CN105642126B - A kind of method of modifying of polypropylene hollow fiber membrane and its application in exhaust gas demercuration - Google Patents

A kind of method of modifying of polypropylene hollow fiber membrane and its application in exhaust gas demercuration Download PDF

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CN105642126B
CN105642126B CN201610003360.6A CN201610003360A CN105642126B CN 105642126 B CN105642126 B CN 105642126B CN 201610003360 A CN201610003360 A CN 201610003360A CN 105642126 B CN105642126 B CN 105642126B
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exhaust gas
hollow fiber
absorbing liquid
fiber membrane
membrane
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CN105642126A (en
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于明磊
杨雪晶
汪华林
马良
李剑平
王依谋
刘安林
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East China University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081After-treatment of organic or inorganic membranes
    • B01D67/0093Chemical modification
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/64Heavy metals or compounds thereof, e.g. mercury
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8665Removing heavy metals or compounds thereof, e.g. mercury
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08Hollow fibre membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/26Polyalkenes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2323/00Details relating to membrane preparation
    • B01D2323/38Graft polymerization
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/10Catalysts being present on the surface of the membrane or in the pores

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Treating Waste Gases (AREA)

Abstract

A kind of a kind of modification the present invention relates to polypropylene hollow fiber membrane and its application in exhaust gas demercuration, it is main to include introducing metallic catalyst in film wire surface and duct with Graft Method, mercurous exhaust gas is passed through mercury removal device, absorbing liquid containing oxidant is pumped into membrane reactor, absorbing liquid is flowed in tube side internal flow, exhaust gas in shell side, and exhaust gas is entered in tube side by the duct on film wire surface, and redox reaction occurs with the oxidant in tube side, so that by Hg0It is oxidized to the Hg for being dissolved in water2+Removing.Acid is added in absorbing liquid or alkali adjusts pH, film reaction wall selects transparent material, introduces the oxidisability that absorbent is strengthened in illumination, final Hg0Efficiency is removed more than 95%.

Description

The method of modifying of a kind of polypropylene hollow fiber membrane and its in exhaust gas demercuration Using
Technical field
A kind of method of modifying the present invention relates to polypropylene hollow fiber membrane and the application in exhaust gas demercuration, especially relate to And it is a kind of nanometer grade gold metal catalyst is introduced using Graft Method on the duct of polypropylene hollow fiber membrane film wire and surface, to increase Oxidant is to Hg in exhaust gas0The method of removal efficiency and application.The invention belongs to chemical industry and field of environment protection.
Background technology
Polypropylene hollow fiber membrane is one kind of ultrafiltration membrane, doughnut 450~460um of outside diameter, 350~360um of internal diameter, Thickness of pipe wall 50um.Ultrafiltration is dynamic filtration process, and being trapped material can exclude with concentration, and pollution resistance is medium, can continuously transport for a long time OK.The specific surface area of membrane contactor is big, loading density is high, gas-liquid two-phase contact area is big, and catalyst is supported in polypropylene In empty fiber membrane film wire surface and duct, the specific surface area of catalyst can be increased, so as to increase the reaction rate of oxidation reaction.
For the coal in China based on lignite, the mercury content in coal is 0.1~5.5mg/kg, average content 0.22mg/kg, is fired The content of mercury is 9~23ug/m in coal exhaust gas3, the form of mercury is varied from the difference of coal-fired species in exhaust gas.Waste coal gives up Elemental Mercury (Hg in gas0) the 20% of total mercury is accounted for, bivalent mercury (Hg2+) the 35% of total mercury is accounted for, particle mercury accounts for the 45% of total mercury;Without useless Elemental Mercury constitutes about 65% in coal exhaust gas, and bivalent mercury accounts for 10%, and particle mercury accounts for 5%;Elemental Mercury accounts for 85%, two in lignite exhaust gas Valency mercury accounts for 10%, and particle mercury accounts for 5%.Mercury is a kind of hypertoxic non-essential element, is widely present in all kinds of surrounding mediums and food In chain, its trace spreads all over the world each corner.Mercury can accumulate in vivo, it is easy to by skin and respiratory tract and digestion Road absorbs.Mercury destroys central nervous system, and counterpart, mucous membrane and tooth have harmful effect.Being exposed to for a long time can in high mercury environment To cause brain damage and death.Although mercury boiling point is very high, indoors at a temperature of the mercury vapour of saturation had reached denaturant The several times of amount.
