CN101053769A - Low-temperature catalytic treating method and device for chemical nitrile action technology waste gas - Google Patents
Low-temperature catalytic treating method and device for chemical nitrile action technology waste gas Download PDFInfo
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- CN101053769A CN101053769A CNA2007100373172A CN200710037317A CN101053769A CN 101053769 A CN101053769 A CN 101053769A CN A2007100373172 A CNA2007100373172 A CN A2007100373172A CN 200710037317 A CN200710037317 A CN 200710037317A CN 101053769 A CN101053769 A CN 101053769A
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Abstract
The invention relates to a low-temperature catalytic treatment method for the exhaust gas of chemical cyanation process and a device thereof. Mn3O4 alveolate oxidation catalyst using Gamma-Al2O3 as a carrier is prepared, and filled into the electric heating catalytic reduction tube of the treatment device, which uses a vertical structure that the electric heating chamber and the catalytic reduction chamber are integrative, and the reaction temperature and time are controlled using the manner of two-stage electric heating catalytic oxidation to absorb the ammonia gas and organic gas in the exhaust gas on the alveolate Gamma-Al2O carrier, and then the ammonia gas and organic gas catalytic oxidation reacts with oxygen in the exhaust gas to produce ammonia in the function of Mn3O4 catalyze medium carried in the carrier to deprive ammonia gas and volatile organic substance effectively. The invention, using the principle of absorption-catalytic oxidation-desorption, has a low reacting temperature and is safe and reliable. The invention is used in treatment for the large discharge of cyanation exhaust gas without secondary pollution at the same time.
Description
Technical field
The present invention relates to a kind of low-temperature catalytic treating method and device of chemical nitrile action technology waste gas.Preparation is with γ-Al
2O
3Mn as carrier
3O
4Cellular oxidation catalyst, ammonia and organic gas in the waste gas that produces in the absorption chemical nitrile action technology, and make it to be converted into CO through catalytic oxidation
2, O
2And N
2, reach the effect of exhaust-gas treatment.
Background technology
In chemical industry nitrilation process, can discharge a large amount of hypertoxic gas that ammonia, meta-xylene etc. have overpowering odor that contains.These gases have corrosion and spread effect to the skin histology of contact, can absorb the moisture in the skin histology, make the histone sex change, and make the tissue fat saponification, destroy membrane structure.The upper respiratory tract to animal or human's body has stimulation and corrosiveness, weakens the resistance of human body to disease.Except corrosiveness, also can cause by the reflex of trigeminal neuralgia tip cardiac arrest and breath stopped during excessive concentration.Enter blood by alveolar easily after being inhaled into lung, be combined with hemoglobin, destroy fortune oxygen function.Suck in a short time can occur shedding tears behind a large amount of ammonias, pharyngalgia, hoarseness, cough, sputum streaked with blood silk, uncomfortable in chest, expiratory dyspnea, can be with dizzy, headache, feel sick, vomiting, weak etc., pulmonary edema, ARDS can take place in severe patient, simultaneously the respiratory tract symptom may take place.
In addition, these gases have special smell when low concentration, and people are included into the ranks of foul gas with them, and people's sense organ is extremely responsive to it, and the low person of odor threshold can reach 0.0001mg/m
3, as long as a small amount of this class material of discharging or leakage just can in very large range cause odor pollution.China formally issued " odorant pollutant discharge standard " (GB14554-1993) in 1993, and had formally issued " discharge standard of air pollutants " (GB16297-1996) in 1996, had stipulated discharge index.
The development experience of ammonia-contaminated gas Prevention Technique a process, namely progressively develop into microbial method, active carbon adsorption of today etc. from initial washing spray process.Common processing method has: methods such as washing spray, soup cleaning, microorganism, active carbon.The washing spray process is actually the transfer of pollutant, and the pollutant that elutes still needs further processing; Soup ablution treatment effect is good, but the cost height, causes secondary pollution easily; Active carbon adsorption faces the problem of processing cost and secondary pollution equally; Although microbial method safety but treating capacity is little, the sludge quantity that produces is big.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of low-temperature catalytic treating method and device of chemical nitrile action technology waste gas are provided, develop high performance catalysis material, adopt catalysed oxidation processes, organic matter and ammonia in poisonous, the inflammable chemical industry nitrilation waste gas are carried out harmless treatment, economical, safety, effective can't cause secondary pollution to environment.
