CN109453647A

CN109453647A - Boiler smoke low-temp desulfurization method of denitration

Info

Publication number: CN109453647A
Application number: CN201811489800.9A
Authority: CN
Inventors: 周稳华; 马广伟
Original assignee: Hubei Shen Tan Environmental Protection New Material Co Ltd; Tongling Pacific Special Material Ltd
Current assignee: Hubei Shen Tan Environmental Protection New Material Co Ltd; Tongling Pacific Special Material Ltd
Priority date: 2018-12-07
Filing date: 2018-12-07
Publication date: 2019-03-12

Abstract

The present invention relates to a kind of method of boiler flue gas desulfurization denitration, mainly solves the problem of that existing boiler flue gas desulfurization denitration operating cost is high and generate secondary pollution.The present invention enters the coke-stove gas or blast furnace gas of boiler combustion by using micro crystal material, before entering boiler, first remove sulfide, it burns again, nitrogen oxides and sulfide in the method removing boiler smoke of absorption, nitrogen oxides in effluent and sulfide after regeneration carry out the technical solution of resource utilization through peroxidating, preferably solves above-mentioned technical problem, this method can be used in the industrial production of boiler flue gas desulfurization denitration.

Description

Boiler smoke low-temp desulfurization method of denitration

Technical field

The invention belongs to desulphurization denitration technical fields, and in particular to a kind of desulfurization denitration method of boiler smoke.

Background technique

SO₂And NO_XIt is the important atmosphere pollution in China, excessive discharge will cause haze, acid rain and photochemical fog Deng serious harm ecological environment and human health.The burning of fossil fuel is SO₂And NO_XMain source.Coal be China most Important natural energy source, as the second largest coal field in China, carbonization of coal is one of industrial coal field primary pollution source, pot Kiln gas is the important pollution sources of atmosphere.

Current boiler flue gas desulfurization field is using more for ammonia process, lime/lime stone method, Dual alkali, magnesium oxide method etc. For the Wet Flue Gas Desulfurization Technique and semi-dry desulphurization technology of representative.Wet desulphurization absorption rate is high, but such as lime/lime Stone-gypsum, Dual alkali contain small hydrophilic ionic in magnesium oxide method slurries, are taken out of by flue gas, and are emitted into big In gas, while these particle surfaces are easily absorbing sulfur dioxide, sulfur trioxide, hydrogen chloride, hydrogen fluoride, nitrogen oxides, nocuousness Organic matter and bacterium etc. cause atmosphere suspended particles (usually said PM100, PM10, PM2.5 etc.) content to dramatically increase, And cause haze and atmospheric photochemical reaction phenomenon, cause serious environmental pollution.Sodium sulfite (potassium) method sulfur removal technology, Wei Er Man-Luo Defa Desulfovibrio technique, organic acid-acylate buffer-solution method sulfur removal technology, regeneration steam energy consumption is big and regenerates Rate is low, therefore it is big to industrialize difficulty.Ammonia corrosion is big in the ammonia process of desulfurization, the production process of equipment burn into and ammonia is caused to be high energy Consumption, high pollution process.Semi-dry desulphurization equipment corrosion compared with wet desulphurization is small, spreads without obvious temperature drop, conducive to chimney exhaust, But desulfuration efficiency is relatively low, reaction speed is slow.

The mainstream technology in denitration of boiler smoke field is NH₃SCR denitration, SCR technology use catalyst, and catalytic action makes Reaction activity reduces.In coke-oven plant, since flue gas self-temperature is very low (200 DEG C ~ 300 DEG C), it need to be urged using low-temperature denitration Agent carries out denitration reaction during this temperature, and need to spray into ammonia into flue gas and make reducing agent.

Individual desulphurization and denitration technique not only takes up a large area, but also invests, operating cost height.Simultaneous SO_2 and NO removal skill Art, which has, reduces device configuration, saves space, material source is wide, and price is low, renewable the advantages that recycling.Wherein, with work Property charcoal (coke) technology be representative dry desulfurization denitrification integral technology be the technology most to the heat energy utilization in flue gas.

