CN104258689B - A kind of adsorption column simultaneously adsorbing heavy metal ion and volatile organic matter in waste gas - Google Patents
A kind of adsorption column simultaneously adsorbing heavy metal ion and volatile organic matter in waste gas Download PDFInfo
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- CN104258689B CN104258689B CN201410556773.8A CN201410556773A CN104258689B CN 104258689 B CN104258689 B CN 104258689B CN 201410556773 A CN201410556773 A CN 201410556773A CN 104258689 B CN104258689 B CN 104258689B
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 49
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- 239000003513 alkali Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
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Abstract
The invention discloses a kind of adsorption column simultaneously adsorbing heavy metal ion and volatile organic matter in waste gas, comprise a metal tube, metal tube exhaust gas entrance end and waste gas outlet end are equipped with ring flange, in the post near waste gas outlet end, cross section is fixedly installed sorbing material interception cloth bag, the ring flange of the waste gas outlet end of metal tube exhaust gas entrance end flanges dish and the toxic emission mouth of pipe or another adsorption column is connected, filled composite sorbing material in metal tube.Set of the present invention carbon nano tube compound material has the advantages that the large and calcium chloride heavy metal of nanostructured, stable performance, specific area has selective adsorption, obtain and there is high-adsorption-capacity, can the composite adsorbing material of simultaneously adsorb volatile organic matter and heavy metal.The flexible structure of adsorption column, can carry out the multiple combination of series, parallel, and can easily be applied to that toxicity is large, low concentration, mobility are strong has in exhaust-gas treatment, adsorption time is short, and adsorption efficiency is high.
Description
Technical field
The present invention relates to a kind of adsorption column simultaneously adsorbing heavy metal ion and volatile organic matter in waste gas, belong to field of environment protection.
Background technology
Along with the propelled at high velocity of industrialized fast development and urbanization process, environmental pollution for topic day by day serious, particularly atmosphere pollution is in recent years particularly serious.Wherein volatile organic matter and heavy metal are two kinds of important pollution sources of atmosphere pollution.
According to the definition boiling point of the World Health Organization at 50-250 DEG C, under room temperature, saturated vapor pressure is more than 133.32Pa, the type organic be present in vapour form at normal temperatures in air belongs to volatile organic matter, and main component comprises: hydro carbons, halogenated hydrocarbons, benzene homologues, Freon series, polycyclic aromatic hydrocarbon etc.Volatile organic matter has significant impact to human health, and can cause headache, Nausea and vomiting, weak etc., and can cause allergy, damage internal organ, Long Term Contact may be carcinogenic.And the important pollution sources that volatile organic matter or haze are formed.
Containing plurality of heavy metal material in the exhaust gas dust of steam power plant, cement plant, garbage burning factory discharge.The toxicity of heavy metal is large, distribution is wide, content is low, not easily degrade, and disperses in the environment for a long time to exist, and eventually through the passive plant absorption of bioconcentration, enters human body by food chain, produces serious influence to the existence of the mankind and health.Therefore, in complex sample, the advanced treating of heavy metal ion just seems very meaningful.
Absorption is a kind of processing method of above-mentioned two pollutants of process conventional at present, and relative to other method, expense is low, easy and simple to handle, not easily causes secondary pollution.Conventional gas absorption equipment is adsorption column.But because heavy metal and volatile organic matter adhere to inorganic matter and organic matter separately, both structures, character are completely different, thus the current adsorbent both to good adsorption properties, has a strong impact on cost and the effect of exhaust-gas treatment.
Carbon back sorbing material has stronger adsorption capacity, is widely used in environmental contaminants absorption.Graphene is a kind of carbon back sorbing material of rising in recent years, and it is the periodic cellular shape two dimension carbonaceous new material formed with hexagonal array by the carbon atom of sp2 hydridization, and its thickness only has 0.335 nm.In recent years, gradually Graphene is used as sorbing material both at home and abroad, uses it for separation and concentration and the mensuration of environmental contaminants in aqueous phase, achieve fruitful result, grapheme material presents good application prospect in alternative traditional adsorbent.
