CN103721746A - Composite catalyst used for industrial wastewater treatment via electrolytic oxidation, and preparation method thereof - Google Patents
Composite catalyst used for industrial wastewater treatment via electrolytic oxidation, and preparation method thereof Download PDFInfo
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- CN103721746A CN103721746A CN201210387072.7A CN201210387072A CN103721746A CN 103721746 A CN103721746 A CN 103721746A CN 201210387072 A CN201210387072 A CN 201210387072A CN 103721746 A CN103721746 A CN 103721746A
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Abstract
The invention discloses a composite catalyst used for industrial wastewater treatment via electrolytic oxidation, and a preparation method thereof, and belongs to the field of waste water treatment via electrolysis. The composite catalyst comprises a catalyst carrier and active components, wherein sulfonated polystyrene resin is used as the catalyst carrier, and metal ions including Fe<2+>, Mn<2+>, Cr<3+>, and Cu<2+> are taken as the active components. According to the preparation method, loading of the active component metal ions on the sulfonated polystyrene resin carrier is realized via ion exchange so as to obtain a catalyst precursor A, a catalyst precursor B, a catalyst precursor C, and a catalyst precursor D; and the catalyst precursors are mixed. The composite catalyst used for industrial wastewater treatment via electrolytic oxidation possesses following advantages: catalytic activity is high; dispersity of the active components is high; sulfuration performance is excellent; carrier true density is low; the composite catalyst possesses corrosion resistance; cost of treatment of waste water, which is difficult for biodegradation, is low; COD treatment efficiency is high; and service life is relatively long. The composite catalyst can be used as a filling material of electrolytic oxidation equipment for electrolytic oxidation of waste water, which is difficult for biodegradation; and waste water COD removal ratio is 75% or more.
Description
Technical field
The present invention is a kind of electrolytic oxidation Industrial Wastewater Treatment composite catalyst and preparation method thereof.Belong to and use Treatment of Wastewater by Electrolysis.
Background technology
The kind of difficult for biological degradation industrial wastewater is many, and intractability is large.
Adopting maximum technique is advanced oxidation, as Fenton reagent oxidation, ozone oxidation, wet oxidation etc. all exist disposal cost high, have shortcomings such as secondary pollution, electrochemical oxidation, especially catalytic and oxidative electrolysis technology method are a kind of quite promising methods growing up gradually in recent years.Catalytic and oxidative electrolysis technology refers to a kind of technique of waste water being carried out electrolytic treatments under the catalytic action of catalyst.The advantage of this technology is:
(1) OH producing in process has strong oxidizing property, can be degraded to carbon dioxide, water and simple organic without selectively directly reacting with the organic pollution in waste water, high and do not produce secondary pollution to the wastewater treatment degree of depth, therefore, be called as " environmental friendliness " technology.
(2) reaction condition is gentle, generally just can carry out at normal temperatures and pressures.
(3) both can process separately, can combine with other treatment technology again, as the pre-treatment as biochemical process, in order to improve the biodegradability of waste water.
(4) electrolysis installation and operation thereof are generally fairly simple, and disposal cost is lower.
At present, people have carried out a large amount of basic research works to catalytic and oxidative electrolysis technology technique, but mainly from the plate material of development high catalytic activity, start with, on organic matter catalytic oxidation mechanism with affect degradation efficiency various factors and be studied.Chinese patent CN102040262A utilizes fluid bed catalytic and oxidative electrolysis technology technique to process low organic matter, high salinity waste water; The article < < electric-multiphase catalytic reaction system that Yue Lin etc. deliver on periodical < < China Environmental Science > > (the 2nd phase in 2008) has been introduced in to the degraded > > of percolate and has been utilized granular activated carbon for electroconductive particle pole plate, with metal oxide-loaded heterogeneous catalyst, substitute insulating packing, build electric-multiphase catalytic oxidation system percolate is processed; Rohit and Misra process organic wastewater with three-dimensional carbon pole plate reactor in patent IN2010MU03118A (Three dimensional carbon electrode reactor for electrochemical degradation of organic pollutants of wastewater).But in numerous research, can about the research of catalyst between pole plate, less and research be mainly in laboratory stage, prepare fluidisation catalyst good, that activity is high, the life-span is long, price is low and be to restrict the key point that can catalytic and oxidative electrolysis technology technology large-scale industrial application.
