CN103706368A - Iron-carbon catalytic filler for treating organic mixed exhaust gases and preparation method of filler - Google Patents
Iron-carbon catalytic filler for treating organic mixed exhaust gases and preparation method of filler Download PDFInfo
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Abstract
The invention belongs to the technical field of catalytic decomposition of organic exhaust gases through iron-carbon micro-electrolysis, and specifically relates to iron-carbon catalytic filler for treating organic mixed exhaust gases and a preparation method of the filler. The finished product filler consists of the following components in percentage by mass: 80-85% of scrap iron, 10-15% of active carbon, 0.1-0.3% of rear earth metals and 1-5% of clay. The diameter of the iron-carbon micro-electrolysis filler is 3.0-6.0cm. The iron-carbon micro-electrolysis filler obtained by the preparation method has good gas penetration mesh path, strength, specific surface area and primary battery reaction effect. As iron atoms are not directly contacted, surface passivation of the filler and hardening of the filler are effectively prevented.
Description
Technical field
The invention belongs to iron-carbon micro-electrolysis organic exhaust gas catalytic decomposition technical field, be specifically related to a kind of processing organic mixed waste gas iron carbon catalytic filler and preparation method thereof.
Background technology
In industrial processes, a large amount of high temperature evaporation concentration technologies that use, be rich in organic liquid in high temperature evaporation concentration process, partial organic substances cracking forms volatile organic matter (VOCs) and mixes foul gas with water vapour and the inorganic salts formation of evaporation process generation, and environment is caused to great harm.The VOCs improvement method of existing report mainly contains:
(1) direct combustion method: be to utilize high-temperature oxydation that VOCs is converted into CO
2and H
2a kind of method of O.VOCs gas enters behind combustion chamber, the process of completing combustion under the condition of high enough temp, excess air, turbulent flow.
(2) catalytic oxidation: with direct combustion method action principle substantially roughly the same, just in reactor, need to install cellular or sheet catalyst.Owing to having used catalyst, it can move at lower temperature, thereby has reduced auxiliary fuel consumption and operating cost.
(3) bioanalysis: be that to utilize microorganism be CO by oxidation operation under aerobic condition
2and H
2o, its course of reaction is similar with oxidizing process, but be not with heat but with biology, remove to destroy VOCs.
(4) absorption process: be to utilize liquid absorption liquid to absorb a kind of method of gaseous state VOCs from air-flow, be usually used in processing high humility VOCs air-flow (>5O%).
(5) absorption method: be a kind of method of utilizing the huge surface area of adsorbent cavernous structure to adsorb VOCs.The organic exhaust gas that the single steady air current of its suitable treatment composition, concentration are 300-5000ppm.
(6) concentration method: be a kind of mode that VOCs air-flow is reached capacity by cooling or pressurization, often use together with other processing method.Be generally used for processing boiling point higher, concentration surpasses 5% VOCs gas.
(7) embrane method: be the process size of VOCs gas molecule optionally being stopped according to film, can partly or entirely VOCs be held back.
Yet in containing the organic exhaust gas of a large amount of steam, due to interference and the masking action of steam, said method all cannot be realized effective processing of VOCs.
Micro electrolysis tech is to utilize Principles of Metal Erosion, forms galvanic cell, by a series of effects, organic matter is carried out to electrochemical treatments.In containing the environment of conductive electrolyte, iron filings and carbon granule form numerous small galvanic cell, at its action space, form an electric field, [H] of nascent state, Fe
2+deng with environment in organic matter generation redox reaction, destroy some group in organic matter, even chain rupture, reaches the effect to organic substance decomposing; The Fe generating
2+be further oxidized to Fe
3+, their hydrate has stronger adsorption-flocculation effect, realizes organic absorption.
And the concentrated mixed flue gas forming of high temperature evaporation is to consist of VOCs, water vapour and inorganic salts, at filling surface, formed the water environment of inorganic salts, between iron atom and carbon atom, can produce a kind of faint intramolecule electric current, [H] of generation, Fe
2+deng the organic matter generation redox reaction with being adsorbed in iron carbon granule surface, realize organic decomposition and produce adsorption-flocculation effect, with drop, depart from iron carbon granule surface.
Summary of the invention
The object of the invention is take iron filings, Powdered Activated Carbon, aerobic activated sludge, rare earth metal powder, clay is raw material, provides a kind of and can be used in high temperature evaporation concentration process, iron-carbon micro-electrolysis filler that organic mixed waste gas is administered and preparation method thereof.This filler has good gas penetration mesh path, intensity, specific area and galvanic cell response effect, due to not directly contact between iron atom, effectively prevents hardening of filling surface passivation and filler.
