CN108579368A - A kind of solid state chemistry absorption techniques purification nitrogen oxides - Google Patents
A kind of solid state chemistry absorption techniques purification nitrogen oxides Download PDFInfo
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- CN108579368A CN108579368A CN201810203701.3A CN201810203701A CN108579368A CN 108579368 A CN108579368 A CN 108579368A CN 201810203701 A CN201810203701 A CN 201810203701A CN 108579368 A CN108579368 A CN 108579368A
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- catalyst
- solid
- hzsm
- absorbent
- divinylbenzene
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000007787 solid Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 9
- 238000000746 purification Methods 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 83
- 239000007789 gas Substances 0.000 claims abstract description 48
- 239000002250 absorbent Substances 0.000 claims abstract description 47
- 230000002745 absorbent Effects 0.000 claims abstract description 47
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 17
- 239000011949 solid catalyst Substances 0.000 claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 63
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 54
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 43
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 39
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 30
- 239000006096 absorbing agent Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 15
- 244000060011 Cocos nucifera Species 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 239000003610 charcoal Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 239000002952 polymeric resin Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- IQZPDFORWZTSKT-UHFFFAOYSA-N nitrosulphonic acid Chemical compound OS(=O)(=O)[N+]([O-])=O IQZPDFORWZTSKT-UHFFFAOYSA-N 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 230000008676 import Effects 0.000 description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 239000003546 flue gas Substances 0.000 description 11
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 alkenyl activated carbon Chemical compound 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002912 waste gas 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step 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
- B01D53/74—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
- 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
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a kind of method that solid state chemistry absorption techniques purify nitrogen oxides, the method is：Pending nitrous oxides exhaust gas is passed sequentially through into catalysis oxidation solid catalyst and chemical absorbing solid reagent, the exhaust gas after being purified；The catalysis oxidation solid catalyst is made of two or more the catalyst in carbon-supported catalysts, molecular sieve catalyst or metal oxide catalyst；The chemical absorbing solid reagent be and NO and NO2The solid absorbent that Chemisorption generates nitro compound occurs.Can be made in room temperature using this method, the NO exhaust gas of low concentration realizes high-efficient purification or even zero-emission, and it is simple for process, easy to operate, efficient, practicability is wide, the high request of current environmental protection that adapts to completely.
Description
(1) technical field
The present invention relates to technical field of air pollution control, the intermediate concentration and half that room temperature discharges, humidity is big is particularly related to
The Processing tecchnics of the low concentration of NO x exhaust gas of enclosed environment.
(2) background technology
Nitrogen oxides (the NO of power plant, chemical plant and motor vehicle exhaust emissionX) be cause atmosphere pollution primary pollution source it
One, the environmental pollution thus brought, especially photochemical pollution, acid rain, haze cause serious economic loss.With constantly
Carve the health that threaten people.Therefore, too impatient to wait to the improvement of nitrogen oxides.
Currently, in numerous denitration technologies, selective catalytic reduction (SCR) technology has efficient denitration characteristic,
Through being applied to most of power plant's denitration.But it is high (account for NOx 90% or more) for some NO contents, oxygen content is low, humidity
High (close to saturated humidity), the flue gas of normal temperature and pressure discharge, it is difficult to be handled using SCR technology.For this kind of NOx exhaust gas
It administers, industrially frequently with liquid phase scrubbing.But (sodium chlorite, sodium hypochlorite China is specially for the strong oxidizer that liquid phase scrubbing uses
Profit：CN1986033, CN1883768, CN1843574), H2O2(Chinese patent：CN102327735, CN106853328A), ozone
(Chinese patent：) and lye absorbent (Chinese patent CN19233410：CN 101259368A) it is of high cost, it is high to equipment requirement,
Enforcement difficulty is big；Simultaneously with the continuous improvement of environmental requirement, country is increasingly stringenter emission limits of nitrogen oxides, oil
Regulation discharged nitrous oxides concentration is 100mg/m in work emission of industrial pollutants standard (GB 31571-2015)3, and liquid phase is inhaled
Concentration of emission is generally in 150~300mg/m after receipts3.In addition for the low concentration of some semiclosed environment (tunnel, parking lot etc.)
