CN115582016A - Special ultralow-temperature desulfurization and denitrification process for lime kiln - Google Patents
Special ultralow-temperature desulfurization and denitrification process for lime kiln Download PDFInfo
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- CN115582016A CN115582016A CN202211390883.2A CN202211390883A CN115582016A CN 115582016 A CN115582016 A CN 115582016A CN 202211390883 A CN202211390883 A CN 202211390883A CN 115582016 A CN115582016 A CN 115582016A
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- lime kiln
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- flue gas
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- 235000008733 Citrus aurantifolia Nutrition 0.000 title claims abstract description 75
- 235000011941 Tilia x europaea Nutrition 0.000 title claims abstract description 75
- 239000004571 lime Substances 0.000 title claims abstract description 75
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 46
- 230000023556 desulfurization Effects 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims abstract description 31
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003546 flue gas Substances 0.000 claims abstract description 51
- 239000000428 dust Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000003245 coal Substances 0.000 claims abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 51
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 38
- 238000000498 ball milling Methods 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 31
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 230000003009 desulfurizing effect Effects 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 229910000281 calcium bentonite Inorganic materials 0.000 claims description 12
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 claims description 12
- 239000001354 calcium citrate Substances 0.000 claims description 12
- 229960004494 calcium gluconate Drugs 0.000 claims description 12
- 239000004227 calcium gluconate Substances 0.000 claims description 12
- 235000013927 calcium gluconate Nutrition 0.000 claims description 12
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- WPEXVRDUEAJUGY-UHFFFAOYSA-B hexacalcium;(2,3,4,5,6-pentaphosphonatooxycyclohexyl) phosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])(=O)OC1C(OP([O-])([O-])=O)C(OP([O-])([O-])=O)C(OP([O-])([O-])=O)C(OP([O-])([O-])=O)C1OP([O-])([O-])=O WPEXVRDUEAJUGY-UHFFFAOYSA-B 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 12
- 235000013337 tricalcium citrate Nutrition 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 229960004256 calcium citrate Drugs 0.000 claims description 10
- 235000011132 calcium sulphate Nutrition 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 8
- 239000004575 stone Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000007613 environmental effect Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 abstract 3
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000779 smoke Substances 0.000 description 7
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 6
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960005069 calcium Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- 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
-
- 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
- B01D53/81—Solid phase processes
- B01D53/82—Solid phase processes with stationary reactants
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- 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
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)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a special ultralow temperature desulfurization and denitrification process for a lime kiln, belonging to the technical field of desulfurization and denitrification, wherein the process comprises low temperature SCR (selective catalytic reduction) denitrification and SDS (sodium dodecyl sulfate) dry desulfurization; the low-temperature SCR denitration comprises the steps of enabling lime kiln flue gas to pass through a blower and then enter an SCR reactor for denitration, moving a calcining zone of the SCR reactor to 27-27.5 m, controlling the coal ratio to be 7.5-7.8%, and controlling the calcining temperature to be 180-185 ℃; the SDS dry desulfurization is that after the denitration lime kiln flue gas is heated to 125-135 ℃, the lime kiln flue gas is introduced into a dust remover, the temperature of the dust remover is controlled to be 110-270 ℃, and a desulfurizer is sprayed on a flue in front of the dust remover; the invention has the advantages of stable process performance, low energy consumption, small occupied area, convenient implementation and capability of being lower than that of the prior artDesulfurizing at 140 deg.C or above 250 deg.C, and increasing sulfur content to over 1000mg/Nm 3 The desulfurization efficiency.
Description
Technical Field
The invention relates to the technical field of desulfurization and denitrification, and particularly relates to an ultralow-temperature desulfurization and denitrification process special for a lime kiln.
Background
The lime kiln, as the technological form of the main equipment for producing lime, occupies a large proportion in lime production in China, and with the continuous increase of atmospheric treatment strength in China, the large-area coverage of flue gas treatment in the power industry and the non-power industry gradually become the key field of flue gas treatment.