For realizing such purpose, the present invention launches research from the angle of design, catalytic performance raising and the practical application of catalysis material, according to the thermokinetics and the engineering characteristic that pollute control and catalyst combustion reaction and process, and preparation employing γ-Al
2O
3Mn as carrier
3O
4Cellular oxidation catalyst, and it is filled in the electrical heating catalytic oxidation pipe for the treatment of apparatus, adopt secondary electrical heating catalytic oxidation mode, control reaction temperature and time, make ammonia and organic gas in the waste gas at first be adsorbed on cellular γ-Al
2O
3On the carrier, and then the Mn of load on carrier
3O
4Under the catalytic action with waste gas in oxygen generation catalytic oxidation, effectively remove ammonia, volatile organic matter class material.
The low-temperature catalyzed treating apparatus of the chemical nitrile action technology waste gas of the present invention's design, comprise heat exchanger, two-stage electrical heating catalytic oxidation pipe, the two-stage electric-heating control system, stepless time adjustment blower fan and escape pipe, it is the vertical structure of one that two-stage electrical heating catalytic oxidation pipe adopts electrical heating chamber and catalytic oxidation chamber, the internal channel import of heat exchanger connects the air inlet flowmeter, the internal channel outlet of heat exchanger connects the bottom of one-level electrical heating catalytic oxidation pipe, the top of one-level electrical heating catalytic oxidation pipe connects the bottom of secondary electrical heating catalytic oxidation pipe, the outlet of one-level electrical heating catalytic oxidation pipe and secondary electrical heating catalytic oxidation pipe is connected with the outer tunnel import of heat exchanger simultaneously, one-level electrical heating catalytic oxidation pipe adopts thin metallic tubd, the casing pack oxidation catalyst also is provided with one-level electric heating system thermometer, and the thin metallic tubd of one-level electrical heating catalytic oxidation pipe and thermometer connect the one-level electric-heating control system; Secondary electrical heating catalytic oxidation pipe adopts thin metallic tubd, and the casing pack oxidation catalyst also is provided with secondary electric heating system thermometer, and the thin metallic tubd of secondary electrical heating catalytic oxidation pipe and thermometer connect the secondary electric-heating control system; The outer tunnel outlet of heat exchanger is connected to escape pipe through the stepless time adjustment blower fan, before the stepless time adjustment blower fan pressure gauge is set.
In apparatus of the present invention when work, start the switch of electrical heating catalytic oxidation pipe, the catalyst in the catalytic oxidation pipe heated gradually and it is controlled at the temperature (180-220 ℃) of catalytic oxidation.Off-gas flows cools off naturally by heat exchanger, and the temperature of air inlet is improved, and is that harmless water, nitrogen and carbon dioxide makes waste gas purification at this waste gas by catalyst oxidation.Produce a large amount of heat after the exhaust fume catalytic oxidation, this part heat energy can reduce electrically heated energy consumption.Purified gas is discharged by the gas outlet.The adsorption process of whole device adopts negative-pressure operation, can avoid organic exhaust gas overflowing at operation room.
Catalyst of the present invention adopts γ-Al
2O
3As carrier, by Mn
3O
4Powder mixes in preparation process by a certain percentage and gets.Catalyst is filled in the electrical heating catalytic oxidation pipe for the treatment of apparatus, adopts secondary electrical heating catalytic oxidation mode, can effectively carry out exhaust-gas treatment.
The low-temperature catalytic treating method of chemical nitrile action technology waste gas of the present invention is specific as follows:
1, the preparation of catalyst: get Al
2O
3, Na (OH) is immersed in the distilled water simultaneously, wherein the Na/Al mol ratio is 1.1-1.2, fully stirs and keep reaction temperature at 65-70 ℃, reacts after 1 hour and places 24 hours in room temperature (10-30 ℃), makes solution produce precipitation; To use the ammonia scrubbing of mass concentration 0.1-0.5% after the above-mentioned sediment vacuum filtration, use then the nitric acid dissolve of mass concentration 0.5-5%, nitric acid dosage and sedimentary mass ratio 3-6: 1, obtain suspension; Add NaOH in suspension, regulator solution pH value is 9-10; Mass ratio is accounted for the Mn of the 1-3% of suspension
3O
4Powder adds above-mentioned suspension, filters immediately after fully mixing, and descends dry 12-24 hour at 70-105 ℃ then, be warming up to 350-360 ℃ of dry 1-2 hour, 600-650 ℃ dry 2-3 hour, naturally cool to then room temperature (10-30 ℃), obtain with honeycomb γ-Al
2O
3Mn as carrier
3O
4Oxidation catalyst, be used for to fill the electrical heating catalytic oxidation pipe that the chemical nitrile action emission-control equipment adopts.
