8 for containing more than 20% sodium sulfite aqueous solution of S-WAT, absorbent recirculation pump 19 is sent lean solution into 8 tops, absorption tower, at 60~65 ℃, under gauge pressure 3kPa condition, carry out absorption reaction, absorbing the rich solution producing is the absorption liquid that is rich in sodium bisulfite, after heat is reclaimed in poor rich liquid heat exchanger 20 and the lean solution heat exchange of entering absorption tower 8, enter regenerative heat solution groove 16 regenerates under 90~130 ℃ of conditions, by steam heating regenerative heater 11, provide regeneration of absorption solution required heat, regeneration makes the sodium bisulfite decomposition of rich solution become S-WAT, the sulfur dioxide gas that regeneration produces is collected by pyrolysis groove 16 tops of regenerating,

4) absorption liquid is objectionable impurities from a small amount of chlorion and the sulfate ion of smoke absorption, cleaner 9 on absorption liquid bypass duct removes to avoid accumulating in absorption liquid, the sodium-chlor that cleaner 9 removes and sodium sulfate are usingd effluent brine form and are drained into cycles of washing groove 21 as the part make up water of washings, and the concentrated and saturated crystallization of the salt of effluent brine smoke evaporative in being washed cooling tower also removes from washings with salt slurry form;

5) sulphur dioxide reduction be take mixed gas and through catalyzed reaction, is completed as reductive agent, and mixed gas contains H 211~15%, CO 24~30% and water vapor.Mixed gas is sent into reduction reactor 10 tops, and the carbon monoxide in mixed gas reacts and generates hydrogen at the first catalyst bed with water vapor, and the volumetric molar concentration of hydrogen in mixed gas is reached more than 30% by 11~15%; Sulfurous gas from regeneration pyrolysis groove 16 splits into two-way, the 70-80% that wherein a road accounts for total amount is entered by the sulfurous gas import B of reduction reactor 10, hydrogen in the second catalyst bed and mixed gas and reaction of carbon monoxide, the sulfurous gas that enters reduction reactor 10 is partly reduced to sulphur, all the other are reduced to hydrogen sulfide, it is cooling that the output gas of reduction reactor 10 enters a sulfur condenser 12, and sulphur steam is condensed and obtains Molten sulphur;

6) the incoagulability tail gas of a sulfur condenser 12 enters claus reaction device 14 after mixing with all the other 20-30% sulfurous gas of described shunting and carries out claus reaction, reaction output gas obtains Molten sulphur through No. two sulfur condenser 15 condensation sulphur steam, uncondensable tail gas is sent into the hot-air duct of air preheater 2 outlets of boiler systems through pipeline, after mixing with warm air, entering boiler 1 burns, the trace hydrogen sulfide containing in tail gas is oxidized to sulfurous gas in boiler 1, enters absorption tower 8 together with the sulfurous gas producing to reclaim with boiler combustion.

Wherein, mixed gas preparation has following characteristics with sulphur dioxide reduction unit:

Mixed gas preparation, the skid suite of equipment that adopts commercialization to purchase.Reduction reactor adopts unique design, has dual catalyst and shifts out reaction heat and control temperature of reaction stable structure.The first layer catalyzer makes reducing degree higher for mixed gas being carried out to transformationreation to improve hydrogen richness.Reduction process settings is, shunts a part of sulfurous gas and directly enters Crouse unit, downstream, and only some sulfurous gas enters second and third catalyst bed of reduction reactor and participates in reduction reaction.The sulfurous gas that enters reduction reactor is partly reduced into sulphur, and all the other are reduced to hydrogen sulfide.Hydrogen sulfide continues in Crouse unit, downstream react and reclaim with the sulfurous gas of shunting.The sulfurous gas flow of shunting by control, can keep meeting claus reaction needs from the hydrogen sulfide of reduction unit and the sulfurous gas mol ratio of shunting.

