CN104759254B - Preparation method of chromium-loaded active carbon as well as condition and device of methylbenzene adsorption using chromium-loaded active carbon - Google Patents
Preparation method of chromium-loaded active carbon as well as condition and device of methylbenzene adsorption using chromium-loaded active carbon Download PDFInfo
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- CN104759254B CN104759254B CN201510177424.XA CN201510177424A CN104759254B CN 104759254 B CN104759254 B CN 104759254B CN 201510177424 A CN201510177424 A CN 201510177424A CN 104759254 B CN104759254 B CN 104759254B
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Abstract
The invention discloses a preparation method of chromium-loaded active carbon as well as the condition and device of methylbenzene adsorption using the chromium-loaded active carbon. The preparation comprises the following steps: (1) preparing impregnating liquid, namely dissolving weighed chromium salt into acid solution of 0.1-10mol/L and preparing the impregnating liquid at the temperature of 20-80 DEG C; (2) impregnating the active carbon, namely by using an isovolumetric impregnating method or excessive impregnating method, impregnating the active carbon with the particle size being 150 microns-1700 microns in the prepared impregnating solution, wherein the mass ratio of the chromium to the active carbon is 0.03 to 0.3 after impregnating; (3) impregnating, namely placing the solution after the active carbon is impregnated at room temperature for 3-15 hours; and (4) drying, namely placing the impregnated active carbon in nitrogen of 150 DEG C for 4-8 hours, so as to obtain the chromium-loaded active carbon. According to the preparation method, the metal chromium element is impregnated on the active carbon to prepare the chromium-loaded active carbon; the adsorption capability of the active carbon is improved and the saturated adsorption of the active carbon to methylbenzene can be increased by 20-110%.
Description
Technical field
The invention belongs to sorbing material and atmosphere pollution processing technology field, and in particular to a kind of preparation of load chromium activated carbon
Method and the condition and device with its absorption toluene.
Background technology
With the aromatic series such as the fast development of modern industry, dichloromethane, toluene, dimethylbenzene, benzene, halogenated hydrocarbons, aldoketones,
The organic solvents such as esters, alcohols are widely used in chemical industry, petrochemical industry, coating, medicine, rubber, resin, printing etc., and each is led
Domain.These volatile organic solvents have toxicity mostly, and wherein quite a few is finally entered greatly in the form of organic exhaust gas
In gas, air is caused to be heavily polluted.If dealt with improperly, that is, the loss of raw material is caused, environment is polluted again, it is even more serious
It is the infringement to human health.The pay attention to day by day of Environmental protection work, the continuous improvement to atmospheric emission standard so that
The recycling of organic exhaust gas is imperative.Organic solvent is reclaimed from the organic exhaust gas of industrial discharge, you can to reduce to ring
The pollution in border, has reclaimed precious resources again.
At present, it is domestic for the process recovery method of industrial organic exhaust gas mainly has：Heating power burning method, condensation method, absorption
Absorption method, wherein adsorption recovery method are to carry out adsorption cleaning with Activated Carbon toward VOCs-Containing Exhausts, be its essence is high-strength using activated carbon
The characteristic of degree absorption is adsorbed onto the organic solvent in waste gas in activated carbon and concentrates, and Jing charcoal absorption purified gases are straight
Run in sky, and this is the process of an Adsorption Concentration, and organic solvent is not disposed, and is a physical process.When absorption
When organic matter reaches the adsorbance of regulation, then stop using, the organic matter after absorption is reclaimed Jing after desorption.Adsorbent is full in absorption
With it is rear, can through reproducer, recycle.
The characterization of adsorption of activated carbon depends on the surface chemical property of its flourishing pore structure and uniqueness.For how to improve
The absorption property of activated carbon, researcher starts with terms of the preparation of new carbon and normal activated carbon modified two, achieves one
Series of studies achievement.NACF is generally referred to used in the new carbon of adsorbing domain, but its preparation process is often non-
Often complicated loaded down with trivial details, cost is also far above normal activated carbon, and use condition is harsher.Disadvantages mentioned above constrains NACF
Widely using in the industry.At present, the material with carbon element for being commercially used for gas removal remains normal activated carbon.
