CN105498509B - A kind of calcium-magnesium combined desulfurization and denitration method meeting flue gas pollutant deep removal - Google Patents
A kind of calcium-magnesium combined desulfurization and denitration method meeting flue gas pollutant deep removal Download PDFInfo
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- CN105498509B CN105498509B CN201510880781.2A CN201510880781A CN105498509B CN 105498509 B CN105498509 B CN 105498509B CN 201510880781 A CN201510880781 A CN 201510880781A CN 105498509 B CN105498509 B CN 105498509B
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- desulfurization
- flue gas
- magnesium
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 162
- 230000023556 desulfurization Effects 0.000 title claims abstract description 111
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003546 flue gas Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 55
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 13
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000007789 gas Substances 0.000 claims abstract description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 15
- 239000011575 calcium Substances 0.000 claims abstract description 15
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 10
- 239000004571 lime Substances 0.000 claims abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- 230000003009 desulfurizing effect Effects 0.000 claims description 16
- 239000000395 magnesium oxide Substances 0.000 claims description 15
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 13
- 239000000347 magnesium hydroxide Substances 0.000 claims description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 8
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- 239000010440 gypsum Substances 0.000 claims description 5
- 229910052602 gypsum Inorganic materials 0.000 claims description 5
- 230000010354 integration Effects 0.000 claims description 5
- 239000000779 smoke Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 235000019504 cigarettes Nutrition 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000006028 limestone Substances 0.000 abstract description 5
- 235000019738 Limestone Nutrition 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 239000007806 chemical reaction intermediate Substances 0.000 abstract 1
- 239000000428 dust Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 30
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 10
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003595 mist Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000013316 zoning Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/12—Methods and means for introducing reactants
- B01D2259/126—Semi-solid reactants, e.g. slurries
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Treating Waste Gases (AREA)
Abstract
本发明公开了一种满足烟气污染物深度脱除的钙‑镁联合脱硫脱硝方法。本发明涉及环境保护领域，是一种针对工业烟气深度脱硫脱硝所开发的一种新技术工艺。本发明所对应的脱硫设备由多区组成，分别包括主脱硫区、深度脱硫区及高效除尘除雾区。在主脱硫区，采用常规钙法(石灰或石灰石)脱硫，使烟气在较经济合理的条件下实现90％以上的脱硫效率；接着，烟气再经过深度脱硫区，利用镁法脱硫工艺，在较低液气比情况下，使烟气中的二氧化硫脱至30mg/m3以下，实现其超低排放要求。另外，还可以在深度脱硫区加入氧化脱硝促进剂，同步实现脱硫脱硝的功能。与现有技术相比，本发明脱硫效率高、成本低，而且反应中间产物能进行循环利用。
The invention discloses a calcium-magnesium combined desulfurization and denitrification method that satisfies the deep removal of flue gas pollutants. The invention relates to the field of environmental protection, and is a new technology developed for deep desulfurization and denitrification of industrial flue gas. The desulfurization equipment corresponding to the present invention is composed of multiple zones, which respectively include a main desulfurization zone, a deep desulfurization zone and a high-efficiency dust removal and fog removal zone. In the main desulfurization zone, the conventional calcium method (lime or limestone) is used for desulfurization, so that the flue gas can achieve a desulfurization efficiency of more than 90% under more economical and reasonable conditions. In the case of a lower liquid-gas ratio, the sulfur dioxide in the flue gas can be removed to below 30mg/m3 to achieve its ultra-low emission requirements. In addition, an oxidative denitration accelerator can also be added to the deep desulfurization zone to simultaneously realize the function of desulfurization and denitrification. Compared with the prior art, the present invention has high desulfurization efficiency and low cost, and the reaction intermediate product can be recycled.
Description
Technical field
The present invention relates to field of environment protection, and in particular to a kind of calcium for meeting flue gas pollutant deep removal-magnesium joint
Desulfurization denitration method.