Wherein, there is following characteristics the improved Crouse of the present invention unit:

The claus reaction that technology of the present invention relates to has the advantages that to be different from classical Crouse, first feature is that the required sulfurous gas of reaction is not the oxidized still that comes from partial combustion process, save the investment that oxidized still investment and dispensing air capacity are controlled, and generated or consumed COS, CS 2, CO, H 2side reaction, make process simplification, investment reduces.The required hydrogen sulfide of claus reaction is from reduction unit, and the sulfurous gas flow of shunting by control is controlled the mol ratio that claus reaction needs.Second, owing to there is no oxidized still, the condition that does not just have the distinctive more than half sulphur of classical claus process to generate in oxidized still, be different from again the lower condition of " shunting " unstripped gas medium sulphide content concentration, so claus reaction device reaction load is very high, the strong heat release meeting of reaction makes the temperature rise of process gas be significantly higher than classical Crouse's reactor, and this reactor need adopt unique design with reply high temperature, and use simple in structure is reliable.The 3rd, the remaining hydrogen sulfide of claus reaction does not arrange special incinerator, but in position Claus tail gases is sent into boiler, can utilize boiler by hydrogen sulfide after-flame.The 4th, classical Crouse's flow process can not make the sulfurous gas of tail gas reach environmental emission standard, if increase retrieving arrangement, makes tail gas up to standard, no matter is with sulfurous gas form, or reclaim after sulphur dioxide reduction is become to hydrogen sulfide, be all costly and need running cost.Technology of the present invention, sulfurous gas itself just derives from smoke absorption, and Claus tail gases flow and residual sulfur content are all inappreciable for absorbing pyrolysis unit, do not increase investment and running cost.The 5th, due to not directly discharge but reclaim through absorbing pyrolysis unit of residual sulfur compound in the solidifying sulphur tail gas of Crouse, can guarantee that fume emission is up to standard, Crouse's per pass conversion is little on the content of sulfur dioxide impact of clean flue gas, so to H 2s and SO 2mol ratio control to require to be different from general Crouse's strict ratio, span of control is 1.90:1-2.10:1, possesses flexible operation condition.

System and device of the present invention removes sulfur dioxide in flue gas and makes the process of sulphur:

Desulfurizer divides three unit: absorb pyrolysis, sulphur dioxide reduction, Crouse.

Absorb absorption and the regenerative process of pyrolysis unit:

From the flue gas of boiler systems, temperature 130-160 ℃, dust-laden is less than 50 milligrams/standard cubic meter, and content of sulfur dioxide is different with ature of coal.Flue gas imports washing tower by flue gas valve, by the washing concentrate circulating that contains dust and salinity, sprays, and in the time of to flue gas washing dedusting, absorbs heat make flue gas cool-down enter absorption tower to 60-65 ℃ by the moisture Evaporation of circulation fluid.The inspissated of hot flue gas makes the crystallization of absorption liquid concentrate salinity, and the dust of accumulation and salinity are discharged from system with solid salt slurry form.

Absorption tower adopts multistage not wait the flow scheme design of flow, and lower semisection adopts large flow semi lean solution circulation to absorb, and upper semisection adopts the lean solution of regeneration to absorb, and can make absorption rate of sulfur dioxide higher, and clean SO 2 from fume content is far below environmental protection standard.The clean flue gas that completes absorption goes out tower and by gas door, imports smoke stack emission by flue.

In absorption process, Micro Amounts of Chlorine and sulphur trioxide, a small amount of S-WAT that absorption liquid meeting enriched flue gas brings can be oxidized, and formation chlorion and sulfate ion cause disadvantageous effect to absorbing.Traditional method adopts the dechlorination of electrolytic brine technique, adopts evaporative crystallization to remove vitriol.The present invention adopts cleaner to remove chlorion and sulfate radical in absorption liquid.Before entering absorption tower, absorption liquid removes muriate and sulfate radical through cleaner, and cleaner blowdown is sodium-chlor and metabisulfite solution, is conveyed to wash cooling tower, becomes salt slurry remove from washings in naturally concentrated mode.This mode plays the effect that maintains the safe handling of system long period equally, without electrolysis process sodium-chlor separated with crystallization processes and sodium sulfate, thereby reduces investment and working cost.

The inspissated that enters the xeothermic flue gas of wash cooling tower can not only can also be for realizing the zero release of the rich salt draining of factory for removing the abraum salt of washings.Be the make up water of washings, can also utilize the water of abandoning of refining de-salted water.Not only saved unboiled water but also found the outlet of factory's brine waste.

Pyrolysis regenerator column makes the sodium bisulfite in absorption liquid decompose under heating condition, makes sulfurous gas with gas form, resolve and collect purity more than 90%.This is also the regenerative process of absorption agent simultaneously, and sodium bisulfite degradation production S-WAT is exactly reusable absorption agent.