The temperature of the lime kiln flue gas is generally 180-240 ℃, and the industrial tail gas dust of the lime kiln contains a large amount of calcium and alkaline earth metals (CaO and K) 2 O、Na 2 O), dust particlesThe method has the advantages that the treatment difficulty of nitrogen oxides and sulfur dioxide is high due to the special conditions of small diameter, high viscosity, low tail gas denitration temperature and the like, and at present, the most common treatment method is the combination of an SCR denitration process and SDS dry desulfurization.
The principle of the SCR denitration process is that a reducing agent NH is used under the action of a catalyst 3 Selectively adding NO and NO at 290-400 deg.C 2 Reduction to N 2 While almost no NH occurs 3 And O 2 Thereby increasing N 2 Selectivity of (2), reduction of NH 3 The consumption of (c). In the reactor with catalyst, ammonia is used as reductant to eliminate nitrogen oxide, and NOx in fume consists of NO in 95 vol% and NO in 5 vol% 2 Composition, NOx is converted into molecular nitrogen and water vapor through a denitration reaction.
However, SCR denitration processes have some significant disadvantages: the activation temperature is 220-400 ℃, and secondary heating is generally needed for temperature rise; the smoke is often complex in components, and certain pollutants can poison the denitration catalyst; the dust particles with high dispersity can cover the surface of the catalyst, so that the activity of the catalyst is reduced; some unreacted NH is present in the SCR denitration system 3 And SO in flue gas 2 Function to generate ammonium sulfate (NH) which is easy to corrode and block denitration equipment 4 ) 2 SO 4 And ammonium bisulfate NH 4 HSO 4 And simultaneously, the utilization rate of ammonia is reduced; the investment and the operating cost of the traditional SCR denitration equipment are high; liquid ammonia used as an SCR reducing agent belongs to dangerous chemicals, and has certain potential safety hazards in the aspects of storage and use; the SCR denitration system uses liquid ammonia or ammonia water as a denitration agent, and the problem of ammonia escape is difficult to solve to form secondary pollution; the SCR denitration device must adopt expensive catalyst, and the denitration catalyst must be returned to a factory for regeneration or scrapping after being used for a certain time limit.
In addition, the traditional SCR denitration process adopts a medium-low temperature SCR denitration process added at the tail of a bag-type dust collector, the original flue gas temperature needs to be increased from 50-80 ℃ to 220 ℃ for denitration treatment, the flue gas needs to be heated, the energy consumption is huge, the operation cost is extremely high, the heating cost of a single kiln needs to be 800-1200 thousands calculated according to 7.5 thousands of air volume, most of lime production enterprises built at present only consider flue gas desulfurization and dust removal in the construction period, and the flue gas denitration problem is not considered, so that enough denitration sites cannot be reserved on site.
