CN104971752B - Magnetic catalyst suitable for catalytic oxidation technique and its preparation method and application - Google Patents
Magnetic catalyst suitable for catalytic oxidation technique and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to catalyst field, it is related to suitable for magnetic catalyst of catalytic oxidation technique and its preparation method and application.Diatomite or atlapulgite are cleaned as catalyst carrier, dried, with being mixed by a certain percentage with tetraethyl orthosilicate and sucrose after plasma modification, cracking presoma is prepared using sol-gal process, and calcine at high temperature, ground after cooling, doped silicon carbide carrier is made.Weigh certain mass transition metal sulfate and doped silicon carbide carrier, it is placed in mixing, dipping, alkali tune, ageing, grinding in certain volume distilled water solution, obtain magnetic catalyst, the weight/mass percentage composition of carborundum is 1.5%~4.5% wherein in doped silicon carbide carrier, and the mass ratio of magnetic transition metal oxide and doped silicon carbide carrier is (0.05~0.3):1.The catalyst manufacture craft is simple, and easy to operate, active component is not easily runed off, it is easy to reclaim, applied widely, and has the advantages that high catalytic activity.
Description
Technical field
The invention belongs to catalyst field, be related to suitable for magnetic catalyst of catalytic oxidation technique and preparation method thereof and
Using.
Background technology
Chemical industry is key pillars of the national economy industry, and total output value accounts for more than the 20% of total industrial output value.However, chemical industry
Industry is high material-consumption, an industry for heavily contaminated again.With continuing to develop for chemical industry, the difficult degradation of chemical industry discharge is organic
The value volume and range of product of thing is sharply increased, the complicated wastewater from chemical industry of such as agricultural chemicals, medicine, dyestuff and coal chemical industry, not only containing a large amount of
Difficult degradation organic poison, and variation water quality is big, biodegradability is poor, and intractability greatly, is caused seriously to water environment
Pollution, or even threatened drinking water safety and human life life and health.Difficult degradation wastewater from chemical industry has turned into the chemical work of restriction China
The bottleneck of industry sustainable development.
Processing method main at present includes Physical, chemical method and bioanalysis etc..Conventional Physical is absorption method, should
Method is single to component, concentration is relatively low and has the system of recovery value more effective, but exists to complicated wastewater from chemical industry easy
Absorb saturation and regeneration difficulty is big, operating cost is expensive, and heavy financial burden is brought to enterprise；Bioanalysis is both economical
Processing means, but be due to that most of wastewater from chemical industry composition is sufficiently complex, and difficult degradation, the meeting of water quality and quantity change greatly are to life
Thing system causes serious impact, causes the stability of a system to decline or even paralyse.Oxidant hardly possible drop organic matter is added in chemical method to be had
Preferable effect, but high expensive；Micro electrolysis tech is relatively economical, but there is easily hardened filler, passivation, processing energy
Power is undesirable.Some high-level oxidation technologies in recent years, such as wet oxidation, catalytic wet oxidation, photochemical catalytic oxidation, have substantially
Treatment effect, but whether being which kind of catalytic oxidation technologies, its most crucial problem is long-life, high efficiency, not easily runed off
The preparation of catalyst and use.Therefore, how to research and develop the catalyst suitable for catalysis oxidation of high-efficiency broad spectrum turns into wastewater from chemical industry
The difficult point of process field.
Preparing the method for catalyst at present mainly has：The precipitation method, gel method, infusion process, ion-exchange, heat melting method
Deng.The catalyst wherein prepared using dipping+heat melting method method can flexibly be selected carrier, be with rate is high, consumption is few, cost is low
Physical structural characteristic needed for catalyst is provided, and shaping of catalyst step is saved, it is method a kind of simple and easy to apply and economic.
The content of the invention
The purpose of the present invention is that not enough there is provided a kind of magnetic suitable for catalytic oxidation technique for prior art above-mentioned
Catalyst.
It is a further object to provide the preparation method of above-mentioned catalyst.