Summary of the invention
For prior art Problems existing, the invention provides a kind of adsorption column simultaneously adsorbing heavy metal ion and volatile organic matter in waste gas, comprise a metal tube, length 0.5-2 rice, internal diameter 200-400 millimeter, metal tube exhaust gas entrance end and waste gas outlet end are equipped with ring flange, in the post near waste gas outlet end, cross section is fixedly installed sorbing material interception cloth bag, the ring flange of the waste gas outlet end of metal tube exhaust gas entrance end flanges dish and the toxic emission mouth of pipe or another adsorption column is connected, filled composite sorbing material in metal tube.Described composite adsorbing material, is made up of the component of following mass percent:
Calcium chloride 34%-45%
CNT 50%-60%
Graphene 5%-6%;
The preparation process of above-mentioned composite adsorbing material comprises the steps:
1) pretreatment of CNT: CNT is put in the mixed solution of red fuming nitric acid (RFNA) and hydrofluoric acid, high pressure hydration under ar gas environment, be cooled to room temperature maintain 10-15 hour at 120-150 DEG C after, then take out CNT and spend deionized water filtration, for subsequent use;
2) preparation of calcium chloride: hydrochloric acid enters retort, lime stone is lifted into retort by bucket elevator, after reaction, gas is after tail gas washing tower water washing and tail gas washing tower alkali cleaning, the standard that reaches is discharged through air-introduced machine, after liquid pH value reaches 5 ~ 7 after reaction, directly enters neutralizing tank by bypass pipe, after adding milk of lime reaction, by in and pump squeeze into settling tank, the liquid flooding after clarification enters to clarify flow container, and calcium chloride clear liquid enters calcium chloride flow container after filtering;
3) calcium chloride load: pretreated for step 1) CNT is put into step 2) in calcium chloride clear liquid in calcium chloride flow container, high-speed stirred forms mixing material in 20 minutes, the dosage of CNT is 1-10g/100ml, above-mentioned mixing material is heated to 80 DEG C and carries out sonic oscillation 30 minutes, then be cooled to room temperature, drip the KBH of 0.04mol/L while stirring
4solution, reacts evaporation drying after 15-24 hour, by solid matter deionized water and absolute ethanol washing 3-4 time, again carries out vacuum drying, obtains the CNT of load calcium chloride;
4) preparation of composite adsorbing material: under sonic oscillation condition, the CNT of load calcium chloride step 3) obtained fully mixes in organic solvent with Graphene, the mass ratio of CNT and Graphene is 10:1, by isolated solid matter deionized water and absolute ethanol washing 3-4 time after 1 hour, again carry out vacuum drying, form Graphene-calcium chloride-CNT composite adsorbing material, described organic solvent is oxolane, acetone, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, N, dinethylformamide any one or two or more.
Supersonic frequency in the step 3) of the preparation process of composite adsorbing material is 20-40KHz.
The present invention has following advantage compared with prior art:
(1) be chemically combined with quartz sand by Graphene, in adsorption process, Graphene and CNT create cooperative effect, significantly promote the absorption property of volatile organic matter, all reach 99.5% to the clearance of volatile organic matter.
(2) calcium chloride heavy metal has good selective adsorption, by calcium chloride load on the carbon nanotubes, defines the system suction-operated of heavy metal, reaches 99.5% to the eliminating rate of absorption of heavy metal in waste gas.
(3) set of the present invention carbon nano tube compound material has the advantages that the large and calcium chloride heavy metal of nanostructured, stable performance, specific area has selective adsorption, obtain and there is high-adsorption-capacity, can the composite adsorbing material of simultaneously adsorb volatile organic matter and heavy metal.
(4) flexible structure of adsorption column, can carry out the multiple combination of series, parallel according to processing requirements, can be applied to that toxicity is large easily, low concentration, mobility are strong has in exhaust-gas treatment, adsorption time is short, and adsorption efficiency is high.
Accompanying drawing explanation
Fig. 1 is the schematic diagram in restoration of the ecosystem cabin of the present invention.
1-metal tube, 2-exhaust gas entrance end flanges dish, 3-waste gas outlet end flanges dish, 4-composite adsorbing material, 5-tackles cloth bag
Detailed description of the invention
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with example but content of the present invention is not only confined to the following examples.