Patent CN102049256A has introduced a kind of wastewater treatment catalyst and preparation method thereof, the catalyst of this invention be take active carbon as carrier, one or more of take in the metal oxides such as copper, iron, manganese, vanadium, zinc, titanium are active component, are used in waste water catalytic oxidation treatment process.The preparation method of this catalyst is complicated, need under hot conditions, react, and energy consumption is high, and active carbon real density is 1.90～2.20g/cm
3, fluidizing performance is poor, in water treatment procedure if make catalyst need to consume higher energy in fluidized state.
Patent CN1429773A has introduced method and the special purpose device that oil field waste is processed in a kind of electricity consumption-heterogeneous catalytic reaction, this invention by organic pollution make oil field waste under the effect of extra electric field at catalyst surface catalytic oxidation.The catalyst using in this patent passes through at SiO
2, Al
2o
3, load Fe, Co, Ni, Mn, Cu, Ti, W or the preparation of Pb isoreactivity component and obtain on zeolite molecular sieve or absorbent charcoal carrier.The catalyst of this invention preparation is prepared from conventional infusion process, has active component bad dispersibility, the easily shortcoming of cluster, and SiO
2real density is 2.2～2.66g/cm
3, Al
2o
3real density is 3.80～4.10g/cm
3, zeolite molecular sieve real density is 2.0～2.5g/cm
3, active carbon real density is 1.90～2.20g/cm
3, fluidizing performance is poor, has in actual applications certain limitation.
In patent CN102040262A, introduced a kind of fluid bed catalytic and oxidative electrolysis technology reaction unit and processing method, the refractory organic in waste water is processed in the free radical that this invention produces by the three-dimensional catalysis pole plate electrolysis such as electrolytic anode, negative electrode and catalyst and the catalytic action of catalyst.The catalyst providing in this patent is granular active carbon, be loaded with the active carbon of catalytically-active metals, molecular sieve or several mixture wherein, this catalyst cost is high, acid-alkali-corrosive-resisting is poor, carrier real density is large, in wastewater treatment process, fluidizing performance is poor, has in actual applications certain limitation.
In sum, electrolytic oxidation Industrial Wastewater Treatment Catalysts and its preparation method of the prior art, exists following not enough:
1. carrier real density is large, and fluidizing performance is not good enough, and practical application energy consumption is high;
2. active component bad dispersibility, easily cluster;
3. catalyst cost is high, acid-alkali-corrosive-resisting is poor;
4. active low, service life is short.
Summary of the invention
The weak point that the object of the invention is to avoid above-mentioned prior art to exist, and provide a kind of catalytic activity high, active component good dispersion, fluidizing performance are superior; Carrier real density is little, corrosion-resistant; Processing waste water difficult for biological degradation cost is low, COD treatment effeciency is high, the electrolytic oxidation Industrial Wastewater Treatment composite catalyst that service life is longer.
The present invention also aims to provide the preparation method of the electrolytic oxidation Industrial Wastewater Treatment composite catalyst that a kind of energy consumption is low, preparation technology simple, manufacturing cost is lower.
