CN108499338A - A kind of denitrification apparatus - Google Patents
A kind of denitrification apparatus Download PDFInfo
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- CN108499338A CN108499338A CN201810295719.0A CN201810295719A CN108499338A CN 108499338 A CN108499338 A CN 108499338A CN 201810295719 A CN201810295719 A CN 201810295719A CN 108499338 A CN108499338 A CN 108499338A
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- China
- Prior art keywords
- activated carbon
- denitrification apparatus
- denitrfying agent
- content
- denitration
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 68
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 238000012544 monitoring process Methods 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 88
- 239000003054 catalyst Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 30
- 229910021529 ammonia Inorganic materials 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 18
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 14
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- WRWKMJCISLXRMU-UHFFFAOYSA-N [Zr].[Ce].[Y].[La] Chemical compound [Zr].[Ce].[Y].[La] WRWKMJCISLXRMU-UHFFFAOYSA-N 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 9
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 235000003642 hunger Nutrition 0.000 claims description 8
- 230000037351 starvation Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 3
- 229910009246 Y(NO3)3.6H2O Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003345 natural gas Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- JCFISKANHFQUCT-UHFFFAOYSA-N [Y].[La] Chemical compound [Y].[La] JCFISKANHFQUCT-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000012806 monitoring device Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000033772 system development Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 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
- B01D53/54—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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
-
- 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
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- 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
-
- 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
Abstract
The present invention provides a kind of denitrification apparatus, described device is provided with axial flow blower, air inlet pipe, denitration region, escape pipe, air blower, liquid ammonia evaporating device, mixer, nitrogen oxides on-line monitoring equipment.The present invention can reduce environmental pollution, can accurately judge denitrfying agent replacing construction, and can monitor whether enterprise opens denitration device in real time, be with a wide range of applications.
Description
Technical field
The invention belongs to technical field of air pollution control more particularly to a kind of denitrification apparatus.
Background technology
With the development of modern industrial production, the problem of atmosphere pollution becomes people's extensive concern, while nitrogen oxides
NOxAtmosphere polluting problem be gradually taken seriously since the seventies.By studying it has been found that NOxCan not only it cause photochemical
Smog is learned, and the health of the mankind can be endangered, cause high-content nitric acid rain, reduce ozone layer and some other problem, is caused
Serious atmosphere pollution.
Nitrogen oxides emission reduction is grabbed in China since " 12th Five-Year Plan ", and " 13 " are even more to be classified as denitration but its prevention and cure of pollution
Emphasis, wherein coal-fired flue-gas are primary management goals.With going deep into for prevention and control of air pollution work, some key areas start to close
Note the denitration work of more areas.Such as：Beijing and Shanghai City take the lead in having revised boiler pollutant discharge standard, are distinctly claimed
The non-coal-burning boiler such as natural gas boiler also needs the discharge of control nitrogen oxides, wherein Beijing to require natural gas boiler flue gas emission
When nitrous oxides concentration be not higher than 30mg/m3。
Existing denitration technology is developed mainly around coal-fired flue-gas processing, and usually desulfurization and denitration is handled together, for
Exhaust gas without sulfur dioxide（Such as：The flue gas of the generations such as natural gas boiler, biomass boiler）Denitration process there is no maturation
Method.Such as natural gas boiler denitration, such as use the ammine selectivity catalytic reduction of existing market mainstream（SCR）Technology into
Row denitration process is then needed boiler waste gas being heated to 300 to 400 degree, extremely be consumed energy, basic without operability.
And SCR catalyst includes mainly noble metal catalyst, molecular sieve (Zeolite) catalyst, carbon-supported catalysts
And metal oxide catalyst.Wherein, it is commonly metal oxide catalyst, such as V2O5、WO3、MoO3Deng such catalysis
Agent is generally with TiO2For carrier, there is also many defects while having the advantages that certain for such catalyst, for example, titanium-based is catalyzed
Agent denitration temperature is higher（300~400℃）, SCR device can only be arranged between economizer and air preheater, but cigarette herein
There are a large amount of flying dusts in gas, contain alkali metal in flying dust, the substances such as arsenic and mercury can corrode and poison catalyst, lead to catalyst
Inactivation reduces its service life, while application temperature window is relatively narrow；On the other hand, vanadium component is easy to run off in such catalyst, right
Environment and human body damage.The replacement of catalyst generally press design service life use, but actually use situation may with set
Meter condition is not exclusively consistent, and causes the time that catalyst actual needs is replaced with design service life there may be large error,
The waste of catalyst can be caused by replacing too early, and too late replacement then can cause denitration efficiency low, pollute air.
