CN105617857B - A kind of PH3The low-temperature catalyzed reduction NO of selectivity method - Google Patents

A kind of PH3The low-temperature catalyzed reduction NO of selectivity method Download PDF

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CN105617857B
CN105617857B CN201610001895.XA CN201610001895A CN105617857B CN 105617857 B CN105617857 B CN 105617857B CN 201610001895 A CN201610001895 A CN 201610001895A CN 105617857 B CN105617857 B CN 105617857B
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nitrate
reduction
low
gas
selectivity
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CN105617857A (en
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宁平
张秋林
宋忠贤
王学谦
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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    • 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
    • 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
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • 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
    • 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 invention discloses a kind of PH3The low-temperature catalyzed reduction NO of selectivity method, this method is with PH3For reducing agent, the Reduction of NO under absorbent charcoal based catalyst existence condition；After reaction in tail gas NO clearance up to more than 60%；The inventive method is simple, cost is low, meets the operating mode of practical application；Solves NH3NH in SCR3The problem of being not easy to transport；This method can be directly used for the other enterprise's denitrations in phosphorous chemical industry enterprise industrial zone so that pollutant phosphine gas can be utilized, and be turned waste into wealth, and reach recycling；Reaction temperature is less than conventional treatment method, saves the energy；Avoid striving the situation of grain with agricultural caused by consuming liquefied ammonia or urea excessively.

Description

A kind of PH3The low-temperature catalyzed reduction NO of selectivity method
Technical field
The present invention relates to atmosphere pollution purification techniques field, specifically a kind of PH3The low-temperature catalyzed reduction NO of selectivity Method.
Background technology
Nitrogen oxides（Wherein NO accounts for more than 90%）It is one of main atmosphere pollution.It can cause photochemical fog and The destruction of ozone layer, or a PM2.5 important precursor source is formed, seriously endanger the health of the mankind.Therefore, remove NO x Have become important topic in field of Environment Protection.
The NO removed at present x Effective technology is NH3Selective Catalytic Reduction of NO（NH3-SCR）Technology.But the technology will Substantial amounts of NH can be consumed3.And liquefied ammonia or urea are the important components of agrochemical, excessive consumption urea or ammonia will cause Agrochemical yield reduction, causes agricultural output to decline.Liquefied ammonia or urea production and NO are synthesized according to China's year x Growing amount comes Calculate, the whole nation removes NO x Can consume 10% year production ammonium salt, will so be formed and strive the situation of grain with agricultural.In NH3- In SCR system, the general NH for adding equivalent or excess3, cause NH3Directly escape into air, bring secondary pollution.And Ammonium salt/nitrous acid ammonium salt can be generated in the reaction, does not only result in catalyst inactivation, it is also possible to explodes, causes safety Hidden danger.In addition, ammonia transport inconvenience, easily causes potential safety hazard.Therefore, new removal NO is developed x Technical method be gesture must OK.
Hydrogen phosphide（PH3）It can be prepared by elemental phosphorous with high alkali liquid, utilize PH3Instead of NH3, Selective Catalytic Reduction of NO is A kind of practicable method.Document report is had not yet to see, this method is simple and easy, has the prospect of commercial Application.
The content of the invention
It is an object of the invention to provide a kind of PH3The low-temperature catalyzed reduction NO of selectivity method, utilizes PH3Gas is gone back Originality, with PH3For reducing agent, the Reduction of NO under absorbent charcoal based catalyst existence condition, this method investment, operating cost It is low, it is easy to industrial applications.
50-120 DEG C of the reaction temperature of the inventive method catalysis reduction, the flue gas containing NO after desulfurizing tower desulfurization can be with Directly utilize PH3Gas and catalyst reduction NO, or using plant gas waste heat entering again after need to handling flue gas Row catalysis reduction.
The concentration range of the NO is 100-600 ppm, PH3It is 0.6-1.2 with NO concentration ratios.
The reaction equation of this method is.