Most common exhaust gas demercuration technology is absorption method, but adsorbent is difficult to regenerate and expensive, is significantly greatly increased de- Mercury cost.Oxidative absorption is a kind of efficient and economic demercuration mode.H2O2It is that a kind of very common and oxidation effectiveness is extraordinary Oxidant, it, which is decomposed, produces water and oxygen, while mercury pollution is removed, does not introduce new pollution, Xi'an Communications University scholar An article (Guangwen chen et al.) is delivered within 2014 on Journal of Hazardous Materials, Use H2O2It is the Hg in oxidant absorption flue gas0, ion liquid addictive is added in absorbing liquid, demercuration effect reaches 98%, from Sub- liquid is expensive, will significantly limit the practical application of this technology.In addition, H2O2Oxidation susceptibility can be reinforced, can be with The methods of by introducing illumination plus Fe catalyst, makes it produce the stronger hydroxyl radical free radical of oxidisability, Hunan University scholar 2013 Year delivers an article (Fuman Zhan et al.) on Chemical Engineering Journal, uses UV/H2O2 Mercury in system removing flue gas, under optimal operating condition, demercuration efficiency reaches 98.5%.
Chinese patent application CN201410093649.2 discloses a kind of absorbing liquid of demercuration.Demercuration absorbing liquid is by imidazoles Ionic liquid and hydrogen peroxide mix, wherein, the mass ratio 9: 10~20 of glyoxaline ion liquid and hydrogen peroxide.The absorbing liquid It can not recycle and H is needed in mixed liquor2O2Volume fraction is 37%, significantly increases cost;And the absorbing liquid absorbs Speed is overly dependent upon the chemical characteristic of demercuration active component.Chinese patent application CN201310497560.8 discloses a kind of copper It is the preparation method of mercury removal agent, mercury removal agent is made in copper dip loading on carrier.Mercury removal agent is as absorbing liquid, it is impossible to circulates Using, it is necessary to largely prepare, cost is added;The speed for absorbing demercuration depends on the chemical property of active component.Need to rely on Reactor realizes the optimization of mass transfer.
Chinese patent application CN 201410047661.X disclose a kind of mercury removal device, its reactor is similar to plate column, Onboard perforate is entered and passed through for flue gas, and whole device has many plates, occupies larger space;Adsorbed using adsorbent bag Demercuration, although compared with the method for pulverized powder adsorbent, avoids the particle contamination of adsorbent, adsorbent bag is difficult to repeat Using, it is necessary to frequently replace, a very big difference of solid absorbent and liquid-absorbant is that the difference of mobility allows The continuity of liquid-absorbant demercuration operation easy to implement, and the device is difficult to realize the continuity of demercuration;Adsorbent heap at the same time Product is packaged together, it is difficult to ensures that adsorbent and exhaust gas have sufficiently large contact area, the rate of adsorption of mercury depends on adsorbent Chemical characteristic.
Chinese patent application CN201510092611.8 discloses the absorption plant and method of a kind of mercury vapour.Absorption plant Including filter, wind turbine, membrane contactor, constant flow pump, deposition filter, absorption flow container.The device uses membrane reactor, tool There is larger mass transfer area.Exhaust gas is flowed through from tube side, and absorbing liquid is flowed through from shell side, using such technique, if exhaust gas Flow increases, then has more exhaust gas without shell side, directly export and flow out from tube side, reduce demercuration efficiency.The device is adopted Contain S in absorbent2—, Hg0Become Hg after being aoxidized2+Can be with S in solution2—Formed HgS precipitation, although have in device it is heavy Shallow lake filtration apparatus, but produce HgS precipitation still can polluted membrane, block the duct in membrane reactor, reduce membrane reactor Effective mass transfer area, so as to reduce demercuration efficiency.