The method of the nitrogen oxides without industrial SO 2 exhaust gas of control such as natural gas boiler flue gas at present, mainly
It is the generation for taking low-NO_x combustion technology control nitrogen oxides.There are many low NO type currently on the market, but to true
It can just realize that nitrogen oxides is less than 30mg/m for a long time3Effluent standard, general home equipment also has certain difficulty, needs to select
Several preferable import brands could be realized.And low nitrogen burning can influence boiler thermal efficiency, to cause boiler operatiopn cost
Increase, also higher is required to the operation of boiler.Some enterprises will deactivate low nitrogen in order to cost-effective in the case of without supervision
Combustion apparatus causes more nitrogen oxides to be discharged into air.Beijing implemented about boiler pollutant discharge new standard
The investigation of journey finds that, since country is fitted without small tonnage boiler the requirement of online monitoring device, some enterprises can be in low nitrogen
Combustion retrofit is completed and by deactivating low nitrogen burning equipment in the routine use after examination, only comes into operation when accepting oversight inspection,
Effective supervision is difficult to carry out to this environmental protection administration.
A kind of it can reduce environmental pollution if can provide, be really achieved tightened up nitrogen oxides of exhaust gas discharge standard and want
It asks, used material itself can accurately judge denitrfying agent replacing construction, and whether can monitor enterprise in real time without secondary pollution
The technical solution for opening denitration device, will be very significant.
Invention content
In order to achieve the above objectives, the present invention provides a kind of denitrification apparatus, described device is provided with axial flow blower, air inlet
Pipe, denitration region, escape pipe, air blower, liquid ammonia evaporating device, mixer, nitrogen oxides on-line monitoring equipment.
Air inlet pipe, escape pipe with denitration region unicom, are provided with the screen frame that several columns are loaded with denitrfying agent in denitration region；Respectively
A screen frame has differential pressure pickup there are one being correspondingly arranged, the pressure for detecting screen frame along denitrfying agent both sides on airflow direction
Difference.
Air inlet pipe inlet is provided with the grid for spraying ammonia, which is connected to liquid ammonia evaporating device by pipeline.
Axial flow blower one end connects source exhaust gas pipe, and one end connects air inlet pipe.
Escape pipe and flue gas emission chimney unicom.
Liquid ammonia evaporating device includes liquefied ammonia bottle and evaporator, and the evaporator is connect with liquefied ammonia bottle, and liquefied ammonia passes through connecting tube
Road is gasificated as ammonia after entering evaporator, and ammonia is input to by pipeline in blower export pipe, with blower exit conduits
Interior air mixing, is input to grid after mixer.
Nitrogen oxides on-line monitoring equipment is restructured by common portable instrumentation in the market, if a set of host and
Two detection ports, detection port are separately positioned on air inlet pipe and an air outlet pipe, and one group of numerical value is measured per 0.5h-4h.Certainly, not
It is limitation necessary two detections ports, can is multiple.
Further, feeding port is arranged in each column screen frame upper end, and lower end is provided with discharge port.
Further, the denitrfying agent includes as the microporous activated Carbon Materials of carrier components and as active component
ZrO2、CeO2And La2O3、Y2O3；Wherein, by weight percentage, CeO2Content is 1% ~ 10%, ZrO2Content is 1% ~ 5%, La2O3
Content is that 0.1% ~ 1%, Y2O3 contents are 0.1% ~ 1%, remaining is absorbent charcoal material.
Further, in denitrfying agent, by weight percentage, CeO2Content is 3.56% ~ 5.59%, ZrO2Content is 2.89%
~ 4.51%, La2O3Content is 0.25% ~ 0.58%, Y2O3Content is 0.28% ~ 0.61%, remaining is activated carbon.