Chinese patent 201410119747.9 recycles stack gases waste heat using stack gases waste-heat recovery device, reduces The temperature of stack gases, the activated adoption ability having using coke and low-temperature denitration catalytic capability realize the de- of stack gases Sulphur, denitration integration.The concrete operation step of the invention is that 1) stack gases first pass through waste gas residual heat recovery unit, and flue is useless The waste heat of gas is recovered, and temperature is reduced to 100 DEG C ~ 150 DEG C, is subsequently entered in low-temperature SCR desulphurization denitration unit, in flue gas SO₂It by coke adsorbing and removing, is mixed by the flue gas of desulfurization with ammonia, take coke as the catalyst of SCR method, denitration reduction occurs NO is completed in reaction_XRemoving；2) coke in low-temperature SCR desulphurization denitration unit is supplied from by elevator and grader leveling blade The coke feed unit of conveyer composition, the coke after denitration reduction reaction is expelled in coke main tank, periodically by outlet vehicle It sends outside；3) flue gas of low-temperature SCR desulphurization denitration unit discharge is sent after gas cleaning unit dust separation to chimney, realizes flue The qualified discharge of exhaust gas.The waste heat recycled in the waste gas residual heat recovery unit is sent in ammonia steaming device, is generated to coke-oven plant Remained ammonia carries out ammonia still process processing, provides necessary ammonia for the denitration reduction reaction in low-temperature SCR desulphurization denitration unit.

Chinese patent 201810438291.0 discloses a kind of low-sulfur flue gas desulfurization and denitrification device.The device includes adsorption tower And vibrating screen, adsorption tower are successively arranged the firstth area, the secondth area and third area along flue gas circulating direction, the firstth area is equipped with flue gas air inlet Mouthful and positioned at smoke air inlet ammonia-spraying grid, third area is equipped with the gas outlet of flue gas, the active carbon flowed is equipped in the secondth area Layer, active carbon layer are flowed into from the top entry of adsorption tower, outlet at bottom outflow；The connection of the outlet at bottom of vibrating screen and adsorption tower, And it is connected by the top entry of conveying mechanism and adsorption tower.

Chinese patent CN201611269710.X discloses a kind of sintering flue gas ammonia charcoal combined desulfurization and denitration method, sintering Flue gas is after the desulfurization of absorbing liquid containing ammonia again through activated carbon adsorption；Carbonaceous raw material, the gold that the active carbon is 2:1 ~ 5:1 by mass ratio Belong to oxide source to roast to obtain in 850 ~ 1100 DEG C of countrysidies；The carbonaceous raw material is semicoke, or is the mixed of coal and biomass Close material.In the present invention, the active carbon as made from by ammonia and the method for the invention is combined, can effective desulphurization denitration, also Help reduce secondary pollution, reduction technique.

Document above is active carbon (coke) simultaneous SO_2 and NO removal, but can not all be detached from ammonia as this step of reducing agent denitration Suddenly.Since boiler flue flow field is uneven, temperature field is uneven, catalyst failure degree is uneven, the volume fraction of escape ammonia is difficult low In design discipline.Escape ammonia is exceeded to will cause secondary pollution, and corrosion pipeline material, deposits danger in the use process of ammonia Property, it is very important to the body harm of people.

In view of the above problems, not using ammonia, simultaneously the invention proposes the technology of molecular sieve adsorption simultaneous SO_2 and NO removal Adsorb the SO in boiler smoke₂And NO_X, and be worth with certain recycling.

Summary of the invention

The technical problem to be solved by the present invention is in existing coke-oven plant's boiler smoke governance process, operating cost height is produced The technical issues of raw secondary pollution, provides a kind of method of boiler flue gas desulfurization denitration, which has process short, if Standby with low investment, regeneration is simple, and low energy consumption, advantage without secondary pollution.

In order to solve the above technical problems, a kind of method that the present invention uses boiler smoke low-temp desulfurization denitration, including it is following Step:

A) coke-stove gas or blast furnace gas for entering boiler combustion, before entering boiler, first with the removing vulcanization of crystallite adsorbent A Object enters back into coke oven combustion；

B) boiler smoke of boiler flue is drawn sulfur compound and nitrogen oxides, is denoted as material flow A, the temperature of the material flow A It is 120 ~ 320 DEG C；

C) material flow A carries out UTILIZATION OF VESIDUAL HEAT IN, produces steam, and the flue gas after cooling forms flow B, and the temperature of the flow B is 110 ~180℃；

D) flow B enters cooling tower, after supercooling, dedusting, forms flow C, the temperature of the flow C is 30 ~ 100 DEG C；

E) flow C enters the adsorption tower comprising crystallite adsorbent B, after adsorbing sulfide and nitrogen oxides, forms logistics D；

F) logistics D enters smoke stack emission after heating up；

G) adsorption tower after adsorbing sulfide and nitrogen oxides saturation in step c), with 100 ~ 10000m³The material flow A of/h regenerates, Regenerated flue gas forms logistics E, wherein the temperature of the logistics E is 120 ~ 350 DEG C；

H) logistics E enters the denitrating tower comprising denitrating catalyst, after catalysis reduction, forms logistics F；

I) logistics F enters the oxidizing tower comprising oxidation catalyst, after catalysis oxidation, forms logistics G；

J) logistics G enters regeneration tail gas desulfurizing tower, after water or lye spray, forms logistics H, spray liquid enters wastewater treatment System or salt extraction system；

K) logistics H enters step the cooling tower in d).