The absorbent charcoal based catalyst is placed in activated carbon in the nitrate solution that concentration is 0.01-5 mol/L, At 60-70 DEG C after ultrasonic 2-8 h, baking 8-24 h at 105 DEG C are placed in, 3-5 h are finally calcined at 300-450 DEG C is made；Wherein Nitrate is cobalt nitrate, manganese nitrate, one or more of mixed in ferric nitrate, cerous nitrate, copper nitrate, zirconium nitrate, nickel nitrate, lanthanum nitrate Compound.
The present invention is for problem present in above-mentioned treatment technology, using PH3The low-temperature catalyzed reduction NO methods of selectivity are gone Except NO, and NO clearances provide a simple and easy approach up to more than 60% for industrial waste gas purifying NO.
Remaining PH after reaction3Phosphoric acid can be prepared by prior art purification, accomplish to turn waste into wealth, do not produce secondary dirt Dye, as used method in patent CN101318124A, CN1345619A and CN1398658A.
Caused P in reaction2O5Phosphoric acid can be prepared by related art method, such as with reference to patent CN101732962A and Method in CN101690866A.
Compared to the prior art, the present invention has the following advantages：
1st, method is simple, cost is low, meets the operating mode of practical application；
2nd, solves NH3NH in-SCR3The problem of being not easy to transport；
3rd, this method can be directly used for the other enterprise's denitrations in phosphorous chemical industry enterprise industrial zone so that pollutant phosphine gas It can be utilized, turn waste into wealth, reach recycling；
4th, reaction temperature is less than conventional treatment method, the energy is saved, in NH3In-SCR systems, reaction temperature is generally 300-400 DEG C, the substantial amounts of energy need to be consumed to maintain pyroreaction, cause operating cost to increase；This method is not required to additionally consume The energy, and to reacted product（PH3And P2O5）It can also be reclaimed, prepare phosphoric acid；
5th, avoid striving the situation of grain with agricultural caused by consuming liquefied ammonia or urea excessively.
Brief description of the drawings
Fig. 1 is one-level denitrification apparatus NO removal efficiency result schematic diagrams of the present invention；
Fig. 2 is one-level denitrification apparatus NO removal efficiency result schematic diagrams of the present invention；
Fig. 3 is one-level denitrification apparatus NO removal efficiency result schematic diagrams of the present invention；
Fig. 4 is two level denitrification apparatus NO removal efficiency result schematic diagrams of the present invention；
Fig. 5 is one-level denitrification apparatus NO removal efficiency result schematic diagrams of the present invention；
Fig. 6 is one-level denitrification apparatus NO removal efficiency result schematic diagrams of the present invention；
Fig. 7 is the method flow schematic diagram of the embodiment of the present invention 6；
Fig. 8 is the method flow schematic diagram of the embodiment of the present invention 7.
Specific embodiment
The present invention is described in further detail below by drawings and examples, but the scope of the present invention is not limited to The content.