The absorption liquid circulating in alkali liquor absorption sulfurous gas process, according to S-WAT be divided into lean solution and rich solutions different from bisulfite sodium content.In tower, the more solution of sulfur dioxide absorption generation sodium bisulfite is called rich solution.Rich solution enters pyrolysis regenerator column, and the S-WAT of take discharge sulfurous gas under heating condition after is that main solution is called lean solution.The lean solution that regeneration obtains is returned to absorption tower sulfur dioxide absorption, recycle again.

The process of mixed gas preparation and sulphur dioxide reduction:

Mixed gas adopts the skid suite of equipment of business procurement, and take coal, air, water vapour is waste, and its composition can meet reduction unit needs, supplies with continuously reduction reactor.

The reduction flow process of system and device of the present invention to sulfurous gas, distinguishing feature is that only some sulfurous gas enters reduction reactor, another part sulfurous gas directly enters Crouse unit, downstream.

Reduction reactor the first layer catalyzer is transformation catalyst, makes carbon monoxide and steam reaction produce more hydrogen.Second and third layer of catalyzer is reducing catalyst, hydrogen reacted with sulfurous gas and generate sulphur and water, and sulfurous gas is partly reduced to hydrogen sulfide.The hydrogen sulfide that reduction process generates continues to react with the sulfurous gas of shunting in Crouse unit, downstream and reclaims, and sulfurous gas per pass conversion is more than 95%.Total conversion rate can reach more than 99.5%.

The catalyzer that reduction reactor adopts is all ripe commerical prod, be widely used in the device that Claus tail gases residual sulfur is processed, these devices are different from system of the present invention, all have the high shortcoming of the complicated investment of flow process, and only for petrochemical industry stink damp system sulphur.

The transformation catalyst that this technology can adopt is sulfur-resistant transformation catalyst, has DNG-303Q, QCS-01, QCS-06 etc.

The sulphur dioxide reduction catalyzer that this technology can adopt has HT-951T, TG2514 etc.

This technology is produced the process of sulphur with mixed gas reduction sulfurous gas, main chemical reactions is as follows:

the present invention's coal gas used is mixed gas listed in upper table, and 130 ℃ of this mixed gas normal tempss and by steam-laden enter before reduction reactor through interchanger re-heat to 250 ℃.

Mixed gas enters reduction reactor and first enters transformation catalyst bed, there is the reaction of above-mentioned (4), reaction heat makes gas be warming up to 340-350 ℃ and leaves transformation catalyst bed, before entering next catalyst bed, the sulfur dioxide gas spraying with sparger mixes, mixed gas temperature is down to below 300 ℃, on the first reducing catalyst bed, there is above-mentioned (1)-(8) reaction, the exothermic effects of reaction makes reactant gases again be warming up to 380 ℃ and leaves the first reducing catalyst bed, heat exchange by waste heat boiler boiler tube makes gas temperature again be down to 300 ℃ and enters the second reducing catalyst bed, at the second reducing catalyst bed, continue to occur above-mentioned (1)-(8) reaction, the output gas that finally leaves reactor contains gaseous sulfur with hydrogen sulfide and reacts remaining steam and rare gas element etc.

Reduction reactor output gas is cooled to 150 ℃ through sulfur condenser, the recovery that is condensed of sulphur major part.The sulfur condenser tail gas that contains hydrogen sulfide enters claus reaction device, and hydrogen sulfide wherein and the sulfurous gas of shunting carry out claus reaction and further reclaimed.

Crouse's unit process process:

Crouse unit mainly consists of claus reaction device, No. two sulfur condensers.

The sulfurous gas of shunting reacts with the hydrogen sulfide in upper level sulfur condenser tail gas, adopts claus reaction device and the sulfur condenser of the present invention's design, has simplified flow process and equipment.

From the tail gas of one-level sulfur condenser and the sulfur dioxide gas of shunting, mix, enter claus reaction device after being heated to catalyst activity temperature, under claus catalyst effect, reaction generates sulphur and water.Output air cooling is but made to sulphur condensation, obtain sulphur and sulfur-containing tail gas.

In final Claus tail gases, contain remaining hydrogen sulfide and the sulfurous gas that can not react again.Hydrogen sulfide residual in tail gas is burned incinerator is not set, incineration ashes sulfurous gas does not adopt Dilution air to drain into atmosphere yet, but tail gas is imported to boiler appropriate location, utilize boiler high temperature and excess oxygen that hydrogen sulfide is all oxidized to sulfurous gas, then through smoke absorption pyrolysis unit, reclaim sulfurous gas and return to sulphur processed unit.So guarantee that clean amount of sulfur contenting in smoke is up to standard all the time, the final transformation efficiency that the Sulphur Dioxide that makes system recoveries is sulphur reaches more than 99.5%.

