CN105214495A - A kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent - Google Patents
A kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent Download PDFInfo
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Abstract
The invention discloses a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent.This technique comprises the following steps: 1) solubilised state H
2the preparation of S; 2) H
2s, NO, NO
2, SO
2the preparation of mist; 3) synchronized desulfuring and denitrifying.Technique of the present invention really achieves the integration of desulfuring and denitrifying apparatus, by NO, NO in coal-fired flue-gas
2be converted into N
2and water, by SO
2and H
2s is converted into high-purity elemental sulfur, except the organic matter in decontaminated water, can also achieve the treatment of wastes with processes of wastes against one another simultaneously.The elemental sulfur that this technique reclaims, a part recycles maintenance equipment operation, and a part is as product output.Reducing agent H in this technique
2s is prepared by the biology in situ reduction of elemental sulfur, with system, buys, remove the cost and potential security risk of purchasing, transport, store link from without the need to outside.The synchronized desulfuring and denitrifying apparatus of this technique is all remarkable in current main-stream device in floor space, construction cost and operating cost etc.
Description
Technical field
The present invention relates to a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent.
Background technology
Coal is the main body energy of China, and the proportion of coal in primary energy consumption maintains about 70% always for a long time, which dictates that the primary energy production and consumption structure of China based on coal is difficult to change within following significant period of time.The SO that a large amount of fire coal produces
2and NO
xand the acid rain formed thus, photochemical fog and haze etc. have serious harm to health and ecological environment, govern society and economic sustainable development.Therefore, necessary to the SO in flue gas
2and NO
xcontrol.
By country " 12 " planning, the coal-fired total amount of China in 2015 will reach 3,800,000,000 tons, and SO
2discharge capacity will drop to 2086.4 ten thousand tons.Calculate according to average sulfur-bearing rate 2%, mean the sulfur-bearing discarded object that will produce more than 6,500 ten thousand tons.This is also just only in S, if with end product as CaSO
4, Na
2sO
3, Na
2sO
4meter, be then far longer than this number.A large amount of desulfuration waste enters natural environment, in fact causes secondary pollution, wastes a large amount of Sulphur ressource simultaneously.At present, build up operation 5.65 hundred million kilowatts of Desulphurization for Coal-fired Power Plant facilities to the Eleventh Five-Year Plan whole nation in latter stage is accumulative, what wherein have more than 90% to adopt is all limestone-gypsum method.In this process, lime stone and SO
2reaction generates byproduct, i.e. desulfurated plaster.But China's plaster of paris aboundresources, and quality of desulphurization gypsum is poor, is difficult to directly utilize, to such an extent as to nearly 4,000 ten thousand tons of desulfurated plasters are had to be abandoned every year or landfill and continue formation secondary pollution.
At present, denitration mainly adopts SCR technology, by catalyst, NO is reduced into N using ammonia etc. as reducibility gas
2.Industrial, flue gas carries out desulphurization denitration two respective independently techniques often, but not integration truly, also exist floor space large, to build and operating cost is high, technological process long, consume ammoniacal liquor in a large number, can produce the shortcomings such as desulfurated plaster the like waste.
In recent years, synchronous catalytic desulfurization and denitrification technique can realize flue gas desulfurization and denitrification in one apparatus, and construction cost is lower and can reclaim elemental sulfur, obtains many concerns.But this technique needs with H
2, CH
4or CO is reducing agent.NH
3during as reducing agent, investment is high with operating cost, and reaction can generate N
2o, causes greenhouse effects; CH
4during as reducing agent, reaction needed high temperature, energy ezpenditure is high, easily produces CO
2, easy carbon deposit; When CO is as reducing agent, a large amount of CO can be produced
2, cause greenhouse effects.And, H
2, CH
4all cannot produce with producing from boiler factory or flue gas with CO, it is purchased, transport, store, use cost is high, constrain the application of synchronous catalysis flue gas desulfurization and denitration technique.
Therefore, a kind of simple, economic, high efficiency synchronous catalysis flue gas desulfurization and denitration technique of exploitation is needed badly.
Summary of the invention
The object of the present invention is to provide a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent.