(50mg/m3NOx below) is administered, and liquid phase scrubbing technique difficulty is implemented, operating difficulties.And existing technique cannot meet nitrogen oxidation
The improvement requirement of object.
For the pollution of the nitrogen oxides of low concentration in this kind of room temperature, there is an urgent need to a kind of not only economic but also practical improvement works
Skill can not only reach environment protection emission requirement or even zero-emission, contribute for Environmental Protection in China cause.
(3) invention content
The object of the present invention is to provide a kind of methods that solid state chemistry absorption techniques purify nitrogen oxides, realize low in room temperature
The efficient removal of concentration NOx exhaust gas, not only implementation easy to operate, but also current environmental requirement or even zero-emission can be met.
In order to achieve the above-mentioned object of the invention, specific technical solution of the present invention is as follows：
A kind of method of solid state chemistry absorption techniques purification nitrogen oxides, the method are：By pending nitrogen oxides
Exhaust gas passes sequentially through catalysis oxidation solid catalyst and chemical absorbing solid reagent, the exhaust gas after being purified；The catalysis
Oxidized solid catalyst by carbon-supported catalysts, molecular sieve catalyst or metal oxide catalyst two or more
Catalyst forms；The chemical absorbing solid reagent be and NO and NO2Chemisorption occurs and generates consolidating for nitro compound
Body absorbent.
Exhaust gas principle is handled in this method is：Wherein catalysis oxidation solid catalyst is import NO and O2Partial Oxidation
At NO2, form a certain proportion of NO2With NO mixed gas.Chemical absorbing solid reagent, and from catalysis oxidation solid catalyst stream
The NO and NO gone out2Chemisorption occurs, generates nitro compound, to thoroughly purify nitrogen oxides (NOx) pollutant.
Further, the catalysis oxidation solid catalyst and chemical absorbing solid reagent can be graininess, bar shaped or
Ensure other industrial catalysts needed for the normal operation of NO purifications and absorbent pattern.
Further, the carbon-supported catalysts are the activated carbon in various sources, such as polyphenyl alkenyl activated carbon, pitch-based activated
Carbon fibe and coconut shell based activated carbon etc..
Further, the molecular sieve catalyst be different silica alumina ratios or total silicon ZSM-5 molecular sieve or beta-molecular sieve,
With metal ion exchangeds HZSM-5, H such as Li, Na, K, Rb, Mg, Ca, Fe, Co, Ni, Cu, Mn beta-molecular sieve or metal oxide
Load HZSM-5, H beta-molecular sieve and some specific zeolite molecular sieves.
Further, the metal oxide catalyst includes the oxidation of the metals such as Mn, Cr, Co, Cu, Fe, Ni, Zn, Ti, Al
Object catalyst.
Further, the catalysis oxidation solid catalyst is preferably 1~50%Co2O3- HZSM-5 (described 1~50%
Co2O3- HZSM-5 is Co2O3It is Co with the composite catalyst of HZSM-5,1~50%2O3Composite catalyst gross mass percentage is accounted for,
Similarly hereinafter), 1~50%Co2O3Cocoanut active charcoal, 30~80%HZSM-5- cocoanut active charcoals or 1~20%Co2O3- 30~55%
HZSM-5- cocoanut active charcoals.
Further, the catalysis oxidation solid catalyst is more preferably 10%Co2O3- HZSM-5,10%Co2O3Coconut husk
Activated carbon, 50%HZSM-5- cocoanut active charcoals or 10%Co2O3- 45%HZSM-5- cocoanut active charcoals.
Further, the solid absorbent is two kinds of inoganic solids absorbent and organic polymer resin solid absorbent
Or the composite absorber of two kinds or more absorbents composition.
Further, the inoganic solids absorbent includes sodium hydroxide, sodium carbonate, sodium bicarbonate, calcium carbonate, hydroxide
Calcium, potassium carbonate or potassium hydroxide etc..