Embodiment 1:
The preparation of composite adsorbing material
1) pretreatment of CNT: put into by CNT in the mixed solution of red fuming nitric acid (RFNA) and hydrofluoric acid, high pressure hydration under ar gas environment, is cooled to room temperature after maintaining 10 hours at 120 DEG C, then takes out CNT and spends deionized water filtration, for subsequent use;
2) preparation of calcium chloride: hydrochloric acid enters retort, lime stone is lifted into retort by bucket elevator, after reaction, gas is after tail gas washing tower water washing and tail gas washing tower alkali cleaning, the standard that reaches is discharged through air-introduced machine, after liquid pH value reaches 5 after reaction, directly enters neutralizing tank by bypass pipe, after adding milk of lime reaction, by in and pump squeeze into settling tank, the liquid flooding after clarification enters to clarify flow container, and calcium chloride clear liquid enters calcium chloride flow container after filtering;
3) calcium chloride load: pretreated for step 1) CNT is put into step 2) in calcium chloride clear liquid in calcium chloride flow container, high-speed stirred forms mixing material in 20 minutes, the dosage of CNT is 10g/100ml, above-mentioned mixing material is heated to 80 DEG C and carries out sonic oscillation 30 minutes, supersonic frequency is 20KHz, then be cooled to room temperature, drip the KBH of 0.04mol/L while stirring
4solution, reacts evaporation drying after 15 hours, by solid matter deionized water and absolute ethanol washing 3 times, again carries out vacuum drying, obtains the CNT of load calcium chloride;
4) preparation of composite adsorbing material: under sonic oscillation condition, the CNT of load calcium chloride step 3) obtained fully mixes in organic solvent with Graphene, the mass ratio of CNT and Graphene is 10:1, by isolated solid matter deionized water and absolute ethanol washing 3 times after 1 hour, again carry out vacuum drying, form Graphene-calcium chloride-CNT composite adsorbing material, described organic solvent is oxolane, acetone, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, N, dinethylformamide any one or two or more,
The composite adsorbing material obtained, is made up of the component of following mass percent:
Calcium chloride 34%
CNT 60%
Graphene 6%.
Above-mentioned composite adsorbing material is filled into length 1 meter, in the metal tube that internal diameter is 200 millimeters, metal tube exhaust gas entrance end and waste gas outlet end are equipped with ring flange, in the post near waste gas outlet end, cross section is fixedly installed sorbing material interception cloth bag, and metal tube exhaust gas entrance end flanges dish is connected with the toxic emission mouth of pipe.
Utilize above-mentioned composite to carry out adsorption treatment to the waste gas containing copper, lead, nickel, polycyclic aromatic hydrocarbon, 98% is reached to the clearance of copper, the clearance of lead reached to 98%, the clearance of nickel reached to 99%, 99% is reached to the clearance of polycyclic aromatic hydrocarbon.
Embodiment 2:
1) pretreatment of CNT: put into by CNT in the mixed solution of red fuming nitric acid (RFNA) and hydrofluoric acid, high pressure hydration under ar gas environment, is cooled to room temperature after maintaining 15 hours at 150 DEG C, then takes out CNT and spends deionized water filtration, for subsequent use;
2) preparation of calcium chloride: hydrochloric acid enters retort, lime stone is lifted into retort by bucket elevator, after reaction, gas is after tail gas washing tower water washing and tail gas washing tower alkali cleaning, the standard that reaches is discharged through air-introduced machine, after liquid pH value reaches 7 after reaction, directly enters neutralizing tank by bypass pipe, after adding milk of lime reaction, by in and pump squeeze into settling tank, the liquid flooding after clarification enters to clarify flow container, and calcium chloride clear liquid enters calcium chloride flow container after filtering;
3) calcium chloride load: pretreated for step 1) CNT is put into step 2) in calcium chloride clear liquid in calcium chloride flow container, high-speed stirred forms mixing material in 20 minutes, the dosage of CNT is 1g/100ml, above-mentioned mixing material is heated to 80 DEG C and carries out sonic oscillation 30 minutes, then be cooled to room temperature, drip the KBH of 0.04mol/L while stirring
4solution, reacts evaporation drying after 24 hours, by solid matter deionized water and absolute ethanol washing 4 times, again carries out vacuum drying, obtains the CNT of load calcium chloride;
4) preparation of composite adsorbing material: under sonic oscillation condition, the CNT of load calcium chloride step 3) obtained fully mixes in organic solvent with Graphene, the mass ratio of CNT and Graphene is 10:1, by isolated solid matter deionized water and absolute ethanol washing 4 times after 1 hour, again carry out vacuum drying, form Graphene-calcium chloride-CNT composite adsorbing material, described organic solvent is oxolane, acetone, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, N, dinethylformamide any one or two or more,
The composite adsorbing material obtained, is made up of the component of following mass percent:
Calcium chloride 45%
CNT 50%
Graphene 5%.