2, low-temperature catalyzed processing chemical nitrile action waste gas: with the two-stage electrical heating catalytic oxidation pipe in the above-mentioned oxidation catalyst filling emission-control equipment for preparing; The volume ratio of oxygen content is introduced treating apparatus greater than 9% chemical nitrile action waste gas, at first arrive 100-150 ℃ through heat exchanger heats, enter then one-level electrical heating catalytic oxidation pipe, further be heated to 180-220 ℃ by the built-in electric heater unit of one-level electrical heating catalytic oxidation pipe, make ammonia and organic gas in the waste gas be adsorbed on cellular γ-Al
2O
3On the carrier, and the Mn of load on carrier
3O
4Under the catalytic action with waste gas in oxygen generation catalytic oxidation, waste gas enters secondary electrical heating catalytic oxidation pipe then; In secondary electrical heating catalytic oxidation pipe, make that unreacted ammonia and organic gas are adsorbed on cellular γ-Al in the waste gas
2O
3On the carrier; And the Mn of load on carrier
3O
4Under the catalytic action with waste gas in oxygen generation catalytic oxidation, EGT reaches 300-400 ℃ because of exothermic heat of reaction; Then waste gas is introduced heat exchanger, carry out heat exchange with import waste gas after temperature be reduced to below 100 ℃, directly emptying through escape pipe.
The present invention has significant technique effect.Catalytic activity height, Heat stability is good and the anti-sintering of the catalysis material of preparation, the difficult poisoning; Cellular γ-Al
2O
3Catalyst carrier has good dynamic performance, has overcome the big shortcoming of particle catalyst carrier bed resistance alive; Method adopts absorption-catalytic oxidation-desorption principle, and reaction temperature is low, and is safe and reliable, and efficient energy-saving is particularly suitable for the improvement of the nitrilation waste gas of big flow, Variable Composition, many components.Emission-control equipment compact conformation of the present invention, layering does not take place in long-time continuous operation Catalytic Layer; Simultaneously pollutant is handled thoroughly, all can be reached more than 90%, can not form secondary pollution simultaneously environment for the clearance that removes ammonia, volatile organic matter class material.
Description of drawings
Fig. 1 is the structural representation of emission-control equipment of the present invention.
Among Fig. 1,1 is the air inlet flowmeter, and 2 is heat exchanger, and 3 is one-level electrical heating catalytic oxidation pipe, 4 is the one-level electric-heating control system, 5 is one-level electric heating system thermometer, and 6 is secondary electrical heating catalytic oxidation pipe, and 7 is the secondary electric-heating control system, 8 is secondary electric heating system thermometer, 9 is the pressure gauge of heat exchanger outlet, and 10 are the stepless time adjustment blower fan, and 11 is escape pipe.
The specific embodiment
Below in conjunction with accompanying drawing technical scheme of the present invention is further described.
The low-temperature catalyzed treating apparatus of the chemical nitrile action technology waste gas that the present invention adopts mainly is made up of two-stage electrical heating catalytic oxidation pipe and two cover electric-heating control systems, and wherein two-stage electrical heating catalytic oxidation pipe adopts the vertical structure that electrical heating chamber and catalytic oxidation chamber are integrated.Fig. 1 is the structural representation of emission-control equipment of the present invention.As shown in Figure 1, emission-control equipment is by air inlet flowmeter 1, heat exchanger 2, one-level electrical heating catalytic oxidation pipe 3, one-level electric-heating control system 4, one-level electric heating system thermometer 5, secondary electrical heating catalytic oxidation pipe 6, secondary electric-heating control system 7, secondary electric heating system thermometer 8, the pressure gauge 9 of heat exchanger outlet, stepless time adjustment blower fan 10, escape pipe 11 are formed.
The internal channel import of heat exchanger 2 connects air inlet flowmeter 1, the internal channel outlet of heat exchanger 2 connects the bottom of one-level electrical heating catalytic oxidation pipe 3, the top of one-level electrical heating catalytic oxidation pipe 3 connects the bottom of secondary electrical heating catalytic oxidation pipe 6, and the outlet of one-level electrical heating catalytic oxidation pipe 3 and secondary electrical heating catalytic oxidation pipe 6 is connected with the outer tunnel import of heat exchanger 2 simultaneously.One-level electrical heating catalytic oxidation pipe 3 adopts thin metallic tubd, and the casing pack oxidation catalyst also is provided with one-level electric heating system thermometer 5, and the thin metallic tubd of one-level electrical heating catalytic oxidation pipe 3 and thermometer 5 connect one-level electric-heating control system 4.Secondary electrical heating catalytic oxidation pipe 6 has the structure identical with one-level electrical heating catalytic oxidation pipe 3, be that secondary electrical heating catalytic oxidation pipe 6 adopts thin metallic tubd, the casing pack oxidation catalyst also is provided with secondary electric heating system thermometer 8, and the thin metallic tubd of secondary electrical heating catalytic oxidation pipe 6 and thermometer 8 connect secondary electric-heating control system 7.The outer tunnel outlet of heat exchanger 2 is connected to escape pipe 11 through stepless time adjustment blower fan 10, and pressure gauge 9 is set before stepless time adjustment blower fan 10.