A kind of magnetic catalyst suitable for catalytic oxidation technique, is that magnetic transition metal oxide is carried on into doped carbon
Gained on the carrier of SiClx；Metallics is Fe in described magnetic transition metal oxide3O4Or MnFe2O4, described carrier
For one kind in diatomite or atlapulgite.Wherein, in the carrier of doped silicon carbide the mass content of carborundum for 1.5%~
4.5%, preferably 1.9%~3.8%；The mass ratio of the carrier of magnetic transition metal oxide and doped silicon carbide for (0.05~
0.3):1, preferably (0.083~0.272):1.
The carrier of described doped silicon carbide be carrier is cleaned, dried, with after plasma modification with tetraethyl orthosilicate
Mixed by a certain percentage with sucrose, cracking presoma prepared using sol-gel process, and calcined at high temperature, ground after cooling,
Doped silicon carbide carrier is made.
Described plasma modification preferably uses DDBD plasma reactors, 10~15kV of voltage is handled, during processing
Between 15~30min.
The preferred following methods of carrier of described doped silicon carbide are prepared：By tetraethyl orthosilicate, sucrose and plasma
Carrier after modifies is according to mass ratio（0.1~0.2）:（0.2~0.4）：1 mixing, adds the second that concentration is 30%~40%
Alcohol solution stirs, in 35~37 DEG C of water-baths after constant temperature, and it is 2~4, ultrasonic disperse to add hydrochloric acid regulation mixed liquor pH value
The hexamethylenetetramine aqueous solution that concentration is 35wt%~40wt% is instilled after 40~60min, gel is formed, 20~24h of aging is put
In 105~120 DEG C of dryings, obtain cracking presoma, dried sample at 1000 DEG C~1400 DEG C of argon gas atmosphere charing 2~
Taken out after 5h, natural cooling and grind and cross 200 mesh sieves, produce doped silicon carbide carrier；Carrier wherein after plasma modification
Mass volume ratio with ethanol water is 1g:（4~6）ml；Carrier and hexamethylenetetramine after plasma modification is water-soluble
The mass volume ratio of liquid is 1g：（0.2~0.5）ml.
Obtained doped silicon carbide carrier magnetic transition metal sulfate and/or chloride solution are impregnated, adjusted by the present invention
Alkali, then it is aged, cool down, grinding obtains magnetic catalyst；It is preferred that by magnetic transition metal sulfate and/or villaumite and
The carrier of doped silicon carbide is added in distilled water, and adds ethylenediamine tetra-acetic acid and polyethylene glycol, 10~12h is impregnated, with 40%
NaOH solution, adjust its pH to 11~13, be placed in 90 DEG C of water-bath 2~5h of ageing, take out, be washed with deionized water into
Property, dried in 100~110 DEG C of baking oven, taken out after natural cooling and grind and cross 200 mesh sieves, obtain magnetic catalyst.
The preparation method of magnetic catalyst of the present invention, is comprised the steps of：
A. carrier cleaned, dried, with standby after plasma modification；
B. it will mix, prepared using sol-gel process before cracking with tetraethyl orthosilicate and sucrose by modified carrier
Body is driven, and in 1000 DEG C~1400 times calcinings, is ground after cooling, doped silicon carbide carrier is made；
C. by obtained doped silicon carbide carrier transition metal sulfate and/or chloride solution dipping, alkali tune；
D. the carrier after step C processing is aged, cooled down, grinding obtains magnetic catalyst.
In step A according to（8~12）g:Carrier is added in distilled water by 100mL, with 30~40KHZ supersound washing 10
~20min, 2~5 times repeatedly, low temperature is placed in DBD plasma reactors after doing bath, carries out corona discharge, handles voltage 10
~15kV, 15~30min of processing time, is modified to carrier.