Further, the organic polymer resin solid absorbent includes that styrene polymer, styrene-divinylbenzene are poly-
Close the height after the functional group modifications such as the macromolecule resins such as object and divinylbenzene polymer and carboxyl, nitro, sulfonic group, amide groups
Molecule resin.
Further, the solid absorbent is preferably 10~50%Na2CO3Divinylbenzene resinoid (described 10~
50%Na2CO3Divinylbenzene resinoid is Na2CO3It is Na with the composite absorber of divinylbenzene resinoid, 10~50%2CO3
Account for composite absorber gross mass percentage, similarly hereinafter), 10%~80% phenolic resin-divinylbenzene resinoid, 10%~80%
CaO-Na2CO3Or 10~50%CaO- divinylbenzene resinoids.
Further, the solid absorbent is more preferably 30%Na2CO3Divinylbenzene resinoid, 30%CaO- bis-
Ethenylbenzene resinoid, 50%CaO-Na2CO3Or 50% phenolic resin-divinylbenzene resinoid.
The present invention can be realized by the method that gas-solid catalysis oxidation and solid phase absorb in room temperature discharge, low concentration of NO x is net
Change or even zero-emission, and it is simple for process, it is easy to operate, it is at low cost.
It is characteristic of the invention that：
1. rationally using catalytic oxidation technologies, the oxygen in exhaust gas is taken full advantage of, NO is oxidized to NO2, improve exhaust gas
The oxidizability of NOx provides basis for subsequent absorption；Meanwhile composite catalyst makes full use of the spy of each single catalyst
Determine function, realize catalyst multifunction, the NO in better catalysis oxidation exhaust gas is NO2, improve the NOX oxidation of exhaust gas
Degree；
2. removing nox contained waste gas using compound solid phase absorbents, both utilize the peculiar absorption of different absorbents special
Property, with absorbent Chemisorption, efficient removal nitrogen oxides of exhaust gas, and easy to operate, cost occur for the NOx in exhaust gas
Low, practicability is wide；
3. carrying out exhaust-gas treatment under normal temperature and pressure, energy consumption is reduced.
Effective effect of the present invention is embodied in：It can make in room temperature, the NO exhaust gas of low concentration realizes high-efficient purification or even zero-emission
It puts, and simple for process, easy to operate, efficient, practicability is wide, the high request of current environmental protection that adapts to completely.
(4) it illustrates
Fig. 1 is the flow chart of the method for the embodiment of the present invention；
(5) specific implementation mode
With reference to the present invention is described further in specific implementation, but protection scope of the present invention is not limited in
This：
Embodiment 1：
NOx exhaust gas passes through solid catalyst bed, import NO and O2Catalyzing part oxidation is at NO2, to form certain proportion
NO2With NO mixed gas, then pass through solid absorbent bed, with solid absorbent chemistry occurs for the nitrogen oxides in exhaust gas
Adsorption reaction generates nitro compound, thoroughly purifies NOx, purified gas discharge emptying.Exhaust gas NO containing 500ppm, 10%
The O of left and right2, remaining is N2.Catalyst is 10%Co2O3- HZSM-5 composite catalysts, wherein Co2O3Account for composite catalyst quality
10%, Co2O3It is uniformly mixed with HZSM-5, composite catalyst quality is 5.0g, and catalyst is graininess；Absorbent is 30%
Na2CO3- divinylbenzene resinoids, wherein Na2CO3 accounts for composite absorber quality 30%, Na2CO3It is equal with divinylbenzene resinoid
Even mixing, composite absorber quality are 5.0g, and absorbent is graininess.Gas flow is 0.6L/min, is reacted under normal temperature and pressure,
Import and export NOx concentration is tested and analyzed by flue gas analyzer (testo 340).
Embodiment 2：
Reactor and operating condition are the same as embodiment 1, exhaust gas NO containing 500ppm, 10% or so O2, remaining is N2.Catalyst
It is 10%Co2O3Cocoanut active charcoal composite catalyst, wherein Co2O3Account for composite catalyst quality 10%, Co2O3With it is coconut activated
Charcoal uniformly mixes, and composite catalyst quality is 5.0g, and catalyst is graininess；Absorbent is 30%Na2CO3Divinylbenzene class tree
Fat, wherein Na2CO3Account for composite absorber quality 30%, Na2CO3It is uniformly mixed with divinylbenzene resinoid, composite absorber matter
Amount is 5.0g, and absorbent is graininess.Gas flow is 0.6L/min, is reacted under normal temperature and pressure, and import and export NOx concentration is by cigarette
Qi leel analyzer (testo340) tests and analyzes.