The SDS dry desulfurizing and spraying technology is to spray high efficiency desulfurizing agent (grain size 20-25 microns) homogeneously inside the pipeline, so that the desulfurizing agent is thermally activated inside the pipeline to increase the specific surface area, and the desulfurizing agent contacts acid fume in large area inside the limited space of the pipeline to produce physical and chemical reaction and absorb and purify the sulfur dioxide and other acid matters. The desulfurizer has high removal rate for acid substances, such as HCl, SO3, HF and the like; however, the desulfurizer in the existing SDS dry desulfurization injection technology has high requirement on the temperature range of flue gas, which is necessarily more than 140 ℃ and less than 250 ℃, and the sulfur content exceeds 1000mg/Nm 3 When it is used, the desulfurization effect is poor.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the ultralow-temperature desulfurization and denitrification process special for the lime kiln, which has the advantages of stable process performance, low energy consumption, small occupied area, convenient implementation, capability of performing desulfurization at the temperature lower than 140 ℃ and higher than 250 ℃, and capability of improving the sulfur content to be over 1000mg/Nm 3 The desulfurization efficiency.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
an ultralow temperature desulfurization and denitrification process special for a lime kiln comprises low temperature SCR denitration and SDS dry desulfurization;
the low-temperature SCR denitration comprises the steps of enabling lime kiln flue gas to enter an SCR reactor for denitration after passing through a blower, moving a calcining zone of the SCR reactor to 27-27.5 m, controlling the coal ratio to be 7.5-7.8%, and controlling the calcining temperature to be 180-185 ℃; periodic continuous feeding is adopted, stone materials are fed for 3 times in one hour, six cars are used each time, 1.6-1.8 tons of stone materials are fed for each car, and low-temperature SCR denitration is finished to obtain the flue gas of the lime kiln furnace after denitration;
the rotating speed of the blower is 32-35Hz, and the air quantity is 20000-22000m 3 /h；
The temperature of the lime kiln flue gas is maintained at 160-170 ℃, and the content of particulate matters is 5-5.6g/m 3 The sulfur dioxide content is 200-1100mg/m 3 The content of nitrogen oxide is 200-350mg/m 3 The flow rate is 75000-75500Nm 3 /h；
The type of the catalyst in the SCR reactor is honeycomb type WDSCR-22, the manufacturer is Shanghai Fuyingyou environmental protection technology limited, the initial catalyst volume is 14.9-15.5m 3 The number of catalyst holes is 22-25, the length of the catalyst monomer is 150-155mm, the width of the monomer is 150-155mm, the height of the monomer is 1150-1180mm, and the specific surface area is 527-530m 2 /m 3 The bulk density is 450-455mg/cm 3 The porosity is 74.88-74.95%.
The SDS dry desulfurization is carried out, the denitrated lime kiln flue gas is heated to 125-135 ℃, and then is introduced into a dust remover, the temperature of the dust remover is controlled to be 110-270 ℃, a desulfurizing agent is sprayed into a flue in front of the dust remover, and the desulfurized lime kiln flue gas is obtained after the desulfurization is finished;
the preparation method of the desulfurizer comprises the following steps: mixing calcium bentonite, magnesium oxide and zeolite powder, performing first ball milling, controlling the ball-to-material ratio during the first ball milling to be 10-12, controlling the rotation speed to be 320-350rpm, controlling the time to be 28-32min, obtaining mixed powder after the ball milling is finished, adding the mixed powder into a surface modification solution for soaking, controlling the temperature to be 50-55 ℃ and the time to be 40-45min, filtering after the soaking is finished, placing filter residues at-30 ℃ to-25 ℃ for freezing treatment for 35-40min, then placing the filter residues at 120-125 ℃ for drying to obtain a matrix, mixing the matrix, calcium gluconate, calcium citrate, calcium phytate, calcium sulfate, sodium bicarbonate and sodium lignosulfonate, performing second ball milling, controlling the ball-to-material ratio during the second ball milling to be 12-15, controlling the rotation speed to be 300-320rpm and the time to be 38-42min, and obtaining a desulfurizer after the second ball milling is finished;
the surface modification liquid comprises the following components in parts by weight: 4-6 parts of sodium dodecyl benzene sulfonate, 3-4 parts of zwitterionic polyacrylamide, 5-8 parts of stearic acid and 50-52 parts of deionized water.
Wherein the weight ratio of the calcium bentonite to the magnesium oxide to the zeolite powder is 50-52;
wherein the weight ratio of the matrix to the calcium gluconate, the calcium citrate, the calcium phytate, the calcium sulfate, the sodium bicarbonate and the sodium lignosulfonate is (50-55).
