CN106310880B - Remove NO device and its removal methods - Google Patents
Remove NO device and its removal methods Download PDFInfo
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- CN106310880B CN106310880B CN201610936862.4A CN201610936862A CN106310880B CN 106310880 B CN106310880 B CN 106310880B CN 201610936862 A CN201610936862 A CN 201610936862A CN 106310880 B CN106310880 B CN 106310880B
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002336 sorption--desorption measurement Methods 0.000 claims abstract description 90
- 239000003546 flue gas Substances 0.000 claims abstract description 65
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000012528 membrane Substances 0.000 claims abstract description 56
- 239000012510 hollow fiber Substances 0.000 claims abstract description 47
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 34
- 230000023556 desulfurization Effects 0.000 claims abstract description 34
- 239000000428 dust Substances 0.000 claims abstract description 26
- 238000010521 absorption reaction Methods 0.000 claims abstract description 21
- 239000003463 adsorbent Substances 0.000 claims abstract description 11
- 238000003795 desorption Methods 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 47
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 5
- 230000008676 import Effects 0.000 description 14
- 238000005192 partition Methods 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000012028 Fenton's reagent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004094 preconcentration Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01D53/14—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 by absorption
-
- 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
- B01D53/14—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 by absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- 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
- B01D53/14—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 by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- 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
- B01D53/22—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 by diffusion
- B01D53/228—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 by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
本发明公开了一种脱除NO装置及其脱除方法，锅炉中产生的烟道气经除尘处理后进入湿法脱硫单元，经脱硫后温度降至50℃左右；然后进入第一个吸附/解吸塔对烟道气中的NO进行吸附去除，烟道气随后进入NO浓度分析仪对NO的浓度进行测量，若NO浓度达标则排放，如果超标则将烟道气切换至第二个吸附/解吸塔对NO进行吸附脱除，同时将部分除尘后高温烟道气通入第一个吸附/解吸塔中对吸附剂进行解吸，解吸出的NO进入中空纤维膜进行化学吸收；当第二个吸附/解吸塔出口NO浓度超标则将烟道气切换到第一个吸附/解吸塔，通过两个吸附/解吸塔的交替运行及中空纤维膜的化学吸收实现烟道气NO的高效脱除。
The invention discloses a device for removing NO and its removal method. The flue gas generated in the boiler enters the wet desulfurization unit after dust removal treatment, and the temperature drops to about 50°C after desulfurization; then enters the first adsorption/ The desorption tower absorbs and removes NO in the flue gas, and the flue gas then enters the NO concentration analyzer to measure the concentration of NO. If the NO concentration reaches the standard, it will be discharged. If it exceeds the standard, the flue gas will be switched to the second adsorption/ The desorption tower adsorbs and removes NO, and at the same time passes part of the dust-removed high-temperature flue gas into the first adsorption/desorption tower to desorb the adsorbent, and the desorbed NO enters the hollow fiber membrane for chemical absorption; when the second If the concentration of NO at the outlet of the adsorption/desorption tower exceeds the standard, the flue gas will be switched to the first adsorption/desorption tower, and the efficient removal of NO from the flue gas will be achieved through the alternate operation of the two adsorption/desorption towers and the chemical absorption of the hollow fiber membrane.
Description
Technical field
The present invention relates to tail gas disposal technique field, it is more particularly related to a kind of removing NO device and its de-
Except method, espespecially using the device and removing NO method of NO pre-concentration and Hollow Fiber Membrane Absorption removing NO.
Background technique
NOxIt is one of the main reason for causing the environmental problems such as acid rain and photochemical fog.With China industry it is continuous
Development, and influenced by the energy resource structure based on coal, China's nitrogen oxides pollution situation is serious, prevention and control situation is severe.According to system
Meter, electric power and thermoelectricity industry discharged nitrous oxides account for the 66.7% of industrial discharged nitrous oxides.With increasingly mentioning for environmental requirement
Height, China creates coal-burning power plant and has all installed denitrification apparatus additional, while stringenter NO is implemented during " 12th Five-Year Plan "xDischarge
Standard, to control the NO that China is got worsexPollution.