Embodiment 3：
Reactor and operating condition are the same as embodiment 1, exhaust gas NO containing 500ppm, 10% or so O2, remaining is N2.Catalyst
It is 50%HZSM-5- cocoanut active charcoal composite catalysts, wherein HZSM-5 accounts for composite catalyst quality 50%, HZSM-5 and coconut husk
Activated carbon uniformly mixes, and composite catalyst quality is 5.0g, and catalyst is graininess；Absorbent is 30%Na2CO3Divinylbenzene
Resinoid, wherein Na2CO3Account for composite absorber quality 30%, Na2CO3It is uniformly mixed with divinylbenzene resinoid, composite absorption
Agent quality is 5.0g, and absorbent is graininess.Gas flow is 0.6L/min, is reacted under normal temperature and pressure, import and export NOx concentration
It is tested and analyzed by flue gas analyzer (testo 340).
Embodiment 4：
Reactor and operating condition are the same as embodiment 1, exhaust gas NO containing 500ppm, 10% or so O2, remaining is N2.Catalyst
It is 10%Co2O3- HZSM-5 composite catalysts, wherein Co2O3 account for composite catalyst quality 10%, Co2O3It is uniformly mixed with HZSM-5
It closes, composite catalyst quality is 5.0g, and catalyst is graininess；Absorbent is 30%CaO- divinylbenzene resinoids, wherein CaO
Composite absorber quality 30% is accounted for, CaO is uniformly mixed with divinylbenzene resinoid, and composite absorber quality is 5.0g, absorbent
For graininess.Gas flow is 0.6L/min, is reacted under normal temperature and pressure, and import and export NOx concentration is by flue gas analyzer (testo
340) it tests and analyzes.
Embodiment 5：
Reactor and operating condition are the same as embodiment 1, exhaust gas NO containing 500ppm, 10% or so O2, remaining is N2.Catalyst
It is 10%Co2O3- HZSM-5 composite catalysts, wherein Co2O3Account for composite catalyst quality 10%, Co2O3It is uniformly mixed with HZSM-5
It closes, composite catalyst quality is 5.0g, and catalyst is graininess；Absorbent is 50%CaO-Na2CO3, and wherein CaO accounts for compound suction
Agent quality 50% is received, CaO is uniformly mixed with Na2CO3, and composite absorber quality is 5.0g, and absorbent is graininess.Gas flow
It for 0.6L/min, is reacted under normal temperature and pressure, import and export NOx concentration is tested and analyzed by flue gas analyzer (testo 340).
Embodiment 6：
Reactor and operating condition are the same as embodiment 1, exhaust gas NO containing 500ppm, 10% or so O2, remaining is N2.Catalyst
It is 10%Co2O3- 45%HZSM-5- cocoanut active charcoal composite catalysts, wherein Co2O3Composite catalyst is accounted for respectively with HZSM-5
Quality 10% and 45%, Co2O3It is uniformly mixed with HZSM-5, composite catalyst quality is 5.0g, and catalyst is graininess；It absorbs
Agent is 30%Na2CO3Divinylbenzene resinoid, wherein Na2CO3Account for composite absorber quality 30%, Na2CO3With divinylbenzene class
Resin uniformly mixes, and composite absorber quality is 5.0g, and absorbent is graininess.Gas flow is 0.6L/min, normal temperature and pressure
Lower reaction, import and export NOx concentration are tested and analyzed by flue gas analyzer (testo 340).
