CN103706368B - A kind of iron carbon catalytic filler for the treatment of organic mixed waste gas and preparation method thereof - Google Patents
A kind of iron carbon catalytic filler for the treatment of organic mixed waste gas and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to iron-carbon micro-electrolysis organic exhaust gas catalytic decomposition technical field, be specifically related to a kind of process organic mixed waste gas iron carbon catalytic filler and preparation method thereof.Its finished filler is made up 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.The iron-carbon micro-electrolysis filler obtained has good gas penetration mesh path, intensity, specific area and galvanic interaction effect, owing to directly not contacting between iron atom, effectively prevents hardening of filling surface passivation and filler.
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 process organic mixed waste gas iron carbon catalytic filler and preparation method thereof.
Background technology
In industrial processes, a large amount of use high temperature evaporation concentration technology, be rich in organic liquid in high temperature evaporation concentration process, the water vapour that partial organic substances cracking formation volatile organic matter (VOCs) and evaporation process produce and inorganic salts are formed and mix foul gas, cause great harm to environment.The VOCs administering method of existing report mainly contains:
(1) direct combustion method: be utilize high-temperature oxydation that VOCs is converted into CO
2and H
2a kind of method of O.After VOCs gas enters combustion chamber, the process of burning completely 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 need in reactor install cellular or sheet catalyst.Owing to employing catalyst, it can run at a lower temperature, thus reduces auxiliary fuel consumption and operating cost.
(3) bioanalysis: be utilize microorganism to 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 go destroy VOCs.
(4) absorption process: be a kind of method utilizing liquid absorption liquid to absorb gaseous state VOCs from air-flow, is usually used in process high humility VOCs air-flow (>5O%).
(5) absorption method: be a kind of method utilizing the huge surface area of adsorbent cavernous structure to adsorb VOCs.The single steady air current of its suitable treatment composition, concentration are the organic exhaust gas of 300-5000ppm.
(6) concentration method: be a kind of mode VOCs air-flow being reached capacity with cooling or pressurization, often use together with other processing method.Be generally used for process boiling point higher, the VOCs gas of concentration more than 5%.
(7) embrane method: be the process optionally stopped according to the size of film to VOCs gas molecule, can partly or entirely VOCs be retained.
But in the organic exhaust gas containing a large amount of steam, due to interference and the masking action of steam, said method all cannot realize effective process of VOCs.
Micro electrolysis tech utilizes Principles of Metal Erosion, forms galvanic cell and carry out electrochemical treatments by a series of effect to organic matter.Containing in the environment of conductive electrolyte, iron filings and carbon granule form numerous small galvanic cell, form an electric field, [H] of nascent state, Fe at its action space
2+deng with the organic matter generation redox reaction in environment, destroy some group in organic matter, even chain rupture, reaches the effect to organic substance decomposing; The Fe generated
2+be further oxidized to Fe
3+, their hydrate has stronger adsorption-flocculation effect, realizes organic absorption.
And the mixed flue gas that high temperature evaporation concentrates formation is made up of VOCs, water vapour and inorganic salts, define the water environment of inorganic salts at filling surface, a kind of faint intramolecule electric current can be produced between iron atom and carbon atom, [H] of generation, Fe
2+deng with the organic matter generation redox reaction being adsorbed in iron carbon granule surface, realize organic decomposition and produce adsorption-flocculation effect, departing from iron carbon granule surface with drop.
Summary of the invention
To the object of the invention is with iron filings, Powdered Activated Carbon, aerobic activated sludge, rare earth metal powder, clay, for raw material, to provide one to can be used in high temperature evaporation concentration process, to 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 interaction effect, owing to directly not contacting 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, with iron filings, Powdered Activated Carbon, aerobic activated sludge, rare earth metal powder, clay for raw material, obtained finished filler is made up 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 filler is made up 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 order.
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 sewage treatment plants, moisture content < 60%.
For the treatment of the preparation method of the iron carbon catalytic filler of organic mixed waste gas, comprise the following steps:
1) with mass concentration be 6 ~ 4% hydrochloric acid to iron filings pickling 20 ~ 30min activate iron filings, after rinsed clean,
2) respectively with iron filings, active carbon powder, rare earth metal powder, aerobic activated sludge and clay for 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) extrude as diameter is the granular blank filler of 3 ~ 6cm under 210kN ~ 250KN pressure with pair roller granulating extruder,
4) after blank paddle dryer in airfree environment, with roasting under 1000 ~ 1200 DEG C of conditions 1 ~ 3 hour, after cooling, namely obtain described catalysis and micro-electrolysis filler.
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 DEG C of conditions 2 hours.