Electric-heating control system 4 of the present invention and 7 is controlled respectively one-level electrical heating catalytic oxidation pipe 3 and the 6 electrically heated unlatchings of secondary electrical heating catalytic oxidation pipe.
The workflow of apparatus of the present invention is as follows:
Start the switch of electrical heating catalytic oxidation pipe, the catalyst in the catalytic oxidation pipe reactor is heated gradually and it is controlled at the temperature (180-220 ℃) of catalytic oxidation.Off-gas flows cools off naturally by heat exchanger 2, and the temperature of air inlet is improved, and is that harmless water, nitrogen and carbon dioxide makes waste gas purification at this waste gas by catalyst oxidation.The rotating speed of stepless time adjustment blower fan 10 is regulated according to the indication of heat exchanger outlet pressure gauge 9, guarantees little negative pressure in the treatment system with this.Produce a large amount of heat after the exhaust fume catalytic oxidation, this part heat energy can reduce electrically heated energy consumption.Purified gas is discharged by escape pipe 11.
Catalyst of the present invention adopts γ-Al
2O
3As carrier, by Mn
3O
4Powder mixes in preparation process by a certain percentage and gets.At first get Al
2O
3, Na (OH) pours in the distilled water and reacts, and is dissolved in after the sediment vacuum filtration of leaving standstill after will reacting then, the washing in 0.7% the nitric acid, adds NaOH regulator solution pH value, adds Mn again
3O
4The mixture of powder filters honeycomb processed then, naturally cools to room temperature and obtain required catalyst after three intensification dryings.This catalyst has the K cryogenic treatment characteristic, can high efficiency realize the mineralization of organic material processing.
Insert two-stage electrical heating catalytic oxidation pipe 3 and 6 shown in Figure 1 after catalyst prepares, open electric-heating control system 4 and 7, making reaction temperature after the heating is 180-220 ℃, can effectively process chemical industry nitrilation waste gas.
Embodiment 1
Get Al
2O
3600 grams, 320 gram Na (OH) (Na/Al is than 1.20) pour in the 1000 gram distilled water simultaneously, fully stir and keep reaction temperature 65 ℃ of reactions 1 hour, place 24 hours in 25 degrees centigrade environment temperature, make solution produce precipitation; With the ammonia scrubbing that after the sediment vacuum filtration with mass concentration is 0.1%, fully be dissolved in then mass concentration and be in 0.7% the nitric acid, nitric acid dosage and sedimentary mass ratio 3: 1 obtain suspension; Add NaOH in suspension, regulator solution pH value is 10.0; Mass ratio is accounted for the Mn of suspension 1%
3O
4Powder adds above-mentioned suspension, filters immediately honeycomb processed after fully mixing, and 105 ℃ of lower dryings 12 hours, is warming up to 360 ℃ of dryings 1.5 hours then, and 650 ℃ of dryings 2.5 hours naturally cool to room temperature then, obtain required with honeycomb γ-Al
2O
3Mn as carrier
3O
4Oxidation catalyst.
The above-mentioned oxidation catalyst for preparing is inserted two-stage electrical heating catalytic oxidation pipe in the emission-control equipment shown in Figure 1, open electric-heating control system 4 and 7, make the one-level of handling nitrilation waste gas, the reaction temperature of secondary electrical heating catalytic oxidation pipe be 200 ℃ after the heating.The volume ratio of oxygen content is introduced treating apparatus greater than 9% chemical nitrile action waste gas, at first be heated to 100-150 ℃ through heat exchanger 2, enter then one-level electrical heating catalytic oxidation pipe 3, further be heated to 200 ℃ by the built-in electric heater unit of one-level electrical heating catalytic oxidation pipe, make ammonia and organic gas in the waste gas be adsorbed on cellular γ-Al
2O
3On the carrier, and the Mn of load on carrier
3O
4Under the catalytic action with waste gas in oxygen generation catalytic oxidation, waste gas enters secondary electrical heating catalytic oxidation pipe 6 then; In secondary electrical heating catalytic oxidation pipe, unreacted ammonia and organic gas are adsorbed on cellular γ-Al in the waste gas
2O
3On the carrier; And the Mn of load on carrier
3O
4Under the catalytic action with waste gas in oxygen generation catalytic oxidation, EGT reaches 300-400 ℃ because of exothermic heat of reaction; Then waste gas is introduced heat exchanger 2, carry out heat exchange with import waste gas after temperature be reduced to below 100 ℃, directly emptying through escape pipe 11.