The technical solution used in the present invention is:
The gas-liquid separator take hydrogen sulfide as a device for the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, comprise anaerobic organism sulphur reduction reactor, being connected with anaerobic organism sulphur reduction reactor by pipeline, the desulfurization and denitrification reaction device be connected with gas-liquid separator by pipeline.
Described anaerobic organism sulphur reduction reactor is provided with organic source input channel, and described gas-liquid separator bottom is provided with coal-fired flue-gas input channel, and described desulfurization and denitrification reaction device is provided with elemental sulfur gathering-device and elemental sulfur output channel.
Described anaerobic organism sulphur reduction reactor is the one in packed bed biofilm reactor, completely stirring reactor, sequencing batch reactor, upflow anaerobic sludge blanket reactor, anaerobic membrane bioreactor, anaerobic baffled reactor.
Described gas-liquid separator is spray stripping tower.
Described desulfurization and denitrification reaction device is the one in tubular reactor, stove formula reactor, suspension type reactor, vertical type reactor, fixed fluidized-bed reactor.
Described elemental sulfur gathering-device is condenser.
What adopt said apparatus take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, comprises the following steps:
1) solubilised state H
2the preparation of S: organic source, elemental sulfur and sulphur reducing bacteria are added anaerobic organism sulphur reduction reactor, make organic source, elemental sulfur fully contacts with sulphur reducing bacteria, under the effect of sulphur reducing bacteria, the oxidized removal of organic matter, elemental sulfur is converted into H
2s, solubilised state H is rich in the water outlet of reactor
2s;
2) H
2s, NO, NO
2, SO
2the preparation of mist: will solubilised state H be rich in
2the water outlet of S passes into gas-liquid separator from top, coal-fired flue-gas is passed into gas-liquid separator from bottom simultaneously, and current contact with flue gas is reverse, carry out gas-liquid separation, obtain H
2s, NO, NO
2, SO
2mist;
3) synchronized desulfuring and denitrifying: by H
2s, NO, NO
2, SO
2mist and catalyst add desulfurization and denitrification reaction device, carry out catalytic reaction, by NO and NO at 100 ~ 800 DEG C
2be converted into N
2and water, by H
2s and SO
2change into the elemental sulfur of gaseous state under high temperature, then condensation, enrichment, recovery elemental sulfur, an elemental sulfur part for recovery joins in anaerobic organism sulphur reduction reactor and recycles, and unnecessary elemental sulfur is collected for subsequent use.
Elemental sulfur described in step 1) is the elemental sulfur prepared through the synchronized desulfuring and denitrifying technique of step 3).
Organic source described in step 1) is at least one in organic sewage, additional organic matter.
Described organic sewage is for containing organic industrial wastewater or city domestic sewage, and described additional organic matter is at least one in carbohydrate, grease, organic acid, organic acid esters, alcohols, ethers.
Sulphur reducing bacteria described in step 1) is sulfate reducing bacteria and elemental sulfur reducing bacteria.
Catalyst described in step 3) is Al
2o
3, TiO
2, rare earth material, Fe
2o
3/ Al
2o
3, CuO/Al
2o
3, Fe
2o
3/ TiO
2, CuO/TiO
2, Pt/Al
2o
3, Fe/Ce-TiO
2, Fe/Ce-Al
2o
3, Ce/Mn-Al
2o
3, Ce/Mn-TiO
2, Ce-TiO
2-SnO
2, NaO-Al
2o
3-SiO
2, Na
12[(AlO
2)
12(SiO
2)
12] 27H
2at least one in O.
Wherein, the organic source in anaerobic organism sulphur reduction reaction device under the effect of sulphur reducing bacteria with the reaction equation of elemental sulfur as shown in (1):
（1）
Wherein, C
orgfor organic matter, S
0for elemental sulfur.
Wherein, H
2sO in S and coal-fired flue-gas
2, NO, NO
2reaction equation as shown in (2), (3), (4):
（2）
（3）
（4）
Wherein, S
0for elemental sulfur.