It is according to mass ratio by the carrier after tetraethyl orthosilicate, sucrose and plasma modification in step B（0.1~0.2）:
（0.2~0.4）：1 mixing, adds concentration and is stirred for 30%~40% ethanol water, the constant temperature in 35~37 DEG C of water-baths
Afterwards, it is 2~4 to add hydrochloric acid regulation mixed liquor pH value, instill that concentration is 35wt%~40wt% after 40~60min of ultrasonic disperse six
The amine aqueous solution of methine four, forms gel, and 20~24h of aging is placed in 105~120 DEG C of dryings, obtains cracking presoma, dries
Sample afterwards carbonizes to take out after 2~5h, natural cooling at 1000 DEG C~1400 DEG C of argon gas atmosphere and grinds and cross 200 mesh sieves, i.e.,
Obtain doped silicon carbide carrier；The mass volume ratio of carrier and ethanol water wherein after plasma modification is 1g:（4~6）
ml；The mass volume ratio of carrier and the hexamethylenetetramine aqueous solution after plasma modification is 1g：（0.2~0.5）ml.
The carrier of magnetic transition metal sulfate and/or villaumite and doped silicon carbide is added to distillation in step C and D
In water, and add ethylenediamine tetra-acetic acid and polyethylene glycol, impregnate 10~12h, with 40% NaOH solution, adjust its pH to 11~
13；2~5h of ageing in 90 DEG C of water-bath is placed in, takes out, is washed with deionized water to neutrality, is dried in 100~110 DEG C of baking oven
It is dry, taken out after natural cooling and grind and cross 200 mesh sieves, obtain magnetic catalyst.
Application of the magnetic catalyst of the present invention in water process, preferably in processing containing phenols, aromatic substance
Application in waste water；Application further preferably in waste water of the processing containing phenol or nitrobenzene.
Beneficial effect：
1st, processing is needed to catalyst carrier with plasma, channel surfaces and internal impurity can be cleared up, increase carrier
Aperture.
2nd, the catalyst prepared has very strong oxidation activity, can realize quick catalysis oxidation；
3rd, the catalyst prepared has loaded magnetic transition metal class compound, with obvious magnetic, its saturated magnetization
Intensity is more than 30emu/g, on the one hand on the other hand be able to can be realized under additional magnetic fields quick with catalytic degradation organic matter
Separation of solid and liquid, reclaims catalyst, reduces the loss of catalyst.
4th, the catalyst prepared has the advantages that stronger stability, long lifespan；
5th, preparation method it is simple, conveniently, production efficiency it is high, cost-effective.
Embodiment
Embodiment 1
Catalyst carrier crosses the diatomite of 200 mesh sieves from 10g, is placed in in 100mL distilled water, with 33KHZ ultrasound
10min is washed, 3 times repeatedly, low temperature is placed in DDBD plasma reactors after doing bath, is carried out corona discharge, is protected using nitrogen
Shield, discharge voltage 10kV, discharge time is 5min, that is, obtains modified carrier；2nd, the modified of the preparation of Overall Steps 1 is taken
Carrier, and by tetraethyl orthosilicate（TEOS）, sucrose and carrier mass ratio be 0.1:0.2:1, weigh tetraethyl orthosilicate（TEOS）
And sucrose, three is added in the ethanol water that 50mL concentration is 35% and stirred, in 35 DEG C of water-baths after constant temperature, plus
Six methines that 3mL concentration is 36.5wt% are added dropwise after entering the ultrasonic disperse 60min that hydrochloric acid regulation mixed liquor pH value is 2,33KHZ
In four amine aqueous solutions, gel is formed, and aging 24h is placed in 110 DEG C of dried samples and carbonizes 5h at 1000 DEG C of argon gas atmosphere,
Taken out after natural cooling and grind and cross 200 mesh sieves, produce the carrier of doped silicon carbide, wherein carborundum content is 1.9%；3rd, take
The carrier of doped silicon carbide prepared by Overall Steps 2, in mass ratio 0.1:0.2:1 weighs FeSO4·7H2O、FeCl3·6H2O and
The carrier of doped silicon carbide, is added in 100mL distilled water, while adding 0.3mL ethylenediamine tetra-acetic acids and the poly- second two of 0.1mL
Alcohol, impregnate 12h, with 40% NaOH solution, adjust its pH to 11,5h be aged in the water-bath for being placed in 90 DEG C, take out, spend from
Son is washed to neutrality, is dried in 105 DEG C of baking oven, is taken out after natural cooling and grinds and cross 200 mesh sieves, obtains Fe3O4Magnetic is urged
Agent, saturation magnetization is 31.98emu/g, wherein Fe3O4Mass ratio with doped silicon carbide carrier is 0.083：1.