Therefore, existing technology is in removing flue gas Hg0Some all more or less shortcomings, in order to lift demercuration efficiency, And make that equipment is simpler, economic benefit is more preferable, it is necessary to improvement project is proposed to the prior art, develops a kind of demercuration efficiency High, equipment simply has the de- Hg of good economic benefits again0Method and apparatus.
The content of the invention
The defects of for the prior art, polypropylene hollow fiber membrane is modified by the present invention, and is applied to oxidative absorption Remove the Hg in exhaust gas0.It is an object of the present invention to the characteristics of making full use of polypropylene hollow fiber membrane specific surface area big, adopts Metallic catalyst is introduced on the surface of polypropylene hollow fiber membrane film wire and duct strengthen absorbent to Hg with Graft Method0Oxidation Removing.Specifically include, can fix metal on polypropylene hollow fiber membrane film wire surface and duct introducing by the way of grafting and urge The functional group of agent, is re-introduced into metallic catalyst, metallic catalyst can be firmly fixed to above film wire very much by functional group.Profit With the specific surface area of polypropylene hollow fiber membrane film wire it is big the characteristics of, to greatest extent play catalyst catalytic effect, strengthen Oxidant is to Hg0Oxidation removal.
The present invention is achieved by the following technical solutions:
A kind of modification of polypropylene hollow fiber membrane, it is characterised in that the modification includes the following steps:
A, modified liquid is prepared:Acrylic acid, potassium peroxydisulfate and ethylene glycol, deionized water are mixed, per 500ml mixing liquids In, containing 50~150ml acrylic acid, 5~15 grams of potassium peroxydisulfates and 5~15ml ethylene glycol, remaining is deionized water;
B, polypropylene hollow fiber membrane film wire is immersed in modified liquid prepared by step a, the film of every 1,000 30mm long Silk 500 milliliters of mixed liquors of collocation, when heating 2~4 is small at 80~90 DEG C, and are passed through N2Protection, 4 it is small when after taking-up deionized water CH is immersed after washing3CH2OH, washes away unreacted CH2Film wire is immersed pH again after cleaning and is by=CHCOOH and accessory substance, taking-up In 9~13 NaOH solution, then into NaOH solution add 50~100mM NaCl, 12 it is small when after take out clean and immerse In 0.01~0.2M ferric chloride solutions 2~4 it is small when, then take out clean again by film wire immerse 0.001~0.1M sodium hydroxides it is molten In liquid 1~2 it is small when, obtain modified polypropylene hollow fiber membrane.
The present invention also provides a kind of application of modification of polypropylene hollow fiber membrane in exhaust gas demercuration.