Further, denitrfying agent, by weight percentage, middle ZrO2 contents are 3.52%, La2O3Content is 0.58%, Y2O3
Content is 0.51%, remaining is activated carbon.
Further, the preparation method of the denitrfying agent is：
Step 1：Prepare activated carbon：Activated carbon is warming up to 350 ~ 500 DEG C in a furnace, N is used in temperature-rise period2Protection rises
Temperature to holding constant temperature after 350 ~ 500 DEG C for a period of time, is passed through O in thermostatic process2And CO2Mixed gas replace N2。
Step 2：Prepare catalyst component：With Ce (NO3)2.6H2O、ZrOCO3、La(NO3)3.6H2O、Y(NO3)3.6H2O it is
Raw material is configured to cerium-zirconium-lanthanum-yttrium mixing salt solution, and H then is added into cerium-zirconium-lanthanum-yttrium mixing salt solution2O2, will be above-mentioned molten
It is stirred after constant volume after liquid mixing, i.e., prepared catalyst component solution.
Step 3：Dipping：Catalyst component solution obtained by step 2 is impregnated into the activated carbon obtained by step 1 will mixing
Solution is stood after being stirred with activated carbon.
Step 4：It is dry：By the impregnated material obtained by step 3, drying obtains dry SCR denitration presoma.
Step 5：Calcining：Dry SCR denitration presoma obtained by step 4 is forged under conditions of starvation
It burns, obtains final denitrfying agent.
Further, in step 2, Ce (NO3)2.6H2O、ZrOCO3、La(NO3)3.6H2O、Y(NO3)3.6H2The weight of O
Percentage is 65%：33%：0.9%：1.1%.
Further, the weight percent that mixed solution accounts for activated carbon is 40% ~ 65%.
Further, in step 2, PVA solution is additionally added into cerium-zirconium-lanthanum-yttrium mixing salt solution.
Further, in step 5, dry SCR denitration presoma is under conditions of starvation in 350 ~ 600
DEG C calcining 1 ~ 3h.
Beneficial effects of the present invention are：
1, device presses Design for Complete Equipment, installs, is easy to operate, and denitration efficiency is high, can effectively realize nitrogen oxides qualified discharge,
Meet higher environmental requirement from now on.
2, device and boiler are direct-connected, no bypass, and the detection information of nitrogen oxides detection device can be transferred to supervisor,
Supervisor is facilitated to monitor whether relevant enterprise opens denitration device in real time, whether discharge is up to standard.
3, it is carried out using the middle low temperature that may be implemented in 80-200 degree（Natural gas）The denitrfying agent of boiler waste gas denitration, and it is big absolutely
The temperature of most natural gas boiler exhaust gas itself is just in 80-200 degree, therefore, the device of the invention be（Natural gas）Boiler
Denitration is directly carried out under exhaust gas temperature, need not be carried out heating treatment to exhaust gas, be reduced energy consumption caused by being heated to exhaust gas.Catalysis
Agent working environment is also purified, and service life is long, and heavy metal of the catalyst without containing pollution environment itself, avoids causing two
Secondary pollution.
4, denitrfying agent is convenient for changing by upper end feeding port and the realization of lower end discharge port, and replacing construction is true according to differential pressure value
It is fixed, the waste and atmosphere pollution of denitrfying agent will not be caused.
5. can effectively reduce denitration material temperature under accident condition, prevent denitrfying agent temperature is excessively high from spontaneous combustion can occur and making
At fire.
Description of the drawings
Fig. 1 is schematic structural view of the invention.
Fig. 2 is denitration region inner side elevational view.
Fig. 3 is vertical view of the present invention.
Fig. 4 is liquid ammonia evaporating device schematic diagram.
In figure：1. air inlet pipe, 2. denitration regions, 3. escape pipes, 4. air blowers, 5. liquid ammonia evaporating devices, 6. mixers, 7. sprays
Shower pipe, 8. grids, 9. screen frames, 10. axial flow blowers, 11. robot control system(RCS) control cabinets, 12. evaporators, 13. liquefied ammonia bottles.