Concrete result is as follows, and wherein waste gas is relevant with the catalyst loading time of contact on catalyst.
Table 1. result
| Ammonia | Initial concentration (g/m 3) | Concentration (g/m after processing 3) |
| Experiment 1 (≈ 0.2S time of contact) experiment 2 (≈ 0.2S time of contact) experiment 3 (≈ 0.2S time of contact) | 28.3 27.6 27.9 | 1.2 1.1 1.2 |
| VOCs (dimethylbenzene) | Initial concentration (mg/m 3) | Concentration (mg/m after processing 3) |
| Experiment 1 (≈ 0.2S time of contact) experiment 2 (≈ 0.2S time of contact) experiment 3 (≈ 0.2S time of contact) | 280 300 300 | 10/8 |
Embodiment 2
Get Al
2O
3600 grams, 320 gram Na (OH) (Na/Al is than 1.20) pour in the 1000 gram distilled water simultaneously, fully stir and keep reaction temperature 70 ℃ of reactions 1 hour, place 24 hours in 20 ℃ environment temperature, make solution produce precipitation; With after the sediment vacuum filtration with 0.3% ammonia scrubbing, fully be dissolved in then mass concentration and be in 2% the nitric acid, nitric acid dosage and sedimentary mass ratio 4: 1 obtain suspension; Add NaOH in suspension, regulator solution pH value is 9; Mass ratio is accounted for the Mn of suspension 1%
3O
4Powder adds above-mentioned suspension, filters immediately honeycomb processed after fully mixing, and 90 ℃ of lower dryings 20 hours, is warming up to 350 ℃ of dryings 2 hours then, and 600 ℃ of dryings 2.5 hours naturally cool to room temperature then, obtain required with honeycomb γ-Al
2O
3Mn as carrier
3O
4Oxidation catalyst.
The above-mentioned oxidation catalyst for preparing is inserted two-stage electrical heating catalytic oxidation pipe in the emission-control equipment shown in Figure 1, open electric-heating control system 4 and 7, make the one-level of handling nitrilation waste gas, the reaction temperature of secondary electrical heating catalytic oxidation pipe be 180 ℃ after the heating.The volume ratio of oxygen content is introduced treating apparatus greater than 9% chemical nitrile action waste gas, at first be heated to 100-150 ℃ through heat exchanger 2, enter then one-level electrical heating catalytic oxidation pipe 3, further be heated to 180 ℃ by the built-in electric heater unit of one-level electrical heating catalytic oxidation pipe, make ammonia and organic gas in the waste gas be adsorbed on cellular γ-Al
2O
3On the carrier, and the Mn of load on carrier
3O
4Under the catalytic action with waste gas in oxygen generation catalytic oxidation, waste gas enters secondary electrical heating catalytic oxidation pipe 6 then; In secondary electrical heating catalytic oxidation pipe, unreacted ammonia and organic gas are adsorbed on cellular γ-Al in the waste gas
2O
3On the carrier; And the Mn of load on carrier
3O
4Under the catalytic action with waste gas in oxygen generation catalytic oxidation, EGT reaches 300-400 ℃ because of exothermic heat of reaction; Then waste gas is introduced heat exchanger 2, carry out heat exchange with import waste gas after temperature be reduced to below 100 ℃, directly emptying through escape pipe 11.