Above-mentioned composite adsorbing material is filled into length 2 meters, in the metal tube that internal diameter is 200 millimeters, metal tube exhaust gas entrance end and waste gas outlet end are equipped with ring flange, in the post near waste gas outlet end, cross section is fixedly installed sorbing material interception cloth bag, and metal tube exhaust gas entrance end flanges dish is connected with the toxic emission mouth of pipe.
Utilize above-mentioned composite to carry out adsorption treatment to the waste gas containing zinc, chromium, cadmium, halogenated hydrocarbons, 99% is reached to the clearance of zinc, the clearance of chromium reached to 98%, the clearance of cadmium reached to 99%, 98% is reached to the clearance of halogenated hydrocarbons.
Embodiment 3:
1) pretreatment of CNT: put into by CNT in the mixed solution of red fuming nitric acid (RFNA) and hydrofluoric acid, high pressure hydration under ar gas environment, is cooled to room temperature after maintaining 18 hours at 130 DEG C, then takes out CNT and spends deionized water filtration, for subsequent use;
2) preparation of calcium chloride: hydrochloric acid enters retort, lime stone is lifted into retort by bucket elevator, after reaction, gas is after tail gas washing tower water washing and tail gas washing tower alkali cleaning, the standard that reaches is discharged through air-introduced machine, after liquid pH value reaches 6 after reaction, directly enters neutralizing tank by bypass pipe, after adding milk of lime reaction, by in and pump squeeze into settling tank, the liquid flooding after clarification enters to clarify flow container, and calcium chloride clear liquid enters calcium chloride flow container after filtering;
3) calcium chloride load: pretreated for step 1) CNT is put into step 2) in calcium chloride clear liquid in calcium chloride flow container, high-speed stirred forms mixing material in 20 minutes, the dosage of CNT is 5g/100ml, above-mentioned mixing material is heated to 80 DEG C and carries out sonic oscillation 30 minutes, then be cooled to room temperature, drip the KBH of 0.04mol/L while stirring
4solution, reacts evaporation drying after 20 hours, by solid matter deionized water and absolute ethanol washing 4 times, again carries out vacuum drying, obtains the CNT of load calcium chloride;
4) preparation of composite adsorbing material: under sonic oscillation condition, the CNT of load calcium chloride step 3) obtained fully mixes in organic solvent with Graphene, the mass ratio of CNT and Graphene is 10:1, by isolated solid matter deionized water and absolute ethanol washing 4 times after 1 hour, again carry out vacuum drying, form Graphene-calcium chloride-CNT composite adsorbing material, described organic solvent is oxolane, acetone, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, N, dinethylformamide any one or two or more,
The composite adsorbing material obtained, is made up of the component of following mass percent:
Calcium chloride 39.5%
CNT 55%
Graphene 5.5%.
Above-mentioned composite adsorbing material is filled into length 1 meter, in the metal tube that internal diameter is 300 millimeters, metal tube exhaust gas entrance end and waste gas outlet end are equipped with ring flange, in the post near waste gas outlet end, cross section is fixedly installed sorbing material interception cloth bag, metal tube exhaust gas entrance end flanges dish is connected with the ring flange of the waste gas outlet end of another adsorption column, forms two-stage tandem adsorption column.