A kind of application of modification of polypropylene hollow fiber membrane in exhaust gas demercuration, it is characterised in that the application side Formula includes the following steps:
1) mercury removal device based on modified polypropylene hollow fiber membrane, is built, it is characterised in that described device includes:
One absorbing liquid storage tank 1, one provides the liquid of 2, control absorption flow quantities of pump of absorbing liquid into reactor Flowmeter body 3 is sequentially connected, and fluid flowmeter 3 is connected with the import of membrane reactor 4, and the outlet of membrane reactor 4 connects one and gives up Liquor collecting device 7, is fixed in membrane reactor 4 by modified polypropylene hollow fiber membrane 5, the top of 4 side of membrane reactor One exhaust gas entrance 8 is set, and the lower part of opposite side connects an exhaust gas processing device 6;
The number of above-mentioned membrane reactor 4 is 1~100, and type of attachment is in parallel or series;
The wall material of the membrane reactor is transparent material;
2) absorbing liquid is prepared:
The pH value of oxidant is adjusted 3~10, the oxidant is selected from H2O2、KMnO4、NaClO、Na2S2O4、 NaCrO4In one or more, oxidant concentration is 5~500mmol/L, adds NaCl, sodium oxalate Na2C2O4, EDTA, height In molecular surface active agent one in or a variety of NaCl, sodium oxalate Na for being configured to absorbing liquid, being added2C2O4, EDTA, high score In sub- surfactant one in or a variety of total concentrations in absorbing liquid be 0~1M;
3) mercury in exhaust gas is removed:Exhaust gas is passed through from exhaust gas entrance to described device, by absorbing liquid from membrane reactor entrance It is pumped into membrane reactor, absorbing liquid flows in tube side, and exhaust gas flows in shell side, and fine by modified hollow polypropylene The duct for tieing up film film wire surface enters in tube side;Gas-liquid flow-rate ratio is 1:(10~100), initial mercury concentration are 0.01~1mg/ m3, absorbing liquid temperature is at 20~80 DEG C;
4) illumination is introduced at membrane reactor, the wave-length coverage of light is 110~760nm, and intensity of illumination is 0~500mW/ cm2
5) tail gas after reacting empties after processing.
Main advantages of the present invention are:
(1) present invention introduces metallic catalyst, profit on hollow polypropylene fibre film film wire surface and duct by grafting method The characteristics of big with the specific surface area of hollow-fibre membrane, play the catalytic effect of catalyst, oxidation agent is to mercury to greatest extent Oxidation removal.
(2) present invention is in removing Hg0During, free of contamination H can be selected2O2, new pollution will not be introduced, be through Help environmentally friendly removing Hg0Method.
(3) appropriate amount of acid is added in absorbing liquid or alkali adjusts pH, increase oxidant is to Hg0Oxidation removal ability.
(4) modified polypropylene hollow fiber membrane film wire can be with long-time service, it is not necessary to frequently replaces.
(5) whole device is simple in structure, and floor space is small.
(6) illumination can be introduced and carry out the oxidisability of oxidation agent to strengthen to Hg0Oxidation removal.
(7) can be taken off at the same time at the same time to other pollution progress oxidative absorptions such as the oxysulfide in exhaust gas, nitrogen oxides Other polluted gas such as the nitrogen oxides of 10~10000ppm of oxysulfide and concentration except 10~10000ppm of concentration.
In short, the present invention need not frequently replace film wire, floor space is small, and can be efficient, economical and pollution-free Removing exhaust gas in Hg0, it is Hg in removing flue gas0A kind of very useful approach.
Brief description of the drawings
Fig. 1 is process flow chart according to an embodiment of the invention.
Wherein, 1:Absorbing liquid storage tank, 2:Pump, 3:Fluid flowmeter, 4:Membrane reactor, 5:Polypropylene hollow fiber membrane, 6: Exhaust gas processing device, 7:Waste collecting device, 8:Exhaust gas entrance.
Fig. 2 is the polypropylene hollow fiber membrane film wire schematic diagram that (left side) and modification introduce (right side) after catalyst before modified, right Small circle represents the catalyst introduced in figure.
Embodiment
Below by embodiment, the present invention is further elaborated.
