CN106179498A - Polystyrene catalysis bead and slurry photocatalytic reactor - Google Patents
Polystyrene catalysis bead and slurry photocatalytic reactor Download PDFInfo
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- CN106179498A CN106179498A CN201610547242.1A CN201610547242A CN106179498A CN 106179498 A CN106179498 A CN 106179498A CN 201610547242 A CN201610547242 A CN 201610547242A CN 106179498 A CN106179498 A CN 106179498A
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- Prior art keywords
- polystyrene
- bead
- catalysis
- acid
- light transmission
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 84
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 83
- 239000011324 bead Substances 0.000 title claims abstract description 50
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 14
- 239000002002 slurry Substances 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000002608 ionic liquid Substances 0.000 claims abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012965 benzophenone Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 4
- 230000005540 biological transmission Effects 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- OPCOHSVHTNQULK-UHFFFAOYSA-N 1-butyl-3-[(4-ethenylphenyl)methyl]-2h-imidazole Chemical compound C1=CN(CCCC)CN1CC1=CC=C(C=C)C=C1 OPCOHSVHTNQULK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001471 micro-filtration Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- -1 Azoles bromide Chemical class 0.000 claims 1
- 239000011260 aqueous acid Substances 0.000 claims 1
- 230000002093 peripheral effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 20
- 239000002351 wastewater Substances 0.000 description 13
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- CVZYZFFCMHSVCM-UHFFFAOYSA-N 1-[(4-ethenylphenyl)methyl]-3-methyl-2h-imidazole Chemical compound C1=CN(C)CN1CC1=CC=C(C=C)C=C1 CVZYZFFCMHSVCM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229920000831 ionic polymer Polymers 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses polystyrene catalysis bead and slurry photocatalytic reactor, polystyrene catalysis bead, make by following method: (1) carries out pretreatment to polystyrene sphere；(2) by pretreatment polystyrene sphere, being dipped in the toluene solution of benzophenone, taking-up is dried, logical nitrogen, irradiates, take out, put in the methanol solution of ionic liquid under ultra-violet lamp, under nitrogen protection, and reaction；Clean, dry, obtain polystyrene graft modification bead；(3) putting in heteropoly acid aqueous solution by polystyrene graft modification bead, lucifuge is reacted, and washes under room temperature, and vacuum lyophilization obtains polystyrene catalysis bead.The polystyrene catalysis bead of the present invention, is immobilized on polystyrene surface by catalyst, in use, is avoided that catalyst loss.The slurry photocatalytic reactor of the present invention runs at normal temperatures, low power consuming, and environmental protection is simple to operate.
Description
Technical field
The invention belongs to water treatment field, be specifically related to a kind of can continuous degradation waste water from dyestuff polystyrene catalysis bead
And slurry photocatalytic reactor.
Background technology
Along with fast development and the growth in the living standard of human industry's technology, substantial amounts of industrial wastewater and sanitary wastewater quilt
It is directly discharged in natural environment, environment is caused serious pollution, the among these directly discharge of a large amount of chemical dyestuff waste water
Harm to environment is particularly acute.Pollute especially chemical dyestuff contaminated wastewater to tackle the most serious water, alleviate water danger
The significant problems such as machine, exploitation green, the dye wastewater treatment technology of environmental protection become the key subjects of facing mankind.
At present, with one of visible light catalytic dye wastewater degradation focus becoming Recent study, this technology has efficiently,
Quickly feature, is that the following mankind solve one of waste water from dyestuff the most promising high-tech technology of pollution.But, directly add
Photocatalyst for degrading waste water from dyestuff not only consumption is big but also catalyst is difficult to reclaim, and causes the pollution to environment, causes simultaneously and urge
A large amount of wastes of agent.
Summary of the invention
It is an object of the invention to the deficiency directly adding photocatalyst for degrading waste water from dyestuff overcoming prior art to exist, carry
For a kind of polystyrene catalysis bead.
Second object of the present invention be to provide one can continuous degradation waste water from dyestuff, directly filter separating catalyst, solve
The certainly slurry photocatalytic reactor of a difficult problem for catalyst loss in photocatalytic degradation.