Embodiment 1：This PH3The low-temperature catalyzed reduction NO of selectivity method, particular content are as follows：
In view of being actually needed, into denitrification apparatus before the EGT containing NO be generally 60-80 DEG C, laboratory simulation contains 100 ppm NO flue gas, while press NO and PH3Concentration ratio is 1 addition PH3Gas, 5% oxygen, N2As Balance Air, with PH3 For reducing agent, the Reduction of NO on absorbent charcoal based catalyst, wherein absorbent charcoal based catalyst are that activated carbon is placed in into concentration to be 0.1 mol/L nitrate solution（Cobalt nitrate and nickel nitrate in mass ratio 1:1 mixing）In, at 60 DEG C after 5 h of ultrasound, it is placed in 15 h are dried at 105 DEG C, 5 h are finally calcined at 300 DEG C and are made；NO clearance such as table 1：
Table 1
。
Embodiment 2：This PH3The low-temperature catalyzed reduction NO of selectivity method, particular content are as follows：
In view of being actually needed, into denitrification apparatus before the EGT containing NO be generally 60-80 DEG C, laboratory simulation contains 600 ppm NO flue gas, while press NO and PH3Concentration ratio is 0.6 addition PH3Gas, 2% oxygen, N2As Balance Air, with PH3For reducing agent, the Reduction of NO on absorbent charcoal based catalyst, wherein absorbent charcoal based catalyst are that activated carbon is placed in into concentration For 0.4 mol/L nitrate（Ferric nitrate and copper nitrate in mass ratio 3:1 mixing）In solution, at 60 DEG C after 8 h of ultrasound, put 20 h are dried at 105 DEG C, 4 h are finally calcined at 350 DEG C and are made；NO clearance such as table 2：
Table 2
Embodiment 3：This PH3The low-temperature catalyzed reduction NO of selectivity method, particular content are as follows：
In view of being actually needed, into denitrification apparatus before the EGT containing NO be generally 60-80 DEG C, laboratory simulation contains 400 ppm NO flue gas, while press NO and PH3Concentration ratio is 1.2 addition PH3Gas, 10% oxygen, N2As Balance Air, with PH3For reducing agent, the Reduction of NO on absorbent charcoal based catalyst, wherein absorbent charcoal based catalyst are that activated carbon is placed in into concentration For 1 mol/L nitrate（Zirconium nitrate and copper nitrate in mass ratio 2:1 mixing）In solution, at 65 DEG C after 3 h of ultrasound, it is placed in 24 h are dried at 105 DEG C, 4 h are finally calcined at 400 DEG C and are made, NO clearance is shown in Fig. 1.
Embodiment 4：This PH3The low-temperature catalyzed reduction NO of selectivity method, particular content are as follows：
In view of being actually needed, into denitrification apparatus before the EGT containing NO be generally 60-80 DEG C, laboratory simulation contains 400 ppm NO flue gas, while press NO and PH3Concentration ratio is 1.2 addition PH3Gas, 5% oxygen, N2As Balance Air, with PH3For reducing agent, the Reduction of NO on absorbent charcoal based catalyst, wherein absorbent charcoal based catalyst are that activated carbon is placed in into concentration For 3 mol/L nitrate solution（Manganese nitrate and ferric nitrate in mass ratio 1:2 ratio mixing）In, 2 h of ultrasound at 70 DEG C Afterwards, it is placed at 105 DEG C and dries 8 h, 3 h is finally calcined at 450 DEG C and are made；When flue-gas temperature is 80 DEG C, NO clearance is reachable 53%（See Fig. 2）.
Embodiment 5：This PH3The low-temperature catalyzed reduction NO of selectivity method, particular content are as follows：
In view of being actually needed, into denitrification apparatus before the EGT containing NO be generally 60-80 DEG C, laboratory simulation contains 500 ppm NO flue gas, while press NO and PH3Concentration ratio is 0.8 addition PH3Gas, 1% oxygen, N2As Balance Air, with PH3For reducing agent, the Reduction of NO on absorbent charcoal based catalyst, wherein absorbent charcoal based catalyst are that activated carbon is placed in into concentration For 4 mol/L nitrate solution（Nickel nitrate and lanthanum nitrate in mass ratio 2:1 ratio mixing）In, 8 h of ultrasound at 60 DEG C Afterwards, it is placed at 105 DEG C and dries 15 h, 5h is finally calcined at 400 DEG C is made；When flue-gas temperature is 80 DEG C, NO clearance is reachable 51%（See Fig. 3）.