Embodiment 1
The Hg in a removing simulated flue gas0Treatment process in, the method according to the invention, to hollow-fibre membrane film wire It is modified, according to 400 ml deionized waters, 100mlCH2=CHCOOH (Sinopharm Chemical Reagent Co., Ltd.), 7.7g K2S2O4(Shanghai Ling Feng chemical reagent Co., Ltd), 5ml C2H6O2(Shanghai Ling Feng chemical reagent Co., Ltd) configuration mixing Liquid, polypropylene hollow fiber membrane film wire (China shipbuilding Industry Group Co., Ltd. 718th Institute) is immersed in mixed liquor, It is put into after 5min in oven and heats and be passed through N2(SPRING RAINFALL AT SHANGHAI special gas Co., Ltd) protects, 4 it is small when after take out and spend CH is immersed after ion water washing3CH2In OH (Shanghai Ling Feng chemical reagent Co., Ltd), unreacted CH is washed away2=CHCOOH (Sinopharm Chemical Reagent Co., Ltd.) and accessory substance.Film wire is immersed into NaOH (the Shanghai Ling Feng chemical reagent that pH is 10 again Co., Ltd) in solution, add the NaCl (Shanghai Ling Feng chemical reagent Co., Ltd) of 68.4mM in solution, 12 it is small when after take Out it is washed with deionized water only, then immerses the FeCl of 0.1M3In (Shanghai Ling Feng chemical reagent Co., Ltd) solution 2 it is small when, take Go out after being washed with deionized, immerse in the NaOH solution of 0.01M, take out and be washed with deionized water only after one hour.
Attached drawing puts up device to specifications, and oxidant used is H2O2(15.0mmol/L, Shanghai Ling Feng chemistry examination Agent Co., Ltd), pH value 5, absorption flow quantity is 50ml/min, simulated flue gas N2, flow 1L/min, mercury concentration is 90ng/min, absorbing liquid are passed through from liquid inlet, and simulated flue gas is passed through from gas access, and it is 4% that tail gas, which is passed through mass fraction, KMnO4(Shanghai Ling Feng chemical reagent Co., Ltd), 10%H2SO4Emptied after (Shanghai Ling Feng chemical reagent Co., Ltd) solution.
Demercuration rate is η=(Cin-Cout)/Cin× 100%
In formula:η is Hg0Removal efficiency;CinAnd CoutRespectively Hg in entrance, exit gas0Content.
Experimental result, demercuration rate is more than 82%.
Embodiment 2
The Hg in a removing simulated flue gas0Treatment process in, using with method of modifying same in embodiment 1 to poly- Propylene hollow-fibre membrane film wire is modified processing.
Attached drawing puts up device to specifications, and oxidant used is H2O2(15.0mmol/L, Shanghai Ling Feng chemistry examination Agent Co., Ltd), pH value 5, adds the NaCl (Shanghai Ling Feng chemical reagent Co., Ltd) and oxalic acid C of 4g/L2H4O2(Shanghai Ling Feng chemical reagent Co., Ltd), absorption flow quantity is 50ml/min, simulated flue gas N2, flow 1L/min, mercury concentration is 90ng/min, absorbing liquid are passed through from liquid inlet, and simulated flue gas is passed through from gas access, and it is 4% that tail gas, which is passed through mass fraction, KMnO4(Shanghai Ling Feng chemical reagent Co., Ltd), 10%H2SO4Emptied after (Shanghai Ling Feng chemical reagent Co., Ltd) solution.
Demercuration rate is η=(Cin-Cout)/Cin× 100%
In formula:η is Hg0Removal efficiency;CinAnd CoutRespectively Hg in entrance, exit gas0Content.
Experimental result, demercuration rate have exceeded 95%.
Embodiment 3
The Hg in a removing simulated flue gas0Treatment process in, using with method of modifying same in embodiment 1 to poly- Propylene hollow-fibre membrane film wire is modified processing.
Attached drawing puts up device to specifications, and oxidant used is H2O2(15.0mmol/L, Shanghai Ling Feng chemistry examination Agent Co., Ltd), pH value 5, adds the NaCl (Shanghai Ling Feng chemical reagent Co., Ltd) and oxalic acid C of 4g/L2H4O2(Shanghai Ling Feng chemical reagent Co., Ltd), analog light source, intensity of illumination 100mW/cm are introduced in experiment2, absorption flow quantity is 50ml/ Min, simulated flue gas N2, flow 1L/min, mercury concentration is 90ng/min, and absorbing liquid is passed through from liquid inlet, simulated flue gas It is passed through from gas access, tail gas is passed through the KMnO that mass fraction is 4%4(Shanghai Ling Feng chemical reagent Co., Ltd), 10% H2SO4Emptied after (Shanghai Ling Feng chemical reagent Co., Ltd) solution.