In the above-mentioned technical solutions, preferred technical solution is that the temperature of the material flow A is 130 ~ 280 DEG C；Nitrogen oxidation Object content is 100 ~ 1000mg/m³, sulfide content is 30 ~ 3000 mg/m³.Preferred technical solution is, the material flow A Temperature is 140 ~ 240 DEG C；

In the above-mentioned technical solutions, preferred technical solution is that UTILIZATION OF VESIDUAL HEAT IN uses steam boiler, production in the step c) Vapor (steam) temperature be 140 ~ 180 DEG C；Cooling tower in the step d) is spray column or heat exchanger types；The temperature of flow C Degree is 30 ~ 100 DEG C.

In the above-mentioned technical solutions, preferred technical solution is, into the coke-stove gas or blast furnace gas of coke oven combustion, Hydrogen sulfide content is 0 ~ 20 mg/m³, 0 ~ 20 mg/m of organic sulfur content³。

In the above-mentioned technical solutions, preferred technical solution is, into the coke-stove gas or blast furnace gas of coke oven combustion, Hydrogen sulfide content is 0 ~ 10 mg/m³, 0 ~ 10 mg/m of organic sulfur content³。

In the above-mentioned technical solutions, preferred technical solution is, into the coke-stove gas or blast furnace gas of coke oven combustion, Hydrogen sulfide content is 0 ~ 5 mg/m³, 0 ~ 5mg/m of organic sulfur content³。

In above-mentioned technical proposal, preferred technical solution is that the temperature of the logistics D is 30 ~ 100 DEG C；Nitrogen oxides Content is 1 ~ 200mg/m³, sulfide content is 0.1 ~ 100 mg/m³。

In above-mentioned technical proposal, preferred technical solution is that the heating mode of the logistics D is heated up using heated by gas Mode or logistics D and material flow A heat exchange heating mode, for logistics D after heating up, temperature is 80 ~ 200 DEG C.

In above-mentioned technical proposal, preferred technical solution is, in step e), the quantity of adsorption tower is inhaled at least more than two Attached bed operation temperature is 30 ~ 100 DEG C, and operating pressure is 0.1 ~ 20KPa.

In above-mentioned technical proposal, preferred technical solution is that the temperature of the material flow A is 200 ~ 300 DEG C；Nitrogen oxides Content is 100-1000mg/m³, sulfide content is 40 ~ 3000 mg/m³。

In the above-mentioned technical solutions, preferred technical solution is, in step e), the quantity of adsorption tower at least more than two, Adsorbent bed operation temperature is 30 ~ 100 DEG C, and operating pressure gauge pressure is 0.5 ~ 10Kpa.

In the above-mentioned technical solutions, preferred technical solution is the crystallite adsorbent A or the choosing of crystallite adsorbent B From including X-type molecular sieve, Y type molecular sieve, A type molecular sieve, SSZ-13 molecular sieve, TS-1, Ti-MWW, Ti-MOR, ZSM type molecule Sieve, modenite, beta molecular sieve, SAPO type molecular sieve, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite, ZSM-5/ β boiling At least one of stone/Y zeolite or ZSM-5/Y zeolite/modenite.

In the above-mentioned technical solutions, preferred technical solution is that also containing in the crystallite adsorbent includes element week At least one of Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element element in phase table.

In the above-mentioned technical solutions, preferred technical solution is that containing in the oxidation catalyst includes period of element At least one of Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element element in table.

In the above-mentioned technical solutions, preferred technical solution is that the lye is sodium hydroxide solution, ammonium hydroxide, residue At least one of ammonium hydroxide, sodium carbonate liquor, calcium hydroxide solution.

In the above-mentioned technical solutions, preferred technical solution is that denitrating catalyst described in step h) is selected from vanadium tungsten titanium Catalyst, or selected from including the Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth in the periodic table of elements The above-mentioned crystallite adsorbent of at least one of race's element element.