Specific implementation mode
As shown in Figure 1, the present invention is provided with axial flow blower 10, air inlet pipe 1, denitration region 2, escape pipe 3, air blower 4, liquefied ammonia
Vaporising device 5, mixer 6.It introduces in detail below.
Air inlet pipe 1, escape pipe 3 with 2 unicom of denitration region.As shown in Fig. 2, being provided with several columns Sheng in the denitration region 2
Screen frame 9 equipped with denitrfying agent.Feeding port is arranged in 9 upper end of each column screen frame of denitration region 2.The feeding port is up-small and down-big, and covering should
Row screen frame 9, opening feeding port can carry out toward the 9 inner addition denitrfying agent of row screen frame.Denitrfying agent can use current material, also may be used
To use the special denitrfying agent developed of the present invention, behind special denitrfying agent can be discussed in detail.
Discharge port is arranged in 9 lower end of each column screen frame.After the sealing for opening discharge port, the denitrfying agent of the row screen frame 9 can topple over
Out.
The present invention preferably installs double-layer flap valve additional in feeding port and discharge port, you can realizes that denitrfying agent is replaced online.
As shown in figure 3,1 inlet of the air inlet pipe is provided with axial flow blower 10, which connects flue gas leading, one end
Connect air inlet pipe 1.The wind turbine is interlocked with 1 end pressure of air inlet pipe, and wind turbine does not start when pressure is higher than setting value, internal logical
Road does not interfere with exhaust gas and passes through enough；Wind turbine starts when pressure is less than setting value, and wind turbine uses frequency control, it is ensured that air inlet pipe 1
End pressure almost constant.1 inlet of air inlet pipe is additionally provided with the grid 8 for spraying ammonia, which is connected by pipeline
To liquid ammonia evaporating device 5.Grid 8 is provided with several ammonia gas outlets, the axial direction of ammonia gas outlet and the axial phase of air inlet pipe 1
Together, direction is opposite.Preferably, 8 both ends of grid are fixed on 1 inner wall of air inlet pipe, the direction that ammonia gas outlet is determined along both ends
It is uniformly distributed so that ammonia energy maximum possible is mixed with exhaust gas.When entering denitration region 2 after the exhaust gas containing nitre is mixed with ammonia
It can be spread to both sides, by making ammonia react with nitrogen oxides under the action of denitrfying agent in screen frame 9 when two row screen frames 9
Nitrogen and water are generated, achievees the purpose that denitration.
3 unicom denitration region 2 of escape pipe and chimney.
As shown in figure 4, liquid ammonia evaporating device 5 include a liquefied ammonia bottle 13 and an evaporator 12, the evaporator 12 with
Liquefied ammonia bottle 13 connects, and liquefied ammonia enters after evaporator 12 to gasify by connecting pipe forms ammonia, which is input to by pipeline
Mixer 6, another side deliver the air to mixer 6, ammonia and air in mixer 6 using air blower 4 and are sufficiently mixed,
Then it is input at the grid 8 of 1 inlet of air inlet pipe by pipeline under the wind-force of air blower 4, passes through the several of grid 8
Gas outlet is mixed with exhaust gas, is entered in denitration region 2 afterwards.
Preferably, denitrfying agent temperature is excessively high in order to prevent can occur spontaneous combustion and cause fire, and the present embodiment is also provided with spray
Shower device is used for emergency processing when denitrfying agent temperature anomaly.As shown in Fig. 2, the spray equipment include spray tube 7 with it is several
Nozzle, the nozzle are distributed in the both sides of each screen frame 9, are sprayed water by the denitrfying agent of the hole on 9 wall of screen frame towards the inside.