Compared with the prior art, the invention has the beneficial effects that:
(1) The ultralow temperature desulfurization and denitrification process special for the lime kiln has the advantages of stable process performance, low energy consumption, small occupied area and convenience in implementation;
(2) The ultralow-temperature desulfurization and denitrification process special for the lime kiln can perform desulfurization at the temperature lower than 140 ℃ and higher than 250 ℃, and can expand the desulfurization temperature range to 110-270 ℃;
(3) The ultralow-temperature desulfurization and denitrification process special for the lime kiln can improve the sulfur content to be over 1000mg/Nm 3 The initial sulfur dioxide content of the sulfur dioxide can be removed to 200-1100mg/m 3 The lime kiln flue gas;
(4) The special ultralow-temperature desulfurization and denitrification process for the lime kiln has the advantages that the content of particulate matters in flue gas of the lime kiln after denitration and desulfurization is 5.2-6.9mg/m 3 The sulfur dioxide content is 11.5-30.4mg/m 3 The content of nitrogen oxide is 6.7-7.5mg/m 3 。
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
An ultra-low temperature desulfurization and denitrification process special for a lime kiln comprises the following steps:
1. and (3) low-temperature SCR denitration: the method comprises the steps of enabling lime kiln flue gas to enter an SCR reactor for denitration after passing through a blower, controlling the rotating speed of the blower to be 32Hz, and controlling the air quantity to be 20000m 3 Moving a calcining zone of the SCR reactor to 27 meters, controlling the coal ratio to be 7.5 percent and controlling the calcining temperature to be 180 ℃; periodic continuous feeding is adopted, stone materials are fed for 3 times in one hour, six cars and 1.6 tons in each car are used, and the low-temperature SCR denitration is finished to obtain the denitrated lime kiln smoke.
The temperature of the lime kiln flue gas is maintained at 160 ℃, and the content of particulate matters is 5g/m 3 The sulfur dioxide content is 200mg/m 3 The content of nitrogen oxides is 200mg/m 3 At a flow rate of 75000Nm 3 /h；
The type of the catalyst in the SCR reactor is honeycomb type WDSCR-22, the manufacturer is Shanghai Fuyingyou environmental protection technology limited, and the initial catalyst volume is 14.9m 3 The number of catalyst holes is 22, the length of the catalyst monomer is 150mm, the width of the monomer is 150mm, the height of the monomer is 1150mm, and the specific surface area is 527m 2 /m 3 Bulk density of 450mg/cm 3 The porosity was 74.88%.
The content of particulate matters in the denitrated lime kiln smoke is 10mg/m 3 The sulfur dioxide content is 190mg/m 3 The content of nitrogen oxides is 10mg/m 3 。
SDS Dry desulfurization: heating the denitrated lime kiln flue gas to 125 ℃, introducing into a dust remover, controlling the temperature of the dust remover to be 110 ℃, spraying a desulfurizing agent on a front flue of the dust remover, wherein the desulfurizing agent is used for spraying SO in the lime kiln flue gas 2 Other acidic media are absorbed and purified to obtain desulfurized lime kiln flue gas;
the preparation method of the desulfurizer comprises the following steps: mixing calcium bentonite, magnesium oxide and zeolite powder, performing first ball milling, controlling the ball-to-material ratio during the first ball milling to be 10, the rotating speed to be 320rpm, the time to be 28min, obtaining mixed powder after the ball milling is finished, adding the mixed powder into surface modification liquid, soaking at the temperature of 50 ℃ for 40min, filtering after the soaking is finished, placing filter residues at-30 ℃ for freezing treatment for 35min, then placing at 120 ℃ for drying to obtain a matrix, mixing the matrix, calcium gluconate, calcium citrate, calcium phytate, calcium sulfate, sodium bicarbonate and sodium lignosulfonate, performing second ball milling, controlling the ball-to-material ratio during the second ball milling to be 12, the rotating speed to be 300rpm, the time to be 38min, and obtaining a desulfurizer after the second ball milling is finished;
the surface modification liquid comprises the following components in parts by weight: 4 parts of sodium dodecyl benzene sulfonate, 3 parts of zwitterionic polyacrylamide, 5 parts of stearic acid and 50 parts of deionized water.