In the above-mentioned technical solutions, preferred technical solution, it includes SSZ-13, TS- that the adsorbent of molecular sieve, which is selected from, 1, Ti-MWW, Ti-MOR, ZSM type molecular sieve, modenite, beta molecular sieve, SAPO type molecular sieve, MCM-22, ZSM-5/ mercerising Zeolite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/Y boiling At least one of stone or ZSM-5/Y zeolite/modenite.

In the above-mentioned technical solutions, the silica alumina ratio of preferred technical solution, the molecular sieve is greater than 2.

In the above-mentioned technical solutions, preferred technical solution, the IIth element A is selected from magnesium and calcium in the periodic table of elements At least one of；Ith B race element is selected from least one of copper, silver；IIIth B race element in lanthanum, cerium, yttrium at least It is a kind of.

In the above-mentioned technical solutions, preferred technical solution, ZSM type molecular sieve is selected from packet in the adsorbent of molecular sieve At least one of ZSM-5, ZSM-23, ZSM-11, ZSM-48 are included, wherein the silica alumina ratio of the molecular sieve is greater than 20.

In the above-mentioned technical solutions, preferred technical solution, adsorbent bed operation temperature are 0 ~ 100 DEG C, operating pressure 0.5 ~ 10Kpa, gauge pressure.

In the above-mentioned technical solutions, preferred technical solution is passed through air, ozone, double water oxygen water in regeneration gas oxidizing tower At least one of.

In the above-mentioned technical solutions, preferred technical solution, after the adsorbent of molecular sieve adsorption saturation, heat first Water rinses, then with 100 ~ 300 DEG C of nitrogen regenerations.

It is known in the art, coal gas is purified using traditional handicraft, using desulfurizing tower again during gas purification process It is middle to use iron oxide desulfurization；Naphthalene is taken off with active carbon using in de- naphthalene tower；Benzene is taken off with active carbon using debenzolizing tower again；3 are used altogether Absorbing unit successively purifies coal gas.In device operation, device exit hydrogen sulfide, benzene and naphthalene are dense, influence production effect Rate.Using method of the invention, have the advantages that (1), can be by benzene, naphthalene and hydrogen sulfide, organic sulfur using adsorbent of molecular sieve It can thoroughly remove completely, solve the problems, such as line clogging.(2) adsorbent is subjected to multifunction, can desulfurization simultaneously, de- benzene, De- naphthalene can carry out comprehensive purifying process simultaneously, reduce the quantity of adsorption tower in this way, reduce production in an adsorption tower Cost.

Using technical solution of the present invention: the coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly enters after de- benzene Comprehensive purifying tower, purifying column is interior to contain molecular sieve adsorbent, while removing the aromatic hydrocarbons and sulfide in coal gas, enters back into coke Furnace burning.De- naphthalene tower exit hydrogen sulfide content is 0 mg/m³, naphthalene content is 0 mg/m³, tar content 0 carries in gas Organic sulfur be also removed, sulfur dioxide in flue gas is emitted on 10m g/m³Hereinafter, device is stable.It is de- to reduce end desulfurization The cost of nitre.

By adopting the above technical scheme, using crystallite adsorbent desulphurization denitration, crystallite adsorbent to gas cleaning handle just like Lower advantage: the sulfur dioxide and nitrogen oxides in flue gas can be effectively adsorbed, discharge standard is made up to；High temperature resistant, structure are steady It is fixed, iterative regenerable；It is high to adsorb precision, other than adsorb sulfur dioxide, can also dedusting simultaneously remove the harmful substances such as dioxin, Make up to discharge standard；Crystallite adsorbent long service life, does not generate dangerous waste.By setting up adsorption tower in exhanst gas outlet, benefit Sulfur dioxide, the nitrogen oxides in flue gas are adsorbed with System of Silica/Aluminum Microparticle hydrochlorate crystallite adsorbent, System of Silica/Aluminum Microparticle in adsorption tower After hydrochlorate crystallite adsorbent adsorption saturation, crystallite adsorbent is regenerated by high-temperature flue gas, the nitrogen oxides and sulphur of desorption Compound enters oxidizing tower, is oxidized to sulfur trioxide and nitrogen dioxide, and regenerated flue gas is absorbed with water spray, after effluent part neutralizes, It is discharged into biochemical system or goes to salt extraction workshop, tail gas enters flue gas spray column circulation.Entire treatment process process is short, equipment investment It saves, regenerative operation is simple and reliable, and low energy consumption, flue gas emission nitrogen oxides≤50mg/m³, sulfur dioxide≤30mg/m³, dust content Less than 5 mg/m³, achieve preferable technical effect.