The invention has the beneficial effects as follows:
1) compared with the separated type desulfurizing and denitrifying process of main flow, the present invention really achieves the integration of desulfuring and denitrifying apparatus, utilizes H
2sO in S catalytic reduction coal-fired flue-gas
2, NO and NO
2, by NO and NO
2be converted into N
2and water, by SO
2and H
2s is converted into high-purity elemental sulfur, carries out Collection utilization, and in this technique, elemental sulfur output is higher than consumption, and except part maintenance equipment operation recycles, remaining elemental sulfur can be used for selling, and plays the object reducing process operation expense;
2) H
2s is prepared by the biology in situ reduction of elemental sulfur, with system, buys, remove the cost and potential security risk of purchasing, transport, store link from without the need to outside;
3) H
2the organic sewage that industrial enterprise self can be used to produce in the biological preparation process of S, not only can efficient output H as electron donor
2s, and the organic matter in sewage can be removed, not only achieve the treatment of wastes with processes of wastes against one another, significantly can also reduce the load of follow-up sewage treatment plant;
4) a large amount of CO is contained in coal-fired flue-gas
2, SO
2deng sour gas, add acid without the need to outside, the pH value of waste water just can be made lower, high-temperature flue gas improves the temperature of waste water simultaneously, is more conducive to H
2the stripping of S;
5) partial heat of coal-fired flue-gas is desulfurized liquid through over-heat-exchanger for heating anaerobic reactor, can ensure anaerobic reaction process in the winter time low temperature time high efficiency, realize UTILIZATION OF VESIDUAL HEAT IN;
6) in air lift operation, the H of coal-fired flue-gas in stripping doctor solution
2while S, also reduce dust content wherein by gas-liquid contact, reach dust removing effects;
7) synchronized desulfuring and denitrifying apparatus of the present invention is all remarkable in current main-stream device in floor space, construction cost and operating cost etc.
Accompanying drawing explanation
Fig. 1 of the present invention a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying process schematic representation of reducing agent.
Fig. 2 of the present invention a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technological reaction installation drawing of reducing agent.
Fig. 3 embodiment a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technological reaction installation drawing of reducing agent.
H in the sulphur reduction reactor water outlet of Fig. 4 embodiment
2the pH figure of S output and water inlet, water outlet.
Organic matter removal design sketch in the sulphur reduction reactor water outlet of Fig. 5 embodiment.
The synchronous catalytic desulfurization and denitrification efficiency chart of flue gas of Fig. 6 embodiment.
The graph of a relation of elemental sulfur productive rate and temperature in the smoke catalytic reaction of Fig. 7 embodiment.
Detailed description of the invention
As shown in Figure 2, a kind of take hydrogen sulfide as the device of the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, comprises anaerobic organism sulphur reduction reactor, by solubilised state H
2the gas-liquid separator that S conveyance conduit is connected with anaerobic organism sulphur reduction reactor, pass through H
2s, NO, NO
2, SO
2the desulfurization and denitrification reaction device that mixed gas delivery pipeline is connected with gas-liquid separator.
Preferably, described anaerobic organism sulphur reduction reactor is provided with organic source input channel, and described gas-liquid separator bottom is provided with coal-fired flue-gas input channel, and described desulfurization and denitrification reaction device is provided with elemental sulfur gathering-device and elemental sulfur output channel.
Preferably, described anaerobic organism sulphur reduction reactor is the one in packed bed biofilm reactor, completely stirring reactor, sequencing batch reactor, upflow anaerobic sludge blanket reactor, anaerobic membrane bioreactor, anaerobic baffled reactor.
Preferably, described gas-liquid separator is spray stripping tower.
Preferably, described desulfurization and denitrification reaction device is the one in tubular reactor, stove formula reactor, suspension type reactor, vertical type reactor, fixed fluidized-bed reactor.
Preferably, described elemental sulfur gathering-device is condenser.