Aerobic activated sludge is formed primarily of aerobic microbiological organism, is carbonized as CO in the environment of high temperature
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 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 template agent in the preparation process of electrolysis filler, and the selection of template agent is very large for meso-hole structure impact, thus affects catalytic effect.We, through a large amount of experiments, find unexpectedly, 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 increase at double obtained, and are conducive to the reaction of galvanic cell.
Beneficial effect of the present invention is:
1, the filler prepared of the present invention is for having inner mesh granulated filler, is beneficial to the distribution of gas, and specific area increase at double, be conducive to the reaction of galvanic cell.
2, contain thulium in the filler that prepared by the present invention, the galvanic interaction efficiency of filler can be promoted and prevent the passivation of filling surface.
3, the filler at high temperature roasting prepared of the present invention, has certain intensity, can keep its intrinsic form in the reaction.
4, the filler prepared of the present invention is not owing to directly contacting between iron atom, prevents the phenomenon that hardens in stuffing operation.
5, present invention utilizes activated sludge, achieve the resource of discarded object.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
First be that the hydrochloric acid of 6% is to iron filings pickling 20min with mass concentration, activation iron filings, after rinsed clean, be 50 object iron filings with particle diameter more respectively, 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, extrude as the diameter granular blank filler that is 3cm under 210kN pressure with pair roller granulating extruder, after blank paddle dryer in the environment of vacuum, with roasting under 1000 DEG C of conditions 2 hours, catalysis and micro-electrolysis filler is qualitatively made after cooling.
Aerobic activated sludge is formed primarily of aerobic microbiological organism, is carbonized as CO in the environment of high temperature
2, the filler after roasting forms mesh gas passage, and because the activated sludge in filler disappears, the ratio of finished filler component is changed into: iron filings 85%, active carbon 12.24%, rare earth metal 0.16%, clay 2.6%.
Embodiment 2:
First be that the hydrochloric acid of 4% is to iron filings pickling 30min with mass concentration, activation iron filings, after rinsed clean, be 100 object iron filings with particle diameter more respectively, 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, extrude as the diameter granular blank filler that is 6cm under 220kNKN pressure with pair roller granulating extruder, after blank paddle dryer in nitrogen environment, to be greater than under 1200 DEG C of conditions roasting 1 hour, catalysis and micro-electrolysis filler is qualitatively made after cooling.
Aerobic activated sludge is formed primarily of aerobic microbiological organism, is carbonized as CO in the environment of high temperature
2, the filler after roasting forms mesh gas passage, and because the activated sludge in filler disappears, the ratio of finished filler component is changed into: iron filings 82.1%, active carbon 15%, rare earth metal 0.12%, clay 2.78%.
Embodiment 3:
First be that the hydrochloric acid of 5% is to iron filings pickling 25min with mass concentration, activation iron filings, after rinsed clean, be 80 object iron filings with particle diameter more respectively, 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, extrude as the diameter granular blank filler that is 5cm under 250KN pressure with pair roller granulating extruder, after blank paddle dryer in the environment of argon gas, to be greater than under 1100 DEG C of conditions roasting 3 hours, catalysis and micro-electrolysis filler is qualitatively made after cooling.
Aerobic activated sludge is formed primarily of aerobic microbiological organism, is carbonized as CO in the environment of high temperature
2, the filler after roasting forms mesh gas passage, and because the activated sludge in filler disappears, the ratio of finished filler component is changed into: iron filings 84.1%, active carbon 11.8%, rare earth metal 0.25%, clay 3.75%.
Embodiment 4:
By the iron-carbon micro-electrolysis organic exhaust gas catalytic decomposition filler process glutamic acid-fermented waste liquid slurry-spraying pelletizing end stench tail gas of the preparation of embodiment 1.
Glutamic acid-fermented waste liquid is after high temperature concentration and evaporation, (500 ~ 550 DEG C) slurry-spraying pelletizing produces organic-inorganic compound fertilizer under the high temperature conditions, but in high temperature evaporation process, organic matter in fermented waste fluid is by coking, form foul gas to evaporate together with water vapour, the pH of this stench flue gas is 3 ~ 4, entering in the decomposition tower that iron carbon granules filler is housed, numerous small galvanic cell is formed, [H] of generation, Fe at iron carbon grain surface
2+deng with the organic matter generation redox reaction in flue gas, 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.
