CN108479335A - A kind of VOCs exhaust gas comprehensive processing technique - Google Patents
A kind of VOCs exhaust gas comprehensive processing technique Download PDFInfo
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
The present invention relates to a kind of VOCs exhaust gas comprehensive processing techniques, belong to the technical field of environmental project.VOCs exhaust gas comprehensive processing techniques include the following steps：Step (1)：Pretreatment：It collects VOCs exhaust gas and by the spray liquid after heating atomization, the gas phase and liquid phase in separation VOCs exhaust gas is handled by gas-liquid separation, to remove the particulate matter in VOCs exhaust gas；Step (2)：Adsorption treatment：Gas phase in step (1) VOCs exhaust gas is passed through in the reactor equipped with adsorbent and carries out adsorption treatment；Step (3)：Treatment by Photocatalysis Oxidation：By step (2), treated that gas is passed through in the reactor equipped with photochemical catalyst, carries out Treatment by Photocatalysis Oxidation, gas is finally discharged.The present invention provides a kind of VOCs exhaust gas comprehensive processing techniques, can effectively improve VOCs removal rates, reduce pollution, while technological operation is simple, operating cost is cheap, are suitable for production application.
Description
Technical field
The present invention relates to a kind of VOCs exhaust gas comprehensive processing techniques, belong to the technical field of environmental project.
Background technology
VOCs (volatile organic compounds), that is, volatile organic matter, it refers to a kind of room temperature
Lower saturated vapor pressure is more than the organic compound that boiling point under 70Pa, normal pressure is not higher than 260 DEG C.The VOCs from the perspective of environmentology
Refer to be to cause the gaseous organic substance of environmental pollution.Currently, the VOCs detected in air about more than 150 is planted, mainly may be used
It is divided into eight major class：Alkanes, aromatic hydrocarbons, olefines, alcohols, esters, aldoketones, acid and anhydride, amides.At this stage,
VOCs in air is essentially from man-made pollution source, including four big discharge links：VOCs production processes, storage and transport process, with
VOCs is technical process, the use process of the product containing VOCs of raw material.The generation and discharge of a large amount of VOCs can cause to seriously endanger,
Such as：Under sunlight, VOCs and NOxPhotochemical reaction occurs, generates photochemical fog, causes secondary pollution, stimulates people
Eyes and respiratory system, the growth to harm the crops；Most VOCs are toxic, foul smelling, make one to have an aptitude to the breathing of accumulation property
Tract disease, or even cause acute poisoning；Most VOCs are inflammable and explosive, and high concentration easily causes explosion when discharging；Part VOCs can be broken
Bad ozone layer.
Currently, common VOCs treatment technologies can be divided into two kinds：One kind is recovery technology, and another kind is technology for eliminating.It returns
Receipts technology is to use physical method, that is, uses the technologies such as temperature, pressure, selective absorbent and permoselective membrane to detach VOCs,
Main includes absorption, absorption, condensation and membrane separation technique etc..Technology for eliminating is to use heat, micro- life using chemistry or biochemical reaction
Organic matter is transformed into carbon dioxide and water by object and catalyst, mainly there is burning, photocatalytic degradation, biodegradation, plasma
Body technique etc..
Since the VOCs concentration distribution ranges in exhaust gas are wide, and the ingredient of VOCs is relative complex, and the characteristic of pollutant is respectively not
Identical, any single VOCs processing methods are influenced by factors such as its scope of application, removal capacity, operating costs.Therefore
Administering VOCs also needs to be further improved control technology, the various solution pools of optimization and the newer control technology of exploitation, to reach
To improving VOCs removal rates, reducing secondary pollution and reducing the purpose of cost, this is the following main development for administering VOCs technologies
Direction.
Invention content
The problem of for current VOCs exhaust-gas treatments, the present invention provides a kind of VOCs exhaust gas General Office science and engineerings
Skill can effectively improve VOCs removal rates, reduce pollution, while technological operation is simple, operating cost is cheap, is answered suitable for production
With.