Currently, for NOxRemoving sulfuldioxide be broadly divided into two classes: one is being removed in burning, that is, use low NOxBurning skill
Art reduces the NO that coal combustion generates in burner hearthxAmount；Another kind is removed after burning, i.e., NO is removed from flue gasx, typically there is choosing
Selecting property catalytic reduction method and selective non-catalytic reduction method.For low NOxCombustion technology, general denitration efficiency is low, and may
It can cause furnace internal corrosion, slagging, or even reduce efficiency of combustion.For selective catalytic reduction and selective non-catalytic reduction
Method, although there is higher removal efficiency, occupation area of equipment is big, and investment and operating cost are high, or even also will cause secondary dirt
Dye.
Chinese patent CN102553416 disclose a kind of power-plant flue gas denitration method and its absorbent used.The party
Method is characterized by absorption tower, using by H2O2Modified Fenton reaction and EDTA with ferric sulfate composition are additive
Aqueous solution is as absorbent, under conditions of 30-80 DEG C, aoxidizes NO in absorption tower and then is absorbed agent absorption
To complete denitration.But this method is in advance by H2O2With Fe2(SO4)3Solution mixing, H2O2Consumption is larger, higher cost.
Chinese patent CN103007753 discloses a kind of heterogeneous Fenton reagent and its preparation method and application.The party
Method is characterized in that the heterogeneous Fenton reagent by H2O2Aqueous solution and Al2O3The pH for loading Fe catalyst composition is 5-6's
Mixed solution.Method of denitration is that heterogeneous Fenton reagent is added in conventional bubble tower, and the NO in flue gas is oxidized to
HNO3.This method H2O2Consumption is big, at high cost.
Chinese patent CN105561769 discloses the denitrification apparatus and method of a kind of salt reinforcing hydrogen peroxide solution oxidation NO.
The method is characterized in that absorbing the nitrogen oxides in flue gas in bubbling reactor using absorbent, absorbent used is H2O2
With the mixed solution of salt.But this method can only handle a small amount of flue gas, H2O2Consumption is big, at high cost, efficiency is lower.
It there is no a kind of efficient, inexpensive method of denitration suitable for medium small boiler flue gas at present, therefore, find one
Kind Low investment and operating cost, efficient denitration technology are still the task of top priority.
Summary of the invention
It is an object of the invention to solve at least the above problems, and provide the advantages of at least will be described later.
It is a still further object of the present invention to provide a kind of removing NO device and its removal methods, espespecially using NO pre-concentration and
Hollow Fiber Membrane Absorption removes the device and removal methods of NO, realizes efficient, the inexpensive denitration of medium small boiler flue gas.
In order to realize these purposes and other advantages according to the present invention, a kind of removing NO device is provided, comprising:
Dust removing units, import are connected to boiler；
Desulfurization unit, import and the dust removing units outlet；
First adsorption/desorption tower, import pass through the first shut-off valve and the desulfurization unit outlet；
First NO concentration analyzer, import pass through the second shut-off valve and the first adsorption/desorption tower outlet, institute
It is outwardly open to state the outlet of the first NO concentration analyzer；
Second adsorption/desorption tower, import pass through the 4th shut-off valve and the desulfurization unit outlet；
2nd NO concentration analyzer, import pass through the 9th shut-off valve and the second adsorption/desorption tower outlet, institute
It is outwardly open to state the outlet of the 2nd NO concentration analyzer；
Hollow fiber membrane reactor, gas access are inhaled with the first adsorption/desorption tower outlet and described second respectively
Attached/desorber egress selection connection, the hollow fiber membrane reactor gas vent are outwardly open；
Wherein, the first heating coil is provided in the first adsorption/desorption tower, the first heating coil import passes through
6th shut-off valve and the dust removing units outlet, the first heating coil outlet pass through the 5th shut-off valve and the desulfurization
Unit inlet is connected to, and is provided with the second heating coil in the second adsorption/desorption tower, the second heating coil import passes through
7th shut-off valve and the dust removing units outlet, the second heating coil outlet pass through the 8th shut-off valve and the desulfurization
Unit inlet connection.
Preferably, the first adsorption/desorption tower and the second adsorption/desorption tower structure are identical, first adsorption/desorption
The partition being evenly arranged in tower equipped with several layers, the partition and tower body are axially vertical, are evenly arranged active carbon on the partition
Adsorbent.
Preferably, first heating coil, which spirals, is arranged in the first adsorption/desorption tower, and first heating
Coil pipe is contacted through each layer partition with the acticarbon.
Preferably, the absorption temperature of the first adsorption/desorption tower and the second adsorption/desorption tower is 50 DEG C, desorption temperature
It is 300 DEG C.