At present, carried active carbon has been used for other systems such as desulfurization or separating ethene-ethane, but is not yet used to adsorb
Toluene system, for toluene in gas adsorbing and removing more use the activated carbon of unsupported metal, such as Chinese invention patent
03159299.6 provides a kind of method for recovering toluene from exhausted air, and up to 65%, the toluene of the purified gas after purification contains toluene recovery rate
Amount ＜ 40mg/m3, up to GB secondary standard.At normal temperatures, the saturated extent of adsorption of activated carbon can meet general adsorption entails, but
The adsorbance of activated carbon but very little under high temperature.
The content of the invention
It is an object of the present invention to provide a kind of preparation method for carrying chromium activated carbon and the condition and device with its absorption toluene.
To reach above-mentioned purpose, the technical solution used in the present invention is：A kind of preparation method for carrying chromium activated carbon, including such as
Lower step：
（1）Prepare maceration extract：Load weighted chromic salts is dissolved in the acid solution of 0.1～10mol/L, at 20～80 DEG C
At a temperature of be configured to maceration extract；
（2）Immesion active carbon：Using infusion process, 150 μm～1700 μm of activated carbon of granularity be impregnated in into above-mentioned dipping
In liquid, chromium and the mass ratio of activated carbon are 0.03～0.3 after dipping；
（3）Dipping：Solution after Immesion active carbon is placed at room temperature 3～15 hours；
（4）It is dried：Activated carbon after dipping is positioned in 150 DEG C of nitrogen and is dried 4～8 hours, obtains carrying chromium activated carbon.
Wherein, the step（1）In chromic salts be chromium chloride, chromic nitrate, chromium sulfate, chromic acetate, chromium+oxalic acid in one kind
Or several mixing；
Acid solution is the hydrochloric acid solution of 1mol/L.
Wherein, the step（2）In infusion process be one kind in equi-volume impregnating and excessive infusion process.
Wherein, the step（2）In activated carbon be wooden, ature of coal, shell or coconut husk granular activated carbon.
Wherein, the step（2）In, chromium and the mass ratio of activated carbon are 0.1 after dipping；
The step（3）In, dip time is 12h, if aiding in dipping process with ultrasonic vibration, dip time can shorten
2～5 hours.
The embodiment of the present invention also provides a kind of adsorption conditionses using above-mentioned load chromium charcoal absorption toluene, is：Toluene
Toluene level ＜ 8% in source of the gas, 0～1MPa of adsorptive pressure, gas flow ＜ 400mL/min, 40～200 DEG C of adsorption temp.
The embodiment of the present invention also provides a kind of device using above-mentioned load chromium charcoal absorption toluene, including nitrogen cylinder,
Pressure-reducing valve, toluene gasification installation, the first valve, the second valve, the 3rd valve, the first rotor flowmeter, the second spinner flowmeter,
Inside set adsorption column, heating furnace, precision pressure gauge, the second Mini-adjustable valve and the six-way valve for carrying chromium activated carbon；
The adsorption column is in heating furnace；
The pressure-reducing valve is arranged on the pipeline of connection nitrogen cylinder and toluene gasification installation；
First valve is set in turn in the air inlet for connecting toluene gasification installation and adsorption column with the first rotor flowmeter
On the pipeline of mouth；
Second valve is arranged in the air inlet duct of connection nitrogen cylinder and adsorption column；
3rd valve is arranged on the pipeline of the second valve of connection and absorption column outlet；
The precision pressure gauge is at the air inlet of adsorption column；
The gas outlet of the adsorption column is by a pipeline for being provided with second Mini-adjustable valve and the second spinner flowmeter
It is connected with six-way valve, purified gas flowed through and emptied after the six-way valve.
The device of above-mentioned load chromium charcoal absorption toluene also includes programmed temperature control instrument, and it is connected with the heating furnace.
The device of above-mentioned load chromium charcoal absorption toluene also includes the first Mini-adjustable valve, and it is arranged at and the absorption
The air inlet of post is connected, for regenerating when on-line analysis tracheae.
The device of above-mentioned load chromium charcoal absorption toluene also includes gas chromatograph, and purified gas is described to be passed through
The hydrogen of six-way valve is carrier gas, and from the six-way valve gas chromatograph is flowed out to.