The invention discloses a kind of VOCs exhaust gas comprehensive processing techniques, include the following steps：
Step (1)：Pretreatment：It collects VOCs exhaust gas and by the spray liquid after heating atomization, is handled by gas-liquid separation
The gas phase and liquid phase in VOCs exhaust gas are detached, to remove the particulate matter in VOCs exhaust gas；
Step (2)：Adsorption treatment：By the gas phase in step (1) VOCs exhaust gas be passed through in the reactor equipped with adsorbent into
Row adsorption treatment；
Step (3)：Treatment by Photocatalysis Oxidation：By step (2), treated that gas is passed through the reactor equipped with photochemical catalyst
In, Treatment by Photocatalysis Oxidation is carried out, gas is finally discharged.
Preferably, the spray liquid in the step (1) is deionized water.
Preferably, the adsorbent in the step (2) is made by following methods：Kaolin is placed in salpeter solution, to
Surfactant is wherein added, 70 DEG C of heating water bath is simultaneously stirred to react, and centrifuges to obtain sediment after reaction, washing precipitate,
And after at 500 DEG C calcining 6h, cooling grinding crosses 500 mesh sieve, obtains the adsorbent.
Preferably, the surfactant be cetyl trimethylammonium bromide, cetyl trimethyl pyridinium chloride,
Dodecyl trimethyl ammonium bromide.
Preferably, in the salpeter solution nitric acid a concentration of 1~3molL-1.It is highly preferred that the nitric acid is molten
A concentration of 2.5molL of nitric acid in liquid-1。
Preferably, the specific surface area of the adsorbent is 200-350m2/g。
Preferably, the photochemical catalyst in step (3) is made by following methods：It will be added drop-wise to second under butyl titanate stirring condition
It obtains homogeneous transparent solution in alcohol, after stirring, then platinum chloride solution is slowly added to above-mentioned solution in being vigorously stirred down, obtain
Lyosol is aged at room temperature, is formed xerogel, is dried after filtering, 2h is heated in 600 DEG C, natural cooling after taking-up is ground
Grind to obtain photochemical catalyst Pt/TiO2。
Preferably, the platinum chloride solution is the solution that platinum chloride is dissolved in hydrochloric acid, mole shared by Chlorine in Solution platinum
Percentage is 3%.
Preferably, the digestion time in photochemical catalyst preparation method is 72~84h.
The present invention has carried out VOCs exhaust gas using the process of pretreatment-adsorption treatment-Treatment by Photocatalysis Oxidation comprehensive
Conjunction is handled, and be can effectively improve VOCs removal rates, is reduced pollution.Specifically, the present invention improves treatment technology, optimisation technique side
Case combines, and the technical solution being used in combination using a variety of processing modes can effectively improve VOCs removal rates.The present invention is at absorption
Reason step in use new and effective adsorbent, the adsorbent by surfactant and it is acidified modified after, can effectively increase
The specific surface area of adsorbent, increases effective adsorption site of adsorbent, and then improves adsorption energy of the adsorbent to VOCs exhaust gas
Power.The present invention uses photochemical catalyst Pt/TiO in Treatment by Photocatalysis Oxidation step2, by the way that precious metals pt is supported on TiO2
On, the Pt oxides of high-valence state can effectively facilitate photoelectron and be detached with hole as photoelectron trap center, extend the hole longevity
Life, and then improve activity of the photochemical catalyst to VOCs exhaust fume catalytics.The entire processing procedure of the present invention is simple to operation, processing is imitated
Rate is high, required equipment is few, has been well positioned to meet requirement of the modern enterprise to energy-saving and emission-reduction, raising productivity effect, has been protected to environment
It protects, economizing on resources is of great significance.
Specific implementation mode
With reference to embodiments, the specific implementation mode of the present invention is described in more details, so as to more preferably
Ground understands the advantages of the solution of the present invention and its various aspects.However, specific embodiments described below and embodiment are only
It is for illustrative purposes, rather than limiting the invention.
Specific surface area in following embodiment and comparative example is tested using dynamic nitrogen adsorption (BET) method, and specific surface area is surveyed
Try the NOVA 2000e that the test equipment used is the production of Kang Ta companies of the U.S..It measures sample and weighs 0.1~0.2g, before test,
Sample deaerates 4h at 300 DEG C, is then measured under -196 DEG C of environment using liquid nitrogen.
VOCs exhaust gas concentrations in following embodiment and comparative example are tested using chromatogram ration analysis, are used
Test equipment is 37 Fourier transformation infrared spectrometers of Tensor of Bruker Optics companies of Germany production.