The spendable catalyzer commodity in Crouse of the present invention unit are various, such as SRC-T, SRC-A series and PSR-1, PSR-21, PSR-31, PSR-41, PSR-51 series etc.

Embodiment

The high-efficiency boiler of large power plant of take is example, and gigawatt generating set consumes the steam coal 400t/h of 5500kcal/kg, exhaust gas volumn 3,200,000 Nm3/h.With coal-fired sulfur-bearing 1.5%, 80%, enter flue gas for benchmark, SO 2 from fume content is 9600kg/h, concentration 3000mg/ Nm3.

Device of the present invention reclaims sulfurous gas from flue gas, and to produce process and the material data of sulphur as follows:

High-temperature flue gas from boiler 1 is cooled to 150 ℃ with the air that enters boiler 1 in air preheater 2 heat exchange, through wash cooling tower 7 cooling of giving a dinner of welcome, at 60-65 ℃, enter 8 bottoms, absorption tower, flue gas in tower on fully contact and absorb with circulating absorption solution while flowing, sulfurous gas in flue gas and the S-WAT in the absorption liquid generation sodium bisulfite that reacts, the clean flue gas removing after sulfurous gas enters chimney 3 emptying by 8 tops, absorption tower through No. two gas doors 5 of bypass flue, clean flue gas SO 2below concentration 50mg/ Nm3, content 160kg/h.

When the washings of wash cooling tower 7 carries out spray washing to flue gas, the evaporation of the moisture of washings makes boiler flue gas cool-down, and washings is concentrated and produces salt crystallization simultaneously.The flue dust of salt and washing forms salt slurry and falls to cycles of washing groove 21 bottoms and through slush pump 18, send into 17 centrifugations of spiral desilt machine again and remove, and keeps circulating cleaning solution stable components.Enter cleaner 9 removing chloride ions and sulfate ion on the lean solution pipeline on absorption tower 8, keep circulating absorption solution stable components.Effluent brine under cleaner 9 removes drains into cycles of washing groove 21 as the part make up water of washings, and make up water insufficient section is supplied by factory's feedwater.

The circulating absorption solution on absorption tower 8 is divided into lean solution and rich solution, enter the lean solution on absorption tower 8 for containing more than 20% sodium sulfite aqueous solution of S-WAT, by absorbent recirculation pump 19, send into 8 tops, absorption tower, absorbing the rich solution producing is the absorption liquid that is rich in sodium bisulfite, by absorption tower lower part outlet, through poor rich liquid heat exchanger 20 and the lean solution of entering absorption tower 8, carry out heat exchange and reclaim heat, enter regeneration pyrolysis groove 16 and regenerate under 90~130 ℃ of conditions.The sulfur dioxide gas that regeneration obtains is collected by pyrolysis groove 16 tops of regenerating, and quantity is 9440 kg/h, supplies with continuously reduction reactor and claus reaction device and produces sulphur.

The reduction reaction of sulfurous gas is completed through reduction reactor catalysis by mixed gas, sulfurous gas from regeneration pyrolysis groove 16 splits into two-way, the 70-80% that wherein a road accounts for total amount is entered by the sulfurous gas import B of reduction reactor 10, the hydrogen in reducing catalyst bed and mixed gas and reaction of carbon monoxide.Mixed gas enters reduction reactor transformation catalyst bed through being preheated to 250 ℃ of gas inlet A by reduction reactor 10.Mixed gas contains H 211~15%, CO 24~30% and water vapor, carbon monoxide reacts and generates hydrogen at catalyst bed with water vapor, and the volumetric molar concentration of hydrogen in mixed gas is reached more than 30% by 13%, and reaction heat makes gas temperature rise to 340-350 ℃.The sulfur dioxide gas of cold conditions charging mixes with coal gas through gas distributor, and mixed gas temperature is down to 300 ℃ of reducing catalyst bed reactions that enter below reduction reactor 10.Sulfurous gas is partly reduced to sulphur, and all the other are reduced to hydrogen sulfide.The output gas of reduction reactor 10 enters that a sulfur condenser 12 is cooling, and sulphur steam is condensed into Molten sulphur, and incoagulability tail gas is sent into claus reaction device 14.