Each screen frame 9 is correspondingly arranged there are one there is differential pressure pickup, for detecting screen frame 9 along the both sides on airflow direction
Pressure difference, for being detected along the pressure of the both sides denitrfying agent on airflow direction to screen frame 9.Since dedicated low temperature is de-
Nitre agent is finely ground particle substance, and huddling mode in the interior use of screen frame 9 loads.The denitrfying agent using after a certain period of time can fragmentation, fragmentation
Exhaust gas can be caused to become larger by the resistance of screen frame 9 afterwards, i.e., the differential pressure before and after screen frame 9 becomes larger.When pressure difference reaches a certain setting value
When, it can determine that denitrfying agent reaches service life, replaced.Meanwhile denitrfying agent is after a period of use, by its own weight
Power influences, and the height of denitrfying agent can be gradually reduced in screen frame 9, and 9 top of screen frame may be caused without denitrfying agent, and exhaust gas is directly from upper
Portion space is by causing short circuit, device to lose the ability of denitration, and the differential pressure before and after screen frame 9 can become smaller at this time, should add in time de-
Nitre agent.Therefore when more than preset maximum differential pressure or less than preset minimum differntial pressure, it is necessary to replace in time
Or addition denitrfying agent.At this point, differential pressure pickup the data obtained is transferred to pipe after converting, handling by wireless transport module
At reason personnel, administrative staff can either APP be notified to add or replace denitrfying agent as early as possible by special system.
Individual robot control system(RCS) control cabinet 11 can be designed, for disposing data processing and transmitting required circuit module.
Nitrogen oxides on-line monitoring equipment is restructured by common portable instrumentation in the market, if a set of host and
Two detection ports, detection port are separately positioned on air inlet pipe 1 and escape pipe 3, and one group of numerical value is measured per 0.5h-4h.
Preferably, further include robot control system(RCS), using SCM Based control system's development, measured using from air inlet pipe 1
Nitrous oxides concentration numerical value interlocked with ammonia straying quatity, control ammonia straying quatity, prevent excessive spray into from leading to the escaping of ammonia
It is exceeded；The related datas such as the nitrous oxides concentration numerical value measured by ammonia straying quatity and from escape pipe 3 pass through internet+technology
It is transmitted to special cell phone application, is checked at any time for related personnel, confirms whether device is in use state, whether discharge is up to standard etc..
Denitrfying agent is illustrated below.
The denitrfying agent of the present invention is SCR denitration, includes as the microporous activated Carbon Materials of carrier components and conduct
ZrO2, CeO2 and La2O3, the Y2O3 of active component.Wherein, by weight percentage, CeO2 contents are 1% ~ 10%, ZrO2 contents
For 1% ~ 5%, La2O3 contents be 0.1% ~ 1%, Y2O3 contents it is 0.1% ~ 1%.Remaining is absorbent charcoal material.Activated carbon is that carrier is former
The advantages of material is environment friendly and pollution-free preparation process and relatively low with cost.
Preferably, CeO2 contents be 3.56% ~ 5.59%, ZrO2 contents be 2.89% ~ 4.51%, La2O3 contents be 0.25% ~
0.58%, Y2O3 content are 0.28% ~ 0.61%, remaining is activated carbon.It is furthermore preferred that CeO2 contents are for 5.51%, ZrO2 contents
3.52%, La2O3 content are that 0.58%, Y2O3 contents are 0.51%, remaining is activated carbon.
Absorbent charcoal material of the present invention includes wood activated charcoal, activated carbon from bamboo, active fruit shell carbon, coaly activated carbon
And one or more of activated carbon fibre etc..
Activated carbon face shaping of the present invention can be column-shaped active carbon, hollow activated carbon, spherical activated charcoal, bee
One or more of nest activated carbon or fibrous activated carbon.
Absorbent charcoal material of the present invention is mainly with aperture<2nm is based on micropore（<The micropore ratio of 2nm >=
80%）, specific surface area>850m2/g.Activated carbon under the index can effectively adsorb NOX molecules, provide more reaction interfaces and
Reaction time.
SCR denitration of the present invention, using absorbent charcoal material as carrier, CeO2 is dominant catalyst, ZrO2, La2O3,
Y2O3 is auxiliary agent.
Activated carbon can improve reaction interface as carrier, increase removal efficiency.Using CeO2 as dominant catalyst,
Reaction temperature can be effectively reduced, low-temperature catalytic activity is increased.Catalyst can be improved using ZrO2 as cocatalyst to live
Property, while improving catalyst thermal stability.Using two kinds of auxiliary agents of La2O3 and Y2O3, the thermostabilization of catalyst can effectively improve
Property, storage oxygen interface is provided, while making up the defect of single atomic radius fixed value, to further increase catalyst activity.