Demercuration rate is η=(Cin-Cout)/Cin× 100%
In formula:η is Hg0Removal efficiency;CinAnd CoutRespectively Hg in entrance, exit gas0Content.
Experimental result, demercuration rate have exceeded 98%.
The method according to the invention, demercuration efficiency have been above 90%, and if be not modified to fiber film wire, directly Using with above example same concentrations H2O2Make absorbent, solution ph is adjusted to 3, use and H2O2The Fe of same concentrations2+Urge Agent, does not also introduce illumination, then demercuration efficiency only has 88%, less than 90%.As it can be seen that polypropylene hollow fiber membrane is modified The oxidation demercuration ability of system can be greatly improved by introducing catalyst.

Claims (4)

1. a kind of method of modifying of polypropylene hollow fiber membrane, it is characterised in that the modification includes the following steps:
A, modified liquid is prepared:Acrylic acid, potassium peroxydisulfate and ethylene glycol, deionized water are mixed, in every 500ml mixing liquids, Containing 50~150ml acrylic acid, 5~15 grams of potassium peroxydisulfates and 5~15ml ethylene glycol, remaining is deionized water;
B, above-mentioned hollow-fibre membrane film wire is immersed in modified liquid prepared by step a, the film wire collocation of every 1,000 30mm long 500 milliliters of mixed liquors, are passed through in 80-90 DEG C of heating and at the same time N2Protect 4 it is small when, then take out be washed with deionized after immerse CH3CH2OH, washes away unreacted CH2=CHCOOH and accessory substance, take out and film wire are immersed the NaOH that pH is 9~13 again after cleaning In solution, then add into NaOH solution the NaCl of 50~100mM, 12 it is small when after take out and clean and immerse 0.01~0.2M chlorinations In ferrous solution 2~4 it is small when, then take out clean again by film wire immerse 0.001~0.1M sodium hydroxide solutions in 1~2 it is small when, obtain To modified polypropylene hollow fiber membrane.
2. application of the method for modifying of polypropylene hollow fiber membrane as claimed in claim 1 in exhaust gas demercuration, its feature exist In the application mode includes the following steps:
1) mercury removal device based on modified polypropylene hollow fiber membrane, is built, described device includes:
One absorbing liquid storage tank (1), one into reactor provide absorbing liquid pump (2), one control absorb flow quantity liquid Flowmeter body (3) is sequentially connected, and fluid flowmeter (3) is connected with the import of membrane reactor (4), and the outlet of membrane reactor (4) connects A waste collecting device (7) is connect, is fixed on by modified polypropylene hollow fiber membrane (5) in membrane reactor (4), film reaction The top of device (4) side sets an exhaust gas entrance (8), and the lower part of opposite side connects an exhaust gas processing device (6);
2) absorbing liquid is prepared:
The pH value of oxidant is adjusted 3~10, the oxidant is selected from H2O2、KMnO4、NaClO、Na2S2O4、NaCrO4In One or more, oxidant concentration is 5~500mmol/L, adds NaCl, sodium oxalate Na2C2O4, EDTA, macromolecule surface One or more in activating agent are configured to absorbing liquid, NaCl, the sodium oxalate Na added2C2O4, EDTA, macromolecule surface live Property agent in one or more total concentration in absorbing liquid be 0~1M;
3) mercury in exhaust gas is removed:Exhaust gas entrance is passed through exhaust gas to described device, and absorbing liquid is pumped into film from membrane reactor entrance In reactor, absorbing liquid flows in tube side, and exhaust gas flows in shell side, and is entered by the duct on film wire surface in tube side; Gas-liquid flow-rate ratio is 1:(10~100), initial mercury concentration are 0.01~1mg/m3, absorbing liquid temperature is at 20~80 DEG C;
4) illumination is introduced at membrane reactor, the wave-length coverage of light is 110~760nm, and intensity of illumination is 0~500mW/cm2
5) tail gas after reacting empties after processing.