Preferably, several film wires, the gas of the hollow fiber membrane reactor are equipped in the hollow fiber membrane reactor
Entrance and gas vent are diagonally provided with hollow fiber membrane reactor shell wall both ends, and gas forward flows through hollow fiber membrane reactor
Shell side, absorbing liquid flows countercurrently through the tube side of film wire.
Preferably, the operation temperature of the hollow fiber membrane reactor is 50~80 DEG C, and gas-liquid flow-rate ratio is 5:1.
Preferably, the hollow fiber membrane reactor is made of polypropylene material, and the absorbing liquid is by 0.5wt%H2O2、
The aqueous solution of 30wt%NaCl forms.
Preferably, the hollow fiber membrane reactor gas access passes through third shut-off valve and first adsorption/desorption
Tower outlet passes through the tenth shut-off valve and the second adsorption/desorption tower outlet.
A kind of removing NO method, comprising the following steps:
Step 1: opening the first, second shut-off valve, third is closed to the tenth shut-off valve, the flue gas generated through boiler passes through
Enter desulfurization unit desulfurization after dust removing units dedusting, the first adsorption/desorption tower removing NO is sent into after flue gas is cooled down, is then sent
Enter and detect NO concentration in the first NO concentration analyzer, if to measure NO concentration up to standard for the first NO concentration analyzer, by flue gas from
First NO concentration analyzer exports direct emission, otherwise enters step two；
Step 2: closing the first, second shut-off valve, the four, the 9th shut-off valves are opened, the flue gas after desulfurization is introduced the
NO is removed in two adsorption/desorption towers, is subsequently sent to detect NO concentration in the 2nd NO concentration analyzer, and open third, the 5th
And the 6th shut-off valve, draw high-temperature flue gas all the way from dust removing units and flows through the first heating coil, it will be in the first adsorption/desorption tower
Desulfurization unit is flowed back into after acticarbon desorption, while the higher concentration NO gas that the first adsorption/desorption tower is desorbed passes through
Direct emission after hollow fiber membrane reactor absorbs；If it is up to standard that the 2nd NO concentration analyzer measures NO concentration, by flue gas from
2nd NO concentration analyzer exports direct emission, otherwise enters step three；
Step 3: closing third to the 9th shut-off valve, the first, second shut-off valve is opened, the flue gas after desulfurization is introduced
NO is removed in first adsorption/desorption tower, and is sent into the first NO concentration analyzer and is detected NO concentration, meanwhile, open the seven, the 8th
And the tenth shut-off valve, draw high-temperature flue gas all the way from dust removing units and flows through the second heating coil, it will be in the second adsorption/desorption tower
Desulfurization unit is flowed back into after acticarbon desorption, while the higher concentration NO gas that the second adsorption/desorption tower is desorbed passes through
Hollow fiber membrane reactor absorbs direct emission after NO；If it is up to standard that the first NO concentration analyzer measures NO concentration, by flue gas
Direct emission is exported from the first NO concentration analyzer, otherwise returns to step 2.
Preferably, the higher concentration NO gas that the first, second adsorption/desorption tower desorbs is passed through hollow fiber membrane reactor
Shell side inlet, absorbing liquid, relative to shell side reverse flow oxidative absorption NO, hollow fiber membrane reactor shell side are gone out in tube side
The gas direct emission of mouth outflow.
The present invention is include at least the following beneficial effects:
1, it is that the concentration of NO is very low using the difficult point of the NO of conventional oxidation method removal flue gas, needs a large amount of absorbing liquid
It is just able to achieve the efficient removal of NO, causes that equipment investment is big, reagent loss is big, operating cost is high, and the present invention passes through two friendships
Concentrate is carried out to the NO in flue gas for the adsorption/desorption tower of operation, then passes through absorbing liquid in hollow fiber membrane reactor
The NO of concentration is efficiently removed, equipment investment is few, plant area is small, absorbing liquid dosage is greatly decreased, operating cost significantly reduces；
2, present invention is especially suited for the nitrogen oxygen of the power-equipment of the enterprises such as middle-size and small-size steam power plant, cement plant, small-sized petrochemical plant
Compound removal is suitable for a wide range of promote.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of present invention removing NO device；
Fig. 2 is the structural schematic diagram of the empty fiber membrane reactor；
Fig. 3 is adsorption/desorption tower structure schematic diagram；
In the figures above: 1: boiler；2: dust removing units；3: desulfurization unit；4: the first adsorption/desorption towers；5: the second absorption/
Desorber；6: the one NO concentration analyzers；7: the two NO concentration analyzers；8: hollow fiber membrane reactor；9: the first drains；
10: the second drains；11~20: the first the~the ten shut-off valve of cut-off；21: gas feed；22: absorbing liquid import；23: gas goes out
Mouthful；24: absorbing liquid outlet；25: the first heating coils；26: the second heating coils；401 (501): adsorption/desorption tower import；402
(502): the outlet of adsorption/desorption tower；403 (503): heating coil import；404 (504): heating coil outlet；405 (505): living
Property carbon adsorbent；406 (506): partition；801: film wire.