Embodiment 7：
Reactor and operating condition are the same as embodiment 1, exhaust gas NO containing 500ppm, 10% or so O2, remaining is N2.Catalyst
It is 10%Co2O3- HZSM-5 composite catalysts, wherein Co2O3 account for composite catalyst quality 10%, Co2O3It is uniformly mixed with HZSM-5
It closes, composite catalyst quality is 5.0g, and catalyst is graininess；Absorbent is 50% phenolic resin-divinylbenzene resins, wherein
Phenolic resin accounts for composite absorber quality 50%, and phenolic resin is uniformly mixed with divinylbenzene resins, and composite absorber quality is
5.0g, absorbent are graininess.Gas flow is 0.6L/min, is reacted under normal temperature and pressure, and import and export NOx concentration is by flue gas point
Analyzer (testo 340) tests and analyzes.
Embodiment 8：
Reactor and operating condition are with embodiment 1, exhaust gas NO containing 500ppm, saturated steam (RH=under room temperature
100%), 10% or so O2, remaining is N2.Catalyst is 10%Co2O3- HZSM-5 composite catalysts, wherein Co2O3It accounts for compound
Catalyst quality 10%, Co2O3It is uniformly mixed with HZSM-5, composite catalyst quality is 5.0g, and catalyst is graininess；It absorbs
Agent is 30%Na2CO3Divinylbenzene resinoid, wherein Na2CO3Account for composite absorber quality 30%, Na2CO3With divinylbenzene class
Resin uniformly mixes, and composite absorber quality is 5.0g, and absorbent is graininess.Gas flow is 0.6L/min, normal temperature and pressure
Lower reaction, import and export NOx concentration are tested and analyzed by flue gas analyzer (testo 340).
Embodiment 9：
Reactor and operating condition are the same as embodiment 1, exhaust gas NO containing 10ppm, 20% or so O2, remaining is N2.Catalyst
It is 10%Co2O3Cocoanut active charcoal composite catalyst, wherein Co2O3Account for composite catalyst quality 10%, Co2O3With it is coconut activated
Charcoal uniformly mixes, and composite catalyst quality is 5.0g, and catalyst is graininess；Absorbent is 30%Na2CO3Divinylbenzene class tree
Fat, wherein Na2CO3Account for composite absorber quality 30%, Na2CO3It is uniformly mixed with divinylbenzene resinoid, composite absorber matter
Amount is 5.0g, and absorbent is graininess.Gas flow is 0.6L/min, is reacted under normal temperature and pressure, and import and export NOx concentration is by cigarette
Qi leel analyzer (testo340) tests and analyzes.
Embodiment 10：
Reactor and operating condition are with embodiment 1, exhaust gas NO containing 10ppm, saturated steam (RH=100%) under room temperature,
20% or so O2, remaining is N2.Catalyst is 10%Co2O3- HZSM-5 composite catalysts, wherein Co2O3Account for composite catalyst
Quality 10%, HZSM-5 are uniformly mixed with cocoanut active charcoal, and composite catalyst quality is 5.0g, and catalyst is graininess；It absorbs
Agent is 50%CaO-Na2CO3, wherein CaO accounts for composite absorber quality 50%, CaO and Na2CO3Uniformly mixing, composite absorber
Quality is 5.0g, and absorbent is graininess.Gas flow is 0.6L/min, is reacted under normal temperature and pressure, import and export NOx concentration by
Flue gas analyzer (testo 340) tests and analyzes.
Embodiment 11：
Reactor and operating condition are the same as embodiment 1, exhaust gas NO containing 500ppm, 10% or so O2, remaining is N2.Catalyst
It is 10%Co2O3- HZSM-5 composite catalysts, wherein Co2O3Account for composite catalyst quality 10%, Co2O3It is uniformly mixed with HZSM-5
It closes, composite catalyst quality is 5.0g, and catalyst is graininess；Absorptive unit is blank pipe.Gas flow is 0.6L/min, room temperature
It is reacted under normal pressure, import and export NOx concentration is tested and analyzed by flue gas analyzer (testo 340).