Be mixed and enter all the other 20-30% sulfurous gas that claus reaction device 14 also has shunting with the incoagulability tail gas of a sulfur condenser 12.The mol ratio of mixed gas is H 2s:SO 2=1.90:1-2.10:1, it is cooling that claus reaction output gas enters No. two sulfur condensers 15, sulphur steam is condensed into Molten sulphur, and incoagulability tail gas is sent into the hot-air duct of air preheater 2 outlets of boiler systems through pipeline, enter boiler 1 burn with warm air after mixing.Reduction and Crouse's cell processing SO 29440 kg/h, obtain sulphur 4484 kg/h, and per pass conversion 95% is sent hydrogen sulfide and the sulfurous gas of boiler burning back to and amounted to sulfurous gas 472 kg/h.The sulfurous gas that the same period, bunker coal produced continues as 9600 kg/h, burns sulphur add up to 10072kg/h with tail gas, enters together absorption tower 8 and reclaims.

Working cycle again:

Absorption tower 8 outlet SO 2concentration 50mg/ Nm3, content 160kg/h.Reclaim SO 29912 kg/h, obtain sulphur 4708kg/h, recovery per pass 95% through reduction.Solidifying sulphur tail gas returns to boiler and burns, flue gas SO 2increase 495kg/h and add up to 10095kg/h.

Absorption tower outlet SO 2concentration 50mg/ Nm3, content 160kg/h.Reclaim SO 29934kg/h, obtains sulphur 4719kg/h, recovery per pass 95% through reduction.Solidifying sulphur tail gas returns to boiler and burns, flue gas SO 2increase 497kg/h and add up to 10097kg/h.

Absorption tower outlet SO 2concentration 50mg/ Nm3, content 160kg/h.Reclaim SO 29937kg/h, obtains sulphur 4720kg/h, recovery per pass 95% through reduction.Solidifying sulphur tail gas returns to boiler and burns, flue gas SO 2increase 497kg/h and add up to SO 210097kg/h.

Tail gas is brought the SO of flue gas into 2return to the SO of reduction unit with recovery system 2equate, it is stable that system reaches.

Steady operational status:

1, ribbing enters sulphur 6000 kg/h, and 80% enters flue gas, and meter 4800 kg/h, amount to SO 29600 kg/h;

2, former flue gas SO 29600 kg/h, clean fume emission 160kg/h, specific absorption 98%, absorbed dose 9440 kg/h, amount to sulphur 4720kg/h.

3, set 10 kg/h processing losses, recovery sulphur product 4710kg/h, total system reduction SO 2gas reforming is that the total conversion rate of sulphur reaches 99.8%.

4, annual 7200 hours sulphur output is 3.39 ten thousand tons:

7200?h×4710kg/h=33912000kg

5, the sulphur output value is enough compensated for flue gas desulfurization (FGD) unit running cost, can realize profit operation.

In sum, because the reliable desulfurization degree of alkali liquor absorption sulfurous gas technology is high, the sulfur dioxide concentration of clean fume emission, far below existing emission standard, can reduce sulfur dioxide pollution.

Meanwhile, transforming the sulphur reclaiming is the precious resources that country lacks, and because can get a profit operation, enterprise may actively become passive desulfurization into initiatively desulfurization.

So, apply technology of the present invention and be conducive to environmental protection and changing rejected material to useful resource recovery, be conducive to improve Business Economic Benefit and flue gas desulfurization enthusiasm.

Claims (12)