Wherein the weight ratio of the calcium bentonite to the magnesium oxide to the zeolite powder is 50;
wherein, the weight ratio of the matrix, calcium gluconate, calcium citrate, calcium phytate, calcium sulfate, sodium bicarbonate and sodium lignosulfonate is 50.
The content of particulate matters in the desulfurized lime kiln flue gas is 6mg/m 3 The sulfur dioxide content is 12mg/m 3 The content of nitrogen oxides is 7mg/m 3 。
Example 2
An ultra-low temperature desulfurization and denitrification process special for a lime kiln comprises the following steps:
1. and (3) low-temperature SCR denitration: the method comprises the steps of enabling lime kiln flue gas to enter an SCR reactor for denitration after passing through a blower, controlling the rotating speed of the blower to be 33Hz and the air volume to be 21000m 3 Moving a calcining zone of the SCR reactor to 27.1 meters, controlling the coal ratio to be 7.6 percent and controlling the calcining temperature to 182 ℃; periodic continuous feeding is adopted, stone materials are fed for 3 times in one hour, six cars are used each time, each car is 1.6 tons, and the low-temperature SCR denitration is finished to obtain the denitrated lime kiln smoke.
The temperature of the lime kiln flue gas is maintained at 163 ℃, and the content of particulate matters is 5.2g/m 3 The sulfur dioxide content is 650mg/m 3 The content of nitrogen oxides is 240mg/m 3 At a flow rate of 75100Nm 3 /h；
The type of the catalyst in the SCR reactor is honeycomb type WDSCR-22, the manufacturer is Shanghai Fuyingyou environmental protection technology limited, the initial catalyst volume is 15.1m 3 The number of catalyst holes is 22, the length of the catalyst monomer is 152mm, the width of the monomer is 151mm, the height of the monomer is 1160mm, and the specific surface area is 528m 2 /m 3 Bulk density of 451mg/cm 3 The porosity was 74.92%.
The content of particulate matters in the denitrated lime kiln flue gas is 11mg/m 3 The sulfur dioxide content is 634mg/m 3 The content of nitrogen oxides is 11mg/m 3 。
SDS Dry desulfurization: heating the denitrated lime kiln flue gas to 128 ℃, introducing into a dust remover, controlling the temperature of the dust remover to be 130 ℃, spraying a desulfurizing agent on a front flue of the dust remover, and using the desulfurizing agent to remove limeSO in kiln flue gas 2 Other acidic media are absorbed and purified to obtain desulfurized lime kiln flue gas;
the preparation method of the desulfurizer comprises the following steps: mixing calcium bentonite, magnesium oxide and zeolite powder, performing first ball milling, controlling the ball-to-material ratio during the first ball milling to be 11, rotating at 330rpm for 29min, obtaining mixed powder after the ball milling is finished, adding the mixed powder into surface modification liquid for soaking, controlling the temperature during the soaking to be 51 ℃ and the time to be 41min, filtering after the soaking is finished, placing filter residues at-30 ℃ for freezing treatment for 36min, then placing at 122 ℃ for drying to obtain a matrix, mixing the matrix, calcium gluconate, calcium citrate, calcium phytate, calcium sulfate, sodium bicarbonate and sodium lignosulfonate, performing second ball milling, controlling the ball-to-material ratio during the second ball milling to be 13, rotating at 310rpm for 39min, and obtaining a desulfurizer after the second ball milling is finished;
the surface modification liquid comprises the following components in parts by weight: 5 parts of sodium dodecyl benzene sulfonate, 3.2 parts of zwitterionic polyacrylamide, 6 parts of stearic acid and 51 parts of deionized water.
Wherein the weight ratio of the calcium bentonite to the magnesium oxide to the zeolite powder is 51;
wherein, the weight ratio of the matrix, the calcium gluconate, the calcium citrate, the calcium phytate, the calcium sulfate, the sodium bicarbonate and the sodium lignosulfonate is 51.5.