The present invention also provides a kind of preparation methods preparing above-mentioned denitrfying agent, include the following steps：
Step 1：Prepare activated carbon.In a furnace by activated carbon（The present embodiment electric tube furnace）In with the speed of 3 ~ 10 DEG C/min
Rate is warming up to 350 ~ 500 DEG C, is protected using N2 in temperature-rise period, is warming up to 350 ~ 500 DEG C of 1 ~ 2h of constant temperature, is passed through in thermostatic process
The mixed gas of O2 and CO2 replaces N2, and it is 75% ~ 95% that wherein O2 contents, which are 5% ~ 25%, CO2 contents,.
The step is modified carrier material using clean pollution-free oxygen and CO2, and modifying process is environment friendly and pollution-free, leads to
The synergistic effect for crossing O2 and CO2 advanced optimizes adjustment to the pore structure of carrier, to increase its oxygen-containing functional group and reaction circle
Face obtains the denitration catalyst carrier haveing excellent performance.
Step 2：Prepare catalyst component.With Ce (NO3) 2.6H2O, ZrOCO3, La (NO3) 3.6H2O, Y (NO3)
3.6H2O is raw material, by said components not according to weight percent 65%：33%：0.9%：1.1% is configured to 10% mass fraction
Cerium-zirconium-lanthanum-yttrium mixing salt solution, then into mixed solution be added 30% H2O2 and 10% PVA solution, be added total amount with
The molar ratio of Ce (NO3) 2.6H2O is 1：1, it is settled to 1.5L after above-mentioned solution is mixed.After constant volume, 0.5h is stirred, that is, is prepared
Good catalyst component solution.
The step uses non-heavy metal elemental cerium-zirconium-lanthanum-yttrium as catalyst component in active component preparation, will not shape
At dangerous waste, secondary pollution is caused, while interacting between each component, promotes catalyst performance.It should be noted that molten
It is preferred embodiment that PVA is added in liquid, is to improve solution in order to further enhance the dispersibility of metallic in mixed solution
Uniformity, while increasing the specific surface of active component, improve catalytic performance.
Step 3：Dipping.Catalyst component solution obtained by step 2 is impregnated into the modified activated carbon of step 1, is mixed
The weight percent that solution accounts for activated carbon is 40% ~ 65%, and mixed solution is proportionally added separately to reaction kettle and is stirred evenly
Afterwards, 30min is stood.
Step 4：It is dry.By the impregnated material obtained by step 3,2-4h is dried at 80 ~ 110 DEG C, it is de- to obtain dry SCR
Denox catalyst presoma.
Step 5：Calcining.Will dry SCR denitration presoma obtained by step 4 under conditions of starvation in
350~600℃（5 ~ 10 DEG C/min of heating rate）Calcine 1 ~ 3h.
The specific embodiment of preparation method is illustrated below.
Specific embodiment 1：
Step 1：Prepare activated carbon.Activated carbon is warming up to 350 DEG C with the rate of 3 DEG C/min in a furnace, is adopted in temperature-rise period
It is protected with N2, is warming up to 350 DEG C of constant temperature 1h, the mixed gas of O2 and CO2 is passed through in thermostatic process instead of N2, wherein O2 contents are
5% and CO2 contents are 95%.
Step 2：Prepare catalyst component.With Ce (NO3) 2.6H2O, ZrOCO3, La (NO3) 3.6H2O, Y (NO3)
3.6H2O is raw material, by said components not according to weight percent 65%：33%：0.9%：1.1% is configured to 10% mass fraction
Cerium-zirconium-lanthanum-yttrium mixing salt solution, then into mixed solution be added 30% H2O2 and 10% PVA solution, be added total amount with
The molar ratio of Ce (NO3) 2.6H2O is 1：1, it is settled to 1.5L after above-mentioned solution is mixed.After constant volume, 0.5h is stirred, that is, is prepared
Good catalyst component solution.
Step 3：Dipping.Catalyst component solution obtained by step 2 is impregnated into the modified activated carbon of step 1, is mixed
The weight percent that solution accounts for activated carbon is 40%, mixed solution is proportionally added separately to after reaction kettle stirs evenly, quiet
Set 30min.