Background technique
The situation is tense for current China's atmosphere pollution, causes serious harm to human health.SO2 is to cause atmosphere pollution
One of major pollutants, effectively controlling SO2 in industrial smoke is current very urgent environmental protection subject.In recent years, both at home and abroad
The requirement of minimum discharge is proposed for industrial waste gas, especially coal-burning power plant's atmosphere pollution, it is desirable that SO2 discharge is lower than
35mg/m3。
The mainstream technology applied at present is taken a broad view of it can be found that either desulfuration in furnace or gas cleaning, core are calcium
Based compound is reacted with SO2 generates gypsum (CaSO4).These method and processes are simple, and production run is safe and reliable, applicable coal
Range is wide, desulfuration efficiency is high, absorbent utilization rate is high, desulfurizing agent-lime stone abundance and cheap.However, calcium is used alone
Method desulfurization is extremely difficult to the requirement of current minimum discharge, needs by increasing spray layer number, improving liquid-gas ratio, increase slurry pool
The means such as volume enhance desulfuration efficiency, especially when desulfuration efficiency is higher, if continuing to improve the measures such as liquid-gas ratio, desulfurization
The increase of efficiency is very slow, to greatly increase the investment and energy consumption of equipment.Therefore, desulfurization is being realized using only calcium method
Cost when deep-controlled is higher.
Currently, the magnesia FGD method as Wet Flue Gas Desulfurization Technology just obtaining in the world relatively broad popularization and
Using.Magnesium oxide method desulfurization technology maturation, desulfuration efficiency are up to 98% or more, it is easy to meet the requirement of discharge standard.In addition,
Magnesium oxide method desulphurization system non-scaling, system is safe and reliable to operation, and work efficiency is high, byproduct recoverable；Desulfurizing agent is adopted
With magnesia powder, sufficient raw, convenient transportation, relative low price.But for fairly large desulfurization, due to de-
Oxidation magnesium amount and generated magnesium sulfate waste water to be processed consumed by sulphur are higher, and there are problems in terms of economy.But
It is, if it is used in combination with calcium method desulfurization, to be used only in deep desulfuration area, then its advantage then becomes apparent from.
In conclusion calcium method desulfurization is extremely difficult to the requirement of current minimum discharge, and magnesium processes desulfurization is difficult to be suitable for big rule
The desulfurization of mould, higher cost.So to probe into, one kind is at low cost, is suitable for extensive desulfurization, the sulfur method that desulfuration efficiency is high,
With good industrial value.
Summary of the invention
Meet smoke pollution it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of
Calcium-magnesium processes combined desulfurization and denitration technology that object is removed in depth.
The purpose of the present invention can be achieved through the following technical solutions: a kind of to meet what flue gas pollutant was removed in depth
Calcium-magnesium combined desulfurization and denitration method, desulfurization uses wet absorption technique, and absorption equipment is used zoning design, respectively includes
Main desulfurization zone and deep desulfuration area, including the following steps:
(1) industrial smoke inputs main desulfurization zone after dedusting, is carried out in advance using the desulfurization of calcium method to flue gas in main desulfurization zone
Desulfurization obtains low-sulfur flue gas；
(2) low-sulfur flue gas obtained by step (1) enters deep desulfuration area, in deep desulfuration area using magnesium processes desulfurization to low-sulfur cigarette
Gas carries out deep desulfuration, handles, is emitted into atmosphere using demisting.
Calcium method desulfurization described in step (1) be using the one or more as desulfurizing agent of agstone, lime or carbide slag,
Soluble in water, being configured to mass concentration is 5~20%, and (pH is easy fouling, institute after being greater than 6.5 to the slurries that pH value is 5.5~6.5
With cannot be too high；PH < 7 still can be with desulfurization), it is pumped into after main desulfurization zone comes into full contact with flue gas and mixes, slough the sulphur in flue gas, take off
Sulphur liquid-gas ratio is 3-8L/m3。
The sulfur dioxide concentration that step (1) inputs in the flue gas of main desulfurization zone is 500-5000mgm3In the case of, through main de-
Sulphur area removes in flue gas 90% or more sulfur dioxide, and is lower than the sulfur dioxide in flue gas concentration of main desulfurization zone discharge
300mg/m3, run the desulfurization of calcium method under most reasonable process conditions.Desulfurization product then through oxidizing and crystallizing, is converted into gypsum.
Magnesium processes desulfurization described in step (2) is soluble in water, the configuration using magnesia or magnesium hydroxide slurry as desulfurizing agent
It is 1~10% at mass concentration, the slurries that pH value is 6.5~9 are pumped into deep desulfuration area and come into full contact with flue gas and mix, and slough
Sulphur in flue gas, desulfurization liquid-gas ratio are 1-3L/m3, handled by this, make system under very low magnesium Expenditure Levels, realize depth
Desulfurization, and the operating pressure of the calcium method desulfurization of main desulfurization zone can be greatly lowered.