What adopt said apparatus take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, comprises the following steps:
1) solubilised state H
2the preparation of S: organic source, elemental sulfur and sulphur reducing bacteria are added anaerobic organism sulphur reduction reactor, make organic source, elemental sulfur fully contacts with sulphur reducing bacteria, under the effect of sulphur reducing bacteria, the oxidized removal of organic matter, elemental sulfur is converted into H
2s, solubilised state H is rich in the water outlet of reactor
2s;
2) H
2s, NO, NO
2, SO
2the preparation of mist: will solubilised state H be rich in
2the water outlet of S passes into gas-liquid separator from top, coal-fired flue-gas is passed into gas-liquid separator from bottom simultaneously, and current contact with flue gas is reverse, carry out gas-liquid separation, obtain H
2s, NO, NO
2, SO
2mist;
3) synchronized desulfuring and denitrifying: by H
2s, NO, NO
2, SO
2mist and catalyst add desulfurization and denitrification reaction device, carry out catalytic reaction, by NO and NO at 100 ~ 800 DEG C
2be converted into N
2and water, by H
2s and SO
2change into the elemental sulfur of gaseous state under high temperature, then condensation, enrichment, recovery elemental sulfur, an elemental sulfur part for recovery joins in anaerobic organism sulphur reduction reactor and recycles, and unnecessary elemental sulfur is collected for subsequent use.
Step 1), 2), 3) constitute a circulatory system, this circulatory system is raw material with coal-fired flue-gas, achieves H
2s's is self-sufficient, and achieves recycling and output of sulphur simple substance.
Preferably, the elemental sulfur described in step 1) is the elemental sulfur prepared through the synchronized desulfuring and denitrifying technique of step 3).
Preferably, the feed way of the elemental sulfur described in step 1) is that hand haulage adds, mechanical transfer add at least one.
Preferably, the organic source described in step 1) is at least one in organic sewage, additional organic matter.
Preferably, described organic sewage is for containing organic industrial wastewater or city domestic sewage, and described additional organic matter is at least one in carbohydrate, grease, organic acid, organic acid esters, alcohols, ethers.
Preferably, the sulphur reducing bacteria described in step 1) is sulfate reducing bacteria and elemental sulfur reducing bacteria.
Preferably, the catalyst described in step 3) is Al
2o
3, TiO
2, rare earth material, Fe
2o
3/ Al
2o
3, CuO/Al
2o
3, Fe
2o
3/ TiO
2, CuO/TiO
2, Pt/Al
2o
3, Fe/Ce-TiO
2, Fe/Ce-Al
2o
3, Ce/Mn-Al
2o
3, Ce/Mn-TiO
2, Ce-TiO
2-SnO
2, NaO-Al
2o
3-SiO
2, Na
12[(AlO
2)
12(SiO
2)
12] 27H
2at least one in O.
Preferred further, the catalyst described in step 3) is the 4A type molecular sieve of Tianjin Zhi Yuan chemical reagent Co., Ltd: Na
12[(AlO
2)
12(SiO
2)
12] 27H
2o.
Of the present invention a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, its technological design schematic diagram is as shown in Figure 1.Its concrete principle is as follows: 1) under the effect of sulphur reducing bacteria, and the oxidized removing in organic source, elemental sulfur is reduced into H
2s, obtains solubilised state H
2s; 2) solubilised state H will be rich in
2the water outlet of S contacts with coal-fired flue-gas is reverse, carries out gas-liquid separation, obtains H
2s, NO, NO
2, SO
2mist; 3) by H
2s, NO, NO
2, SO
2mist and catalyst exposure, catalytic reaction, by NO and NO
2be converted into N
2and water, by H
2s and SO
2change into elemental sulfur, a part of elemental sulfur is that raw material proceeds above-mentioned reaction, and unnecessary elemental sulfur is collected stand-by.
Below in conjunction with specific embodiment, the present invention is made further explanation and description.
embodiment:
As shown in Figure 3, a kind of is that the reaction unit of the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent comprises following critical piece with hydrogen sulfide: packed bed biofilm reactor, tube furnace reactor, spray stripping tower.