1. one kind is reclaimed the system and device that sulfurous gas is produced sulphur from flue gas, this device comprises boiler systems, it is characterized in that comprising absorption pyrolysis unit, reduction unit and Crouse unit, described unit and boiler systems are used in conjunction with, wherein, described absorption pyrolysis unit is by wash cooling tower (7), absorption tower (8), cleaner (9), cycles of washing groove (21), cleaning circulation pump (22), regeneration pyrolysis groove (16), regenerative heater (11), absorbent recirculation pump (19), poor rich liquid heat exchanger (20), slush pump (18) and spiral desilt machine (17) form, described reduction unit is comprised of mixed gas generation systems (13), reduction reactor (10) and a sulfur condenser (12), described Crouse unit is comprised of claus reaction device (14) and No. two sulfur condensers (15), described boiler systems is comprised of boiler (1), air preheater (2), chimney (3), a gas door (4), No. two gas doors (5) and No. three gas doors (6), flue from air preheater (2) is connected with the gas approach of wash cooling tower (7) by a gas door (4) before at No. three gas doors (6), described wash cooling tower (7) communicates with the exhaust gases passes of absorption tower (8), and the exhanst gas outlet of absorption tower (8) is connected with chimney (3) by pipeline and No. two gas doors (5), described cleaning circulation pump (22) entrance end is connected with cycles of washing groove (21) by pipeline, described cleaning circulation pump (22) exit end is connected with the washings import of wash cooling tower (7) by pipeline, the washings outlet of described wash cooling tower (7) is connected with cycles of washing groove (21) by pipeline, slush pump (18) entrance end is connected with cycles of washing groove (21) by pipeline, the exit end of slush pump (18) is connected with spiral desilt machine (17) by pipeline, the entrance end of absorbent recirculation pump (19) is connected with the lean solution outlet of regeneration pyrolysis groove (16) by pipeline, absorbent recirculation pump (19) exit end is connected with poor rich liquid heat exchanger (20) lean solution import by pipeline, the lean solution outlet of described poor rich liquid heat exchanger (20) is connected with absorption tower (8) lean solution import by pipeline, exports on the pipeline of connection absorption tower (8) lean solution import be connected with cleaner (9) with bypass duct by valve in the lean solution of poor rich liquid heat exchanger (20), the sewage draining exit of described cleaner (9) is connected with cycles of washing groove (21) by pipeline, the rich solution outlet on described absorption tower (8) is connected by pipeline with the rich solution import of poor rich liquid heat exchanger (20), and the rich solution outlet of poor rich liquid heat exchanger (20) is connected by pipeline with the rich solution import of regeneration pyrolysis groove (16), the cold liquid import of regenerative heater (11) and hydrothermal solution outlet are connected with regeneration pyrolysis groove (16) by pipeline, the pneumatic outlet of described regeneration pyrolysis groove (16) is connected with reduction reactor (10) sulfurous gas import by pipeline, the outlet of mixed gas generation systems (13) mixed gas is connected with reduction reactor (10) mixed gas import by pipeline, reduction reactor (10) pneumatic outlet is connected with a sulfur condenser (12) gas feed by pipeline, the outlet of a sulfur condenser (12) tail gas is connected with claus reaction device (14) gas feed by pipeline, the described shunting sulfurous gas pipeline from regeneration pyrolysis groove (16) is connected with the pipeline between claus reaction device (14) through valve and a sulfur condenser (12), described No. two sulfur condensers (15) gas feed is connected with claus reaction device (14) by pipeline, the tail gas outlet of No. two sulfur condensers (15) is connected with air preheater (2) to the hot-air duct between boiler (1) by pipeline.
2. from flue gas, reclaim according to claim 1 the system and device that sulfurous gas is produced sulphur, it is characterized in that described reduction reactor (10) outside establishes manhole, discharge opening and two reacting gas inlets and a pneumatic outlet, the inner catalyst bed being formed by grating plate, porcelain ball and catalyzer that at least three series connection are set, to be one deck carry out for catalytic mixing coal gas carbon monoxide and water vapor the reducing catalyst that the transformation catalyst of transformationreation and the two-layer hydrogen for catalytic mixing coal gas and carbon monoxide and sulfurous gas carry out reduction reaction with described catalyzer, mixed gas import (A) is established in the upper end of described shell of reactor (35), and pneumatic outlet (E) is established in lower end, and middle part is established sulfurous gas import (B) and is connected by flange with the gas distributor (34) of inside reactor, the first manhole (23), the second manhole (25), drum (26) and spigot discharge (30) are established in the side of described shell of reactor (35), described drum (26) is provided with byproduct steam outlet (C) and is connected 2-6 header group with oiler feed import (D) and