Deep desulfuration area described in step (2) can will take off from the sulfur dioxide in flue gas of main desulfurization zone to 30mg/m3
Within.
Denitration hardening agent is added into magnesium processes desulfurization desulfurizer therefor slurries in the deep desulfuration area, carries out denitration.
The denitration hardening agent includes that ozone, hydrogen peroxide, peromag or persulfuric acid magnesium etc. are halogen-free or alkali metal
One or more of oxidant；The pH of magnesia has the ability for activating these oxidants to absorb denitration, has preferable
Denitration effect；The additive amount of the out of stock hardening agent is to make its mass concentration in magnesium processes desulfurization desulfurizer therefor slurries are as follows:
1%-15%.
Desulphurization denitration by-product obtained by the deep desulfuration area is magnesium sulfate or magnesium nitrate solution, by resulting magnesium sulfate
Or magnesium nitrate solution is used as the buffer of main desulfurization zone, can improve the desulfurization effect of main desulfurization zone.
Resulting magnesium sulfate and magnesium nitrate solution are passed through doctor solution circulatory pool, with ammonia precipitation process, obtaining magnesium hydroxide can
It is recycled；Ammonium sulfate caused by regenerating, which then recycles lime to replace again, becomes ammonium hydroxide, is recycled；It is produced
After raw calcium sulfate precipitation is washed, collected together with desulfurized gypsum.
The main desulfurization zone and deep desulfuration area is located in integration apparatus or in two independent towers.
The integration apparatus sequentially consists of tower reactor area, main desulfurization zone, deep desulfuration area and dedusting mist eliminating zone；
Raw material flue gas enters equipment from main desulfurization zone,
Compared with prior art, the beneficial effects of the present invention are embodied in following several respects:
(1) traditional desulfurization method of limestone-gypsum technique is compared, desulfuration efficiency significantly improves；
(2) it due to the efficient removal effect of deep desulfuration area magnesia, avoids to reach minimum discharge and increases spray
Layer number improves liquid-gas ratio, increases the means such as slurries pool volume, reduces costs, makes system under very low magnesium Expenditure Levels,
It realizes deep desulfuration, and the operating pressure of the calcium method desulfurization of main desulfurization zone is greatly lowered；
(3) magnesia non-scaling, therefore, equipment be not perishable, reduces maintenance cost；
(4) in deep desulfuration area, addition is halogen-free using ozone, hydrogen peroxide, peromag, persulfuric acid magnesium etc. or alkali is golden
One of oxidant of category is a variety of, can carry out denitration simultaneously, and there are the pH of magnesia these oxidants of activation to absorb
The ability of denitration has preferable denitration effect；
(5) the obtained desulphurization denitration by-product in deep desulfuration area, can be directly as the buffer of main desulfurization zone doctor solution
It uses, the desulfurization effect of main desulfurization zone can be improved；It can also be precipitated with ammonium hydroxide, obtained magnesium hydroxide, which can carry out circulation, to be made
With ammonium sulfate caused by regeneration, which then recycles lime to be re-converted into displacement, becomes ammonium hydroxide, is recycled.
Detailed description of the invention
Fig. 1 is process schematic representation of the invention.
Wherein 1 is main desulfurization zone, and 2 be deep desulfuration area, and 3 be dedusting mist eliminating zone, and 4 be doctor solution circulatory pool, and 5 be tower reactor
Area.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
As shown in Figure 1, the present embodiment uses integration apparatus, tower reactor area 5, main desulfurization zone 1, depth are sequentially consisted of
Desulfurization zone 2 and dedusting mist eliminating zone 3.The solution in deep desulfuration area 2 is passed through doctor solution circulatory pool 4, and ammonium hydroxide is added, obtains magnesium hydroxide
It is recycled, the specific steps are as follows:
(1) concentration of raw material sulfur dioxide in flue gas is 500mg/m3, the concentration of nitrogen oxides is 150mg/m3, wherein one
Nitrogen oxide 80mg/m3, nitrogen dioxide 70mg/m3, flue-gas temperature is 180 DEG C；By the raw material flue gas with 100m3The flow of/h is discharged into
Main desulfurization zone 1；The desulfurizing agent solution that main desulfurization zone addition flow is 300L/h, which is to be dissolved in water system by lime
, concentration 20wt%, pH 6.5 after reacted, obtains low-sulfur flue gas, and sulfur dioxide concentration therein is 50mg/m3,
Removal efficiency is 90%.