Concrete outcome is as follows:
Table 2. result
| Ammonia | Initial concentration (g/m 3) | Concentration (g/m after processing 3) |
| Experiment 1 (≈ 0.5S time of contact) experiment 2 (≈ 0.5S time of contact) experiment 3 (≈ 0.5S time of contact) | 28.3 27.6 27.9 | 0.2 0.2 0.2 |
| VOCs (dimethylbenzene) | Initial concentration (mg/m 3) | Concentration (mg/m after processing 3) |
| Experiment 1 (≈ 0.5S time of contact) experiment 2 (≈ 0.5S time of contact) experiment 3 (≈ 0.5S time of contact) | 280 300 300 | 523 |
Embodiment 3
Get Al
2O
3600 grams, 293 gram Na (OH) (Na/Al is than 1.10) pour in the 1000 gram distilled water simultaneously, fully stir and keep reaction temperature 65 ℃ of reactions 1 hour, at room temperature place 24 hours, make solution produce precipitation; With the ammonia scrubbing that after the sediment vacuum filtration with mass concentration is 0.5%, fully be dissolved in then mass concentration and be in 5% the nitric acid, nitric acid dosage and sedimentary mass ratio 6: 1 obtain suspension; Add NaOH in suspension, regulator solution pH value is 10.0; Mass ratio is accounted for the Mn of suspension 3%
3O
4Powder adds above-mentioned suspension, filters immediately honeycomb processed after fully mixing, and 70 ℃ of lower dryings 24 hours, is warming up to 360 ℃ of dryings 1.5 hours then, and 600 ℃ of dryings 3 hours naturally cool to room temperature then, obtain required with honeycomb γ-Al
2O
3Mn as carrier
3O
4Oxidation catalyst.
The above-mentioned oxidation catalyst for preparing is inserted two-stage electrical heating catalytic oxidation pipe in the emission-control equipment shown in Figure 1, open electric-heating control system 4 and 7, make the one-level of handling nitrilation waste gas, the reaction temperature of secondary electrical heating catalytic oxidation pipe be 200 ℃ after the heating.The volume ratio of oxygen content is introduced treating apparatus greater than 9% chemical nitrile action waste gas, at first be heated to 100-150 ℃ through heat exchanger 2, enter then one-level electrical heating catalytic oxidation pipe 3, further be heated to 200 ℃ by the built-in electric heater unit of one-level electrical heating catalytic oxidation pipe, make ammonia and organic gas in the waste gas be adsorbed on cellular γ-Al
2O
3On the carrier, and the Mn of load on carrier
3O
4Under the catalytic action with waste gas in oxygen generation catalytic oxidation, waste gas enters secondary electrical heating catalytic oxidation pipe 6 then; In secondary electrical heating catalytic oxidation pipe, unreacted ammonia and organic gas are adsorbed on cellular γ-Al in the waste gas
2O
3On the carrier; And the Mn of load on carrier
3O
4Under the catalytic action with waste gas in oxygen generation catalytic oxidation, EGT reaches 300-400 ℃ because of exothermic heat of reaction; Then waste gas is introduced heat exchanger 2, carry out heat exchange with import waste gas after temperature be reduced to below 100 ℃, directly emptying through escape pipe 11.
Concrete outcome is as follows:
Table 3. result (ammonia)
| Initial ammonia concentration (g/m 3) | Concentration (g/m after processing 3) | |
| Experiment 1 (≈ 1S time of contact) experiment 2 (≈ 0.2S time of contact) | 23 25.8 | 0.2 2.2 |
Get Al
2O
3600 grams, 320 gram Na (OH) (Na/Al is than 1.20) pour in the 1000 gram distilled water simultaneously, fully stir and keep reaction temperature 65 ℃ of reactions 1 hour, place 24 hours in 25 degrees centigrade environment temperature, make solution produce precipitation; With the ammonia scrubbing that after the sediment vacuum filtration with mass concentration is 0.1%, fully be dissolved in then mass concentration and be in 0.7% the nitric acid, nitric acid dosage and sedimentary mass ratio 3: 1 obtain suspension; Add NaOH in suspension, regulator solution pH value is 10.0; Mass ratio is accounted for the Mn of suspension 2%
3O
4Powder adds above-mentioned suspension, filters immediately honeycomb processed after fully mixing, and 105 ℃ of lower dryings 12 hours, is warming up to 360 ℃ of dryings 1.5 hours then, and 650 ℃ of dryings 2.5 hours naturally cool to room temperature then, obtain required with honeycomb γ-Al
2O
3Mn as carrier
3O
4Oxidation catalyst.
The above-mentioned oxidation catalyst for preparing is inserted two-stage electrical heating catalytic oxidation pipe in the emission-control equipment shown in Figure 1, and the temperature control in the processing procedure is with embodiment 1.