Technical scheme is summarized as follows:
A kind of polystyrene catalysis bead, makes by following method:
1) polystyrene sphere is carried out pretreatment: successively with dehydrated alcohol, deionized water, 2-10% inorganic base water-soluble
Liquid, the inorganic acid aqueous solution of 2-10% clean polystyrene sphere, are washed with deionized water to neutrality, vacuum lyophilization, obtain
Pretreatment polystyrene sphere；
(2) preparation of polystyrene graft modification bead: pretreatment polystyrene sphere step (1) obtained, is dipped in
5-30min in the toluene solution of 5-25mM benzophenone or the n-heptane solution of 5-25mM benzophenone, takes out and dries in atmosphere,
Be placed in hermetic container logical nitrogen 5-180min, then at wavelength be 254-365nm, power be 4-12W ultra-violet lamp under, irradiate
Distance is 5-20cm, irradiates 5-30min, takes out, in the methanol solution of the ionic liquid putting into 0.1-0.5M, under nitrogen protection,
At 55-65 DEG C, react 12-48h；Successively with deionized water, washes of absolute alcohol, vacuum freezing drying, ionic liquid is poly-
Styrene bead surface forms poly ion liquid, obtains polystyrene graft modification bead；The polyphenyl second that described step (1) obtains
Alkene bead is 1g:20-30mL with the ratio of the methanol solution of ionic liquid；
(3) in proportion the polystyrene graft modification bead that 1g step (2) obtains is put into the 10-25mM's of 10-100mL
In heteropoly acid aqueous solution, under the conditions of lucifuge, water-bath 12-48h at 15-35 DEG C, wash 12-48h under room temperature, vacuum freezing is done
Dry that polystyrene is catalyzed bead.
Preferably: described inorganic base is sodium hydroxide or potassium hydroxide.
Described mineral acid is hydrochloric acid or sulphuric acid.
Described ionic liquid is 1-(4-vinyl benzyl)-3-Methylimidazole. villaumite, 1-(4-vinyl benzyl)-3-butyl
Imidazoles villaumite, 1-(4 vinyl benzyl)-3-Methylimidazole. bromide or 1-(4-vinyl benzyl)-3-1-Butyl-1H-imidazole smelling salts.
Described heteropoly acid is: phosphomolybdic acid, phosphotungstic acid or silicomolybdic acid.
Slurry photocatalytic reactor includes light transmission container 10, is provided with aeration head 7, is arranged on printing opacity in light transmission container
Aeration pump 5 outside container is connected with gas flowmeter 6 and aeration head 7 successively by pipeline；It is provided with the feed pipe of the 1st valve 2
One end is connected with feed pump 1, and the other end is arranged in light transmission container 10, is outside equipped with daylight lamp 8 at light transmission container 10, at printing opacity
Flat polyvinylidene fluoride micro-filtration membrane original paper 9 and above-mentioned polystyrene catalysis bead 11, Kynoar it is additionally provided with in container 10
Flat micro-filtration original paper 9 is connected with the 2nd valve 3 being arranged on outside light transmission container 10 and discharging pump 4 successively by pipeline.
Slurry photocatalytic reactor the most according to claim 6, is characterized in that the material of described light transmission container is
Glass or polymethyl methacrylate.
Advantages of the present invention:
The polystyrene catalysis bead of the present invention, with polystyrene as substrate, is immobilized on catalyst its surface, is using
Time, the problem being avoided that the catalyst loss occurred in traditional method.The slurry photocatalytic reactor of the present invention is at normal temperatures
Running, low power consuming, environmental protection, simple to operate, what easy scale was applicable to that following infant industry produces can continuous degradation dyestuff
The Technology of waste water.
The slurry photocatalytic reactor of the present invention is more stable during running degraded Acid Orange II molecule continuously,
This is important in actual commercial Application.
Accompanying drawing explanation
Fig. 1 is slurry photocatalytic reactor structural representation.