(2) desulfurizing agent solution after main desulfurization zone 1 is reacted is fallen into tower reactor area 5, which passes through a circulation
Pump is extracted out from tower reactor area 5, is returned through piping to the top of main desulfurization zone 1, is carried out recycling for desulfurizing agent solution；
(3) low-sulfur flue gas is discharged into deep desulfuration area 2, the absorbent slurry that addition flow is 100L/h, absorbent slurry
Liquid is that magnesium hydroxide adds water and the magnesium hydroxide slurry that is formed, concentration 10wt%, PH 9, while being added in the slurries
Hydrogen peroxide (makes solution containing hydrogen peroxide concentration 1%), after carrying out deep desulfuration denitration, obtains that flue gas can be discharged；
(4) resulting slurries are discharged into doctor solution circulatory pool 4 after handling in deep desulfuration area 2, and in doctor solution circulatory pool 4
15% ammonium hydroxide of middle addition (addition the ratio between volume and liquor capacity to be regenerated are 1:3), generation is precipitated as magnesium hydroxide, and water is added
Become magnesium hydroxide slurry again afterwards and is recycled to deep desulfuration area 2；Enough lime is added in the solution of generation, makes solution again
Become ammonium hydroxide and calcium sulfate precipitation, calcium sulfate precipitation is recycled；
(5) flue gas can be discharged and be discharged into dedusting mist eliminating zone 3, be discharged into atmosphere after carrying out the processing of depth dedusting demisting.
It is detected, the concentration for being discharged into the sulfur dioxide in flue gas of atmosphere is 6mg/m3, nitric oxide production concentration is reduced to 30mg/
m3, content of nitrogen dioxide is reduced to 10mg/m3, the concentration of sulfur dioxide reaches emission request, desulfurization degree 98.8%.
Embodiment 2
The present embodiment use integration apparatus, be followed successively by from top to bottom dedusting mist eliminating zone, deep desulfuration area, main desulfurization zone,
Tower reactor area.The solution in deep desulfuration area is passed through doctor solution circulatory pool, and ammonium hydroxide is added, obtains magnesium hydroxide and is recycled, and has
Steps are as follows for body:
(1) concentration of raw material sulfur dioxide in flue gas is 5000mg/m3, the concentration of nitrogen oxides is 450mg/m3, wherein one
Nitrogen oxide 250mg/m3, nitrogen dioxide 200mg/m3, flue-gas temperature is 180 DEG C；By the raw material flue gas with 100m3The flow of/h is arranged
Become owner of desulfurization zone；The desulfurizing agent solution that main desulfurization zone addition flow is 800L/h, which is to be dissolved in water system by lime
, concentration 5wt%, pH 5.5 after reacted, obtains low-sulfur flue gas, after reacted, obtain low-sulfur flue gas, therein two
Sulfur oxide concentration is 300mg/m3, removal efficiency is 94%.；
(2) desulfurizing agent solution after main desulfurization zone reaction is fallen into tower reactor area, which passes through a circulating pump
It is extracted out from tower reactor area, returns through piping to the top of main desulfurization zone, carry out recycling for desulfurizing agent solution；
(3) low-sulfur flue gas is discharged into deep desulfuration area, the absorbent slurry that addition flow is 300L/h, the absorbent slurry
It is that magnesium hydroxide adds water and the magnesium hydroxide slurry that is formed, concentration 1wt%, PH 6.5, while adding in the slurries double
Oxygen water makes the hydrogen peroxide content in absorbing liquid maintain 0.5% or so, after carrying out deep desulfuration denitration, obtains that flue gas can be discharged；
(4) resulting solution is magnesium sulfate and magnesium nitrate after handling in deep desulfuration area, by resulting magnesium sulfate or nitre
Sour magnesium solution is used as the buffer of main desulfurization zone, can improve the desulfurization effect of main desulfurization zone；
(5) flue gas can be discharged and be discharged into dedusting mist eliminating zone 3, be discharged into atmosphere after carrying out the processing of depth dedusting demisting.