Concrete result is as follows:
Table 4. result (ammonia)
| Initial ammonia concentration (g/m 3) | Concentration (g/m after processing 3) | |
| Experiment 1 (≈ 1S time of contact) experiment 2 (≈ 0.2S time of contact) | 23 25.8 | 0.2 2.2 |
Embodiment 5
Get Al
2O
3600 grams, 320 gram Na (OH) (Na/Al is than 1.20) pour in the 1000 gram distilled water simultaneously, fully stir and keep reaction temperature 65 ℃ of reactions 1 hour, place 24 hours in 25 degrees centigrade environment temperature, make solution produce precipitation; With the ammonia scrubbing that after the sediment vacuum filtration with mass concentration is 0.1%, fully be dissolved in then mass concentration and be in 0.7% the nitric acid, nitric acid dosage and sedimentary mass ratio are 5: 1, obtain suspension; Add NaOH in suspension, regulator solution pH value is 10.0; Mass ratio is accounted for the Mn of suspension 3%
3O
4Powder adds above-mentioned suspension, filters immediately honeycomb processed after fully mixing, and 105 ℃ of lower dryings 12 hours, is warming up to 360 ℃ of dryings 1.5 hours then, and 650 ℃ of dryings 2.5 hours naturally cool to room temperature then, obtain with honeycomb γ-Al
2O
3Mn as carrier
3O
4Oxidation catalyst.
The above-mentioned oxidation catalyst for preparing is inserted two-stage electrical heating catalytic oxidation pipe in the emission-control equipment shown in Figure 1, and the temperature control in the processing procedure is with embodiment 1.
Concrete outcome is as follows:
Table 5. result
| Initial ammonia concentration (g/m 3) | Concentration (g/m after processing 3) | |
| Time of contact ≈ 1S | ＞30 | 0.02 |
Embodiment 6
Get Al
2O
3600 grams, 320 gram Na (OH) (Na/Al is than 1.20) pour in the 1000 gram distilled water simultaneously, fully stir and keep reaction temperature 65 ℃ of reactions 1 hour, place 24 hours in 25 degrees centigrade environment temperature, make solution produce precipitation; With the ammonia scrubbing that after the sediment vacuum filtration with mass concentration is 0.1%, fully be dissolved in then mass concentration and be in 0.7% the nitric acid, nitric acid dosage and sedimentary mass ratio are 6: 1, obtain suspension; Add NaOH in suspension, regulator solution pH value is 10.0; Mass ratio is accounted for the Mn of suspension 3%
3O
4Powder adds above-mentioned suspension, filters immediately honeycomb processed after fully mixing, and 105 ℃ of lower dryings 12 hours, is warming up to 360 ℃ of dryings 1.5 hours then, and 650 ℃ of dryings 2.5 hours naturally cool to room temperature then, obtain with honeycomb γ-Al
2O
3Mn as carrier
3O
4Oxidation catalyst.
The above-mentioned oxidation catalyst for preparing is inserted two-stage electrical heating catalytic oxidation pipe in the emission-control equipment shown in Figure 1, and the temperature control in the processing procedure is with embodiment 2.
Result is as follows:
Table 6. result
| Initial ammonia concentration (g/m 3) | Concentration (g/m after processing 3) | |
| Time of contact ≈ 1S | ＞30 | 0.04 |
Claims (3)
1, a kind of low-temperature catalytic treating method of chemical nitrile action technology waste gas is characterized in that comprising the steps:
1) preparation of catalyst: get Al
2O
3, Na (OH) is immersed in the distilled water simultaneously, wherein the Na/Al mol ratio is 1.1-1.2, fully stirs and keep reaction temperature at 65-70 ℃, reacts after 1 hour and places 24 hours in 10-30 ℃, makes solution produce precipitation; To use the ammonia scrubbing of mass concentration 0.1-0.5% after the above-mentioned sediment vacuum filtration, use then the nitric acid dissolve of mass concentration 0.5-5%, nitric acid dosage and sedimentary mass ratio are 3-6: 1, obtain suspension; Add NaOH in suspension, regulator solution pH value is 9-10; Mass ratio is accounted for the Mn of the 1-3% of suspension
3O
4Powder adds above-mentioned suspension, filter immediately after fully mixing, then 70-105 ℃ lower dry 12-24 hour, be warming up to 350-360 ℃ of dry 1-2 hour, 600-650 ℃ dry 2-3 hour, naturally cool to then 10-30 ℃, obtain with honeycomb γ-Al
2O
3Mn as carrier
3O
4Oxidation catalyst; Be used for filling the two-stage electrical heating catalytic oxidation pipe that the chemical nitrile action emission-control equipment adopts;
2) low-temperature catalyzed processing chemical nitrile action waste gas: with the two-stage electrical heating catalytic oxidation pipe in the above-mentioned oxidation catalyst filling emission-control equipment for preparing; The volume ratio of oxygen content is introduced treating apparatus greater than 9% chemical nitrile action waste gas, at first be heated to 100-150 ℃ through heat exchanger (2), enter then one-level electrical heating catalytic oxidation pipe (3), further be heated to 180-220 ℃ by the built-in electric heater unit of one-level electrical heating catalytic oxidation pipe, make ammonia and organic gas in the waste gas be adsorbed on cellular γ-Al
2O
3On the carrier, and the Mn of load on carrier
3O
4Under the catalytic action with waste gas in oxygen generation catalytic oxidation, waste gas enters secondary electrical heating catalytic oxidation pipe (6) then; In secondary electrical heating catalytic oxidation pipe, make that unreacted ammonia and organic gas are adsorbed on cellular γ-Al in the waste gas
2O
3On the carrier; And the Mn of load on carrier
3O
4Under the catalytic action with waste gas in oxygen generation catalytic oxidation, EGT reaches 300-400 ℃ because of exothermic heat of reaction; Then waste gas is introduced heat exchanger (2), carry out heat exchange with import waste gas after temperature be reduced to below 100 ℃, directly emptying through escape pipe (11).