Specific embodiment
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art referring to specification text
Word can be implemented accordingly.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
In a kind of embodiment, as shown in Figures 1 to 3, flue gas removing NO device is built as shown in Figure 1, specifically,
Boiler 1 is connected with a dust removing units 2 by pipeline, the outlet of dust removing units 2 is connected with wet desulphurization unit 3 all the way, dedusting
2 second tunnel of unit is connected with the first heating coil 25 in the first adsorption/desorption tower 4 by pipeline, and the 6th is equipped on pipeline
Shut-off valve 16,2 third road of dust removing units is connected with the second heating coil 26 in the second adsorption/desorption tower 5 by pipeline, on pipeline
7th shut-off valve 17 is installed；The outlet of the first heating coil 25 and 3 import of wet desulphurization unit in first adsorption/desorption tower 4
It is connected by pipeline, the 5th shut-off valve 15 is installed on pipeline, the second heating coil 26 outlet in the second adsorption/desorption tower 5
It is connected with 3 import of wet desulphurization unit by pipeline, the 8th shut-off valve 18 is installed on pipeline；By the flue gas of desulfurization unit
It is connected all the way with the first adsorption/desorption tower 4 by pipeline, pipeline is equipped with the first shut-off valve 11, the flue gas of desulfurization unit
Two tunnels are connected with the second adsorption/desorption tower 5 by pipeline, and pipeline is equipped with the 4th shut-off valve 14；First adsorption/desorption tower 4
Outlet is connected with the first NO concentration analyzer 6 by pipeline all the way, and the second shut-off valve 12, the first absorption/solution are equipped on pipeline
In addition the outlet for inhaling tower 4 is connected with the gas access 21 of hollow fiber membrane reactor 8 by pipeline all the way, the is equipped on pipeline
Three shut-off valves 13；The outlet of second adsorption/desorption tower 5 is connected with the 2nd NO concentration analyzer 7 by pipeline all the way, is pacified on pipeline
Equipped with the 9th shut-off valve 19, the other gas access with hollow fiber membrane reactor 8 all the way in the outlet of the second adsorption/desorption tower 5
21 are connected by pipeline, and the tenth shut-off valve 20 is equipped on pipeline；The gas vent 23 of hollow-fibre membrane 8 and the first NO concentration point
The outlet of analyzer 6 is connected with the first drain 9 respectively；The outlet of 2nd NO concentration analyzer 7 is connected with the second drain 10.
The flue gas generated in boiler enters wet desulphurization unit after dust removal process, and temperature is down to 50 DEG C of left sides after desulfurization
It is right；Adsorption is carried out to the NO in flue gas subsequently into first adsorption/desorption tower, flue gas subsequently enters NO concentration point
Analyzer measures the concentration of NO, discharges if NO concentration is up to standard, if it is exceeded by flue gas switch to second absorption/
Desorber carries out adsorbing and removing to NO, while high-temperature flue gas after the dedusting of part being passed through in first adsorption/desorption tower to suction
Attached dose is desorbed, and the NO desorbed enters hollow-fibre membrane and carries out chemical absorbing；When second adsorption/desorption tower outlet NO is dense
It spends exceeded, flue gas is switched to first adsorption/desorption tower, while high-temperature flue gas after the dedusting of part is passed through second
Adsorbent is desorbed in adsorption/desorption tower, the NO desorbed enters hollow-fibre membrane and carries out chemical absorbing；It is inhaled by two
The alternate run of attached/desorber and the chemical absorbing of hollow-fibre membrane realize the efficient removal of flue gas NO.