It is detected, the concentration for being discharged into the sulfur dioxide in flue gas of atmosphere is 20mg/m3, nitric oxide production concentration is reduced to
45mg/m3, content of nitrogen dioxide is reduced to 15mg/m3, the concentration of sulfur dioxide reaches emission request, and the removal efficiency of sulfur dioxide is
99.6%.
Embodiment 3
Field test 1: it is process object with the practical flue gas of coal-burning power plant, 100m is drawn from flue3The practical cigarette of/h
Gas, wherein the concentration of sulfur dioxide is 800mg/m3, nitric oxide production concentration is 200mg/m3, content of nitrogen dioxide 180mg/
m3(ozone filling).Main desulfurization zone desulfurizing agent uses agstone, and solution concentration is in 10% or so, desulfurization liquid-gas ratio in 5L/m3,
Deep desulfuration area desulfurizing agent is magnesia, and doctor solution pH value is controlled 7, and concentration of slurry 2%, desulfurization liquid-gas ratio are 2L/m3, and
The hydrogen peroxide of addition 1% in deep desulfuration area.Using the step identical as embodiment (1), desulphurization denitration is carried out to raw material flue gas
Processing.It being obtained by test analysis, the desulfuration efficiency of main desulfurization zone reaches 90% or so, behind deep desulfuration area, outlet
Sulfur dioxide concentration is 25mg/m3, nitric oxide concentration is reduced to 60mg/m3, content of nitrogen dioxide is reduced to 10mg/m3。
Embodiment 4
Field test 2: it is process object with the practical flue gas of power plant, 10000m is drawn from flue3The practical flue gas of/h,
Wherein the concentration of sulfur dioxide is 1800mg/m3, nitric oxide production concentration is 250mg/m3, content of nitrogen dioxide 200mg/m3
(ozone filling).Main desulfurization zone desulfurizing agent uses lime, and concentration of slurry is in 8%, desulfurization liquid-gas ratio in 4L/m3, pass through main desulfurization
Qu Hou, remaining content of sulfur dioxide is in 200mg/m in flue gas3, deep desulfuration area desulfurizing agent is magnesia, and concentration of slurry is
2%, desulfurization liquid-gas ratio is 2L/m3, 1% hydrogen peroxide is additionally incorporated, it is 28mg/m that deep desulfuration area, which exports sulfur dioxide concentration,3,
Nitric oxide is 75mg/m3, nitrogen dioxide 8mg/m3。
Embodiment 5
Laboratory simulation test 1: simulated flue gas flow is 500ml/min, and the concentration of sulfur dioxide is 1000mg/m3, cigarette
Temperature is 180 DEG C or so.
By simulated flue gas pass sequentially through in the solution containing 10% lime stone and 2% magnesium hydroxide slurry, utilize flue gas
The concentration that analyzer measures outlet sulfur dioxide is 20mg/m3Left and right, desulfuration efficiency 98%.
By simulated flue gas separately through in the solution containing 10% lime stone, outlet titanium dioxide is measured using flue gas analyzer
The concentration of sulphur is 100mg/m3Left and right, desulfuration efficiency are 90% or so；By simulated flue gas separately through the solution for containing 3% magnesia
When middle, measuring outlet sulfur dioxide concentration is 30mg/m3Left and right, desulfuration efficiency 97%.
The embodiment shows calcium-magnesium combinatorial association technique, can be used to solve independent calcium method desulfurization meeting minimum discharge
The problems of.
Embodiment 6
Laboratory simulation test 2: simulated flue gas flow is 500ml/min, and the concentration of sulfur dioxide is 1000mg/m3, nitrogen
The concentration of oxide is 150mg/m3(wherein nitric oxide 80mg/m3, nitrogen dioxide 70mg/m3), smoke temperature is 180 DEG C or so.Tool
Body experiment is as follows:
Flue gas is first passed through in the solution containing 10% lime stone, is then passed in the solution of 2% magnesia, wherein magnesia
1% hydrogen peroxide is added in solution, measuring outlet sulfur dioxide concentration is 0mg/m3Left and right, nitric oxide production concentration are 30mg/m3
Left and right, the concentration of nitrogen dioxide are 2mg/m3, desulfuration efficiency is up to 100%, and nitric oxide removal efficiency is up to 62.5%.