Embodiment 6：This PH3The low-temperature catalyzed reduction NO of selectivity method, particular content are as follows：
Laboratory simulation contains 300 ppm NO flue gas, while presses NO and PH3Concentration ratio is 0.7 addition PH3Gas, 10% Oxygen, N2As Balance Air, with PH3For reducing agent, the catalysis of the Reduction of NO on absorbent charcoal based catalyst, wherein activated carbon base Agent is that activated carbon is placed in into the nitrate solution that concentration is 1 mol/L（Nickel nitrate, lanthanum nitrate, copper nitrate in mass ratio 1:1:1 Ratio mixes）In, at 60 DEG C after ultrasonic 8h, it is placed at 105 DEG C and dries 10 h, 5 h is finally calcined at 350 DEG C and are made.Through de- After nitre device, a small amount of PH is still contained in flue gas3With NO gases, then to PH3Tail gas is purified, the tail containing NO after processing Gas is re-added in denitrification apparatus, and so, gas completes the removal to NO during a closed waste gas purification, does not produce Raw secondary pollution, flow chart are shown in Fig. 7, NO clearance such as table 3：
Table 3
Embodiment 7
Laboratory simulation contains 400 ppm NO flue gas, while presses NO and PH3Concentration ratio is 0.9 addition PH3Gas, 5% Oxygen, N2As Balance Air, with PH3For reducing agent, the catalysis of the Reduction of NO on absorbent charcoal based catalyst, wherein activated carbon base Agent is that activated carbon is placed in into the nitrate solution that concentration is 2 mol/L（Manganese nitrate, ferric nitrate, cerous nitrate in mass ratio 1:1:1 Ratio mixes）In, at 60 DEG C after 8 h of ultrasound, it is placed at 105 DEG C and dries 10 h, 5 h are finally calcined at 350 DEG C and are made；Reaction Temperature is 70 DEG C, and after one-level denitrification apparatus, part PH is still contained in flue gas3With NO gases, then these gases are passed through two level Denitrification apparatus, NO clearances still contain part PH up to 75% in gas3（As shown in Fig. 4,8）.Again to PH3Purified treatment system Standby phosphoric acid, the tail gas after processing can enter a purification process.
Embodiment 8
Laboratory simulation contains 400 ppm NO flue gas, while presses NO and PH3Concentration ratio concentration ratio is 1 addition PH3Gas, 5% oxygen, N2As Balance Air, with PH3For reducing agent, Reduction of NO, wherein activated carbon base are urged on absorbent charcoal based catalyst Agent is that activated carbon is placed in into the nitrate solution that concentration is 2mol/L（Nickel nitrate and cobalt nitrate in mass ratio 2:1 ratio is mixed Close）In, at 60 DEG C after 8 h of ultrasound, it is placed at 105 DEG C and dries 15 h, 5 h are finally calcined at 400 DEG C and are made；Work as flue-gas temperature For 50 DEG C, the reaction time is 180 min, and NO clearance is shown in Fig. 5.
Embodiment 9
Laboratory simulation contains 400 ppm NO flue gas, while presses NO and PH3Concentration ratio concentration ratio is addition PH3Gas, 5% Oxygen, N2As Balance Air, with PH3For reducing agent, Reduction of NO, wherein activated carbon base are catalyzed on absorbent charcoal based catalyst Agent is that activated carbon is placed in into the nitrate solution that concentration is 1 mol/L（Nickel nitrate, cobalt nitrate and ferric nitrate in mass ratio 1:1:1 Ratio mixing）In, at 60 DEG C after 8 h of ultrasound, it is placed at 105 DEG C and dries 15 h, 5 h are finally calcined at 400 DEG C and are made；When Flue-gas temperature is 120 DEG C, and the reaction time is 180 min, and NO clearance is shown in Fig. 6.

Claims (1)

  1. A kind of 1. PH3The low-temperature catalyzed reduction NO of selectivity method, it is characterised in that：With PH3For reducing agent, urged in activated carbon base Reduction of NO under agent existence condition；
    The concentration of the NO is 100-600 ppm, NO and PH3Concentration ratio is 0.6-1.2；It is catalyzed the reaction temperature 50-120 of reduction ℃；
    The absorbent charcoal based catalyst is placed in activated carbon in the nitrate solution that concentration is 0.01-5 mol/L, in 60-70 At DEG C after ultrasonic 2-8 h, baking 8-24 h at 105 DEG C are placed in, 3-5 h are finally calcined at 300-450 DEG C is made；Wherein nitrate For cobalt nitrate, manganese nitrate, one or more of mixtures in ferric nitrate, cerous nitrate, copper nitrate, zirconium nitrate, nickel nitrate, lanthanum nitrate.
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