The content of particulate matters in the desulfurized lime kiln flue gas is 6.2mg/m 3 The sulfur dioxide content is 25.5mg/m 3 The content of nitrogen oxides is 7.2mg/m 3 。
Example 3
An ultra-low temperature desulfurization and denitrification process special for a lime kiln comprises the following steps:
1. and (3) low-temperature SCR denitration: the method comprises the steps of enabling lime kiln flue gas to enter an SCR reactor for denitration after passing through a blower, controlling the rotating speed of the blower to be 34Hz and the air volume to be 21500m 3 Moving a calcining zone of the SCR reactor to 27.2 meters, controlling the coal ratio to be 7.7 percent and controlling the calcining temperature to be 184 ℃; the method adopts periodic continuous feeding, stone materials are fed for 3 times in one hour, six cars are fed each time, and each car is fed1.7 tons, and finishing the low-temperature SCR denitration to obtain the denitrated lime kiln smoke.
The temperature of the lime kiln flue gas is kept at 165 ℃, and the content of particulate matters is 5.3g/m 3 The sulfur dioxide content is 900mg/m 3 The content of nitrogen oxides is 280mg/m 3 At a flow rate of 75200Nm 3 /h；
The type of the catalyst in the SCR reactor is honeycomb type WDSCR-22, the manufacturer is Shanghai Fuyingyou environmental protection technology limited, and the initial catalyst volume is 15.3m 3 The number of catalyst holes is 24, the length of the catalyst monomer is 153mm, the width of the monomer is 152mm, the height of the monomer is 1170mm, and the specific surface area is 529m 2 /m 3 Bulk density of 452mg/cm 3 The porosity was 74.93%.
The content of particulate matters in the denitrated lime kiln smoke is 13mg/m 3 The sulfur dioxide content is 875mg/m 3 The content of nitrogen oxides is 12mg/m 3 。
SDS Dry desulfurization: heating the denitrated lime kiln flue gas to 130 ℃, introducing into a dust remover, controlling the temperature of the dust remover to be 200 ℃, spraying a desulfurizing agent on a front flue of the dust remover, wherein the desulfurizing agent is used for spraying SO in the lime kiln flue gas 2 Other acidic media are absorbed and purified to obtain desulfurized lime kiln flue gas;
the preparation method of the desulfurizer comprises the following steps: mixing calcium bentonite, magnesium oxide and zeolite powder, performing primary ball milling, controlling the ball-to-material ratio during primary ball milling to be 11, rotating speed to be 340rpm, and time to be 30min, obtaining mixed powder after ball milling, adding the mixed powder into surface modification liquid for soaking, controlling the temperature during soaking to be 53 ℃ and the time to be 43min, filtering after soaking, placing filter residues at-28 ℃ for freezing treatment for 37min, then placing at 124 ℃ for drying to obtain a matrix, mixing the matrix, calcium gluconate, calcium citrate, calcium phytate, calcium sulfate, sodium bicarbonate and sodium lignosulfonate, performing secondary ball milling, controlling the ball-to-material ratio during secondary ball milling to be 14, rotating speed to be 315rpm, and time to be 40min, and obtaining a desulfurizer after secondary ball milling;
the surface modification liquid comprises the following components in parts by weight: 5.5 parts of sodium dodecyl benzene sulfonate, 3.5 parts of zwitterionic polyacrylamide, 7 parts of stearic acid and 51.5 parts of deionized water.
Wherein, the weight ratio of the calcium bentonite, the magnesium oxide and the zeolite powder is 51.5;
wherein, the weight ratio of the matrix, calcium gluconate, calcium citrate, calcium phytate, calcium sulfate, sodium bicarbonate and sodium lignosulfonate is 53.