3. application of the method for modifying of polypropylene hollow fiber membrane as claimed in claim 2 in exhaust gas demercuration, its feature exist In in the mercury removal device of the step 1), the number of the membrane reactor (4) is 1~100, and type of attachment is in parallel or string Connection.
4. application of the method for modifying of polypropylene hollow fiber membrane as claimed in claim 2 in exhaust gas demercuration, its feature exist In in the mercury removal device of the step 1), the wall material of the membrane reactor is transparent material.
CN201610003360.6A 2016-01-04 2016-01-04 A kind of method of modifying of polypropylene hollow fiber membrane and its application in exhaust gas demercuration Expired - Fee Related CN105642126B (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5009871A (en) * 1984-08-31 1991-04-23 Nippon Kokan Kabushiki Kaisha Method of removing mercury in exhaust gases from a waster incinerator
CN101011645A (en) * 2006-12-27 2007-08-08 南京工业大学 Hydrophilic modification method of amphiphilic molecules on surface of polypropylene porous membrane
KR20070119799A (en) * 2006-06-16 2007-12-21 (주)에어레인 Preparation method of gas seperation membrane and gas seperation membrane prepared therefrom
WO2008043507A1 (en) * 2006-10-11 2008-04-17 Lydall Solutech B.V. Humidifier membrane
JP2008200589A (en) * 2007-02-19 2008-09-04 Kansai Electric Power Co Inc:The Method and apparatus for separation of gas
CN101590370A (en) * 2009-06-11 2009-12-02 上海交通大学 The method of catalytically oxidizing elemental mercury by oxidant controlledly released by porous ceramic membrane
CN103933880A (en) * 2014-03-24 2014-07-23 贵州省材料产业技术研究院 Preparation method of high-throughput hydrophilic modified polypropylene hollow fiber membrane
CN104548959A (en) * 2013-10-11 2015-04-29 中国石油化工股份有限公司 Anti-pollution modification method of polypropylene hollow fiber membrane module
CN104722188A (en) * 2015-03-02 2015-06-24 江苏汇维特新材料科技有限公司 Mercury vapor absorbing device and mercury vapor absorbing method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5009871A (en) * 1984-08-31 1991-04-23 Nippon Kokan Kabushiki Kaisha Method of removing mercury in exhaust gases from a waster incinerator
KR20070119799A (en) * 2006-06-16 2007-12-21 (주)에어레인 Preparation method of gas seperation membrane and gas seperation membrane prepared therefrom
WO2008043507A1 (en) * 2006-10-11 2008-04-17 Lydall Solutech B.V. Humidifier membrane
CN101011645A (en) * 2006-12-27 2007-08-08 南京工业大学 Hydrophilic modification method of amphiphilic molecules on surface of polypropylene porous membrane
JP2008200589A (en) * 2007-02-19 2008-09-04 Kansai Electric Power Co Inc:The Method and apparatus for separation of gas
CN101590370A (en) * 2009-06-11 2009-12-02 上海交通大学 The method of catalytically oxidizing elemental mercury by oxidant controlledly released by porous ceramic membrane
CN104548959A (en) * 2013-10-11 2015-04-29 中国石油化工股份有限公司 Anti-pollution modification method of polypropylene hollow fiber membrane module
CN103933880A (en) * 2014-03-24 2014-07-23 贵州省材料产业技术研究院 Preparation method of high-throughput hydrophilic modified polypropylene hollow fiber membrane
CN104722188A (en) * 2015-03-02 2015-06-24 江苏汇维特新材料科技有限公司 Mercury vapor absorbing device and mercury vapor absorbing method

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