Packed bed biofilm reactor selected by anaerobic organism sulphur reduction reactor, its dissolved oxygen concentration < 0.2mg/L, and reactor cumulative volume is 1.3L, filler is sulphur, packing volume is 0.5L, and dischargeable capacity is 0.8L, and reactor is made by lucite.Gas-liquid separator adopts spray stripping tower, spray stripping tower adopts conventional fillers pattern, filler is polyhedron empty ball, and adopt top water inlet, bottom leads to flue gas mode, cowling panel is arranged at top, the cumulative volume of stripping tower is 2.5L, and packing volume is 1.8L, and gas-water ratio is 1:(2500 ~ 3500), the flow velocity of void tower is 1.5 ~ 2.3m/s, and lucite makes.Blower fan is corrosion resistant glass centrifugal blower, and airduct adopts polyfluortetraethylene pipe.Desulfurization and denitrification reaction device adopts tube furnace reactor, and liner is quartz ampoule, Guan Gaowei 40cm, and bore is 15mm, and cumulative volume is 0.07L, and quartz ampoule lower end is connected to spherical condensation tube, and material is quartz glass.
Of the present invention a kind of be that the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent is specific as follows with hydrogen sulfide:
1) start-up and functionning of sulphur reduction reactor:
A) startup of sulphur reduction reactor: sulfur in lump form is fixed in sulphur reduction reactor, (the sulphur reducing bacteria of domestication cultivation in 1 year is reached from laboratory) by seed sludge injecting reactor, the simulated domestic wastewater injecting reactor will configured again, carries out biofilm in static 24 hours.Because reactor volume is less, reactor does not establish backflow.This reactor method of operation is up flow type, i.e. bottom water inlet top water outlet.Adopt this kind of mode, be in order to sewage can fully contact with sulphur reducing bacteria with sulphur, and be conducive to sludge settling, avoid being taken away by water outlet.After 12 days, TOC(total organic carbon) clearance is stabilized in more than 80%, namely starts successfully.
The configuration of simulation sewage: C
6h
12o
6h
2o0.122g/L, CH
3cOONa0.163g/L, KH
2pO
40.0045g/L, K
2hPO
43H
2o0.012g/L, NH
4cl0.115g/L, yeast extract 0.061g/L, trace element 2.5ml/L.Wherein, trace element formula is: FeCl
36H
2o2000mg/L, H
3bO
3200mg/L, CuSO
450mg/L, KI50mg/L, MnSO
4h
2o250mg/L, ZnSO
47H
2o150mg/L, CoCl
26H
2o200mg/L.
B) operation of sulphur reduction reactor: the startup stage that the first stage being (0 ~ 12 day), this stage water inlet TOC(total organic carbon) theoretical concentration be 208mgC/L, adding high carbon source is that TOC clearance reaches 65% in order to ensure that bacterium can grow fast; Second stage is stable operation stage (13 ~ 19 days), and this stage water inlet TOC concentration is 104mgC/L, TOC clearance is 85 ± 10%; Phase III is basicity debug phase (20 ~ 100 days), and basicity debugging is two cycles, and the period 1 (20 ~ 40 days), wherein 20 ~ 30 days basicity is 500mgCaCO
3/ L, 30 ~ 40 days basicity is 250mgCaCO
3/ L; Second round (41 ~ 100 days), wherein 40 ~ 53 days, basicity was 500mgCaCO
3/ L; 54 ~ 70 days, basicity was 250mgCaCO
3/ L; 71 ~ 100 days, do not add basicity completely and run.The object of basicity debugging is while guarantee reactor normally runs, and reduces pH as much as possible, to guarantee the H of follow-up spray stripping device
2s stripping efficiency.The change of start-up and operation stage each test parameters of sulphur reduction reactor is as shown in table 1.
Start-up and functionning stage each test parameters change list of table 1 sulphur reduction reactor
From Fig. 4, Fig. 5 and table 1, when moving to 12 days from reactor start-up, inlet flow-patterm is 8.16, and water outlet pH is 7.18, HRT(hydraulic detention time) reach 64.87%, H for 12h, TOC clearance
2s output is up to 493mgS/L; Afterwards, HRT remains unchanged, reactor stable operation one week under 104mgC/L, and clearance is stable reaches 71.54%, because in water inlet, the amount of carbon source reduces by half, and H
2s output is down to 254mgS/L; From 20 days, be the basicity debug phase.