Embodiment 12：
Reactor and operating condition are the same as embodiment 1, exhaust gas NO containing 500ppm, 10% or so O2, remaining is N2.Catalysis is single
Member is blank pipe；Absorbent is 30%Na2CO3Divinylbenzene resinoid, wherein Na2CO3Composite absorber quality 30% is accounted for,
Na2CO3It is uniformly mixed with divinylbenzene resinoid, composite absorber quality is 5.0g, and absorbent is graininess.Gas flow is
0.6L/min reacts under normal temperature and pressure, and import and export NOx concentration is tested and analyzed by flue gas analyzer (testo340).
The purification efficiency effect of NOx is shown in Table 1 under each embodiment different condition.
Table 1：The purification efficiency treatment effect of NOx under different condition
Claims (7)
1. a kind of method of solid state chemistry absorption techniques purification nitrogen oxides, it is characterised in that the method is：
Pending nitrous oxides exhaust gas is passed sequentially through into catalysis oxidation solid catalyst and chemical absorbing solid reagent, is obtained net
Exhaust gas after change；The catalysis oxidation solid catalyst is by carbon-supported catalysts, molecular sieve catalyst or metal oxide oxidation catalyst
Two or more catalyst composition in agent；The chemical absorbing solid reagent be and NO and NO2Chemisorption occurs
Reaction generates the solid absorbent of nitro compound.
2. the method as described in claim 1, it is characterised in that：The solid absorbent is inoganic solids absorbent and organic
The composite absorber of macromolecule resin solid absorbent two or more absorbent composition；The inoganic solids absorbent is
Sodium hydroxide, sodium carbonate, sodium bicarbonate, calcium carbonate, calcium hydroxide, potassium carbonate or potassium hydroxide；The organic polymer resin
Solid absorbent is styrene polymer, styrene-divinylbenzene polymer, divinylbenzene polymer or carboxyl, nitro, sulfonic acid
The modified macromolecule resin of base, amido functionality.
3. method as claimed in claim 1 or 2, it is characterised in that：The carbon-supported catalysts are activated carbon；The molecule
Sieve catalyst be different silica alumina ratios or total silicon ZSM-5 molecular sieve or beta-molecular sieve, with Li, Na, K, Rb, Mg, Ca, Fe, Co,
Ni, Cu or Mn metal ion exchanged HZSM-5, H beta-molecular sieve either metal oxide supported HZSM-5, H beta-molecular sieve or zeolite
Molecular sieve；The metal oxide catalyst is Mn, Cr, Co, Cu, Fe, Ni, Zn, Ti or Al metal oxide catalyst.
4. method as claimed in claim 1 or 2, it is characterised in that：The catalysis oxidation solid catalyst is 1~50%
Co2O3- HZSM-5,1~50%Co2O3Cocoanut active charcoal, 30~80%HZSM-5- cocoanut active charcoals or 1~20%Co2O3-30
~55%HZSM-5- cocoanut active charcoals；1~the 50%Co2O3- HZSM-5 is Co2O3With the composite catalyst of HZSM-5,1~
50% is Co2O3Composite catalyst gross mass percentage is accounted for, remaining catalysis oxidation solid catalyst is identical.
5. method as claimed in claim 2, it is characterised in that：The solid absorbent is 10~50%Na2CO3Divinyl
Benzene resinoid, 10%~80% phenolic resin-divinylbenzene resinoid, 10%~80%CaO-Na2CO3Or 10~50%CaO-
Divinylbenzene resinoid；10~the 50%Na2CO3Divinylbenzene resinoid is Na2CO3It is compound with divinylbenzene resinoid
Absorbent, 10~50% be Na2CO3Composite absorber gross mass percentage is accounted for, remaining solid absorbent is identical.
6. method as claimed in claim 5, it is characterised in that：The solid absorbent is 30%Na2CO3Divinylbenzene class
Resin, 30%CaO- divinylbenzenes resinoid, 50%CaO-Na2CO3Or 50% phenolic resin-divinylbenzene resinoid.
7. method as claimed in claim 4, it is characterised in that：The catalysis oxidation solid catalyst is 10%Co2O3-HZSM-
5,10%Co2O3Cocoanut active charcoal, 50%HZSM-5- cocoanut active charcoals or 10%Co2O3- 45%HZSM-5- cocoanut active charcoals.
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Application publication date: 20180928 |