Object of the present invention can reach by following measure:
Electrolytic oxidation Industrial Wastewater Treatment composite catalyst of the present invention, comprises catalyst carrier and active component, it is characterized in that take that sulfonated polystyrene ion exchange resin is as carrier, with metal cations Fe
2+, Mn
2+, Cr
3+, Cu
2+for active component, adopt ion-exchange, by activity component metal ion, be carried on respectively on described sulfonated polystyrene ion exchange resin carrier, make catalyst precarsor A, catalyst precarsor B, catalyst precarsor C and catalyst precarsor D; Electrolytic oxidation Industrial Wastewater Treatment composite catalyst is by forming according to the catalyst precarsor of mass percent meter as follows:
Wherein:
1. described catalyst carrier sulfonated polystyrene ion exchange resin, selecting diameter is 0.25～1.0mm, specific surface is 100～600m
2the macropore polystyrene resin (ps) particle of/g, processes and obtains through sulfonation; The real density of the sulfonated polystyrene ion exchange resin obtaining after sulfonation is 1.30～1.50g/cm
3;
2. described activity component metal ion Fe
2+, Mn
2+, Cr
3+, Cu
2+, by the aqueous solution of water soluble salt separately, being provided, in the aqueous solution, the mass percent concentration of metal ion is respectively:
3. the load capacity of described active component on described carrier is 1%～20% of described each catalyst precarsor quality.
Catalyst of the present invention be take sulfonated polystyrene ion exchange resin as carrier, Fe
2+mn
2+cr
3+cu
2+for active component, activity component load quantity is 1%～20%, can effectively prevent active component generation cluster, guarantees that the active sites of active component exposes fully, and through measuring, as catalyst carrier sulfonated polystyrene ion exchange resin, its real density is 1.30～1.50g/cm
3, more bigger than water, be but less than aluminium oxide (3.80～4.10g/cm
3), silica (2.2～2.66g/cm
3), active carbon (1.90～2.20g/cm
3) and zeolite molecular sieve (2.0～2.5g/cm
3) etc. the density of carrier, thereby there is good fluidizing performance, solved the problem of existing catalyst fluidization poor performance; Adopt active component chromium, make catalyst activity higher.Be applied in electrolysis-catalytic oxidation device, can effectively remove the COD in waste water difficult for biological degradation, COD clearance reaches more than 75%.Thereby solved problems of the prior art, completed task of the present invention.
Object of the present invention can also reach by following measure:
Electrolytic oxidation Industrial Wastewater Treatment composite catalyst of the present invention, electrolytic oxidation Industrial Wastewater Treatment composite catalyst is by forming according to the catalyst precarsor of mass percent meter as follows:
Wherein:
1. described catalyst carrier sulfonated polystyrene ion exchange resin, selecting diameter is 0.5～0.75mm, specific surface is 300～550m
2the macropore polystyrene resin (ps) particle of/g, processes and obtains through sulfonation;
2. described activity component metal ion Fe
2+, Mn
2+, Cr
3+, Cu
2+, by the aqueous solution of water soluble salt separately, being provided, in the aqueous solution, the mass percent concentration of metal ion is respectively:
3. the load capacity of described active component on described carrier is 5%～7% of described each catalyst precarsor quality.
It is preferred technical scheme.
The preparation method of electrolytic oxidation Industrial Wastewater Treatment composite catalyst of the present invention, is characterized in that comprising the steps:
1. the preparation of carrier-sulfonated polystyrene ion exchange resin
In the flask of stirring is housed, drop into chloroform 100ml, macropore polystyrene resin (ps) particle 10g, under room temperature, stirring, slowly adds the oleum 50ml of 30%-50%; Then, at 60～80 ℃ of temperature, sulfonation 160～200 minutes; After sulfonation finishes, slowly add absolute ethanol washing 3 times, suction filtration; Again with deionized water wash in cleaning solution without SO
4 2～, dry, make catalyst carrier-sulfonated polystyrene ion exchange resin;
2. the preparation of catalyst precarsor:
A. activity component metal ion Fe
2+, Mn
2+, Cr
3+, Cu
2+the preparation of the aqueous solution
According to drafting formula, take respectively and contain metal cations Fe
2+, Mn
2+, Cr
3+, Cu
2+water soluble salt, be dissolved in gauge water, make the activity component metal solion of desired concn, standby;
B. ion-exchange
Take catalyst carrier-sulfonated polystyrene ion exchange resin that 1. quantitative step is prepared, drop into respectively catalyst precarsor A, B prepared by wish, C, D the metal cations Fe prepared of step a separately
2+, Mn
2+, Cr
3+, Cu
2+in the aqueous solution, be controlled at 15 ℃～45 ℃ temperature, carry out ion-exchange, the reaction time is 60min～1200min, and then, filtering and washing 5 times, places in baking oven, in 80 ℃ of dry 360min, makes catalyst precarsor;
3.. the preparation of electrolytic oxidation Industrial Wastewater Treatment composite catalyst
According to drafting formula, take each component of catalyst precarsor, mix, obtain electrolytic oxidation Industrial Wastewater Treatment composite catalyst product.