For achieving the above object, the present invention adopts following technical proposals:
A kind of iron carbon catalytic filler for the treatment of organic mixed waste gas, take iron filings, Powdered Activated Carbon, aerobic activated sludge, rare earth metal powder, clay is raw material, the finished product filler making is comprised of the component of following mass percent: iron filings 80～85%, active carbon 10～15%, rare earth metal 0.1～0.3%, clay 1～5%; The diameter of iron-carbon micro-electrolysis filler is 3.0～6.0cm.
Preferably, the described iron carbon catalytic filler for the treatment of organic mixed waste gas, its finished product filler is comprised of the component of following mass percent: iron filings 80-85%, active carbon 10～15%, rare earth metal 0.15～0.2%, clay 2～4%.
Preferably, described active carbon is Powdered Activated Carbon, granularity 80～120 orders.
Preferably, described rare earth metal comprises Ce, La, Pr, Nd, and described rare earth metal is Powdered, and rare earth metal powder particle diameter is 90～130 orders.
Preferably, the particle diameter of described iron filings is 50～100 orders.
Described aerobic activated sludge is the aerobic activated sludge of life sewage treatment plant, moisture content < 60%.
Preparation method for the treatment of the iron carbon catalytic filler of organic mixed waste gas, comprises the following steps:
1) take hydrochloric acid that mass concentration is 6～4% to iron filings pickling 20～30min activation iron filings, after rinsing is clean,
2) take respectively iron filings, active carbon powder, rare earth metal powder, aerobic activated sludge and clay as raw material, according to mass percent, be: iron filings 55-65%, Powdered Activated Carbon 8-11%, rare earth metal powder 0.1～0.2%, aerobic activated sludge (butt) 23-35%, clay 1.5～3%, fully stirs and evenly mixs.
3) take the pair roller granulating extruder granular blank filler that to push as diameter be 3～6cm under 210kN～250KN pressure,
4) after blank paddle dryer in airfree environment, with roasting under 1000～1200 ℃ of conditions 1～3 hour, obtain described catalysis and micro-electrolysis filler after cooling.
Preferably, the pressure described in step 3) is 210～220KN.
Preferably, the airfree environment described in step 4), comprises vacuum, inert gas environment.Described inert gas environment comprises nitrogen, ar gas environment.
Preferably, in step 4) with roasting under 1000～1100 ℃ of conditions 2 hours.
Aerobic activated sludge mainly consists of aerobic microbiological organism, in the environment of high temperature, is carbonized as CO
2, the filler after roasting forms mesh gas passage, and because the activated sludge in filler disappears, the mass ratio of each component of finished product filler is changed into: iron filings 80～85%, active carbon 10～15%, rare earth metal 0.1～0.3%, clay 1～5%.Aerobic activated sludge plays the effect of masterplate agent in the preparation process of electrolysis filler, and the selection of masterplate agent is very large for meso-hole structure impact, thereby affects catalytic effect.We find unexpectedly through a large amount of experiments, use aerobic activated sludge, not only can realize the resource of discarded object, reduce the discharge of the three wastes, and the iron-carbon micro-electrolysis filler specific area obtaining increase at double, are conducive to the reaction of galvanic cell.
Beneficial effect of the present invention is:
1, the filler that prepared by the present invention, for having inner mesh granulated filler, is beneficial to the distribution of gas, and specific area increase at double, is conducive to the reaction of galvanic cell.
2, in the filler that prepared by the present invention, contain thulium, can promote the galvanic cell reaction efficiency and the passivation that prevents filling surface of filler.
3, the at high temperature roasting of filler that prepared by the present invention, has certain intensity, can keep its intrinsic form in reaction.
4, the filler that prepared by the present invention, due to not directly contact between iron atom, has stoped the phenomenon that hardens in stuffing operation.
5, the present invention has utilized activated sludge, has realized the resource of discarded object.
The specific embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
First the hydrochloric acid that the mass concentration of take is 6% is to iron filings pickling 20min, activation iron filings, after rinsing is clean, take particle diameter more respectively as 50 object iron filings, particle diameter is 80 object active carbon powders, particle diameter is 90 object rare earth metal Ce powder, aerobic activated sludge and clay are raw material, according to each raw material components mass percent, be: iron filings 55.3%, Powdered Activated Carbon 8%, rare earth metal powder 0.1%, aerobic activated sludge (butt) 35%, clay 1.6%, fully stir and evenly mix, the granular blank filler that it is 3cm that the pair roller granulating extruder of take pushes as diameter under 210kN pressure, after blank paddle dryer in the environment of vacuum, with roasting under 1000 ℃ of conditions 2 hours, after cooling, make catalysis and micro-electrolysis filler qualitatively.