2, a kind of low-temperature catalyzed treating apparatus of chemical nitrile action technology waste gas is characterized in that comprising heat exchanger (2), two-stage electrical heating catalytic oxidation pipe (3,6), two-stage electric-heating control system (4,7), stepless time adjustment blower fan (10) and escape pipe (11); It is the vertical structure of one that two-stage electrical heating catalytic oxidation pipe (3,6) adopts electrical heating chamber and catalytic oxidation chamber; The internal channel import of heat exchanger (2) connects air inlet flowmeter (1), the internal channel outlet of heat exchanger (2) connects the bottom of one-level electrical heating catalytic oxidation pipe (3), the top of one-level electrical heating catalytic oxidation pipe (3) connects the bottom of secondary electrical heating catalytic oxidation pipe (6), the outlet of one-level electrical heating catalytic oxidation pipe (3) and secondary electrical heating catalytic oxidation pipe (6) is connected with the outer tunnel import of heat exchanger (2) simultaneously, one-level electrical heating catalytic oxidation pipe (3) adopts thin metallic tubd, the casing pack oxidation catalyst also is provided with one-level electric heating system thermometer (5), and the thin metallic tubd of one-level electrical heating catalytic oxidation pipe (3) and thermometer (5) connect one-level electric-heating control system (4); Secondary electrical heating catalytic oxidation pipe (6) adopts thin metallic tubd, the casing pack oxidation catalyst also is provided with secondary electric heating system thermometer (8), and the thin metallic tubd of secondary electrical heating catalytic oxidation pipe (6) and thermometer (8) connect secondary electric-heating control system (7); The outer tunnel outlet of heat exchanger (2) is connected to escape pipe (11) through stepless time adjustment blower fan (10), at the preceding pressure gauge (9) that is provided with of stepless time adjustment blower fan (10).
3, according to the low-temperature catalyzed treating apparatus of the chemical nitrile action technology waste gas of claim 2, the oxidation catalyst that it is characterized in that the interior filling of described electrical heating catalytic oxidation pipe (3) is for honeycomb γ-Al
2O
3Mn as carrier
3O
4Oxidation catalyst.
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| CNA2007100373172A CN101053769A (en) | 2007-02-08 | 2007-02-08 | Low-temperature catalytic treating method and device for chemical nitrile action technology waste gas |
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| CNA2007100373172A CN101053769A (en) | 2007-02-08 | 2007-02-08 | Low-temperature catalytic treating method and device for chemical nitrile action technology waste gas |
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| CN101444701B (en) * | 2008-12-02 | 2011-02-09 | 杨杭生 | Equipment for removing nitrogen oxides and dioxin in waste gas at low-ash area of burning facility |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101444701B (en) * | 2008-12-02 | 2011-02-09 | 杨杭生 | Equipment for removing nitrogen oxides and dioxin in waste gas at low-ash area of burning facility |
| CN102000501A (en) * | 2010-10-22 | 2011-04-06 | 惠州市鼎晨实业发展有限公司 | Catalytic adsorption integrated equipment for treating organic waste gas |
| CN103055675A (en) * | 2013-01-18 | 2013-04-24 | 大恩(天津)环境技术研发有限公司 | Industrial smoke comprehensive treatment system and method based on advanced oxidation |
| CN106823690A (en) * | 2017-01-09 | 2017-06-13 | 安徽省化工设计院 | A kind of benzonitrile produces the handling process of tail gas |
| CN110935309A (en) * | 2018-10-23 | 2020-03-31 | 北京市环境保护科学研究院 | Two-stage low-concentration VOC catalytic degradation method |
| CN110935309B (en) * | 2018-10-23 | 2022-03-22 | 北京市生态环境保护科学研究院 | Two-stage low-concentration VOC catalytic degradation method |
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