Embodiment 1
Integrated treatment is carried out to VOCs exhaust gas, is included the following steps：
Step (1)：It collects VOCs exhaust gas and by the deionized water spray liquid after heating atomization, is handled by gas-liquid separation
The gas phase and liquid phase in VOCs exhaust gas are detached, the particulate matter in VOCs exhaust gas is removed；
Step (2)：By weight, 20 parts of kaolin are placed in 200 parts of 1molL-1In salpeter solution, 5 are added
Part surfactant cetyl trimethylammonium bromide, heating water bath are stirred to react 5h to 70 DEG C.Centrifuge after reaction heavy
Starch distills water washing precipitate, and sediment is calcined 6h at 500 DEG C, is ground after cooling, 500 mesh is crossed and sieves to obtain the suction
Attached dose.The gas phase in step (1) VOCs exhaust gas is passed through in the reactor equipped with adsorbent again and carries out adsorption treatment.
Step (3)：It will be added drop-wise in ethyl alcohol under butyl titanate stirring condition, homogeneous transparent solution obtained after stirring, then will
Dissolved with platinum chloride (PtCl4) (doping Pt4+Mole percent be hydrochloric acid solution 3%) in be vigorously stirred down be slowly added to it is above-mentioned
Solution, obtained lyosol are aged 72h in room temperature, form xerogel, and baking oven 10h drying is put into after being filtered, is slowly risen
Temperature takes out natural cooling to 600 DEG C, constant temperature 2h, grinds spare, obtained photochemical catalyst Pt/TiO2.It again will be after step (2) processing
Gas be passed through in the reactor equipped with photochemical catalyst, carry out Treatment by Photocatalysis Oxidation, gas is finally discharged.
Embodiment 2
Integrated treatment is carried out to VOCs exhaust gas, is included the following steps：
Step (1)：It collects VOCs exhaust gas and by the deionized water spray liquid after heating atomization, is handled by gas-liquid separation
The gas phase and liquid phase in VOCs exhaust gas are detached, the particulate matter in VOCs exhaust gas is removed；
Step (2)：By weight, 20 parts of kaolin are placed in 200 parts of 2.5molL-1In salpeter solution, add
5 parts of surfactant cetyl trimethylammonium bromides, heating water bath are stirred to react 5h to 70 DEG C.It centrifuges after reaction
Sediment distills water washing precipitate, and sediment is calcined 6h at 500 DEG C, is ground after cooling down, and 500 mesh excessively sieve to obtain described
Adsorbent.The gas phase in step (1) VOCs exhaust gas is passed through in the reactor equipped with adsorbent again and carries out adsorption treatment.
Step (3)：It will be added drop-wise in ethyl alcohol under butyl titanate stirring condition, homogeneous transparent solution obtained after stirring, then will
Dissolved with platinum chloride (PtCl4) (doping Pt4+Mole percent be hydrochloric acid solution 3%) in be vigorously stirred down be slowly added to it is above-mentioned
Solution, obtained lyosol are aged 72h at room temperature, form xerogel, baking oven 10h drying are put into after being filtered, slowly
600 DEG C, constant temperature 2h are warming up to, natural cooling is taken out, grinds spare, obtained photochemical catalyst Pt/TiO2.Step (2) are handled again
Gas afterwards is passed through in the reactor equipped with photochemical catalyst, carries out Treatment by Photocatalysis Oxidation, gas is finally discharged.
Embodiment 3
Integrated treatment is carried out to VOCs exhaust gas, is included the following steps：
Step (1)：It collects VOCs exhaust gas and by the deionized water spray liquid after heating atomization, is handled by gas-liquid separation
The gas phase and liquid phase in VOCs exhaust gas are detached, the particulate matter in VOCs exhaust gas is removed；
Step (2)：By weight, 20 parts of kaolin are placed in 200 parts of 3molL-1In salpeter solution, 5 are added
Part surfactant cetyl trimethylammonium bromide, heating water bath are stirred to react 5h to 70 DEG C.Centrifuge after reaction heavy
Starch distills water washing precipitate, and sediment is calcined 6h at 500 DEG C, is ground after cooling, 500 mesh is crossed and sieves to obtain the suction
Attached dose.The gas phase in step (1) VOCs exhaust gas is passed through in the reactor equipped with adsorbent again and carries out adsorption treatment.
