CN103961991B - A kind for the treatment of fluid for the treatment of nitrogen oxides of exhaust gas - Google Patents
A kind for the treatment of fluid for the treatment of nitrogen oxides of exhaust gas Download PDFInfo
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- CN103961991B CN103961991B CN201410195884.0A CN201410195884A CN103961991B CN 103961991 B CN103961991 B CN 103961991B CN 201410195884 A CN201410195884 A CN 201410195884A CN 103961991 B CN103961991 B CN 103961991B
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Abstract
The present invention relates to a kind for the treatment of fluid for the treatment of nitrogen oxides of exhaust gas, described treatment fluid is formulated by reactant, complex catalyst and desalted water; Described reactant is one or both the composition be selected from ammoniacal liquor or urea; Described complex catalyst be by complexing agent and transition metal salt formulated, wherein said complexing agent is selected from the composition of one or more in diethylenetriamine, triethylene tetramine, TEPA, five ethene hexamines or polymine; Wherein transition metal salt is selected from one or both the combination in cabaltous nitrate hexahydrate (II) or cobalt chloride hexahydrate (II); The concentration of described reactant in treatment fluid is: 1-20% (w%); The concentration of described complex catalyst in treatment fluid is: 1-100mmol/L.Treatment fluid for the treatment of the nitrogen oxide in waste gas of the present invention and disposal methods efficiency high, without discharging of waste liquid, secondary pollution problem can not be produced, be a kind of low input, green, efficient nitrogen oxides treatment technology, there is application value widely.
Description
Technical field
The present invention relates to a kind for the treatment of fluid for the treatment of nitrogen oxides of exhaust gas, particularly small-scale, blocking nitrous oxides exhaust gas governing problem, namely every day, waste gas output was no more than the treatment fluid of the nitrogen oxides of exhaust gas of the production unit of 500kg.
Background technology
NOx in industrial waste gas, is mainly nitrogen dioxide and nitric oxide, shows as brown color smog, be commonly called as Huanglong, can be generated as nitric acid rain after water-soluble, acid rain can bring environment and endanger widely, cause huge economic loss, as: corrosion building and industrial equipment; Destroy outdoor cultural relics and historic sites; Damage plant leaf surface, cause forest extinction; Make fishes and shrimps in lake dead; Spoiled soil composition, makes crop production reduction even dead; The underground water that drinking acid compound is polluted, harmful.
In addition, NOx, when solar ultraviolet irradiation exists with the hydrocarbon in vehicle exhaust simultaneously, can generate a kind of noxious material nitro compound azury, can form photochemical fog.Photochemical fog has very large excitant, murder by poisoning and carcinogenesis to human body.
The main source of nitrogen oxide is the waste gas such as coal-burning boiler flue gas, automobile exhaust gas, pharmaceutical factory's nitration processes waste gas, the nitrated glossing waste gas of aluminium alloy, graphite acidifying purifying technique waste gas, metal nitrate acidolysis controlling catalyst, directly be discharged in air if do not administered, serious environmental hazard can be caused.And national requirements nitrogen oxides of exhaust gas concentration must not higher than 200mg/L, so, must take measures to be administered.
The coal-burning boiler flue gases such as steam power plant are administered, and exhaust gas volumn is large, invests huge, and general employing high-temperature catalytic reducing process, the present invention does not relate to.
Vehicle exhaust generally adopts vehicle-mounted three-way catalytic apparatus process, and the present invention does not also relate to.
The present invention only relates to nitrous oxides exhaust gas governing problem on a small scale, and namely every day, waste gas output was no more than the production unit of 500kg.
Current relatively conventional processing method absorbs with caustic soda, due to nitric oxide can not separately and NaOH react, cause the discharge of nitrogen oxide to be difficult to up to standard, improvement requirement cannot be met, urgently improve.
The Lanzhou Chemistry and Physics Institute proposes and drops into the Urea treatment technique of application, there is treatment effeciency very low (50-60%), and urea consumption is large, and discharging of waste liquid amount is large, and difficult treatment, also urgently improves.
The units such as South China Science & Engineering University deliver the paper of the urea nitrogen oxides reduction of triethylenediamine cobalt catalysis, two stage treatment efficiency reaches more than 95%, the universities such as East China science and engineering also have postgraduate's thesis of chemistry similar technological design specialty to study, but because operating temperature is higher, ethylenediamine highly volatile lost efficacy, also containing the ethylenediamine certain density, there is intense stimulus, secondary ambient air pollution problem can be caused, brings difficulty to application in emission.If need the discharge reducing ethylenediamine, must cool gas.Because needs are cooled to less than 15 DEG C, not only complex process, and drop into and energy consumption will greatly increase.
The absorption technique of Nanjing chemical patent CN103331091A nitrogen oxide, propose first to add urea absorption part nitrogen dioxide with dust technology, nitrogen dioxide and nitric oxide production mixed air is absorbed again with NaOH, and this technique may be effective to the waste gas pollution control and treatment containing more than 70% nitrogen dioxide, other is then difficult to improvement up to standard.And by a large amount of urea wastewater of generation and caustic soda waste liquid, certainly lead to serious secondary pollution problem.