Aerobic activated sludge mainly consists of aerobic microbiological organism, in the environment of high temperature, is carbonized as CO
2, the filler after roasting forms mesh gas passage, and because the activated sludge in filler disappears, the ratio of finished product filler component is changed into: iron filings 85%, active carbon 12.24%, rare earth metal 0.16%, clay 2.6%.
Embodiment 2:
First the hydrochloric acid that the mass concentration of take is 4% is to iron filings pickling 30min, activation iron filings, after rinsing is clean, take particle diameter more respectively as 100 object iron filings, particle diameter is 100 object active carbon powders, particle diameter is 110 object rare-earth metal La powder, aerobic activated sludge and clay are raw material, according to each raw material components mass percent, be: iron filings 60%, Powdered Activated Carbon 11%, rare earth metal powder 0.1%, aerobic activated sludge (butt) 27.8%, clay 2%, fully stir and evenly mix, the granular blank filler that it is 6cm that the pair roller granulating extruder of take pushes as diameter under 220kNKN pressure, after blank paddle dryer in nitrogen environment, to be greater than under 1200 ℃ of conditions roasting 1 hour, after cooling, make catalysis and micro-electrolysis filler qualitatively.
Aerobic activated sludge mainly consists of aerobic microbiological organism, in the environment of high temperature, is carbonized as CO
2, the filler after roasting forms mesh gas passage, and because the activated sludge in filler disappears, the ratio of finished product filler component is changed into: iron filings 82.1%, active carbon 15%, rare earth metal 0.12%, clay 2.78%.
Embodiment 3:
First the hydrochloric acid that the mass concentration of take is 5% is to iron filings pickling 25min, activation iron filings, after rinsing is clean, take particle diameter more respectively as 80 object iron filings, particle diameter is 120 object active carbon powders, particle diameter is 30 object rare earth metal Nd powder, aerobic activated sludge and clay are raw material, according to each raw material components mass percent, be: iron filings 65%, Powdered Activated Carbon 9%, rare earth metal powder 0.15%, aerobic activated sludge (butt) 23%, clay 2.85%, fully stir and evenly mix, the granular blank filler that it is 5cm that the pair roller granulating extruder of take pushes as diameter under 250KN pressure, after blank paddle dryer in the environment of argon gas, to be greater than under 1100 ℃ of conditions roasting 3 hours, after cooling, make catalysis and micro-electrolysis filler qualitatively.
Aerobic activated sludge mainly consists of aerobic microbiological organism, in the environment of high temperature, is carbonized as CO
2, the filler after roasting forms mesh gas passage, and because the activated sludge in filler disappears, the ratio of finished product filler component is changed into: iron filings 84.1%, active carbon 11.8%, rare earth metal 0.25%, clay 3.75%.
Embodiment 4:
The iron-carbon micro-electrolysis organic exhaust gas catalytic decomposition filler of the preparation of embodiment 1 is processed to glutamic acid-fermented waste liquid slurry-spraying pelletizing end stench tail gas.
Glutamic acid-fermented waste liquid is after high temperature concentration and evaporation, under hot conditions, (500～550 ℃) slurry-spraying pelletizing is produced organic-inorganic compound fertilizer, yet in high temperature evaporation process, organic matter in fermented waste fluid is by coking, form foul gas and evaporate together with water vapour, the pH of this stench flue gas is 3～4, in entering the decomposition tower that iron carbon granules filler is housed, at iron carbon grain surface, form numerous small galvanic cell, [H] of generation, Fe
2+deng with flue gas in organic matter generation redox reaction, the VOCs in flue gas is decomposed.Operation result shows, stench peculiar smell is governed, and inner mesh granulated filler keeps good permeability, does not occur the phenomenon that hardens.
Mou amino acid fermentation factory utilizes after the iron-carbon micro-electrolysis organic exhaust gas catalytic decomposition filler of preparation of embodiment 1, and the discharge index of environmental administration's Site Detection is as follows: particle: 17.33mg/m
3, sulfur dioxide 0mg/m
3, nitrogen oxide 0mg/m
3, benzene 0mg/m
3, phenyl amines 0mg/m
3, NMHC 1.32mg/m
3, ammonia 0.3mg/m
3.Measured data is obviously better than the primary standard in State Standard of the People's Republic of China < < discharge standard of air pollutants > > (GB16297-1996) and < < emission standard for odor pollutants > > (GB14554-93).