Step (3)：It will be added drop-wise in ethyl alcohol under butyl titanate stirring condition, homogeneous transparent solution obtained after stirring, then will
Dissolved with platinum chloride (PtCl4) (doping Pt4+Mole percent be hydrochloric acid solution 3%) in be vigorously stirred down be slowly added to it is above-mentioned
Solution, obtained lyosol are aged 84h at room temperature, form xerogel, baking oven 10h drying are put into after being filtered, slowly
600 DEG C, constant temperature 2h are warming up to, natural cooling is taken out, grinds spare, obtained photochemical catalyst Pt/TiO2.Step (2) are handled again
Gas afterwards is passed through in the reactor equipped with photochemical catalyst, carries out Treatment by Photocatalysis Oxidation, gas is finally discharged.
Comparative example 1
Integrated treatment is carried out to VOCs exhaust gas, is included the following steps：
Step (1)：It collects VOCs exhaust gas and by the deionized water spray liquid after heating atomization, is handled by gas-liquid separation
The gas phase and liquid phase in VOCs exhaust gas are detached, the particulate matter in VOCs exhaust gas is removed；
Step (2)：It will be added drop-wise in ethyl alcohol under butyl titanate stirring condition, homogeneous transparent solution obtained after stirring, then will
Dissolved with platinum chloride (PtCl4) (doping Pt4+Mole percent be hydrochloric acid solution 3%) in be vigorously stirred down be slowly added to it is above-mentioned
Solution, obtained lyosol are aged 72h at room temperature, form xerogel, baking oven 10h drying are put into after being filtered, slowly
600 DEG C, constant temperature 2h are warming up to, natural cooling is taken out, grinds spare, obtained photochemical catalyst Pt/TiO2.Step (2) are handled again
Gas afterwards is passed through in the reactor equipped with photochemical catalyst, carries out Treatment by Photocatalysis Oxidation, gas is finally discharged.
Comparative example 2
Integrated treatment is carried out to VOCs exhaust gas, is included the following steps：
Step (1)：It collects VOCs exhaust gas and by the deionized water spray liquid after heating atomization, is handled by gas-liquid separation
The gas phase and liquid phase in VOCs exhaust gas are detached, the particulate matter in VOCs exhaust gas is removed；
Step (2)：By weight, 20 parts of kaolin are placed in 200 parts of 0.5molL-1In salpeter solution, add
5 parts of surfactant dodecyltrimethylammoniums, heating water bath are stirred to react 5h to 70 DEG C.It centrifuges after reaction
Sediment distills water washing precipitate, and sediment is calcined 6h at 500 DEG C, is ground after cooling down, and 500 mesh excessively sieve to obtain described
Adsorbent.The gas phase in step (1) VOCs exhaust gas is passed through in the reactor equipped with adsorbent again and carries out adsorption treatment.
Step (3)：It will be added drop-wise in ethyl alcohol under butyl titanate stirring condition, homogeneous transparent solution obtained after stirring, be added
Deionized water is vigorously stirred, and obtained lyosol is aged 72h at room temperature, forms xerogel, baking oven is put into after being filtered
10h is dried, and is slowly warming up to 600 DEG C, constant temperature 2h, takes out natural cooling, grinds spare, obtained photochemical catalyst TiO2.It again will step
Suddenly (2) treated, and gas is passed through in the reactor equipped with photochemical catalyst, carries out Treatment by Photocatalysis Oxidation, gas is finally discharged.
Exhaust gas concentration test result in embodiment and comparative example after VOCs exhaust-gas treatments see the table below：
* total place to go rate=[1- (the C toluene+C formaldehyde+C methane/original exhaust gas of CVOCs)] × 100%, C is expressed as concentration.