Summary of the invention
The present invention proposes a kind of employing first and has no irritating odor and the treatment fluid of the lower polyethylene polyamine of saturated vapor pressure and high-valence state transition metals cobalt coordination catalysis nitrogen oxides reduction and processing method, after the catalyzed reduction of nitrogen oxide handled by this method, its reduzate is nitrogen, carbon dioxide and water, and two stage treatment efficiency can reach 98%.After process, tail gas colorless and odorless, need not carry out cooling processing can directly discharge, and can greatly reduce equipment investment cost and operating cost.
For the treatment of a treatment fluid for nitrogen oxides of exhaust gas, described treatment fluid is formulated by reactant, complex catalyst and desalted water;
Described reactant is one or both the composition be selected from ammoniacal liquor or urea;
Described complex catalyst be by complexing agent and transition metal salt formulated, wherein said complexing agent is selected from the composition of one or more in diethylenetriamine, triethylene tetramine, TEPA, five ethene hexamines or polymine; Wherein transition metal salt is selected from one or both the combination in cabaltous nitrate hexahydrate (II) or cobalt chloride hexahydrate (II);
The concentration of described reactant in treatment fluid is: 1-20% (w%); The concentration of described complex catalyst in treatment fluid is: 1-100mmol/L.
Process a method for nitrogen oxides of exhaust gas, concrete preparation method is:
(1) preparation for the treatment of fluid: take reactant, complexing agent and transition metal salt according to quantity, joins in desalted water, fully stirs and makes it to dissolve and react completely;
(2) in above-mentioned treatment fluid, add (or passing into) start agent, be heated to 30-80 DEG C, constantly stir 2h; Described startup agent is one or both the composition in 18-99% oxygen or 27-35% hydrogen peroxide, starts the 1-10% that agent addition is treatment fluid weight;
(3) process of nitrogen oxide:
First the waste gas of nitrogen-containing oxide enter into reflux condenser, and the nitric acid evaporated in waste gas is condensed into liquid; Enter gas-liquid separator afterwards, the nitric acid of liquefaction is separated with nitrous oxides exhaust gas; Gas through gas-liquid separation enters bubble absorption reaction unit, and the treatment fluid prepared through step (2) in nox contained waste gas and bubble absorption reaction unit reacts, and the temperature for the treatment of fluid is 30-80 DEG C, and the flow velocity of waste gas is 1-20m
3/ min; The residual gas eventually passed in bubble absorption reaction unit after treatment fluid process enters jet pump recirculation reactor, treatment fluid (step (2) preparation) in reactor and the nitrogen oxide do not eliminated react further, the temperature for the treatment of fluid is 30-80 DEG C, and the flow velocity of waste gas is 1-20m
3/ min.Every 4 hours, supplement the constancy of volume that desalted water maintains treatment fluid.
Treatment fluid for the treatment of the nitrogen oxide in waste gas of the present invention and disposal methods efficiency high, without discharging of waste liquid, secondary pollution problem can not be produced, be a kind of low input, green, efficient nitrogen oxides treatment technology, there is application value widely.
Detailed description of the invention
Following examples, only for the present invention will be further described, are not for limiting the scope of the invention.
Material used in following embodiment, reagent, equipment etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1
Test nitrous oxides exhaust gas produces way: added by 5kg carbon steel in the mouth plastic barrel of 50% nitric acid 10kg, produces nitrogen oxide brownish red smog.On the gas treatment equipment of independent development, blower fan gas flow rate 10-20m
3/ min is adjustable, and hand-held tester display nitrous oxides concentration is 5000mg/L.Because flue gas concentration is unstable, gets peak concentration time section and test, all get new reaction raw material at every turn, prevent nitric acid from diluting and cause adverse effect.The initial reaction temperature that nitrogen oxide occurs is room temperature, and be about 20-25 DEG C, course of reaction is exothermic process.
Prepare 5 tons for the treatment of fluids, consisting of for the treatment of fluid:
15% urea, 20mmol/L TEPA close cobalt, and temperature 60 C, continuous blowing air 2h starts.
First above-mentioned nitrous oxides exhaust gas is entered into reflux condenser, the nitric acid evaporated in waste gas is condensed into liquid; Enter gas-liquid separator afterwards, the nitric acid of liquefaction is separated with nitrous oxides exhaust gas; Gas through gas-liquid separation enters bubble absorption reaction unit, and the above-mentioned treatment fluid in nox contained waste gas and bubble absorption reaction unit reacts, and the temperature for the treatment of fluid is 60 DEG C, and the flow velocity of waste gas is 15m
3/ min; The residual gas eventually passed in bubble absorption reaction unit after treatment fluid process enters jet pump recirculation reactor, and the treatment fluid in reactor and the nitrogen oxide do not eliminated react further, and the temperature for the treatment of fluid is 60 DEG C, and the flow velocity of waste gas is 15m
3/ min finally, is 175mg/L at exit on-line checkingi display nitrous oxides concentration, treatment effeciency 96.5%.Tail gas smog presents white, is air contained water, without pungent amine smell.Embodiment 2.