Preparation method of the present invention improves the preparation method of the catalyst of prior art, makes active component dispersive property good and have high catalytic activity; And can be according to the water quality of water treatment and treatment process demand, the component of the correction of maneuverability, conciliation catalyst, makes its specific aim better.To completing task of the present invention, outstanding contributions have been made.
The preparation method of electrolytic oxidation Industrial Wastewater Treatment composite catalyst of the present invention, the reaction time of the ion-exchange in step b is 90min～120min, reaction temperature is 25 ℃～30 ℃.It is preferred technical scheme.
The application of electrolytic oxidation Industrial Wastewater Treatment composite catalyst of the present invention, is characterized in that processing for catalytic oxidation waste water difficult for biological degradation as the filler of electrolysis-catalytic oxidation device waste water COD clearance >=75%.
Electrolytic oxidation Industrial Wastewater Treatment composite catalyst of the present invention and preparation method thereof, has following good effect compared to existing technology:
1. provide a kind of catalytic activity high, active component good dispersion, fluidizing performance are superior; Carrier real density is little, corrosion-resistant; Process the electrolytic oxidation Industrial Wastewater Treatment composite catalyst that waste water difficult for biological degradation cost is low, COD treatment effeciency is high.
2. provide that a kind of energy consumption is low, preparation technology is simple, active component dispersive property is good, catalyst has high catalytic activity, the preparation method of the electrolytic oxidation Industrial Wastewater Treatment composite catalyst that manufacturing cost is lower.
3. catalyst activity component is uniformly dispersed, forms various, and different types of waste water difficult for biological degradation is had to good catalytic activity and treatment effect.
4. the carrier that catalyst adopts is because its real density is than the bigger carriers such as aluminium oxide, silica, active carbon and molecular sieve that are but less than of water, there is good fluidizing performance, in course of reaction, there is higher mass transfer ability, there is the feature of high treatment effect and low energy consumption.
5. lower as the slaine cost of material of catalyst activity component, preparation cost is low; Catalyst has higher catalytic activity, and low to electrode material requirement, electrolysis installation investment is low, so the disposal cost of waste water is low.
6. as the filler of electrolysis-catalytic oxidation device, for catalytic oxidation waste water difficult for biological degradation, process waste water COD clearance >=75%.
The specific embodiment
The present invention will now be further detailed embodiment:
Embodiment 1
Take 10g polystyrene resin bead, add in 100ml chloroform, add in chloroform, under room temperature, slowly add while stirring the oleum of 50ml30%-50%, then sulfonation 180min in 60 ℃ of water-baths, sulfonation finishes the rear absolute ethyl alcohol that slowly adds, suction filtration, washing 3 times, then deionized water wash in cleaning solution without SO
4 2-detect, then with hair-dryer, dry up standby.It is standby that this step is repeatedly prepared enough sulfonated polystyrene ion exchange resins.