The present invention is by improving treatment technology, the combination of optimisation technique scheme, the skill being used in combination using a variety of processing modes
Art scheme can effectively improve VOCs removal rates.By comparing it can be found that VOCs exhaust-gas treatments in 1-3 of the embodiment of the present invention
Removal rate has reached 92% or more, meets the discharge standard requirement being continuously improved in existing waste gas pollution control and treatment technology, eliminates
Exhaust emission of the VOCs exhaust gas to environment.Compared with comparative example 1, the adsorbent in embodiment 1-3 passes through surfactant and acid
Change modified, can effectively increase the specific surface area of adsorbent, increase effective adsorption site of adsorbent, and then improve adsorbent
To the adsorption capacity of VOCs exhaust gas.Compared with comparative example 2, photochemical catalyst Pt/TiO is used in embodiment 1-32, by will be expensive
Pt metal is supported on TiO2On, activity of the photochemical catalyst to VOCs exhaust fume catalytics can be effectively improved.Further, relative to implementation
Example 1 and 3 uses concentration 2.5molL in embodiment 2-1After salpeter solution acidification, the specific surface area of adsorbent can obtain more
High level, the removal rate of VOCs exhaust-gas treatments are even more to have reached 95% or more.Process operations of the present invention are simple, treatment effeciency
Height has a good application prospect and is worth.
It should be noted that each embodiment described above is merely to illustrate the model that the present invention is not intended to limit the present invention
Enclose, it will be understood by those of ordinary skill in the art that, under the premise without departing from the spirit and scope of the present invention to the present invention into
Capable modification or equivalent replacement, should all cover within the scope of the present invention.In addition, it is signified outer unless the context, with list
The word that number form formula occurs includes plural form, and vice versa.In addition, unless stated otherwise, then the whole of any embodiment or
A part is used in combination with all or part of of any other embodiment.
Claims (10)
1. a kind of VOCs exhaust gas comprehensive processing technique, which is characterized in that include the following steps：
Step (1)：Pretreatment：It collects VOCs exhaust gas and by the spray liquid after heating atomization, handles and detach by gas-liquid separation
Gas phase in VOCs exhaust gas and liquid phase, to remove the particulate matter in VOCs exhaust gas；
Step (2)：Adsorption treatment：Gas phase in step (1) VOCs exhaust gas is passed through in the reactor equipped with adsorbent and is inhaled
Attached processing；
Step (3)：Treatment by Photocatalysis Oxidation：By step (2), treated that gas is passed through in the reactor equipped with photochemical catalyst, into
Row Treatment by Photocatalysis Oxidation, is finally discharged gas.
2. VOCs exhaust gas comprehensive processing technique according to claim 1, which is characterized in that the spray in the step (1)
Liquid is deionized water.
3. VOCs exhaust gas comprehensive processing technique according to claim 1, which is characterized in that the absorption in the step (2)
Agent is made by following methods：Kaolin is placed in salpeter solution, surfactant is added thereto, 70 DEG C of heating water bath simultaneously stirs
Reaction is mixed, centrifuges to obtain sediment, washing precipitate after reaction, and at 500 DEG C after calcining 6h, 500 mesh are crossed in cooling grinding
Sieve obtains the adsorbent.
4. VOCs exhaust gas comprehensive processing technique according to claim 3, which is characterized in that the concentration of the salpeter solution
For 1~3molL-1。
5. VOCs exhaust gas comprehensive processing technique according to claim 4, which is characterized in that the concentration of the salpeter solution
For 2.5molL-1。
6. VOCs exhaust gas comprehensive processing technique according to claim 3, which is characterized in that the surfactant is 16
Alkyl trimethyl ammonium bromide, cetyl trimethyl pyridinium chloride, dodecyl trimethyl ammonium bromide.
7. VOCs exhaust gas comprehensive processing technique according to claim 3, which is characterized in that the specific surface area of the adsorbent
For 200-350m2/g。
8. VOCs exhaust gas comprehensive processing technique according to claim 1, which is characterized in that the photochemical catalyst in step (3)
It is made by following methods：It will be added drop-wise in ethyl alcohol under butyl titanate stirring condition, obtain homogeneous transparent solution after stirring, then by chlorine
Change platinum solution and be slowly added to above-mentioned solution in being vigorously stirred down, obtained lyosol is aged at room temperature, forms xerogel, mistake
It is dried after filter, 2h is heated in 600 DEG C, natural cooling after taking-up grinds and photochemical catalyst Pt/TiO is made2。
9. VOCs exhaust gas comprehensive processing technique according to claim 8, which is characterized in that the platinum chloride solution is chlorine
Change the solution that platinum is dissolved in hydrochloric acid, the mole percent shared by Chlorine in Solution platinum is 3%.
10. VOCs exhaust gas comprehensive processing technique according to claim 8, which is characterized in that in photochemical catalyst preparation method
Digestion time be 72-84h.
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