In another embodiment, the flue gas that boiler generates is 2000Nm3/ hour, the concentration of NO are 300ppm.The first,
Second adsorption/desorption tower structure as shown in figure 3, and the first adsorption/desorption tower and the second adsorption/desorption tower structure it is identical,
Tower body material is stainless steel, and tower internal diameter is 1400mm, tower height 2500mm, and tower is interior to be evenly arranged 4 layers of partition partition 406 along axial direction
(506), that is, the partition and tower body it is axially vertical, acticarbon 405 (505) is evenly arranged on partition, inside tower
Serpentine METAL HEATING PROCESS coil pipe 25,26 is installed, coil pipe nominal diameter is 50mm, and heating coil through each layer partition with
The acticarbon contact, to improve the contact area contacted with acticarbon, and then improves acticarbon
Desorption efficiency.The absorption temperature of the first adsorption/desorption tower and the second adsorption/desorption tower is 50 DEG C, desorption temperature 300
DEG C, the NO in flue gas is efficiently absorbed in the first adsorption/desorption tower and the second adsorption/desorption tower.
Hollow fiber membrane reactor 8 is as shown in Fig. 2, material polypropylene material, the length of hollow fiber membrane reactor are
2000mm, reactor inside diameter 1500mm, outer diameter 1540mm, reactor is interior to contain 12000 film wires 801, and film wire internal diameter is
0.38mm, the outer diameter of film wire are 0.5mm, and the effective length of film wire is 2000mm, and film wire porosity is 65%, film wire average pore size
It is 0.21 μm.The gas access of the hollow fiber membrane reactor and gas vent are diagonally provided with hollow fiber membrane reactor shell
Wall both ends, gas forward flow through the shell side of hollow fiber membrane reactor, and absorbing liquid is inversely from the inflow of absorbing liquid import 22, absorbing liquid
24 outflow of outlet, flows through the tube side of film wire, that is to say, that absorbing liquid is walked inside film wire, and flue is made leave with rage outside film wire, flow direction
With gas on the contrary, the operation temperature of the hollow fiber membrane reactor is 50~80 DEG C, gas-liquid flow-rate ratio is 5:1, the absorption
Liquid is by 0.5wt%H2O2, 30wt%NaCl aqueous solution composition.In the first adsorption/desorption tower and the second adsorption/desorption tower
The higher concentration NO gas that acticarbon parses direct emission after the absorption of hollow fiber membrane reactor 8, realizes flue
Qi exhaustion removes the continuous operation of NO, and the concentration of NO is consistently lower than 50ppm in blowdown stack gas, and absorbing liquid dosage is greatly decreased and can
Repetitive cycling uses, and operating cost significantly reduces.
It is as follows to remove NO method:
Step 1: opening the first shut-off valve 11, the second shut-off valve 12,13 to the tenth shut-off valve 20 of third shut-off valve is closed,
The flue gas generated through boiler 1 enters 3 desulfurization of desulfurization unit after 2 dedusting of dust removing units, and by flue gas cool-down to 50 DEG C or so,
Subsequently into the first adsorption/desorption tower 4, flue gas selectively adsorbs NO, subsequent flue gas by activated carbon adsorbent in tower
Into the first NO concentration analyzer 6, NO concentration is respectively less than 50ppm, symbol in 2 hours in 6 exhaust pass gas of NO concentration analyzer
Cyclization guaranteed request, 6 exhaust pass gas of NO concentration analyzer are directly vented in atmosphere；After operation 2 hours, the first NO concentration analysis
NO concentration is greater than 50ppm in 6 exhaust pass gas of instrument, then enters step two；
Step 2: closing the first shut-off valve 11, the second shut-off valve 12, the 4th shut-off valve 14 and the 9th shut-off valve 19 are opened,
Flue gas after desulfurization unit 3 is introduced into progress NO removing in the second adsorption/desorption tower 5, meanwhile, open third shut-off valve
13, the 5th shut-off valve 15 and the 6th shut-off valve 16 draw 300 DEG C all the way of flue gas through the first adsorption/desorption from dust removing units 2
The first heating coil 25 in tower 4 to entering desulfurization unit 3 after acticarbon desorption, with through dust removing units 2 directly into
Enter in the second adsorption/desorption tower 5 after entering the flue gas mixing of desulfurization unit 3, flue gas is selected in tower by activated carbon adsorbent
NO is adsorbed to selecting property, subsequent flue gas enters the 2nd NO concentration analyzer 7, NO concentration in 7 exhaust pass gas of NO concentration analyzer