Fig. 2 is the ATR-IR infrared spectrum of polystyrene sphere and modified bead, wherein:
A is the ATR-IR infrared spectrum of polystyrene sphere；
B is the ATR-IR infrared spectrum of polystyrene graft modification bead；
C is the ATR-IR infrared spectrum of polystyrene catalysis bead.
Detailed description of the invention
Be will assist in by following example and understand the present invention, but be not limiting as present disclosure.In addition, it is to be understood that
After having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, these etc.
Valency form falls within the scope of following claims equally.
Below by embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
A kind of polystyrene catalysis bead, makes by following method:
(1) polystyrene sphere is carried out pretreatment: successively with dehydrated alcohol, deionized water, 5% sodium hydroxide water-soluble
Liquid, the aqueous hydrochloric acid solution of 5% clean polystyrene sphere, are washed with deionized water to neutrality, vacuum lyophilization, obtain pretreatment
Polystyrene sphere；
(2) preparation of polystyrene graft modification bead: pretreatment polystyrene sphere step (1) obtained, is dipped in
15min in the toluene solution of 15mM benzophenone, takes out and dries in atmosphere, is placed in hermetic container logical nitrogen 90min, then at
Wavelength is 365nm, power is under 8W ultra-violet lamp, and irradiation distance is 10cm, irradiates 10min, takes out, puts into the ionic liquid of 0.3M
In the methanol solution of body, under nitrogen protection, at 60 DEG C, react 36h；Successively with deionized water, washes of absolute alcohol, vacuum is cold
Freezing drying, ionic liquid forms poly ion liquid on polystyrene sphere surface, obtains polystyrene graft modification bead；Described
The polystyrene sphere that step (1) obtains is 1g:25mL with the ratio of the methanol solution of ionic liquid；
The ionic liquid of the present embodiment is: 1-(4-vinyl benzyl)-3-Methylimidazole. villaumite；
(3) in proportion the polystyrene graft modification bead that 1g step (2) obtains is put into the phosphomolybdic acid of the 20mM of 50mL
In aqueous solution, under the conditions of lucifuge, water-bath 30h at 25 DEG C, wash 30h under room temperature, vacuum lyophilization obtains polystyrene and urges
Change bead.
Embodiment 2
A kind of polystyrene catalysis bead, makes by following method:
(1) polystyrene sphere is carried out pretreatment: successively with dehydrated alcohol, deionized water, 2% potassium hydroxide water-soluble
Liquid, the aqueous sulfuric acid of 2% clean polystyrene sphere, are washed with deionized water to neutrality, vacuum lyophilization, obtain pretreatment
Polystyrene sphere；
(2) preparation of polystyrene graft modification bead: pretreatment polystyrene sphere step (1) obtained, is dipped in
30min in the toluene solution of 5mM benzophenone, takes out and dries in atmosphere, is placed in hermetic container logical nitrogen 5min, then at ripple
A length of 254nm, power are under the ultra-violet lamp of 4W, and irradiation distance is 5cm, irradiate 5min, take out, put into the ionic liquid of 0.1M
Methanol solution in, nitrogen protection under, at 55 DEG C, react 48h；Successively with deionized water, washes of absolute alcohol, vacuum freezing
Drying, ionic liquid forms poly ion liquid on polystyrene sphere surface, obtains polystyrene graft modification bead；Described step
Suddenly the polystyrene sphere that (1) obtains is 1g:20mL with the ratio of the methanol solution of ionic liquid；
The ionic liquid of the present embodiment is: 1-(4-vinyl benzyl)-3-1-Butyl-1H-imidazole villaumite
(3) in proportion the polystyrene graft modification bead that 1g step (2) obtains is put into the phosphotungstic acid of the 25mM of 10mL
In aqueous solution, under the conditions of lucifuge, water-bath 48h at 15 DEG C, wash 12h under room temperature, vacuum lyophilization obtains polystyrene and urges
Change bead.