Detailed description of the invention

Fig. 1 is the flow diagram of boiler flue gas desulfurization method of denitration of the invention.

1 is boiler smoke in Fig. 1, and 2 be waste heat steam boiler, and 3 be spray column, and 4 be heat exchanger, and 5 be electric fishing mist, and 6 be suction Attached tower, 7 be blower, and 8 be heater, and 9 be denitrating tower, and 10 be oxidizing tower, and 11 be sedimentation basin, and 12 be cooling tower, and 13 be chimney.

The present invention will be further described below by way of examples, but is not limited only to the present embodiment.

Specific embodiment

[embodiment 1]

The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, wherein benzene concentration exists in logistics I 1000~4000mg/m³Between, naphthalene concentration is in 200~500mg/m³Between, concentration of hydrogen sulfide is in 100~500mg/m³Between；Object Stream I enters comprehensive purifying tower, ZSM molecular sieve class adsorbent is contained in the comprehensive purifying tower, while removing in coal gas Aromatic hydrocarbons and sulfide form logistics II, and benzene concentration is less than 1000mg/m in logistics II³, naphthalene concentration is less than 4 mg/m³, hydrogen sulfide is dense Degree is less than 4mg/m³；Organic sulfur concentration is less than 4mg/m³；Logistics II enters boiler combustion.

The boiler smoke of 16 240 DEG C of ten thousand steres, amount of nitrogen oxides 500mg/m³, sulfide content is 200 mg/ m³, into waste heat boiler, steam is generated, flue-gas temperature is reduced to 180 DEG C or so；180 DEG C of flue gas passes through spraying cooling to 50 DEG C, shower water after effluent part neutralizes, removes biochemical system by being recycled；After flue gas after cooling passes through defogging equipment, into Enter adsorption tower；Using 3 200m³Adsorption tower, two open one standby, and 120m is loaded in each adsorption tower³Micro crystal material amounts to 360 m³Micro crystal material modenite；Adsorption tower specification is 4.8 meters of diameter, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, Into from after heat exchanger and hot fume heat exchange, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m³, sulfide content is 20 mg/m³.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, after adsorption saturation certainly Dynamic switching circular regeneration；Automatically switch within every 7 days a tower regeneration, the adsorption tower 3000m of saturation³The hot fume of/h carries out again Raw, the nitrogen oxides and sulfide of desorption are introduced into the denitrating tower containing ZSM-5 molecular sieve, in 300 DEG C of progress denitration reactions, nitrogen Oxide is reduced into nitrogen, and the gas after reaction enters back into oxidizing tower, and sulfide is oxidized to sulfur trioxide with vanadium series catalyst；It is mixed It after closing gas cooling, is absorbed with water spray, after effluent part neutralizes, being discharged into produces salt extraction workshop, and tail gas enters flue gas spray column.

[embodiment 2]

Specific embodiment device process as shown in Fig. 1, the flue gas of 15 260 DEG C of ten thousand steres, nitrogen oxides contain Amount is 400mg/m³, sulfide content is 100 mg/m³, into waste heat boiler, 150 DEG C of steam are generated, flue-gas temperature is reduced to 120 DEG C or so；By spraying cooling to 40 DEG C, shower water after effluent part neutralizes, is gone 120 DEG C of flue gas by being recycled Biochemical system；After flue gas after cooling passes through defogging equipment, into adsorption tower；Using 3 200m³Adsorption tower, two open it is one standby, 120m is loaded in each adsorption tower³Micro crystal material amounts to 360 m³Micro crystal material ZSM-5 molecular sieve；Adsorption tower specification is diameter It is 4.8 meters, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m³, sulfide content is 20 mg/m³.Adsorption tower is built-in Desulphurization and denitration, dedusting crystallite adsorbent are filled out, automatically switches circular regeneration after adsorption saturation；One tower of automatic switchover in every 7 days is again It is raw, the adsorption tower 3000m of saturation³The hot fume of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidizing tower, oxygen It is melted into sulfur trioxide and nitrogen dioxide；It after mixed gas cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into department of biochemistry Salt extraction workshop is united or goes, tail gas enters flue gas spray column.