The device of above-mentioned load chromium charcoal absorption toluene includes 3 paths, is respectively：
（1）On-line analysis path during regeneration, pressure-reducing valve, the second valve, the 3rd valve and the first Mini-adjustable valve are opened, the
One valve and the second Mini-adjustable valve are closed, and nitrogen is flowed into as purge gass from adsorption column lower section, and top is flowed out, and absorption is existed
Out, desorption gas enters gas-chromatography on-line analysis to toluene replacement on adsorbent.
（2）Purification path containing toluene source of the gas, pressure-reducing valve, the first valve and the second Mini-adjustable valve are opened, the second valve,
3rd valve and the first Mini-adjustable valve are closed, normality gasify in toluene gasification installation for the toluene of liquid after with nitrogen cylinder stream
The nitrogen mixing for coming over, the then toluene via absorption column purification in it, purified gas is emptied by six-way valve.
（3）Adsorption effect checks path, pressure-reducing valve, the first valve and the second Mini-adjustable valve to open, the second valve, the 3rd
Valve and the first Mini-adjustable valve are closed, and normality flows through after gasifying in toluene gasification installation for the toluene of liquid with nitrogen cylinder
Nitrogen mixing, the then toluene via absorption column purification in it, purified gas is admitted to gas phase color by carrier gas of hydrogen
Spectrometer, the chromatogram shown by gas chromatograph is analyzing the adsorption effect of adsorption column.
It is of the invention to be using the theoretical foundation for carrying chromium charcoal absorption toluene：In toluene the conjugatedπbond of phenyl ring can with chromium from
Sub- outer layer s unoccupied orbitals overlap to form σ keys, at the same time, the π of benzene*Antibonding unoccupied orbital forms π complexings with the d Orbital Overlaps of metal
Key.This π Absorptive complex waves active force is better than physisorption power.Therefore under some occasions, such as high temperature, physical absorption is worked as
When active force is very weak, π Absorptive complex waves still can play a role, so as to strengthen the adsorption capacity of adsorbent.And π Absorptive complex waves are made
Firmly it is weaker than chemisorption power again, therefore and can very easily realizes the regeneration of adsorbent.
Because above-mentioned technical proposal is used, the present invention has compared with prior art following advantages：
The present invention impregnated in metallic element chromium on activated carbon, make load chromium activated carbon, improve the adsorption capacity of activated carbon,
20%～110% can be improved to the saturated extent of adsorption of toluene.
Description of the drawings
Fig. 1 is using the structural representation of the device for carrying chromium charcoal absorption toluene in the present invention；
Fig. 2 is the characterization of adsorption comparison diagram of identical adsorption conditionses in the embodiment of the present invention one, the adsorbent of different loads amount.
Wherein：1st, nitrogen cylinder；2nd, pressure-reducing valve；3rd, toluene gasification installation；4th, the first valve；5th, the second valve；6th, first turn
Subflow gauge；7th, the second spinner flowmeter；8th, adsorption column；9th, heating furnace；10th, programmed temperature control instrument；11st, precision pressure gauge；12nd,
One Mini-adjustable valve；13rd, the second Mini-adjustable valve；14th, gas chromatograph；15th, six-way valve；16th, the 3rd valve.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment the invention will be further described：
A kind of preparation method for carrying chromium activated carbon, comprises the steps：
（1）Prepare maceration extract：Load weighted chromic salts is dissolved in the acid solution of 0.1～10mol/L, at 20～80 DEG C
At a temperature of be configured to maceration extract；
Wherein, chromic salts is chromium chloride, and acid solution is preferably the hydrochloric acid solution of 1mol/L.
（2）Immesion active carbon：Using equi-volume impregnating or excessive infusion process, by 150 μm～1700 μm of activity of granularity
Charcoal impregnated in above-mentioned maceration extract, and chromium and the mass ratio of activated carbon are 0.03～0.3 after dipping；
Wherein, activated carbon can select one or more mixing in wooden, ature of coal, shell and coconut husk granular activated carbon.Leaching
Chromium and the optimum mass ratio of activated carbon are 0.1 after stain.
（3）Dipping：Solution after Immesion active carbon is placed at room temperature 3～15 hours；
Wherein, optimum dip time is 12h, if aiding in dipping process with ultrasonic vibration, dip time can shorten 2～
5 hours.
（4）It is dried：Activated carbon after dipping is positioned in 150 DEG C of nitrogen and is dried 4～8 hours, obtains carrying chromium activated carbon.