Embodiment 5:
Utilize the iron-carbon micro-electrolysis organic exhaust gas catalytic decomposition filler of implementing 1 preparation to administer pharmaceutical industry fermentation gas, the waste gas that fermentation tank is discharged passes in the spray decomposition tower that iron carbon granules filler is housed, the absorption liquid that tower top spray pH is 3, at iron carbon grain surface, form numerous small galvanic cell, [H] of generation, Fe
2+deng with fermentation waste gas in organic matter generation redox reaction, the VOCs in waste gas is decomposed, after operation certain hour, pH value rises, and regularly replaces spray liquid.Operation result shows, elimination of off flavor in waste gas, and there is not the phenomenon that hardens in inner mesh granulated filler.After Mou pharmacy fermentation enterprise is used, the discharge index of environmental administration's Site Detection is as follows: particle: 15mg/m
3, sulfur dioxide 0mg/m
3, nitrogen oxide 0mg/m
3, benzene 0mg/m
3, phenyl amines 0mg/m
3, NMHC 1.21mg/m
3, ammonia 0.78mg/m
3.Measured data is obviously better than the primary standard in State Standard of the People's Republic of China < < discharge standard of air pollutants > > (GB16297-1996) and < < emission standard for odor pollutants > > (GB14554-93).
Although above-mentioned, the specific embodiment of the present invention is described; but be not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various modifications that creative work can make or distortion still in protection scope of the present invention.
Claims (9)
1. for the treatment of an iron carbon catalytic filler for organic mixed waste gas, its finished product filler is comprised of the component of following mass percent: iron filings 80～85%, active carbon 10～15%, rare earth metal 0.1～0.3%, clay 1～5%; The diameter of iron-carbon micro-electrolysis filler is 3.0～6.0cm.
2. the iron carbon catalytic filler for the treatment of organic mixed waste gas as claimed in claim 1, it is characterized in that, the iron-carbon micro-electrolysis filler that described organic mixed waste gas is administered, its finished product filler is comprised of the component of following mass percent: iron filings 80～85%, active carbon 10～15%, rare earth metal 0.15～0.2%, clay 2～4%.
3. the iron carbon catalytic filler for the treatment of organic mixed waste gas as claimed in claim 1 or 2, is characterized in that, described active carbon is Powdered Activated Carbon, granularity 80～120 orders.
4. the iron carbon catalytic filler for the treatment of organic mixed waste gas as claimed in claim 1 or 2, is characterized in that, described rare earth metal comprises Ce, La, Pr, Nd, and described rare earth metal is Powdered, and particle diameter is 90～130 orders.
5. the iron carbon catalytic filler for the treatment of organic mixed waste gas as claimed in claim 1 or 2, is characterized in that, the particle diameter of described iron filings is 50～100 orders.
6. the preparation method of the iron carbon catalytic filler for the treatment of organic mixed waste gas claimed in claim 1, comprises the following steps:
1) take hydrochloric acid that mass concentration is 6～4% to iron filings pickling 20～30min activation iron filings, rinsing is clean;
2) take respectively iron filings, active carbon powder, rare earth metal powder, aerobic activated sludge and clay as raw material, according to mass percent, be: iron filings 55～65%, Powdered Activated Carbon 8～11%, rare earth metal powder 0.1～0.2%, aerobic activated sludge (butt) 23～35%, clay 1.5～3%, fully stirs and evenly mixs;
3) take the pair roller granulating extruder granular blank filler that to push as diameter be 3～6cm under 210kN～250KN pressure;
4) after blank paddle dryer in airfree environment, with roasting under 1000～1200 ℃ of conditions 1～3 hour, obtain described catalysis and micro-electrolysis filler after cooling.
7. the preparation method of the iron carbon catalytic filler for the treatment of organic mixed waste gas as claimed in claim 6, is characterized in that, the pressure described in step 3) is 210～220KN.
8. the preparation method of the iron carbon catalytic filler for the treatment of organic mixed waste gas as claimed in claim 6, is characterized in that, the airfree environment described in step 4), comprises vacuum, inert gas environment.Described inert gas environment comprises nitrogen, ar gas environment.
9. the preparation method of the iron carbon catalytic filler for the treatment of organic mixed waste gas as claimed in claim 1, is characterized in that, in step 4) with roasting under 1000～1100 ℃ of conditions 2 hours.
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| CN101704565B (en) * | 2009-11-16 | 2011-12-07 | 同济大学 | Preparation method of iron-carbon micro-electrolytic filler |
| CN101817574B (en) * | 2010-04-16 | 2012-06-13 | 吉林大学 | Preparation method of regular iron-carbon micro-electrolysis filler |
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| CN112915739A (en) * | 2021-01-25 | 2021-06-08 | 中山大学 | Heterogeneous catalytic oxidation processing system of organic waste gas and foul smell waste gas |
| CN116891297A (en) * | 2023-09-08 | 2023-10-17 | 北京泷涛环境科技有限公司 | Recyclable cyclic treatment method based on iron-sulfur morphology transformation and treated filler |
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