Prepare 5 tons for the treatment of fluids, consist of: 15% (w) urea, 30mmol/L TEPA close cobalt, heat temperature raising treatment fluid to operating temperature 58 DEG C, adding startup agent 50kg concentration is 30% hydrogen peroxide, reaction 1h.
First nitrous oxides exhaust gas obtained for embodiment 1 is entered into reflux condenser, the nitric acid evaporated in waste gas is condensed into liquid; Enter gas-liquid separator afterwards, the nitric acid of liquefaction is separated with nitrous oxides exhaust gas; Gas through gas-liquid separation enters bubble absorption reaction unit, and the above-mentioned treatment fluid in nox contained waste gas and bubble absorption reaction unit reacts, and the temperature for the treatment of fluid is 58 DEG C, and the flow velocity of waste gas is 18m
3/ min; The residual gas eventually passed in bubble absorption reaction unit after treatment fluid process enters jet pump recirculation reactor, and the treatment fluid in reactor and the nitrogen oxide do not eliminated react further, and the temperature for the treatment of fluid is 58 DEG C, and the flow velocity of waste gas is 18m
3/ min finally, is 97mg/L at exit on-line checkingi display nitrous oxides concentration, treatment effeciency 98.06%.Tail gas smog presents white, is air contained water, without pungent amine smell.
Embodiment 3.
Run 12h continuously by embodiment 2, every 4 hours, supplement the constancy of volume that desalted water maintains treatment fluid.Outlet on-line checkingi concentration is 99mg/L, treatment effeciency 98.02%.
Claims (1)
1. process a method for nitrogen oxides of exhaust gas, it is characterized in that concrete preparation method is:
(1) preparation for the treatment of fluid: take reactant, complexing agent and transition metal salt according to quantity, joins in desalted water, fully stirs and makes it to dissolve and react completely;
(2) in above-mentioned treatment fluid, add (or passing into) start agent, be heated to 30-80 DEG C, constantly stir 2h; Described startup agent is one or both the composition in 18-99% oxygen or 27-35% hydrogen peroxide, starts the 1-10% that agent addition is treatment fluid weight;
(3) process of nitrogen oxide:
First the waste gas of nitrogen-containing oxide enter into reflux condenser, and the nitric acid evaporated in waste gas is condensed into liquid; Enter gas-liquid separator afterwards, the nitric acid of liquefaction is separated with nitrous oxides exhaust gas; Gas through gas-liquid separation enters bubble absorption reaction unit, and the treatment fluid prepared through step (2) in nox contained waste gas and bubble absorption reaction unit reacts, and the temperature for the treatment of fluid is 30-80 DEG C, and the flow velocity of waste gas is 1-20m
3/ min, every 4 hours, supplements the constancy of volume that desalted water maintains treatment fluid; The residual gas eventually passed in bubble absorption reaction unit after treatment fluid process enters jet pump recirculation reactor, treatment fluid prepared by the step (2) in reactor reacts further with the nitrogen oxide do not eliminated, the temperature for the treatment of fluid is 30-80 DEG C, and the flow velocity of waste gas is 1-20m
3/ min;
Described reactant is one or both the composition be selected from ammoniacal liquor or urea;
Described complex catalyst be by complexing agent and transition metal salt formulated, wherein said complexing agent is selected from the composition of one or more in diethylenetriamine, triethylene tetramine, TEPA, five ethene hexamines or polymine; Wherein transition metal salt is selected from one or both the combination in cabaltous nitrate hexahydrate (II) or cobalt chloride hexahydrate (II);
The concentration of described reactant in treatment fluid is: 1-20% (wt%); The concentration of described complex catalyst in treatment fluid is: 1-100mmol/L.
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| CN201410195884.0A CN103961991B (en) | 2014-05-01 | 2014-05-01 | A kind for the treatment of fluid for the treatment of nitrogen oxides of exhaust gas |
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| CN201410195884.0A CN103961991B (en) | 2014-05-01 | 2014-05-01 | A kind for the treatment of fluid for the treatment of nitrogen oxides of exhaust gas |
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| CN103961991B true CN103961991B (en) | 2016-04-27 |
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| CN107261805B (en) * | 2017-08-22 | 2020-10-02 | 周凯 | Hydrazine solution special for chimney flue gas desulfurization and denitrification and preparation method thereof |
| EP3549661A1 (en) * | 2018-04-06 | 2019-10-09 | Yara International ASA | Nox removal from gaseous effluents |
| CN110433657A (en) * | 2019-07-06 | 2019-11-12 | 新三和石化(福建)股份公司 | A kind of diesel engine vent gas minimum discharge liquid and preparation method thereof |
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