The content of particulate matters in the desulfurized lime kiln flue gas is 5.2mg/m 3 The sulfur dioxide content is 27.5mg/m 3 The content of nitrogen oxides is 6.7mg/m 3 。
Example 4
An ultra-low temperature desulfurization and denitrification process special for a lime kiln comprises the following steps:
1. and (3) low-temperature SCR denitration: the method comprises the steps of enabling lime kiln flue gas to enter an SCR reactor for denitration after passing through a blower, controlling the rotating speed of the blower to be 35Hz and the air volume to be 22000m 3 Moving the calcining zone of the SCR reactor to 27.5 meters, controlling the coal ratio to be 7.8 percent and controlling the calcining temperature to 185 ℃; periodic continuous feeding is adopted, stone materials are fed for 3 times in one hour, six cars and 1.8 tons in each car are used, and the low-temperature SCR denitration is finished to obtain the denitrated lime kiln smoke.
The temperature of the lime kiln flue gas is maintained at 170 ℃, and the content of particulate matters is 5.6g/m 3 The sulfur dioxide content is 1100mg/m 3 The content of nitrogen oxides is 350mg/m 3 The flow rate is 75500Nm 3 /h；
The type of the catalyst in the SCR reactor is honeycomb type WDSCR-22, the manufacturer is Shanghai Fuyingyou environmental protection technology limited, and the initial catalyst volume is 15.5m 3 The number of catalyst holes is 25, the length of the catalyst monomer is 155mm, the width of the monomer is 155mm, the height of the monomer is 1180mm, and the specific surface area is 530m 2 /m 3 Bulk density of 455mg/cm 3 The porosity was 74.95%.
The content of particulate matters in the denitrated lime kiln flue gas is 15mg/m 3 The sulfur dioxide content is 1054mg/m 3 Nitrogen oxides containingThe amount is 14mg/m 3 。
SDS Dry desulfurization: heating the denitrated lime kiln flue gas to 135 ℃, introducing into a dust remover, controlling the temperature of the dust remover to be 270 ℃, spraying a desulfurizing agent on a front flue of the dust remover, wherein the desulfurizing agent is used for carrying out SO (sulfur oxide) treatment on the lime kiln flue gas 2 Other acidic media are absorbed and purified to obtain desulfurized lime kiln flue gas;
the preparation method of the desulfurizer comprises the following steps: mixing calcium bentonite, magnesium oxide and zeolite powder, performing primary ball milling, controlling the ball-to-material ratio during primary ball milling to be 12, the rotation speed to be 350rpm, the time to be 32min, obtaining mixed powder after ball milling, adding the mixed powder into a surface modification solution, soaking at the temperature of 55 ℃ for 45min, filtering after soaking, placing filter residues at-25 ℃ for freezing treatment for 40min, then placing at 125 ℃ for drying to obtain a matrix, mixing the matrix, calcium gluconate, calcium citrate, calcium phytate, calcium sulfate, sodium bicarbonate and sodium lignosulfonate, performing secondary ball milling, controlling the ball-to-material ratio during secondary ball milling to be 15, the rotation speed to be 320rpm, the time to be 42min, and obtaining a desulfurizer after secondary ball milling;
the surface modification liquid comprises the following components in parts by weight: 6 parts of sodium dodecyl benzene sulfonate, 4 parts of zwitterionic polyacrylamide, 8 parts of stearic acid and 52 parts of deionized water.
Wherein the weight ratio of the calcium bentonite to the magnesium oxide to the zeolite powder is 52;
wherein, the weight ratio of the matrix, calcium gluconate, calcium citrate, calcium phytate, calcium sulfate, sodium bicarbonate and sodium lignosulfonate is 55.