From Fig. 4, Fig. 5 and table 1, in the debugging period 1, under identical HRT, low pH has certain inhibitory action, at 500mgCaCO to sulphur reducing bacteria
3under/L service condition, the pH value of water inlet and water outlet is respectively 7.75 and 7.06, at 250mgCaCO
3under/L service condition, the pH value of water inlet and water outlet is respectively 7.43 and 6.69, now, and H
2s output declines to some extent, is respectively 192mgS/L and 222mgS/L, but, later stage H
2s output is gone up again to some extent, shows that sulphur reducing bacteria creates certain tolerance to low pH.
In order to ensure the normal growth of bacterium, carry out second round, there are three basicity gradients, i.e. 500mgCaCO in this cycle
3/ L, 250mgCaCO
3/ L and 0mgCaCO
3/ L, meanwhile, shortens HRT gradually, observing response device ruuning situation.From Fig. 3, Fig. 4 and table 1, at 500mgCaCO
3during/L, HRT is still 12h, and now, the pH value of water inlet and water outlet is respectively 7.93 and 7.00, H
2s output is that 250mgS/L, TOC clearance is more than 75%.Afterwards, at 250mgCaCO
3during/L, HRT is reduced to 8h, and the pH value of water inlet and water outlet is respectively 7.73 and 6.49, and change is comparatively apparent that, H
2s output and TOC clearance significantly rise, H
2s output is that 343mgS/L, TOC clearance is about 86%, proves sulphur reducing bacteria at a low ph, and produced comparatively significantly tolerance, and operational effect is good, organic removal rate is higher.Whether be applicable to lower HRT and lower pH to continue to explore reactor, HRT is reduced to 4h by us simultaneously, and does not supply basicity completely, and the pH value of now water inlet and water outlet is respectively 6.68 and 6.01, and H
2s output still remains on 300mgS/L, and organic removal rate still remains on more than 80%.
From above-mentioned data, sulphur reducing bacteria can produce certain tolerance at a low ph, and sulphur reduction reactor can normally run at a low ph, ensure that the demand of follow-up spray stripping and smoke catalytic and normal operation.
2) commissioning & operation of stripping device is sprayed:
Spray stripping mainly utilizes H
2the feature that S solubility in water is little, reduces H with gas
2the gaseous phase partial pressure of S, makes H
2s is separated with water.In order to improve stripping efficiency, when requiring pH < 5.0 in aqueous phase, the S of 98%
2-with H
2s form exists, and now stripping is most effective.Stripping gas is preferably containing a large amount of CO
2burnt gas, to maintain the low ph value of water, improve stripping efficiency, the high temperature of burnt gas is conducive to water temperature and rises simultaneously, accelerates H
2the stripping of S.
Spray stripping tower adopt counter-current operation, tower built with the polypropylene polyhedron empty ball filler of certain altitude, to increase gas-liquid mass transferring area thus to be conducive to gaseous state H
2s is from being rich in solubilised state H
2desorb in the water outlet of S.Be rich in solubilised state H
2the water outlet of S is thus lifted to the tower top of packed tower, is sprayed the whole surface of filler by shower nozzle equably, and by filler toward dirty, bottom passes into flue gas simultaneously, and current contact with flue gas is reverse, and hydrogen sulfide is desorbed from aqueous phase.
Major parameter is as follows:
The pH value of former water: 6.0 ~ 6.5;
Gas-water ratio: 1:(2500 ~ 4000);
Void tower flow velocity: 1.5 ~ 2.3m/s;
Filler: polypropylene polyhedron empty ball;
Packed height: 60cm.
The main component of coal-fired flue-gas comprises: SO
2, NO
x, CO
2, steam, O
2, N
2and dust.Different according to ature of coal, the ratio of concrete composition is different.General SO
2content is about 50%, and concentration is about 2300mg/Nm
3, O
2content is about 7%; CO
2content is about 12%; Water vapour content is about 6%; NO
xcontent is about 22%(NO and accounts for 98%), concentration is about 930mg/Nm
3.Wherein, x is 1 or 2.
Owing to containing a large amount of CO in coal-fired flue-gas
2, SO
2deng sour gas, add acid without the need to outside, the pH value of waste water just can be made lower, high-temperature flue gas improves the temperature of waste water simultaneously, is more conducive to the stripping of hydrogen sulfide.Calculate theoretically, the hydrogen sulfide that stripping tower desorbs enough meets the demand of follow-up smoke catalytic desulfurization.