It is respectively less than 50ppm in 2-4 hours bringing into operation from device, meets environmental requirement, 7 exhaust pass gas of NO concentration analyzer is direct
It is vented in atmosphere.The gas containing 99%NO that first adsorption/desorption tower 4 desorbs is passed through hollow fiber membrane reactor 8
Shell side gas access 21, absorbing liquid in tube side relative to shell side reverse flow oxidative absorption NO, from hollow fiber membrane reactor 8
The gas that shell side gas vent 23 flows out directly is vented, and the adsorption/desorption tower of two alternate runs is dense to NO in flue gas as a result,
Degree carries out concentrate to 99% from 300ppm, finally parses this higher concentration NO gas and is absorbed by hollow fiber membrane reactor 8.In
The operation temperature of empty fiber membrane reactor 8 is 50-80 DEG C, and gas-liquid flow-rate ratio is 5:1.The group of absorbing liquid becomes 0.5wt%H2O2、
The aqueous solution of 30wt%NaCl.After device brings into operation 4 hours, 7 exit NO concentration of the 2nd NO concentration analyzer is greater than
50ppm enters step three；
Step 3: closing third to the 9th shut-off valve, opening the first shut-off valve 11, the second shut-off valve 12 will be through desulfurization lists
Flue gas after member 3 is introduced into progress NO removing in the first adsorption/desorption tower 4.Meanwhile opening the cut-off of the 7th shut-off valve the 17, the 8th
Valve 18, the tenth shut-off valve 20, the flue gas for drawing 300 DEG C all the way from dust removing units 2 add through second in the second adsorption/desorption tower 5
Hot coil 26 enters desulfurization unit 3 after desorbing to acticarbon, is being directly entered desulfurization unit 3 with through dust removing units 2
Entering in the first adsorption/desorption tower 4 after flue gas mixing, flue gas selectively adsorbs NO by activated carbon adsorbent in tower,
Subsequent flue gas enters the first NO concentration analyzer 6, and NO concentration was in operation 4-6 hours in 6 exhaust pass gas of NO concentration analyzer
It is interior to be respectively less than 50ppm, meet environmental requirement, then the flue gas of the first NO concentration analyzer 6 outlet is directly vented in atmosphere.It will
The highly concentrated NO gas that second adsorption/desorption tower 5 desorbs is passed through the shell side inlet of hollow fiber membrane reactor 8, and absorbing liquid is in pipe
Relative to shell side reverse flow oxidative absorption NO, the gas flowed out from 8 shell-side outlet of hollow fiber membrane reactor is directly vented journey.
As continuous service returns to step 2, repeats step until being greater than 50ppm when 6 exit NO concentration of the first NO concentration analyzer
Two and step 3, realize the continuous operation of flue gas removing NO, the concentration of NO is consistently lower than 50ppm in blowdown stack gas.
By embodiment as it can be seen that the present invention by the adsorption/desorption towers of two alternate runs to NO concentration in flue gas from
300ppm carries out concentrate to 99%, is then efficiently removed the NO of concentration by absorbing liquid in hollow fiber membrane reactor, real
The continuous operation of flue gas removing NO is showed, the concentration of NO is consistently lower than 50ppm in blowdown stack gas.The invention is relatively traditional
Flue-gas denitration process, equipment are mainly the stainless head tower and a hollow fiber membrane reactor of two normal pressures, and equipment investment is few, fills
It sets and takes up little area；The absorbing liquid dosage of use is greatly decreased and repeats recycling, and operating cost significantly reduces.Meanwhile this hair
The bright nitrogen oxides removal for being particularly suitable for the power-equipments of enterprises such as middle-size and small-size steam power plant, cement plant, small-sized petrochemical plant, is suitable for big
Range is promoted.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (10)
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| CN105561769A (en) * | 2014-10-17 | 2016-05-11 | 华东理工大学 | Denitration device achieving denitration by using salt reinforcing hydrogen peroxide solution to oxidize NO and denitration method |
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| JPS6316030A (en) * | 1986-07-07 | 1988-01-23 | Mitsubishi Heavy Ind Ltd | Recovery of solvent |
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| US5118328A (en) * | 1990-02-14 | 1992-06-02 | Fraunhofer Gesellschaft | Process for regenerating adsorbers |
| US6454837B1 (en) * | 1998-08-20 | 2002-09-24 | Solvay Fluor Und Derivate Gmbh | Separation of gases containing SF6 |
| JP2012239958A (en) * | 2011-05-17 | 2012-12-10 | Babcock Hitachi Kk | Wet type flue gas desulfurizing apparatus and method |
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