The catalyst produced with this method, takes 1g to be put into quartz reactor, add concentration be 200mg/L nitrobenzene or
200mg/L phenol synthetic water 100mL, under microwave reinforced catalysis oxidation synergy, reaction time 5min, nitrobenzene is gone
Except efficiency is 90%, the removal efficiency of phenol is 87%.
Embodiment 2：
1st, carrier crosses the atlapulgite of 200 mesh sieves from 10g, is placed in in 100mL distilled water, is washed with 33KHZ ultrasound
10min is washed, 3 times repeatedly, low temperature is placed in DDBD plasma reactors after doing bath, is protected using nitrogen, discharge voltage 15kV,
Discharge time is 10min, that is, obtains modified carrier；2nd, the modified carrier for taking Overall Steps 1 to prepare, and by positive silicic acid
Ethyl ester（TEOS）, sucrose and modified carrier mass ratio be 0.2:0.4:1, weigh tetraethyl orthosilicate（TEOS）And sucrose,
Three is added in the ethanol water that 50mL concentration is 35% and stirred, in 35 DEG C of water-baths after constant temperature, hydrochloric acid is added and adjusts
Save and the hexamethylenetetramine solution that 1mL concentration is 36.5wt% is added dropwise after the ultrasonic disperse 60min that mixed liquor pH value is 3,33KHZ
In, form gel, and aging 20h is placed in 110 DEG C of dried samples and carbonizes 4h, natural cooling at 1200 DEG C of argon gas atmosphere
Take out afterwards and grind and cross 200 mesh sieves, produce the carrier of doped silicon carbide, wherein carborundum content is 3.8%；3rd, Overall Steps 2 are taken
The carrier of the doped silicon carbide of preparation, in mass ratio 0.2:0.4:1 weighs FeSO4·7H2O、FeCl3·6H2O and doping are carbonized
The carrier of silicon, is added in 100mL distilled water, while 0.1mL ethylenediamine tetra-acetic acids and 0.2mL polyethylene glycol are added, dipping
12h, with 40% NaOH solution, adjusts its pH to 13, and 3h is aged in the water-bath for being placed in 90 DEG C, take out, be washed with deionized water to
Neutrality, is dried in 105 DEG C of baking oven, is taken out after natural cooling and is ground and cross 200 mesh sieves, obtains Fe3O4Magnetic catalyst, satisfies
It is 33.17emu/g, wherein Fe with the intensity of magnetization3O4Mass ratio with the carrier of doped silicon carbide is 0.166：1.
The catalyst produced with this method, takes 1g to be put into quartz reactor, add concentration be 200mg/L nitrobenzene or
200mg/L phenol synthetic water 100mL, under microwave reinforced catalysis oxidation synergy, reaction time 5min, nitrobenzene is gone
Except efficiency is 93%, the removal efficiency of phenol is 95%.