Embodiment 3
A kind of polystyrene catalysis bead, makes by following method:
(1) polystyrene sphere is carried out pretreatment: successively with dehydrated alcohol, deionized water, the sodium hydroxide water of 10%
Solution, the aqueous hydrochloric acid solution of 10% clean polystyrene sphere, are washed with deionized water to neutrality, vacuum lyophilization, obtain pre-
Process polystyrene sphere；
(2) preparation of polystyrene graft modification bead: pretreatment polystyrene sphere step (1) obtained, is dipped in
5min in the toluene solution of 25mM benzophenone, takes out and dries in atmosphere, is placed in hermetic container logical nitrogen 180min, then at
Wavelength is 365nm, power be 12W ultra-violet lamp under, irradiation distance is 20cm, irradiate 30min, take out, put into 0.5M from
In the methanol solution of sub-liquid, under nitrogen protection, at 65 DEG C, react 12h；Successively with deionized water, washes of absolute alcohol, very
Air cooling freezes drying, and ionic liquid forms poly ion liquid on polystyrene sphere surface, obtains polystyrene graft modification bead；
The polystyrene sphere that described step (1) obtains is 1g:30mL with the ratio of the methanol solution of ionic liquid；
The ionic liquid of the present embodiment is: 1-(4 vinyl benzyl)-3-Methylimidazole. bromide；
(3) in proportion the polystyrene graft modification bead that 1g step (2) obtains is put into the silicomolybdic acid of the 10mM of 100mL
In aqueous solution, under the conditions of lucifuge, water-bath 12h at 35 DEG C, wash 48h under room temperature, vacuum lyophilization obtains polystyrene and urges
Change bead.
Experiment proves: substitute 1-(4 vinyls of the present embodiment with 1-(4-vinyl benzyl)-3-1-Butyl-1H-imidazole smelling salts
Benzyl)-3-Methylimidazole. bromide, other same the present embodiment, polystyrene catalysis bead can be prepared.
Experiment proves: the solvent of the benzophenone solution of embodiment 1-3 also can use heptane.
Slurry photocatalytic reactor is shown in Fig. 1, is 10L rectangular glass transmission container (10) including volume, at glass
Be provided with aeration head (7) in light transmission container, the aeration pump (5) being arranged on outside glass transmission container by pipeline successively with gas stream
Gauge (6) and aeration head (7) connect；The feed pipe one end being provided with the 1st valve (2) is connected with feed pump (1), and the other end is arranged
In glass transmission container (10), it is outside equipped with two 55W daylight lamp (8) at glass transmission container (10), holds at glass transmission
Flat polyvinylidene fluoride micro-filtration membrane original paper (9) and polystyrene catalysis bead (11), Kynoar it is additionally provided with in device (10)
Flat micro-filtration original paper (9) by pipeline successively be arranged on glass transmission container (10) the 2nd valve (3) and discharging pump outward
(4) connect.
Experiment:
In glass transmission container, it is passed through 6L waste water from dyestuff (dyestuff is Acid Orange II), prepares in pH=1, embodiment 1
When polystyrene catalysis concentration of small ball is 0.5g/L, Hydraulic retention time is 4h, aeration rate is 4L/min, degraded 0.2g/L acid
Property orange II dyestuff, Acid Orange II degradation rate reaches 100% in 100min.
In glass transmission container, it is passed through 6L waste water from dyestuff (dyestuff is Acid Orange II), prepares in pH=1, embodiment 2
When polystyrene catalysis concentration of small ball is 0.5g/L, Hydraulic retention time is 4h, aeration rate is 4L/min, degraded 0.1g/L acid
Property orange II dyestuff, Acid Orange II degradation rate reaches 94% in 100min.
In glass transmission container, it is passed through 6L waste water from dyestuff (dyestuff is Acid Orange II), prepares in pH=1, embodiment 3
When polystyrene catalysis concentration of small ball is 0.2g/L, Hydraulic retention time is 4h, aeration rate is 4L/min, degraded 0.2g/L acid
Property orange II dyestuff Acid Orange II degradation rate reaches 84% in 100min.
It is demonstrated experimentally that the material of light transmission container can also select polymethyl methacrylate.