The present invention also provides a kind of adsorption conditionses using above-mentioned load chromium charcoal absorption toluene, is：In toluene source of the gas
Toluene level ＜ 8%, 0～1MPa of adsorptive pressure, gas flow ＜ 400mL/min, 40～200 DEG C of adsorption temp.
The present invention also provides a kind of device using above-mentioned load chromium charcoal absorption toluene, structure as shown in figure 1, including
Nitrogen cylinder 1, pressure-reducing valve 2, toluene gasification installation 3, the first valve 4, the second valve 5, the first rotor flowmeter 6, the second rotor stream
Gauge 7, interior setting carry the adsorption column 8 of chromium activated carbon, heating furnace 9, its programmed temperature control instrument 10, precision for being connected with the heating furnace 9
Pressure gauge 11, the first Mini-adjustable valve 12, the second Mini-adjustable valve 13, gas chromatograph 14, the valve 16 of six-way valve 15 and the 3rd.
The adsorption column is in heating furnace.
The pressure-reducing valve is arranged on the pipeline of connection nitrogen cylinder and toluene gasification installation.
First valve is set in turn in the air inlet for connecting toluene gasification installation and adsorption column with the first rotor flowmeter
On the pipeline of mouth.
Second valve is arranged in the air inlet duct of connection nitrogen cylinder and adsorption column.
3rd valve is arranged on the pipeline of the second valve of connection and absorption column outlet；
The precision pressure gauge is at the air inlet of adsorption column.
First Mini-adjustable valve be arranged at be connected with the air inlet of the adsorption column, for regenerating when on-line analysis
On tracheae.
The gas outlet of the adsorption column is by a pipeline for being provided with second Mini-adjustable valve and the second spinner flowmeter
It is connected with six-way valve, purified gas flowed through and emptied after the six-way valve.
Purified gas flows out to gas-chromatography to be passed through the hydrogen of the six-way valve as carrier gas from the six-way valve
Instrument.
The device of above-mentioned load chromium charcoal absorption toluene includes 3 paths, is respectively：
（1）On-line analysis path during regeneration, pressure-reducing valve, the second valve, the 3rd valve and the first Mini-adjustable valve are opened, the
One valve and the second Mini-adjustable valve are closed, and nitrogen is flowed into as purge gass from adsorption column lower section, and top is flowed out, and absorption is existed
Out, desorption gas enters gas-chromatography on-line analysis to toluene replacement on adsorbent.
（2）Purification path containing toluene source of the gas, pressure-reducing valve, the first valve and the second Mini-adjustable valve are opened, the second valve,
3rd valve and the first Mini-adjustable valve are closed, normality gasify in toluene gasification installation for the toluene of liquid after with nitrogen cylinder stream
The nitrogen mixing for coming over, the then toluene via absorption column purification in it, purified gas is emptied by six-way valve.
（3）Adsorption effect checks path, pressure-reducing valve, the first valve and the second Mini-adjustable valve to open, the second valve, the 3rd
Valve and the first Mini-adjustable valve are closed, and normality flows through after gasifying in toluene gasification installation for the toluene of liquid with nitrogen cylinder
Nitrogen mixing, the then toluene via absorption column purification in it, purified gas is admitted to gas phase color by carrier gas of hydrogen
Spectrometer, the chromatogram shown by gas chromatograph is analyzing the adsorption effect of adsorption column.
The adsorbance for carrying the relatively common activated carbon of chromium activated carbon to illustrate the invention increases, below with several enforcements
Example is illustrated.
Embodiment one：(AC is designated as by taking the cocoanut active charcoal of 20～40 mesh as an example without the activated carbon of load0), by chromium chloride
In being dissolved in the HCl solution of the 1mol/L of certain volume, then by AC0Dipping is wherein.Place under room temperature after 12h, 150 DEG C of nitrogen
Middle drying.The mass ratio of chromium and activated carbon is respectively 0.052 in dipping system:1、0.104:1、0.156:1、0.208:1, gained
Acticarbon is designated as respectively AC1、AC2、AC3And AC4。
By AC0、AC1、AC2、AC3And AC4The adsorption experiment of toluene is carried out, adsorption conditionses are：Toluene contains in toluene source of the gas
Measure as 5%, adsorptive pressure is 0.2MPa, gas flow 250mL/min.
When identical adsorption conditionses, different loads amount, load chromium activated carbon is to the adsorption capacity of toluene as shown in table 1 and Fig. 2.