Embodiment 3：
1st, catalyst carrier crosses the diatomite of 200 mesh sieves from 10g, is placed in in 100mL distilled water, with surpassing for 33KHZ
Sound washs 10min, and 3 times repeatedly, low temperature is placed in DDBD plasma reactors after doing bath, is protected using nitrogen, discharge voltage
12kV, discharge time is 15min, that is, obtains modified carrier；2nd, the modified carrier for taking Overall Steps 1 to prepare, and press
Tetraethyl orthosilicate（TEOS）, sucrose and modified carrier mass ratio be 0.1:0.2:1, weigh tetraethyl orthosilicate（TEOS）With
Sucrose, three is added in the ethanol water that 50mL concentration is 35% and stirred, and in 35 DEG C of water-baths after constant temperature, is added
Six methines four that 2mL concentration is 36.5wt% are added dropwise after the ultrasonic disperse 60min that hydrochloric acid regulation mixed liquor pH value is 2,33KHZ
In amine aqueous solution, gel is formed, and aging 24h is placed in 110 DEG C of dried samples and carbonizes 2h at 1500 DEG C of argon gas atmosphere, from
So taken out after cooling and grind and cross 200 mesh sieves, produce the carrier of doped silicon carbide, wherein carborundum content is 1.9%；3rd, take complete
The carrier of doped silicon carbide prepared by portion's step 2, in mass ratio 0.1:0.3:1 weighs MnSO4·H2O、FeSO4·7H2O and mix
The carrier of miscellaneous carborundum, is added in 100mL distilled water, while 0.2mL ethylenediamine tetra-acetic acids and 0.3mL polyethylene glycol are added,
12h is impregnated, with 40% NaOH solution, its pH to 13 is adjusted, 2h is aged in the water-bath for being placed in 90 DEG C, takes out, uses deionized water
Neutrality is washed till, is dried in 105 DEG C of baking oven, is taken out after natural cooling and grinds and cross 200 mesh sieves, obtain MnFe2O4Magnetic is catalyzed
Agent, saturation magnetization is 38.01emu/g, wherein MnFe2O4Mass ratio with the carrier of doped silicon carbide is 0.136：1.
The catalyst produced with this method, takes 1g to be put into quartz reactor, add concentration be 200mg/L nitrobenzene or
200mg/L phenol synthetic water 100mL, under microwave reinforced catalysis oxidation synergy, reaction time 5min, nitrobenzene is gone
Except efficiency is 89%, the removal efficiency of phenol is 92%.
Embodiment 4：
1st, catalyst carrier crosses the atlapulgite of 200 mesh sieves from 10g, is placed in in 100mL distilled water, with 33KHZ's
Supersound washing 10min, 3 times repeatedly, low temperature is placed in DDBD plasma reactors after doing bath, is protected using nitrogen, electric discharge electricity
13kV is pressed, discharge time is 12min, that is, obtains modified carrier；2nd, the modified carrier for taking Overall Steps 1 to prepare, and
By tetraethyl orthosilicate（TEOS）, sucrose and modified carrier mass ratio be 0.2:0.4:1, weigh tetraethyl orthosilicate（TEOS）
And sucrose, three is added in the ethanol water that 50mL concentration is 35% and stirred, in 35 DEG C of water-baths after constant temperature, plus
Six methines that 3mL concentration is 36.5wt% are added dropwise after entering the ultrasonic disperse 60min that hydrochloric acid regulation mixed liquor pH value is 3,33KHZ
In four amine aqueous solutions, gel is formed, and aging 24h is placed in 110 DEG C of dried samples and carbonizes 3h at 1200 DEG C of argon gas atmosphere,
Taken out after natural cooling and grind and cross 200 mesh sieves, produce the carrier of doped silicon carbide, wherein carborundum content is 3.8%；3rd, take
The carrier of doped silicon carbide prepared by Overall Steps 2, in mass ratio 0.2:0.6:1 weighs MnSO4·H2O、FeSO4·7H2O and
The carrier of doped silicon carbide, is added in 100mL distilled water, while adding 0.2mL ethylenediamine tetra-acetic acids and the poly- second two of 0.2mL
Alcohol, impregnate 12h, with 40% NaOH solution, adjust its pH to 13,4h be aged in the water-bath for being placed in 90 DEG C, take out, spend from
Son is washed to neutrality, is dried in 105 DEG C of baking oven, is taken out after natural cooling and grinds and cross 200 mesh sieves, obtains MnFe2O4Magnetic
Catalyst, saturation magnetization is 40.53emu/g, wherein MnFe2O4Mass ratio with the carrier of doped silicon carbide is 0.272：
1。
The catalyst produced with this method, takes 1g to be put into quartz reactor, add concentration be 200mg/L nitrobenzene or
200mg/L phenol synthetic water 100mL, under microwave reinforced catalysis oxidation synergy, reaction time 5min, nitrobenzene is gone
Except efficiency is 95%, the removal efficiency of phenol is 97%.