Acid Orange II selected by the dyestuff of the present invention, merely to enable those skilled in the art to be more fully understood that this
Bright, other similar to Acid Orange II character stains thing all can be catalyzed bead with the polystyrene of the present invention and floated light be urged
Change reactor and carry out degraded removal.
Claims (7)
1. a polystyrene catalysis bead, is characterized in that making by following method:
(1) polystyrene sphere is carried out pretreatment: successively with dehydrated alcohol, deionized water, the inorganic base aqueous solution of 2-10%,
The inorganic acid aqueous solution of 2-10% cleans polystyrene sphere, is washed with deionized water to neutrality, vacuum lyophilization, obtains pre-place
Reason polystyrene sphere；
(2) preparation of polystyrene graft modification bead: pretreatment polystyrene sphere step (1) obtained, is dipped in 5-
5-30min in the toluene solution of 25mM benzophenone or the n-heptane solution of 5-25mM benzophenone, takes out and dries in atmosphere, put
Logical nitrogen 5-180min in hermetic container, then at wavelength be 254-365nm, power be 4-12W ultra-violet lamp under, irradiate away from
From for 5-20cm, irradiate 5-30min, take out, in the methanol solution of the ionic liquid putting into 0.1-0.5M, under nitrogen protection,
At 55-65 DEG C, react 12-48h；Successively with deionized water, washes of absolute alcohol, vacuum freezing is dried, is obtained polystyrene and connect
The modified bead of branch；The polystyrene sphere that described step (1) obtains is 1g:20-30mL with the ratio of the methanol solution of ionic liquid；
(3) in proportion the polystyrene graft modification bead that 1g step (2) obtains is put into 10-25mM miscellaneous many of 10-100mL
In aqueous acid, under the conditions of lucifuge, water-bath 12-48h at 15-35 DEG C, wash 12-48h under room temperature, vacuum lyophilization obtains
Polystyrene catalysis bead.
The most according to claim 1, polystyrene catalysis bead, is characterized in that described inorganic base is sodium hydroxide or hydroxide
Potassium.
The most according to claim 1, polystyrene catalysis bead, is characterized in that described mineral acid is hydrochloric acid or sulphuric acid.
The most according to claim 1, polystyrene catalysis bead, is characterized in that described ionic liquid is 1-(4-vinyl benzyl
Base)-3-Methylimidazole. villaumite, 1-(4-vinyl benzyl)-3-1-Butyl-1H-imidazole villaumite, 1-(4 vinyl benzyl)-3-methyl miaow
Azoles bromide or 1-(4-vinyl benzyl)-3-1-Butyl-1H-imidazole smelling salts.
The most according to claim 1 polystyrene catalysis bead, it is characterized in that described heteropoly acid is: phosphomolybdic acid, phosphotungstic acid or
Silicomolybdic acid.
6. slurry photocatalytic reactor includes light transmission container (10), is provided with aeration head (7), is arranged in light transmission container
Aeration pump (5) outside light container is connected with gas flowmeter (6) and aeration head (7) successively by pipeline；It is provided with the 1st valve
(2) feed pipe one end is connected with feed pump (1), and the other end is arranged in light transmission container (10), at light transmission container (10) peripheral hardware
It is equipped with daylight lamp (8), it is characterized in that in light transmission container (10), be additionally provided with flat polyvinylidene fluoride micro-filtration membrane original paper (9) and power
Profit require one of 1-5 polystyrene catalysis bead (11), flat polyvinylidene fluoride micro-filtration membrane original paper (9) by pipeline successively with
It is arranged on outer the 2nd valve (3) of light transmission container (10) and discharging pump (4) connects.
Slurry photocatalytic reactor the most according to claim 6, is characterized in that the material of described light transmission container is glass
Or polymethyl methacrylate.
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| CN201610547242.1A CN106179498A (en) | 2016-07-12 | 2016-07-12 | Polystyrene catalysis bead and slurry photocatalytic reactor |
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Cited By (1)
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| CN110193380A (en) * | 2019-05-24 | 2019-09-03 | 武汉工程大学 | It is a kind of using waste polystyrene as catalysis material of aggregate and its preparation method and application |
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Application publication date: 20161207 |