3) commissioning & operation of smoke catalytic reactor:
Building of smoke catalytic reaction unit, each pipeline adopts 314 stainless steel tubes and resistance to, the resistant to elevated temperatures polyfluortetraethylene pipe of acid and alkali resistance.Flow-control adopts Beijing seven-star electronic flowmeter and is equipped with mass flow controller, and its gas flow control accuracy is ± 1%.Open tubular furnace is equipped with temperature controller, and its precision is ± 0.5 DEG C.Condenser pipe adopts two serpentine condenser.Flue gas analyzer adopts German testo350 reinforced, detects each constituent concentration in flue gas in real time.Tail gas is emptying after alkali liquor absorption bottle absorbs.
The selection of catalyst, catalyst adopts the 4A type molecular sieve of Tianjin Zhi Yuan chemical reagent Co., Ltd, and the chemical formula of this molecular sieve is Na
12[(AlO
2)
12(SiO
2)
12] 27H
2o, this molecular sieve low price, is easy to get, and is the most conventional industrial catalyst.
Catalyst is ground to 20 ~ 40 orders, loading catalyst in open tubular furnace, the amount of catalyst controls to be 0.5 ~ 3.0g, both sides adopt silica wool to be fixed, reactor draw ratio is made to be greater than 50 ~ 100, caliber and particle diameter ratio are greater than 8 ~ 10, and beds is greater than 6 with caliber ratio, prevents channel.Pass into the whole gas circuit 30min of argon purge, then the flue gas after stripping tower is passed through, in catalytic reactor, charge flow rate to be controlled at 500ml/min.After at room temperature stablizing 30min, the current hydrogen sulfide of flue gas analyzer record, sulfur dioxide and nitric oxide concentration separately.Then start to heat up with 50 DEG C/stage, after 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 600 DEG C each self-stabilization 30min, record sulfureous in flue gas hydrogen, sulfur dioxide and nitric oxide production concentration, investigate this catalytic reaction desulfurized effect and elemental sulfur productive rate.
As shown in Figure 6, sulfur dioxide is at 200 ~ 350 DEG C of clearances about 50%, and after temperature is more than 350 DEG C, along with the rising of temperature, the clearance of sulfur dioxide raises significantly, and 600 DEG C time, clearance reaches more than 80%.Nitric oxide production clearance along with the rising of temperature be steady growth state, 600 DEG C time, nitric oxide production clearance reaches more than 90%.
As shown in Figure 7, this smoke catalytic reactor elemental sulfur yield stable is about 80%, and between 200 ~ 300 DEG C, elemental sulfur productive rate reaches 90%.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. be a device for the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent with hydrogen sulfide, it is characterized in that: the gas-liquid separator comprise anaerobic organism sulphur reduction reactor, being connected by pipeline with anaerobic organism sulphur reduction reactor, the desulfurization and denitrification reaction device be connected with gas-liquid separator by pipeline;
Described anaerobic organism sulphur reduction reactor is provided with organic source input channel, and described gas-liquid separator bottom is provided with coal-fired flue-gas input channel, and described desulfurization and denitrification reaction device is provided with elemental sulfur gathering-device and elemental sulfur output channel.
2. according to claim 1 a kind of take hydrogen sulfide as the device of the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, it is characterized in that: described anaerobic organism sulphur reduction reactor is the one in packed bed biofilm reactor, completely stirring reactor, sequencing batch reactor, upflow anaerobic sludge blanket reactor, anaerobic membrane bioreactor, anaerobic baffled reactor.
3. according to claim 1 a kind of take hydrogen sulfide as the device of the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, it is characterized in that: described gas-liquid separator is spray stripping tower.
4. according to claim 1 a kind of take hydrogen sulfide as the device of the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, it is characterized in that: described desulfurization and denitrification reaction device is the one in tubular reactor, stove formula reactor, suspension type reactor, vertical type reactor, fixed fluidized-bed reactor; Described elemental sulfur gathering-device is condenser.