Utilize above-mentioned composite to carry out adsorption treatment to the waste gas containing manganese, chromium, nickel, trifluorotrichloroethane, 99.5% is reached to the clearance of manganese, the clearance of chromium reached to 99.5%, the clearance of nickel reached to 99.5%, 99.5% is reached to the clearance of trifluorotrichloroethane.
Claims (2)
1. one kind adsorbs the adsorption column of heavy metal ion and volatile organic matter in waste gas simultaneously, comprise a metal tube, length 0.5-2 rice, internal diameter 200-400 millimeter, metal tube exhaust gas entrance end and waste gas outlet end are equipped with ring flange, in the post near waste gas outlet end, cross section is fixedly installed sorbing material interception cloth bag, the ring flange of the waste gas outlet end of metal tube exhaust gas entrance end flanges dish and the toxic emission mouth of pipe or another adsorption column is connected, filled composite sorbing material in metal tube, described composite adsorbing material, is made up of the component of following mass percent:
Calcium chloride 34%-45%
CNT 50%-60%
Graphene 5%-6%;
It is characterized in that the preparation process of above-mentioned composite adsorbing material comprises the steps:
1) pretreatment of CNT: CNT is put in the mixed solution of red fuming nitric acid (RFNA) and hydrofluoric acid, high pressure hydration under ar gas environment, be cooled to room temperature maintain 10-15 hour at 120-150 DEG C after, then take out CNT and spend deionized water filtration, for subsequent use;
2) preparation of calcium chloride: hydrochloric acid enters retort, lime stone is lifted into retort by bucket elevator, after reaction, gas is after tail gas washing tower water washing and tail gas washing tower alkali cleaning, the standard that reaches is discharged through air-introduced machine, after liquid pH value reaches 5 ~ 7 after reaction, directly enters neutralizing tank by bypass pipe, after adding milk of lime reaction, by in and pump squeeze into settling tank, the liquid flooding after clarification enters to clarify flow container, and calcium chloride clear liquid enters calcium chloride flow container after filtering;
3) calcium chloride load: pretreated for step 1) CNT is put into step 2) in calcium chloride clear liquid in calcium chloride flow container, high-speed stirred forms mixing material in 20 minutes, the dosage of CNT is 1-10g/100ml, above-mentioned mixing material is heated to 80 DEG C and carries out sonic oscillation 30 minutes, then be cooled to room temperature, drip the KBH of 0.04mol/L while stirring
4solution, reacts evaporation drying after 15-24 hour, by solid matter deionized water and absolute ethanol washing 3-4 time, again carries out vacuum drying, obtains the CNT of load calcium chloride;
4) preparation of composite adsorbing material: under sonic oscillation condition, the CNT of load calcium chloride step 3) obtained fully mixes in organic solvent with Graphene, the mass ratio of CNT and Graphene is 10:1, by isolated solid matter deionized water and absolute ethanol washing 3-4 time after 1 hour, again carry out vacuum drying, form the three-dimensional composite adsorbing material of Graphene-calcium chloride-CNT, described organic solvent is oxolane, acetone, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, N, dinethylformamide any one or two or more.
2. adsorption column as claimed in claim 1, is characterized in that: the supersonic frequency in the step 3) of the preparation process of composite adsorbing material is 20-40KHz.
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| CN1605816A (en) * | 2003-10-10 | 2005-04-13 | 欧阳永定 | Improved solid absorbent bed |
| WO2006055670A3 (en) * | 2004-11-16 | 2006-12-07 | Hyperion Catalysis Int | Methods for preparing catalysts supported on carbon nanotube networks |
| CN101480499A (en) * | 2008-12-25 | 2009-07-15 | 杭州轩爱科技有限公司 | Air purification material and preparation method thereof |
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| CN1605816A (en) * | 2003-10-10 | 2005-04-13 | 欧阳永定 | Improved solid absorbent bed |
| WO2006055670A3 (en) * | 2004-11-16 | 2006-12-07 | Hyperion Catalysis Int | Methods for preparing catalysts supported on carbon nanotube networks |
| CN101480499A (en) * | 2008-12-25 | 2009-07-15 | 杭州轩爱科技有限公司 | Air purification material and preparation method thereof |
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