by pipeline, described header group is comprised of a header (27-1) and another header (27-2), the header (27-1,27-2) of described header group is interconnected by waste heat boiler boiler tube (32) and is connected with shell of reactor (35) by flange, described catalyst bed is arranged from top to bottom at shell of reactor (35) inner chamber, the first layer grating plate (29-1) is connected with shell of reactor (35) on top, put the porcelain ball two (31-1) on it, transformation catalyst (24) forms the first catalyst bed with the porcelain ball one (33-1) of covering catalyst, second layer grating plate (29-2) is connected with shell of reactor (35) at middle part, put another porcelain ball two (31-2) on it, reducing catalyst (28-1) forms the second catalyst bed with another porcelain ball one (33-2) of covering catalyst, the 3rd layer of grating plate (29-3) is connected with shell of reactor (35) in bottom, put the porcelain ball two (31-3) again on it, another transformation catalyst (28-2) forms the 3rd catalyst bed with a porcelain ball one (33-3) again of covering catalyst.
3. from flue gas, reclaim according to claim 2 the system and device that sulfurous gas is produced sulphur, the first catalyst bed that it is characterized in that described reduction reactor (10) is mixed gas transformation catalyst bed, and the second catalyst bed and the 3rd catalyst bed are sulphur dioxide reduction catalyst bed.
4. from flue gas, reclaim according to claim 2 the system and device that sulfurous gas is produced sulphur, it is characterized in that the gas distributor (34) of described reduction reactor (10) sulfurous gas import (B) connection is between transformation catalyst bed and reducing catalyst bed.
5. from flue gas, reclaim according to claim 2 the system and device that sulfurous gas is produced sulphur, it is characterized in that the waste heat boiler boiler tube (32) of described reduction reactor (10) is between described the second catalyst bed and described the 3rd catalyst bed.
6. from flue gas, reclaim according to claim 1 the system and device that sulfurous gas is produced sulphur, it is characterized in that described claus reaction device (14) structure is as follows: catalyzer (50) is positioned at alumina ball (48) top in the middle of stainless steel inner core (47), stainless steel inner core (47) is connected with the upper tubesheet (46) that is positioned at its below, upper tubesheet (46) is connected with the tubulation group (44) that is positioned at its below, tubulation group (44) is connected with the lower tubesheet (43) that is positioned at its below, lower tubesheet (43) is connected with the hypomere inner side of hypomere urceolus (40), forming lower end, one of the inside of the outer tube inner chamber internals that fixedly upper end can unmanaged flexibility combines, the top cover of epimere urceolus (36) connects manhole (37), stage casing cone cylinder (38) connects bearing (39), gas feed (41) is established in hypomere urceolus (40) side, and pneumatic outlet (42) is established in bottom surface, between stainless steel inner core (47) and epimere urceolus (36), is annular space, the gas feed (41) of hypomere urceolus (40) side is suitable for reading the communicating with stainless steel inner core (47) by the annular space between space between the pipeline of tubulation group (44) and stainless steel inner core (47) and urceolus, and the end opening of stainless steel inner core (47) communicates with the pneumatic outlet (42) bottom hypomere urceolus (40) by space in the pipe of the tubulation group (44) of its below, stainless steel inner core (47) outside surrounding is connected with flap centralizer (49), connects a ring baffle plate (45-1) and another ring baffle plate (45-2) between the pipe of tubulation group (44).
7. from flue gas, reclaim the method that sulfurous gas is produced sulphur, it is characterized in that carrying out in the steps below:
1), high-temperature flue gas from boiler (1) is cooled to 130 ℃~160 ℃ with the air that enters boiler (1) in air preheater (2) heat exchange, through a gas door of bypass flue (4), be admitted to wash cooling tower (7) cooling of giving a dinner of welcome, with 60-65 ℃, approach water saturated state and enter bottom, absorption tower (8), in absorption tower (8), fully contact with circulating absorption solution, sulfurous gas in flue gas and the S-WAT in the absorption liquid generation sodium bisulfite that reacts, the clean flue gas removing after sulfurous gas enters chimney (3) emptying by absorption tower (8) top through bypass No. two gas doors of flue (5),
2), the washings of wash cooling tower (7) is saturated brine, washings delivers into through cleaning circulation pump (22) circulation the dust that wash cooling tower (7) carries flue gas by cycles of washing groove (21) and carries out spray washing, the moisture evaporation of washings makes boiler flue gas cool-down and makes the crystallization of the concentrated generation of washings salt, together with the flue dust that the salt of washings crystallization carries with washings, form salt slurry and fall to cycles of washing groove (21) bottom, through slush pump (18), sending into spiral desilt machine (17) centrifugation removes, isolated clear liquid returns to cycles of washing groove (21) by spiral desilt machine (17) and recycles,