The content of particulate matters in the desulfurized lime kiln flue gas is 6.9mg/m 3 The sulfur dioxide content is 30.4mg/m 3 The content of nitrogen oxides is 7.5mg/m 3 。
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A special ultralow temperature desulfurization and denitrification process for a lime kiln is characterized by comprising low temperature SCR denitration and SDS dry desulfurization;
the low-temperature SCR denitration comprises the steps of enabling lime kiln flue gas to enter an SCR reactor for denitration after passing through a blower, moving a calcining zone of the SCR reactor to 27-27.5 m, controlling the coal ratio to be 7.5-7.8%, and controlling the calcining temperature to be 180-185 ℃; periodic continuous feeding is adopted, stone materials are fed for 3 times in one hour, six cars are used each time, 1.6-1.8 tons of stone materials are fed for each car, and low-temperature SCR denitration is finished to obtain the flue gas of the lime kiln furnace after denitration;
and (3) performing SDS dry desulfurization, namely heating the denitrated lime kiln flue gas to 125-135 ℃, introducing the denitrated lime kiln flue gas into a dust remover, controlling the temperature of the dust remover to be 110-270 ℃, spraying a desulfurizing agent into a front flue of the dust remover, and obtaining the desulfurized lime kiln flue gas after desulfurization is finished.
2. The ultra-low temperature desulfurization and denitrification process special for the lime kiln as claimed in claim 1, wherein the rotating speed of the blower is 32-35Hz, and the air volume is 20000-22000m 3 /h。
3. The ultra-low temperature desulfurization and denitrification process special for the lime kiln as claimed in claim 1, wherein the temperature of the flue gas of the lime kiln is maintained at 160-170 ℃, and the content of particulate matters is 5-5.6g/m 3 The sulfur dioxide content is 200-1100mg/m 3 The content of nitrogen oxide is 200-350mg/m 3 The flow rate is 75000-75500Nm 3 /h。
4. The ultra-low temperature special for the lime kiln furnace as claimed in claim 1The desulfurization and denitrification process is characterized in that the type of a catalyst in the SCR reactor is honeycomb type WDSCR-22, a manufacturer is Shanghai Fuyingfen environmental protection technology Co., ltd, and the volume of an initial catalyst is 14.9-15.5m 3 The number of catalyst holes is 22-25, the length of the catalyst monomer is 150-155mm, the width of the monomer is 150-155mm, the height of the monomer is 1150-1180mm, and the specific surface area is 527-530m 2 /m 3 The bulk density is 450-455mg/cm 3 The porosity is 74.88-74.95%.
5. The ultra-low temperature desulfurization and denitrification process special for the lime kiln as claimed in claim 1, wherein the preparation method of the desulfurizer comprises the following steps: mixing calcium bentonite, magnesium oxide and zeolite powder, performing first ball milling, controlling the ball-to-material ratio during the first ball milling to be 10-12, controlling the rotation speed to be 320-350rpm, controlling the time to be 28-32min, obtaining mixed powder after the ball milling is finished, adding the mixed powder into a surface modification solution for soaking, controlling the temperature to be 50-55 ℃ and the time to be 40-45min, filtering after the soaking is finished, placing filter residues at-30 ℃ to-25 ℃ for freezing treatment for 35-40min, then placing the filter residues at 120-125 ℃ for drying to obtain a matrix, mixing the matrix, calcium gluconate, calcium citrate, calcium phytate, calcium sulfate, sodium bicarbonate and sodium lignosulfonate, performing second ball milling, controlling the ball-to-material ratio during the second ball milling to be 12-15, controlling the rotation speed to be 300-320rpm and the time to be 38-42min, and obtaining the desulfurizer after the second ball milling is finished.
6. The ultra-low temperature desulfurization and denitrification process special for the lime kiln as claimed in claim 5, wherein the surface modification solution comprises the following components in parts by weight: 4-6 parts of sodium dodecyl benzene sulfonate, 3-4 parts of zwitterionic polyacrylamide, 5-8 parts of stearic acid and 50-52 parts of deionized water.
7. The ultra-low temperature desulfurization and denitrification process special for the lime kiln as claimed in claim 5, wherein the weight ratio of the calcium bentonite, the magnesium oxide and the zeolite powder is 50-52.
8. The ultra-low temperature desulfurization and denitrification process special for the lime kiln furnace as claimed in claim 5, is characterized in that the weight ratio of matrix, calcium gluconate, calcium citrate, calcium phytate, calcium sulfate, sodium bicarbonate and sodium lignosulfonate is 50-55.
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