Table 1：The characterization of adsorption of different loads amount adsorbent
From table 1 and Fig. 2, under identical adsorption conditionses, the load chromium activated carbon of different loads amount compares unmodified activated carbon
Adsorbance have a different degrees of raising, increase rate is 20%～110%.
Embodiment two：Chromium chloride is dissolved in the HCl solution of the 1mol/L of certain volume, is then impregnated activated carbon AC
Wherein, chromium and the mass ratio of activated carbon are 0.07 in dipping system:1, place under room temperature after 12h, it is dried in 150 DEG C of nitrogen, so
The adsorption experiment of toluene is carried out afterwards.
Toluene level is 3% in toluene source of the gas, and adsorptive pressure is 0.2MPa, gas flow 250mL/min, and adsorption temp is
40 DEG C, the saturated extent of adsorption of toluene reaches 192.46mg/g activated carbons, than the adsorbance of unmodified activated carbon under similarity condition
155.91 mg/g activated carbons, improve 23.44%.
Embodiment three：Chromium chloride is dissolved in the HCl solution of the 1mol/L of certain volume, is then impregnated activated carbon AC
Wherein, chromium and the mass ratio of activated carbon are 0.18 in dipping system:1, place under room temperature after 12h, it is dried in 150 DEG C of nitrogen, so
The adsorption experiment of toluene is carried out afterwards.
Toluene level is 5% in toluene source of the gas, and adsorptive pressure is 0.6MPa, gas flow 300mL/min, and adsorption temp is
120 DEG C, the saturated extent of adsorption of toluene reaches 153.84mg/g activated carbons, than the adsorbance of unmodified activated carbon under similarity condition
101.68mg/g activated carbon, improves 51.30%.
Example IV：Chromium chloride is dissolved in the HCl solution of the 1mol/L of certain volume, is then impregnated activated carbon AC
Wherein, chromium and the mass ratio of activated carbon are 0.25 in dipping system:1, place under room temperature after 12h, it is dried in 150 DEG C of nitrogen, so
The adsorption experiment of toluene is carried out afterwards.
Toluene level is 5% in toluene source of the gas, and adsorptive pressure is 0.3MPa, gas flow 250mL/min, and adsorption temp is
200 DEG C, the saturated extent of adsorption of toluene reaches 107.50mg/g activated carbons, than the adsorbance of unmodified activated carbon under the same terms
60.90mg/g activated carbons, improve 76.52%.
The above embodiments two, three, four illustrate different adsorption conditionses, different loads amount, carry chromium activated carbon and do not change relatively
The saturated extent of adsorption of property activated carbon increases.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, on the premise of without departing from principle of the present invention, some improvement or replacement can also be made, such as chromium chloride is converted
For other chromic salts, the modified activated carbon of carried metal chromium is prepared using the preparation method in the present invention, also should be regarded as the present invention's
Protection domain.
Claims (9)
1. a kind of application for carrying chromium activated carbon in absorption toluene, it is characterised in that the preparation method bag of the load chromium activated carbon
Include following steps：
（1）Prepare maceration extract：Load weighted chromic salts is dissolved in the acid solution of 0.1～10mol/L, in 20～80 DEG C of temperature
Maceration extract is configured under degree；
（2）Immesion active carbon：Using infusion process, 150 μm～1700 μm of activated carbon of granularity impregnated in above-mentioned maceration extract,
Chromium and the mass ratio of activated carbon are 0.03～0.3 after dipping；
（3）Dipping：Solution after Immesion active carbon is placed at room temperature 3～15 hours；
（4）It is dried：Activated carbon after dipping is positioned in 150 DEG C of nitrogen and is dried 4～8 hours, obtains carrying chromium activated carbon；
It is described carry chromium charcoal absorption toluene adsorption conditionses be：Toluene level ＜ 8% in toluene source of the gas, adsorptive pressure 0～
1MPa, gas flow ＜ 400mL/min, 40～200 DEG C of adsorption temp.
2. the application for carrying chromium activated carbon in absorption toluene according to claim 1, it is characterised in that the step（1）
In chromic salts be chromium chloride, chromic nitrate, chromium sulfate, chromic acetate, chromium+oxalic acid in one or more mixing；
Acid solution is the hydrochloric acid solution of 1mol/L.