3), the circulating absorption solution of absorption tower (8) is divided into lean solution and rich solution according to the content of sodium bisulfite wherein, enter the lean solution on absorption tower (8) for containing more than 20% sodium sulfite aqueous solution of S-WAT, absorbent recirculation pump (19) is sent lean solution into top, absorption tower (8), under 60~65 ℃, gauge pressure 3kPa condition, carry out absorption reaction, absorbing the rich solution producing is the absorption liquid that is rich in sodium bisulfite; After heat is reclaimed in poor rich liquid heat exchanger (20) and the lean solution heat exchange of entering absorption tower (8), enter regenerative heat solution groove (16) regenerates under 90~130 ℃ of conditions, to the regeneration of rich solution, make sodium bisulfite decomposition wherein become S-WAT, the sulfur dioxide gas that rich solution regeneration produces is collected through regeneration pyrolysis groove (16) top, and steam provides regeneration of absorption solution required heat by regenerative heater (11);
4) absorption liquid removes to avoid accumulating in absorption liquid from a small amount of chlorion and the cleaner (9) of sulfate ion through absorption liquid bypass duct of smoke absorption, and the sodium-chlor that cleaner (9) removes and sodium sulfate are usingd effluent brine form and drained into cycles of washing groove (21) as the part make up water of washings;
5) reduction reaction of sulfurous gas is completed through reduction reactor (10) catalysis by mixed gas, and mixed gas contains H 211~15%, CO 24~30% and water vapor, mixed gas enters reduction reactor top the first catalyst bed by the gas inlet (A) of reduction reactor (10), carbon monoxide reacts and generates hydrogen at catalyst bed with water vapor, and the volumetric molar concentration of hydrogen in mixed gas is reached more than 30% by 11-15%; Sulfurous gas from regeneration pyrolysis groove (16) splits into two-way, the 70-80% that wherein a road accounts for total amount is entered by the sulfurous gas import (B) of reduction reactor (10), hydrogen in the second catalyst bed and mixed gas and reaction of carbon monoxide, the sulfurous gas that enters reduction reactor (10) is partly reduced to sulphur, and all the other are reduced to hydrogen sulfide.The output gas of reduction reactor (10) enters that a sulfur condenser (12) is cooling, and sulphur steam is condensed into Molten sulphur, and incoagulability tail gas is sent into claus reaction device (14);
6) the incoagulability tail gas of a described sulfur condenser (12) enters claus reaction device (14) after mixing with all the other 20-30% sulfurous gas of described shunting and carries out claus reaction, it is cooling that reaction output gas enters No. two sulfur condensers (15), sulphur steam is condensed into Molten sulphur, incoagulability tail gas is sent into the hot-air duct of air preheater (2) outlet of boiler systems through pipeline, after mixing with warm air, entering boiler (1) burns, the trace hydrogen sulfide containing in tail gas is oxidized to sulfurous gas in boiler (1), together with the sulfurous gas producing with boiler combustion, entering absorption tower (8) reclaims.
8. produce according to claim 7 the method for sulphur, it is characterized in that chlorion and sulfate ion that the absorption liquid on described absorption tower (8) absorbs from flue gas remove through cleaner (9), the chlorion of removing and sulfate ion are usingd effluent brine form and are drained into cycles of washing groove (21) as the part make up water of washings, and the contained salt of effluent brine removes by flue gas condensing crystal at wash cooling tower (7).
9. produce according to claim 7 the method for sulphur, it is characterized in that described sulphur dioxide reduction, by described mixed gas, reacted through the catalyst of described reduction reactor (10) with described sulfurous gas, generate sulphur and hydrogen sulfide.
10. produce according to claim 7 the method for sulphur, it is characterized in that the hydrogen sulfide that described reduction reaction generates reacts generation sulphur with the sulfurous gas of described shunting at claus reaction device (14).
11. produce the method for sulphur according to claim 7, enter the H of claus reaction device (14) described in it is characterized in that 2s and SO 2mol ratio span of control be 1.90:1-2.10:1.
12. produce the method for sulphur according to claim 7, it is characterized in that No. two sulfur condensers (15) tail gas is admitted to air preheater (2) and burns to entering boiler (1) after the hot-air duct of boiler (1) mixes with warm air, the trace hydrogen sulfide containing in tail gas is oxidized to sulfurous gas in boiler (1), together with the sulfurous gas producing with boiler (1) burning, enter absorption tower (8) and reclaim, the final transformation efficiency that the Sulphur Dioxide that described absorption pyrolysis unit is reclaimed is sulphur reaches more than 99.5%.
CN201310277794.1A 2013-07-04 2013-07-04 System device and method for recycling sulfur dioxide from fume to prepare sulfur CN103303872B (en)

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