Step 4：It is dry.By the impregnated material obtained by step 3,2-4h is dried at 80 ~ 110 DEG C, it is de- to obtain dry SCR
Denox catalyst presoma.
Step 5：Calcining.Will dry SCR denitration presoma obtained by step 4 under conditions of starvation in
350℃（5 DEG C/min of heating rate）Calcine 1h.
Specific embodiment 2：
Step 1：Prepare activated carbon.Activated carbon is warming up to 500 DEG C, in temperature-rise period with the rate of 10 DEG C/min in a furnace
It is protected using N2, is warming up to 500 DEG C of constant temperature 2h, the mixed gas that O2 and CO2 is passed through in thermostatic process replaces N2, wherein O2 contents
It is 75% for 25%, CO2 contents.
Step 2：Prepare catalyst component.With Ce (NO3) 2.6H2O, ZrOCO3, La (NO3) 3.6H2O, Y (NO3) 3.6H2O
For raw material, by said components not according to weight percent 65%：33%：0.9%：1.1% is configured to cerium-zirconium-of 10% mass fraction
Then the PVA solution of 30% H2O2 and 10%, addition and Ce (NO3) is added in lanthanum-yttrium mixing salt solution into mixed solution
The molar ratio of 2.6H2O is 1：1, it is settled to 1.5L after above-mentioned solution is mixed.After constant volume, 0.5h, i.e., prepared catalysis are stirred
Component solution.
Step 3：Dipping.Catalyst component solution obtained by step 2 is impregnated into the modified activated carbon of step 1, is mixed
The weight percent that solution accounts for activated carbon is 65%, mixed solution is proportionally added separately to after reaction kettle stirs evenly, quiet
Set 30min.
Step 4：It is dry.By the impregnated material obtained by step 3,4h is dried at 110 DEG C, dry SCR denitration is obtained and urges
Agent presoma.
Step 5：Calcining.Will dry SCR denitration presoma obtained by step 4 under conditions of starvation in
600℃（10 DEG C/min of heating rate）Calcine 3h.
Specific embodiment 3：
Step 1：Prepare activated carbon.Activated carbon is warming up to 450 DEG C with the rate of 7 DEG C/min in a furnace, is adopted in temperature-rise period
It is protected with N2, is warming up to 450 DEG C of constant temperature 1.5h, the mixed gas that O2 and CO2 is passed through in thermostatic process replaces N2, wherein O2 contents
It is 80% for 20% and CO2 contents.
Step 2：Prepare catalyst component.With Ce (NO3) 2.6H2O, ZrOCO3, La (NO3) 3.6H2O, Y (NO3)
3.6H2O is raw material, by said components not according to weight percent 65%：33%：0.9%：1.1% is configured to 10% mass fraction
Then the PVA solution of 30% H2O2 and 10%, addition and Ce is added in cerium-zirconium-lanthanum-yttrium mixing salt solution into mixed solution
(NO3) molar ratio of 2.6H2O is 1：1, it is settled to 1.5L after above-mentioned solution is mixed.After constant volume, 0.5h is stirred, that is, is prepared
Catalyst component solution.
Step 3：Dipping.Catalyst component solution obtained by step 2 is impregnated into the modified activated carbon of step 1, is mixed
The weight percent that solution accounts for activated carbon is 50%, mixed solution is proportionally added separately to after reaction kettle stirs evenly, quiet
Set 30min.
Step 4：It is dry.By the impregnated material obtained by step 3,2-4h is dried at 100 DEG C, obtains dry SCR denitration
Catalyst precursor.
Step 5：Calcining.Will dry SCR denitration presoma obtained by step 4 under conditions of starvation in
500℃（710 DEG C/min of heating rate）Calcine 2h.