[embodiment 3]

The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, wherein benzene concentration exists in logistics I 1000~3500mg/m³Between, naphthalene concentration is in 200~500mg/m³Between, concentration of hydrogen sulfide is in 100~500mg/m³Between；Object Stream I enters comprehensive purifying tower, and the ZSM-5 molecular sieve class adsorbent containing zinc modification in the comprehensive purifying tower removes simultaneously Fall the aromatic hydrocarbons and sulfide in coal gas, forms logistics II, benzene concentration is less than 60mg/m in logistics II³, naphthalene concentration is less than 1 mg/m³, Concentration of hydrogen sulfide is less than 1mg/m³；Toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, the concentration in Kun are less than 1 mg/m³；Vulcanization Object is hydrogen sulfide, the concentration in sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, Dimethyl sulfide is less than 1 mg/m³, logistics II, which enters boiler, generates electricity.

Specific embodiment device process as shown in Fig. 1, the flue gas of 14 140 DEG C of ten thousand steres, nitrogen oxides contain Amount is 450mg/m³, sulfide content is 200 mg/m³, into waste heat boiler, 160 DEG C of steam are generated, flue-gas temperature is reduced to 110 DEG C or so；By spraying cooling to 50 DEG C, shower water after effluent part neutralizes, is gone 110 DEG C of flue gas by being recycled Biochemical system；After flue gas after cooling passes through defogging equipment, into adsorption tower；Using 3 200m³Adsorption tower, two open it is one standby, 120m is loaded in each adsorption tower³Micro crystal material amounts to 360 m³Micro crystal material ZSM-5 molecular sieve；Adsorption tower specification is diameter It is 4.8 meters, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 110 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 40mg/m³, sulfide content is 10 mg/m³.Adsorption tower is built-in Desulphurization and denitration, dedusting crystallite adsorbent are filled out, after adsorption saturation, automatically switches circular regeneration with high-temperature flue gas；Automatically it cuts within every 7 days Change a tower regeneration, the adsorption tower 3000m of saturation³240 DEG C of flue gases of/h are regenerated, the nitrogen oxides and sulfide of desorption Into the denitrating tower for being introduced into the mordenite catalyst containing copper load, in 350 DEG C of progress denitration reactions, nitrogen oxides reduction At nitrogen, the oxidizing tower containing vanadium series catalyst is entered back into, sulfur trioxide and nitrogen dioxide are oxidized to；After mixed gas cooling, It is absorbed with water spray, after effluent part neutralizes, is discharged into biochemical system or goes to salt extraction workshop, tail gas enters flue gas spray column.

[embodiment 4]

Specific embodiment device process as shown in Fig. 1, the flue gas of 20 180 DEG C of ten thousand steres, amount of nitrogen oxides are 1000mg/m³, sulfide content is 500 mg/m³, into waste heat boiler, 10 tons of 165 DEG C of steam, flue-gas temperature are generated per hour It is reduced to 120 DEG C or so；120 DEG C of flue gas is by spraying cooling to 40 DEG C, and by being recycled, effluent part neutralizes shower water Afterwards, the salt extraction system that going produces；After flue gas after cooling passes through defogging equipment, into adsorption tower；Using 4 200m³Absorption Tower, three open standby, a filling 120m in each adsorption tower³Micro crystal material amounts to 480 m³Micro crystal material SSZ-13 molecular sieve；Absorption Tower specification is 4.8 meters of diameter, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, changed into from heat exchanger and hot fume After heat, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m³, sulfide content is 20 mg/ m³.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, automatically switch circular regeneration after adsorption saturation；Every 7 days automatic Switch a tower regeneration, the adsorption tower 2000m of saturation³The hot fume of/h is regenerated, the nitrogen oxides and sulfide of desorption Into the oxidizing tower containing Cu-series catalyst, it is oxidized to sulfur trioxide and nitrogen dioxide；After mixed gas cooling, inhaled with water spray It receives, after effluent part neutralizes, being discharged into produces salt extraction workshop, and tail gas enters flue gas spray column.

[embodiment 5]