It is indicated above that the sulfur dioxide in flue gas can be made to further decrease in the case where adding hydrogen peroxide, realize that it is super
Low emission requirement, while realizing the function of synchronous denitration.
Claims (7)
1. a kind of calcium-magnesium combined desulfurization and denitration method for meeting flue gas pollutant deep removal, which is characterized in that this method includes
Following steps:
(1) industrial smoke inputs main desulfurization zone (1) after dedusting, is carried out using the desulfurization of calcium method to flue gas in main desulfurization zone (1)
Pre- desulfurization obtains low-sulfur flue gas；
(2) low-sulfur flue gas obtained by step (1) enters deep desulfuration area (2), uses magnesium processes desulfurization to low-sulfur in deep desulfuration area (2)
Flue gas carries out deep desulfuration, handles, is emitted into atmosphere using demisting；
Calcium method desulfurization described in step (1) is dissolved in using the one or more as desulfurizing agent of agstone, lime or carbide slag
In water, being configured to mass concentration is 5~20%, and the slurries that pH value is 5.5~6.5 are pumped into main desulfurization zone (1) and sufficiently connect with flue gas
It mixes after touch, sloughs the sulphur in flue gas, desulfurization liquid-gas ratio is 3-8L/m3；
Magnesium processes desulfurization described in step (2) be using magnesia or magnesium hydroxide slurry as desulfurizing agent, it is soluble in water, be configured to matter
Measuring concentration is 1~10%, the slurries that pH value is 6.5~9, is pumped into deep desulfuration area (2) and comes into full contact with flue gas and mixes, and sloughs cigarette
Sulphur in gas, desulfurization liquid-gas ratio are 1-3L/m3；
Denitration hardening agent is added into magnesium processes desulfurization desulfurizer therefor slurries in the deep desulfuration area (2), carries out denitration.
2. a kind of calcium-magnesium combined desulfurization and denitration method for meeting flue gas pollutant deep removal according to claim 1,
It is characterized in that, the sulfur dioxide concentration that step (1) inputs in the flue gas of main desulfurization zone (1) is 500-5000mg/m3In the case of, warp
90% or more sulfur dioxide in main desulfurization zone (1) removing flue gas, and the sulfur dioxide in flue gas that main desulfurization zone (1) is discharged is dense
Degree is lower than 300mg/m3。
3. a kind of calcium-magnesium combined desulfurization and denitration method for meeting flue gas pollutant deep removal according to claim 1,
Be characterized in that, deep desulfuration area (2) described in step (2) can by from the sulfur dioxide in flue gas of main desulfurization zone take off to
30mg/m3Within.
4. a kind of calcium-magnesium combined desulfurization and denitration method for meeting flue gas pollutant deep removal according to claim 1,
It is characterized in that, the denitration hardening agent includes one or more of ozone, hydrogen peroxide, peromag or persulfuric acid magnesium；Institute
The additive amount for stating denitration hardening agent is to make its mass concentration in magnesium processes desulfurization desulfurizer therefor slurries are as follows: 1%-15%.
5. a kind of calcium-magnesium combined desulfurization and denitration method for meeting flue gas pollutant deep removal according to claim 1,
It is characterized in that, desulphurization denitration by-product obtained by the deep desulfuration area (2) is magnesium sulfate or magnesium nitrate solution, by resulting sulphur
Sour magnesium or magnesium nitrate solution are used as the buffer of main desulfurization zone (1).
6. a kind of calcium-magnesium combined desulfurization and denitration method for meeting flue gas pollutant deep removal according to claim 5,
It is characterized in that, resulting magnesium sulfate and magnesium nitrate solution is passed through doctor solution circulatory pool (4) and obtain hydroxide with ammonia precipitation process
Magnesium can be recycled；Ammonium sulfate caused by regenerating, which then recycles lime to replace again, becomes ammonium hydroxide, is recycled；
After generated calcium sulfate precipitation is washed, collected together with desulfurized gypsum.
7. a kind of calcium-magnesium combined desulfurization and denitration method for meeting flue gas pollutant deep removal according to claim 1,
It is characterized in that, the main desulfurization zone (1) and deep desulfuration area (2) are located in integration apparatus or two independent towers
In.
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| CN102764583A (en) * | 2012-08-14 | 2012-11-07 | 中电投远达环保工程有限公司 | Dual-circulation single-tower desulfurization systems and process thereof |
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