Claims (10)
1. a kind of denitrification apparatus, which is characterized in that described device is provided with axial flow blower, air inlet pipe, denitration region, escape pipe, drum
Wind turbine, liquid ammonia evaporating device, mixer, nitrogen oxides on-line monitoring equipment；
Air inlet pipe, escape pipe with denitration region unicom, are provided with the screen frame that several columns are loaded with denitrfying agent in denitration region；Each net
Frame has been correspondingly arranged on differential pressure pickup, the pressure difference for detecting screen frame along denitrfying agent both sides on airflow direction；
Axial flow blower one end connects source exhaust gas pipe, and one end connects air inlet pipe；
Air inlet pipe inlet is provided with the grid for spraying ammonia, which is connected to liquid ammonia evaporating device by pipeline；
Liquid ammonia evaporating device includes liquefied ammonia bottle and evaporator, and the evaporator connect with liquefied ammonia bottle, liquefied ammonia by connecting pipe into
It is gasificated as ammonia after entering evaporator, ammonia is being mixed by pipeline input mixer with the air in blower exit conduits
In device grid is input to after mixing；
Air inlet pipe and an air outlet pipe is both provided with the detection port of nitrogen oxides on-line monitoring equipment.
2. denitrification apparatus as described in claim 1, which is characterized in that feeding port is arranged in each column screen frame upper end, and lower end is provided with
Discharge port.
3. denitrification apparatus as described in claim 1, which is characterized in that the denitrfying agent includes the micropore work as carrier components
Property Carbon Materials and the ZrO as active component2、CeO2And La2O3、Y2O3；Wherein, by weight percentage, CeO2Content be 1% ~
10%, ZrO2Content is 1% ~ 5%, La2O3Content is that 0.1% ~ 1%, Y2O3 contents are 0.1% ~ 1%, remaining is absorbent charcoal material.
4. denitrification apparatus as claimed in claim 3, which is characterized in that in denitrfying agent, by weight percentage, CeO2Content is
3.56% ~ 5.59%, ZrO2Content is 2.89% ~ 4.51%, La2O3Content is 0.25% ~ 0.58%, Y2O3Content is 0.28% ~ 0.61%,
Remaining is activated carbon.
5. denitrification apparatus as claimed in claim 3, which is characterized in that denitrfying agent, by weight percentage, middle ZrO2 contents are
3.52%, La2O3Content is 0.58%, Y2O3Content is 0.51%, remaining is activated carbon.
6. denitrification apparatus as claimed in claim 3, which is characterized in that the preparation method of the denitrfying agent is：
Step 1：Prepare activated carbon：Activated carbon is warming up to 350 ~ 500 DEG C in a furnace, N is used in temperature-rise period2Protection rises
Temperature to holding constant temperature after 350 ~ 500 DEG C for a period of time, is passed through O in thermostatic process2And CO2Mixed gas replace N2;
Step 2：Prepare catalyst component：With Ce (NO3)2.6H2O、ZrOCO3、La(NO3)3.6H2O、Y(NO3)3.6H2O it is raw material
It is configured to cerium-zirconium-lanthanum-yttrium mixing salt solution, H then is added into cerium-zirconium-lanthanum-yttrium mixing salt solution2O2, above-mentioned solution is mixed
It is stirred after constant volume after conjunction, i.e., prepared catalyst component solution;
Step 3：Dipping：Catalyst component solution obtained by step 2 is impregnated into mixed solution in the activated carbon obtained by step 1
It is stood after being stirred with activated carbon；
Step 4：It is dry：By the impregnated material obtained by step 3, drying obtains dry SCR denitration presoma;
Step 5：Calcining：Dry SCR denitration presoma obtained by step 4 is calcined under conditions of starvation, is obtained
To final denitrfying agent.
7. denitrification apparatus as claimed in claim 6, which is characterized in that in step 2, Ce (NO3)2.6H2O、ZrOCO3、La
(NO3)3.6H2O、Y(NO3)3.6H2The weight percent of O is 65%：33%：0.9%：1.1%.
8. denitrification apparatus as claimed in claim 6, which is characterized in that mixed solution account for activated carbon weight percent be 40% ~
65%。
9. denitrification apparatus as claimed in claim 6, which is characterized in that in step 2, into cerium-zirconium-lanthanum-yttrium mixing salt solution
It is additionally added PVA solution.
10. denitrification apparatus as claimed in claim 6, which is characterized in that in step 5, dry SCR denitration presoma
Under conditions of starvation 1 ~ 3h is calcined in 350 ~ 600 DEG C.
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