Claims (12)
1. a kind of magnetic catalyst suitable for catalytic oxidation technique, it is characterised in that magnetic transition metal oxide, which is carried on, to be mixed
On the carrier of miscellaneous carborundum；Metallics is Fe in described magnetic transition metal oxide3O4Or MnFe2O4, described carrier
For one kind in diatomite or atlapulgite；Wherein, in the carrier of doped silicon carbide the weight/mass percentage composition of carborundum for 1.5% ~
4.5%, the mass ratio of magnetic transition metal oxide and doped silicon carbide carrier is (0.05 ~ 0.3):1；Described doping carbonization
The carrier of silicon is cleaned carrier, dried, with being mixed by a certain percentage with tetraethyl orthosilicate and sucrose after plasma modification, is adopted
Cracking presoma is prepared with sol-gel process, and is calcined at high temperature, is ground after cooling, doped silicon carbide carrier is made.
2. magnetic catalyst according to claim 1, it is characterised in that described plasma modification using DDBD etc. from
Daughter reactor, handles 10 ~ 15kV of voltage, 15 ~ 30min of processing time.
3. magnetic catalyst according to claim 1, it is characterised in that by tetraethyl orthosilicate, sucrose and plasma modification
Carrier afterwards is according to mass ratio（0.1~0.2）:（0.2~0.4）：1 mixing, adds concentration and is stirred for 30% ~ 40% ethanol water
Mix uniform, in 35 ~ 37 DEG C of water-baths after constant temperature, it is 2 ~ 4, ultrasonic disperse 40 ~ 60 to add hydrochloric acid regulation mixed liquor pH value
The hexamethylenetetramine aqueous solution that concentration is 35wt% ~ 40wt% is instilled after min, gel is formed, 20 ~ 24h of aging, it is placed in 105 ~
120 DEG C of dryings, obtain cracking presoma, dried sample carbonizes 2 ~ 5h at 1000 DEG C ~ 1400 DEG C of argon gas atmosphere, naturally cold
But take out afterwards and grind and cross 200 mesh sieves, produce doped silicon carbide carrier；Carrier and ethanol water wherein after plasma modification
The mass volume ratio of solution is 1g:（4~6）ml；The mass body of carrier and the hexamethylenetetramine aqueous solution after plasma modification
Product is than being 1g：（0.2~0.5）ml.
4. magnetic catalyst according to claim 3, it is characterised in that by obtained doped silicon carbide carrier magnetic mistake
Metal sulfate and/or chloride solution dipping, alkali tune are crossed, then it is aged, cool down, grinding obtains magnetic catalyst.
5. magnetic catalyst according to claim 4, it is characterised in that by magnetic transition metal sulfate and/or villaumite with
And the carrier of doped silicon carbide is added in distilled water, and ethylenediamine tetra-acetic acid and polyethylene glycol are added, impregnate 10 ~ 12h, use
40% NaOH solution, adjusts its pH to 11 ~ 13, is placed in 90 DEG C of water-bath 2 ~ 5h of ageing, takes out, be washed with deionized water to
Neutrality, is dried in 100 ~ 110 DEG C of baking oven, is taken out after natural cooling and is ground and cross 200 mesh sieves, obtains magnetic catalyst.
6. the preparation method of the magnetic catalyst described in claim 1, it is characterised in that comprise the steps of：
A. carrier cleaned, dried, with standby after plasma modification；
B. it will be mixed by modified carrier with tetraethyl orthosilicate and sucrose, cracking forerunner prepared using sol-gel process
Body, and in 1000 DEG C ~ 1400 times calcinings, ground after cooling, doped silicon carbide carrier is made；
C. by obtained doped silicon carbide carrier transition metal sulfate and/or chloride solution dipping, alkali tune；
D. the carrier after step C processing is aged, cooled down, grinding obtains magnetic catalyst.
7. the preparation method of magnetic catalyst according to claim 6, it is characterised in that in step A according to（8~12）g:
Carrier is added in distilled water by 100mL, and with 30 ~ 40KHZ 10 ~ 20min of supersound washing, 2 ~ 5 times repeatedly, it is rearmounted that low temperature does bath
In in DDBD plasma reactors, corona discharge is carried out, 10 ~ 15kV of voltage, 15 ~ 30min of processing time is handled, carrier is entered
Row is modified.