Specific embodiment device process as shown in Figure 1, the flue gas of 20 180 DEG C of ten thousand steres, amount of nitrogen oxides are 1000mg/m³, sulfide content is 500 mg/m³, into waste heat boiler, generate 150 DEG C of steam, flue gas cool-down is to 170 DEG C, cigarette Gas enters spray column, and by spraying cooling to 40 DEG C, shower water is by being recycled, and after effluent part neutralizes, what going produced is mentioned Salt system；After flue gas after cooling passes through defogging equipment, into adsorption tower；Using 4 200m³Adsorption tower, three open it is one standby, often 120m is loaded in a adsorption tower³Micro crystal material, amount to 480 m³Micro crystal material copper ZSM-5 molecular sieve；Adsorption tower specification is diameter It is 4.8 meters, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 40mg/m³, sulfide content is 10 mg/m³.Adsorption tower is built-in Desulphurization and denitration, dedusting crystallite adsorbent are filled out, automatically switches circular regeneration after adsorption saturation；One tower of automatic switchover in every 7 days is again It is raw, the adsorption tower 3000m of saturation³180 DEG C of flue gases of/h are regenerated, and the nitrogen oxides and sulfide of desorption, which enter, contains copper The oxidizing tower of series catalysts, is oxidized to sulfur trioxide and nitrogen dioxide；It after mixed gas cooling, is absorbed with water spray, part is useless After water neutralizes, being discharged into produces salt extraction workshop, and tail gas enters flue gas spray column.

[embodiment 6]

Specific embodiment device process as shown in Figure 1, the flue gas of 180 DEG C of 200,000 sides rice, amount of nitrogen oxides are 400mg/m³, sulfide content is 100 mg/m³, into waste heat boiler, 170 DEG C of steam are generated, flue gas cool-down enters to 175 DEG C For spraying cooling to 50 DEG C, shower water after effluent part neutralizes, removes biochemical system by being recycled；Flue gas after cooling passes through After defogging equipment, into adsorption tower；Using 3 200m³Adsorption tower, two open one standby, and 120m is loaded in each adsorption tower³Crystallite Material amounts to 360 m³Micro crystal material, micro crystal material include the ZSM-5 molecular sieve of lanthanum and zinc modification；Adsorption tower specification is diameter It is 4.8 meters, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, into smoke stack emission, nitrogen oxides in effluent content is 30mg/m³, sulfide content 5mg/m³.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, it is automatic after adsorption saturation Switch circular regeneration；Automatically switch within every 7 days a tower regeneration, the adsorption tower 4000m of saturation³180 DEG C of the flue gas of/h carries out Regeneration, the nitrogen oxides and sulfide of desorption enter oxidizing tower, are oxidized to sulfur trioxide and nitrogen dioxide at 250 DEG C；Gaseous mixture It after body cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into biochemical system or goes to salt extraction workshop, tail gas enters flue gas Spray column.

[embodiment 7]

Specific embodiment device process as shown in Fig. 1, the flue gas of 18 240 DEG C of ten thousand steres, amount of nitrogen oxides are 400mg/m³, sulfide content is 100 mg/m³, into waste heat steam boiler, generate 145 DEG C of steam, flue gas cool-down to 160 DEG C, By spraying cooling to 40 DEG C, shower water after effluent part neutralizes, removes biochemical system by being recycled；Flue gas after cooling After defogging equipment, into adsorption tower；Using 3 200m³Adsorption tower, two open one standby, and 120m is loaded in each adsorption tower³ Micro crystal material amounts to 360 m³Micro crystal material ZSM-5 molecular sieve；Adsorption tower specification is 4.8 meters of diameter, 12.0 meters high；Flue gas removes After desulfuration compound and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 100 DEG C or more, into smoke stack emission, cigarette Amount of nitrogen oxides is 50mg/m in gas³, sulfide content is 20 mg/m³.Desulphurization and denitration, dedusting crystallite are loaded in adsorption tower Adsorbent automatically switches circular regeneration after adsorption saturation；Automatically switch within every 7 days a tower regeneration, the adsorption tower of saturation is used 3000m³The hot fume of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidizing tower, is oxidized to sulfur trioxide and two Nitrogen oxide；It after mixed gas cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into biochemical system or goes to salt extraction workshop, Tail gas enters flue gas spray column.

[embodiment 8]

Specific embodiment device process as shown in Fig. 1, the flue gas of 18 210 DEG C of ten thousand steres, amount of nitrogen oxides are 400mg/m³, sulfide content is 100 mg/m³, into waste heat boiler, 160 DEG C of steam are generated, flue gas cool-down passes through to 185 DEG C For spraying cooling to 50 DEG C, shower water after effluent part neutralizes, goes to the salt extraction workshop of coking by being recycled；Cigarette after cooling After gas passes through defogging equipment, into adsorption tower；Using 4 200m³Adsorption tower, three open one standby, filling in each adsorption tower 150m³Micro crystal material amounts to 600 m³Micro crystal material containing modenite and ZSM-5 molecular sieve；Adsorption tower specification is diameter It is 4.8 meters, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m³, sulfide content is 20 mg/m³.Adsorption tower is built-in Desulphurization and denitration, dedusting crystallite adsorbent are filled out, automatically switches circular regeneration after adsorption saturation；One tower of automatic switchover in every 7 days is again It is raw, the adsorption tower 4000m of saturation³240 DEG C of the flue gas of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidation Tower is oxidized to sulfur trioxide and nitrogen dioxide；It after mixed gas cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into life Change system goes to salt extraction workshop, and tail gas enters flue gas spray column.