3. the application for carrying chromium activated carbon in absorption toluene according to claim 1, it is characterised in that the step（2）
In infusion process be one kind in equi-volume impregnating and excessive infusion process.
4. the application for carrying chromium activated carbon in absorption toluene according to claim 1, it is characterised in that the step（2）
In activated carbon be wooden, ature of coal, shell or coconut husk granular activated carbon.
5. the application for carrying chromium activated carbon in absorption toluene according to claim 1, it is characterised in that the step（2）
In, chromium and the mass ratio of activated carbon are 0.1 after dipping；
The step（3）In, dip time is 12h, if aiding in dipping process with ultrasonic vibration, it is little that dip time shortens 2～5
When.
6. it is a kind of carry chromium charcoal absorption toluene device, it is characterised in that including nitrogen cylinder, pressure-reducing valve, toluene gasification installation,
First valve, the second valve, the 3rd valve, the first rotor flowmeter, the second spinner flowmeter, interior set as in claim 1-5
The load adsorption column of chromium activated carbon that application described in any one is used, heating furnace, precision pressure gauge, the second Mini-adjustable valve and
Six-way valve；
The adsorption column is in heating furnace；
The pressure-reducing valve is arranged on the pipeline of connection nitrogen cylinder and toluene gasification installation；
First valve is set in turn in the air inlet that connects toluene gasification installation and adsorption column with the first rotor flowmeter
On pipeline；
Second valve is arranged in the air inlet duct of connection nitrogen cylinder and adsorption column；
3rd valve is arranged on the pipeline of the second valve of connection and absorption column outlet；
The precision pressure gauge is at the air inlet of adsorption column；
The gas outlet of the adsorption column is by a pipeline and six for being provided with second Mini-adjustable valve and the second spinner flowmeter
Port valve is connected, and purified gas flowed through and emptied after the six-way valve.
7. it is according to claim 6 carry chromium charcoal absorption toluene device, it is characterised in that also including temperature programmed control
Instrument, it is connected with the heating furnace.
8. it is according to claim 6 carry chromium charcoal absorption toluene device, it is characterised in that also including the first micro tune
Section valve, its be arranged at be connected with the air inlet of the adsorption column, for regenerating when on-line analysis tracheae.
9. it is according to claim 6 carry chromium charcoal absorption toluene device, it is characterised in that also including gas-chromatography
Instrument, purified gas flows out to gas chromatograph as carrier gas with the hydrogen for being passed through the six-way valve from the six-way valve.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510177424.XA CN104759254B (en) | 2015-04-15 | 2015-04-15 | Preparation method of chromium-loaded active carbon as well as condition and device of methylbenzene adsorption using chromium-loaded active carbon |
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| CN201510177424.XA CN104759254B (en) | 2015-04-15 | 2015-04-15 | Preparation method of chromium-loaded active carbon as well as condition and device of methylbenzene adsorption using chromium-loaded active carbon |
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| CN107519944B (en) * | 2017-09-06 | 2023-02-21 | 新地能源工程技术有限公司 | Catalyst continuous production equipment and method |
| CN112875699A (en) * | 2021-02-07 | 2021-06-01 | 西安科技大学 | Preparation method and application of special steel slag-based biomass activated carbon |
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| CN1307930A (en) * | 2000-12-18 | 2001-08-15 | 中国人民解放军63971部队 | Chromium-free soaked active carbon and its preparation |
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| WO2013169811A4 (en) * | 2012-05-07 | 2014-04-03 | Biogenic Reagents LLC | Biogenic activated carbon and methods of making and using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030102267A1 (en) * | 2001-11-30 | 2003-06-05 | Kim Dae K. | Process for purification of aromatic monomers |
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| CN1307930A (en) * | 2000-12-18 | 2001-08-15 | 中国人民解放军63971部队 | Chromium-free soaked active carbon and its preparation |
| CN1377729A (en) * | 2001-04-05 | 2002-11-06 | 上海欧臣环境高科技有限责任公司 | Purifying material capable of removing organic gas in air and its preparing method |
| CN1597051A (en) * | 2003-09-15 | 2005-03-23 | 傅太平 | Method for recovering toluene from exhausted air |
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| CN1994555A (en) * | 2006-12-15 | 2007-07-11 | 四川省林业科学研究院 | Impregnated active carbon and preparation method thereof |
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