8. the preparation method of magnetic catalyst according to claim 7, it is characterised in that in step B by tetraethyl orthosilicate,
Carrier after sucrose and plasma modification is according to mass ratio（0.1~0.2）:（0.2~0.4）：1 mixing, it is 30% to add concentration
~ 40% ethanol water stirs, in 35 ~ 37 DEG C of water-baths after constant temperature, add hydrochloric acid regulation mixed liquor pH value be 2 ~
The hexamethylenetetramine aqueous solution that concentration is 35wt% ~ 40wt% is instilled after 4, the min of ultrasonic disperse 40 ~ 60, gel, aging is formed
20 ~ 24h, is placed in 105 ~ 120 DEG C of dryings, obtains cracking presoma, dried sample is at 1000 DEG C ~ 1400 DEG C of argon gas atmosphere
Carbonize to take out after 2 ~ 5h, natural cooling and grind and cross 200 mesh sieves, produce doped silicon carbide carrier；Wherein plasma modification
Carrier and the mass volume ratio of ethanol water afterwards is 1g:（4~6）ml；Carrier and six methines four after plasma modification
The mass volume ratio of amine aqueous solution is 1g：（0.2~0.5）ml.
9. the preparation method of magnetic catalyst according to claim 7, it is characterised in that by magnetic transition in step C and D
The carrier of metal sulfate and/or villaumite and doped silicon carbide is added in distilled water, and adds ethylenediamine tetra-acetic acid and poly-
Ethylene glycol, impregnates 10 ~ 12h, with 40% NaOH solution, adjusts its pH to 11 ~ 13；2 ~ 5h of ageing in 90 DEG C of water-bath is placed in,
Take out, be washed with deionized water to neutrality, dried in 100 ~ 110 DEG C of baking oven, taken out after natural cooling and grind and cross 200 mesh
Sieve, obtains magnetic catalyst.
10. application of the magnetic catalyst described in claim 1 in water process.
11. application according to claim 10, it is characterised in that the magnetic catalyst described in claim 1 contains phenol in processing
Application in class, the waste water of aromatic substance.
12. application according to claim 11, it is characterised in that the magnetic catalyst described in claim 1 contains benzene in processing
Application in the waste water of phenol or nitrobenzene.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5678430A (en) * | 1979-11-29 | 1981-06-27 | Mitsui Toatsu Chem Inc | Production of iron compound particle for magnetic recording |
| CN101185888A (en) * | 2007-12-04 | 2008-05-28 | 南京工业大学 | Catalyst for inducing catalytic oxidation technique and preparation method thereof |
| CN103406094A (en) * | 2013-06-04 | 2013-11-27 | 北京林业大学 | Method for manufacturing magnetic sludge-based active carbon |
| CN103432986A (en) * | 2013-08-15 | 2013-12-11 | 南京工业大学 | Magnetic kieselgur based adsorbent, and preparation method and application thereof |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5678430A (en) * | 1979-11-29 | 1981-06-27 | Mitsui Toatsu Chem Inc | Production of iron compound particle for magnetic recording |
| CN101185888A (en) * | 2007-12-04 | 2008-05-28 | 南京工业大学 | Catalyst for inducing catalytic oxidation technique and preparation method thereof |
| CN103406094A (en) * | 2013-06-04 | 2013-11-27 | 北京林业大学 | Method for manufacturing magnetic sludge-based active carbon |
| CN103432986A (en) * | 2013-08-15 | 2013-12-11 | 南京工业大学 | Magnetic kieselgur based adsorbent, and preparation method and application thereof |
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