Claims

1. a kind of method of boiler smoke low-temp desulfurization denitration, comprising the following steps:

A) coke-stove gas or blast furnace gas for entering boiler combustion first remove sulphur with crystallite adsorbent A before entering boiler Compound enters back into coke oven combustion；

C) material flow A carries out UTILIZATION OF VESIDUAL HEAT IN, produces steam, and the flue gas after cooling forms flow B, and the temperature of the flow B is 110~180℃；

D) flow B enters cooling tower, after supercooling, forms flow C, the temperature of the flow C is 30 ~ 100 DEG C；

F) logistics D enters smoke stack emission after heating up；

G) adsorption tower after adsorbing sulfide and nitrogen oxides saturation in step e), with 100 ~ 10000m³The material flow A of/h regenerates, Regenerated flue gas forms logistics E, wherein the temperature of the logistics E is 120 ~ 350 DEG C；

J) logistics G enters regeneration tail gas desulfurizing tower, after water or lye spray, forms logistics H, spray liquid enters at waste water Reason system or salt extraction system；

K) logistics H enters step the cooling tower in d).

2. the method for boiler flue gas desulfurization denitration according to claim 1, it is characterised in that the temperature of the material flow A is 130~280℃；Amount of nitrogen oxides is 100 ~ 1000mg/m³, sulfide content is 30 ~ 3000 mg/m³；Into boiler combustion Coke-stove gas or blast furnace gas, hydrogen sulfide content are 0 ~ 20 mg/m³, 0 ~ 20 mg/m of organic sulfur content³。

3. the method for boiler smoke low-temp desulfurization denitration according to claim 1, it is characterised in that in the step b) UTILIZATION OF VESIDUAL HEAT IN uses steam boiler, and the vapor (steam) temperature of production is 140 ~ 180 DEG C；Cooling tower in the step d) is spray column Or heat exchanger types；The temperature of flow C is 30 ~ 100 DEG C.

4. the method for boiler smoke low-temp desulfurization denitration according to claim 1, it is characterised in that the temperature of the logistics D Degree is 30 ~ 100 DEG C；Amount of nitrogen oxides is 1 ~ 200mg/m³, sulfide content is 0.1 ~ 100 mg/m³。

5. the method for boiler smoke low-temp desulfurization denitration according to claim 1, it is characterised in that the liter of the logistics D Warm mode is using heated by gas heating mode or logistics D and material flow A heat exchange heating mode, and after heating up, temperature is logistics D 80~200℃；In step e), the quantity of adsorption tower is at least more than two, and adsorbent bed operation temperature is 30 ~ 100 DEG C, operating pressure For 0.1 ~ 20KPa；In the step i), lye is sodium hydroxide solution, ammonium hydroxide, remained ammonia, sodium carbonate liquor, hydroxide At least one of calcium solution.

6. the method for boiler smoke low-temp desulfurization denitration according to claim 1, it is characterised in that the crystallite absorption It includes X-type molecular sieve, Y type molecular sieve, A type molecular sieve, SSZ-13 molecular sieve, TS-1, Ti-MWW, Ti-MOR, ZSM type that agent, which is selected from, Molecular sieve, modenite, beta molecular sieve, SAPO type molecular sieve, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite, ZSM- 5/ β zeolite/at least one of Y zeolite or ZSM-5/Y zeolite/modenite.

7. the method for boiler smoke low-temp desulfurization denitration according to claim 7, it is characterised in that the crystallite absorption It further include the Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B in the periodic table of elements in agent A or crystallite adsorbent B Or the VIIIth at least one of race's element element.

8. the method for boiler smoke low-temp desulfurization denitration according to claim 1, it is characterised in that in the oxidation catalyst Containing include in the periodic table of elements in the Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element extremely A kind of few element.

9. the method for boiler smoke low-temp desulfurization denitration according to claim 1, it is characterised in that denitration described in step h) Catalyst is selected from vanadium tungsten titanium catalyst, or selected from including the Ith A, II A, V A, I B, II B, III B, IV B, V in the periodic table of elements B, the above-mentioned crystallite adsorbent of at least one of VI B, VII B or the VIIIth race's element element.