Utilize the iron-carbon micro-electrolysis organic exhaust gas catalytic decomposition filler of the preparation of embodiment 1 in certain amino acid fermentation factory after, 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 National 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:
The iron-carbon micro-electrolysis organic exhaust gas catalytic decomposition filler utilizing enforcement 1 to prepare is administered pharmaceutical industry fermentation gas, the waste gas that fermentation tank is discharged is passed in the spray decomposition tower that iron carbon granules filler is housed, tower top spray pH is the absorbing liquid of 3, numerous small galvanic cell is formed, [H] of generation, Fe at iron carbon grain surface
2+deng with the organic matter generation redox reaction in fermentation waste gas, the VOCs in waste gas is decomposed, runs after certain hour, pH value rises, periodic replacement spray liquid.Operation result shows, elimination of off flavor in waste gas, and the phenomenon that hardens does not appear in inner mesh granulated filler.After certain pharmacy fermentation enterprise uses, 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 National 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 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 amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (8)
1., for a preparation method for the iron carbon catalytic filler of organic mixed waste gas improvement, comprise the following steps:
1) with mass percent be 6-4% hydrochloric acid to iron filings pickling 20-30min activate iron filings, rinsed clean,
2) respectively with iron filings, active carbon powder, rare earth metal powder, aerobic activated sludge and clay for raw material, according to mass percent iron filings 55-65%, Powdered Activated Carbon 8-11%, rare earth metal powder 0.1 ~ 0.2%, aerobic activated sludge 23-35%, clay 1.5 ~ 3%, fully stirs and evenly mixs, and described aerobic activated sludge is aerobic activated sludge butt;
3) extrude as diameter is the granular blank filler of 3-6cm under 210kN ~ 250KN pressure with pair roller granulating extruder;
4) after blank paddle dryer in airfree environment, with roasting 1-3 hour under 1000 ~ 1200 DEG C of conditions, after cooling, namely obtain described iron carbon catalytic filler; Described iron carbon catalytic filler, its finished filler is made up 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 catalytic filler is 3.0 ~ 6.0cm.
2. as claimed in claim 1 for the preparation method of the iron carbon catalytic filler of organic mixed waste gas improvement, it is characterized in that, the iron carbon catalytic filler that described organic mixed waste gas is administered, its finished filler is made up 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%, the summation of described component is 100%.
3., as claimed in claim 1 or 2 for the preparation method of the iron carbon catalytic filler of organic mixed waste gas improvement, it is characterized in that, described active carbon is Powdered Activated Carbon, granularity 80-120 order.
4., as claimed in claim 1 or 2 for the preparation method of the iron carbon catalytic filler of organic mixed waste gas improvement, it 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 order.
5., as claimed in claim 1 or 2 for the preparation method of the iron carbon catalytic filler of organic mixed waste gas improvement, it is characterized in that, the particle diameter of described iron filings is 50-100 order.
6., as claimed in claim 1 for the preparation method of the iron carbon catalytic filler of organic mixed waste gas improvement, it is characterized in that, the pressure described in step 3) is 210 ~ 220KN.
7. as claimed in claim 1 for the preparation method of the iron carbon catalytic filler of organic mixed waste gas improvement, it is characterized in that, airfree environment described in step 4), comprises vacuum, inert gas environment, and described inert gas environment comprises nitrogen, ar gas environment.
8., as claimed in claim 1 for the preparation method of the iron carbon catalytic filler of organic mixed waste gas improvement, it is characterized in that, with roasting under 1000 ~ 1100 DEG C of conditions 2 hours in step 4).
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| CN105084470A (en) * | 2014-05-09 | 2015-11-25 | 广州桑尼环保科技有限公司 | Spherical catalytic microelectrolytic environment-friendly material and preparation method therefor |
| CN106139835A (en) * | 2015-04-16 | 2016-11-23 | 杭州中兵环保股份有限公司 | A kind of preparation method of iron-carbon micro-electrolysis filler |
| CN106268169A (en) * | 2015-06-01 | 2017-01-04 | 杭州中兵环保股份有限公司 | The apparatus and method of the collaborative light electrolysis cleaning organic waste gas of plasma cracking oxidation |
| CN106006858A (en) * | 2016-07-21 | 2016-10-12 | 株洲冶炼集团股份有限公司 | High-activity micro-electrolysis filler and preparation method thereof |
| CN107754594A (en) * | 2017-11-22 | 2018-03-06 | 深圳市利源水务设计咨询有限公司 | A kind of high-performance bio deodorization process and its filtrate and device |
| CN108479341A (en) * | 2018-06-05 | 2018-09-04 | 广东佳德环保科技有限公司 | A kind of plasma body cooperative iron-carbon micro-electrolysis handles the device of organic flue gas |
| CN110642337A (en) * | 2019-10-14 | 2020-01-03 | 北京中科奥水环保工程技术有限公司 | Internal electrolysis composite material with catalytic activity and preparation method thereof |
| 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 |
| CN116891297B (en) * | 2023-09-08 | 2023-12-01 | 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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