5. be a coal-fired flue-gas synchronized desulfuring and denitrifying technique for reducing agent with hydrogen sulfide, comprise the following steps:
1) solubilised state H
2the preparation of S: organic source, elemental sulfur and sulphur reducing bacteria are added anaerobic organism sulphur reduction reactor, make organic source, elemental sulfur fully contacts with sulphur reducing bacteria, under the effect of sulphur reducing bacteria, the oxidized removal of organic matter, elemental sulfur is converted into H
2s, solubilised state H is rich in the water outlet of reactor
2s;
2) H
2s, NO, NO
2, SO
2the preparation of mist: will solubilised state H be rich in
2the water outlet of S passes into gas-liquid separator from top, coal-fired flue-gas is passed into gas-liquid separator from bottom simultaneously, and current contact with flue gas is reverse, carry out gas-liquid separation, obtain H
2s, NO, NO
2, SO
2mist;
3) synchronized desulfuring and denitrifying: by H
2s, NO, NO
2, SO
2mist and catalyst add desulfurization and denitrification reaction device, carry out catalytic reaction, by NO and NO at 100 ~ 800 DEG C
2be converted into N
2and water, by H
2s and SO
2change into the elemental sulfur of gaseous state under high temperature, then condensation, enrichment, recovery elemental sulfur, an elemental sulfur part for recovery joins in anaerobic organism sulphur reduction reactor and recycles, and unnecessary elemental sulfur is collected for subsequent use.
6. according to claim 5 a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, it is characterized in that: the elemental sulfur described in step 1) is the elemental sulfur obtained through the synchronized desulfuring and denitrifying of step 3).
7. according to claim 5 a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, it is characterized in that: the organic source described in step 1) is at least one in organic sewage, additional organic matter.
8. according to claim 7 a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, it is characterized in that: described organic sewage is for containing organic industrial wastewater or city domestic sewage, and described additional organic matter is at least one in carbohydrate, grease, organic acid, organic acid esters, alcohols, ethers.
9. according to claim 5 a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, it is characterized in that: the sulphur reducing bacteria described in step 1) is sulfate reducing bacteria and elemental sulfur reducing bacteria.
10. according to claim 5 a kind of take hydrogen sulfide as the coal-fired flue-gas synchronized desulfuring and denitrifying technique of reducing agent, it is characterized in that: the catalyst described in step 3) is Al
2o
3, TiO
2, rare earth material, Fe
2o
3/ Al
2o
3, CuO/Al
2o
3, Fe
2o
3/ TiO
2, CuO/TiO
2, Pt/Al
2o
3, Fe/Ce-TiO
2, Fe/Ce-Al
2o
3, Ce/Mn-Al
2o
3, Ce/Mn-TiO
2, Ce-TiO
2-SnO
2, NaO-Al
2o
3-SiO
2, Na
12[(AlO
2)
12(SiO
2)
12] 27H
2at least one in O.
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| CN106975474A (en) * | 2017-03-10 | 2017-07-25 | 华南师范大学 | A kind of Ce based composite catalysts for being applied to vulcanization hydrogen catalysis reduction and desulfurization denitrating technique and preparation method thereof |
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| CN112566706A (en) * | 2018-06-04 | 2021-03-26 | 布莱恩·奥泽罗 | Process for the recovery of ethylene oxide |
| CN112566706B (en) * | 2018-06-04 | 2023-10-13 | 布莱恩·奥泽罗 | Process for the recovery of ethylene oxide |
| CN108970353A (en) * | 2018-07-16 | 2018-12-11 | 西安华大骄阳绿色科技有限公司 | A kind of synthesis desulfurating method of denitration being catalyzed flue gas and the sour gas containing ammonia |
| CN108970353B (en) * | 2018-07-16 | 2021-04-30 | 西安华大骄阳绿色科技有限公司 | Comprehensive desulfurization and denitrification method for catalytic flue gas and ammonia-containing acid gas |
| CN109395555A (en) * | 2018-12-27 | 2019-03-01 | 陈萌 | A kind of method of sulfur trioxide in removing flue gas during smelting |
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| CN115028332A (en) * | 2022-05-19 | 2022-09-09 | 同济大学 | Flue gas denitration and sludge anaerobic digestion cooperative treatment circulation method |
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