The Fe that outfit mass fraction is 8.10%
2+salting liquid 120ml adds in 200ml beaker and carries out ion-exchange with 25 ℃ of 20g sulfonated polystyrene ion exchange resins, and the reaction time is 90min, then to catalyst precarsor filtering and washing 5 times, places in baking oven in 80 ℃ of dry 360min, obtains catalyst precarsor A; The Mn that outfit mass fraction is 10.92%
2+salting liquid 120ml adds in 200ml beaker and carries out ion-exchange with 25 ℃ of 20g sulfonated polystyrene ion exchange resins, and the reaction time is 90min, then to catalyst precarsor filtering and washing 5 times, places in baking oven in 80 ℃ of dry 360min, obtains catalyst precarsor B; The Cr that outfit mass fraction is 6.56%
3+salting liquid 120ml adds in 200ml beaker and carries out ion-exchange with 25 ℃ of 20g sulfonated polystyrene ion exchange resins, and the reaction time is 90min, then to catalyst precarsor filtering and washing 5 times, places in baking oven in 80 ℃ of dry 360min, obtains catalyst precarsor C; The Cu that outfit mass fraction is 7.2%
2+salting liquid 120ml adds in 200ml beaker and carries out ion-exchange with 25 ℃ of 20g sulfonated polystyrene ion exchange resins, and the reaction time is 90min, then to catalyst precarsor filtering and washing 5 times, places in baking oven in 80 ℃ of dry 360min, obtains catalyst precarsor D; The ratio that is 8:1.5:1:1 according to mass ratio, the catalyst as catalytic and oxidative electrolysis technology waste water difficult for biological degradation after each catalyst precarsor of above-mentioned preparation is evenly mixed comes into operation.After testing, its real density of sulfonated polystyrene ion exchange resin as carrier is 1.37g/cm
3, Fe in precursor A
2+load capacity be Mn in 6.8%, B
2+load capacity be Cr in 5.2%, C
3+load capacity be Cu in 6.2%, D
2+load capacity be 6.0%.
The dense water COD that the reverse osmosis unit in certain oil refinery waste water reuse workshop produces is 150mg/L, pH=7.9.It is graphite electrode plate that catalytic and oxidative electrolysis technology reaction unit is selected pole plate, main technique service condition is: under normal temperature and pressure, operating current 3A, operating voltage 7.6V, regulate entrance used water difficult to degradate pH=3.0, the volume ratio of loaded catalyst and catalytic and oxidative electrolysis technology reaction tank is 0.4, and inflow is 9L/h, lift gas adopts air, and air inflow is 45L/h.After treatment, water outlet COD is 30mg/L, and COD clearance is 80%.
Embodiment 2
Adopt the step identical with embodiment 1 to carry out after sulfonation the carrier of selecting, the Fe that is 5.52% with mass fraction respectively
2+the Mn that salting liquid, mass fraction are 7.28%
2+the Cr that salting liquid, mass fraction are 3.28%
3+the Cu that salting liquid, mass fraction are 4.80%
2+carrier after salting liquid and sulfonation carries out ion-exchange at 20 ℃, and reaction finishes by detection, Fe in A
2+load capacity be Mn in 3.3%, B
2+load capacity be Cr in 3.4%, C
3+load capacity be Cu in 2.9%, D
2+load capacity be 3.3%.By the step identical with embodiment 1, Kaolinite Preparation of Catalyst is used.
Adopt the technological parameter of embodiment 1, process the waste water identical with embodiment 1, after treatment, water outlet COD is 39mg/L, and COD clearance is 74%.
Embodiment 3
Adopt the step identical with embodiment 1 carrier of selecting being carried out to, after sulfonation, use respectively the Fe with embodiment 1 equal in quality mark
2+, Mn
2+, Cr
3+, Cu
2+salting liquid and 45 ℃, the carrier after sulfonation carry out ion-exchange, the reaction time is 900min, reaction finishes by detection, Fe in A
2+load capacity be Mn in 7.3%, B
2+load capacity be Cr in 5.9%, C
3+load capacity be Cu in 7.5%, D
2+load capacity be 7.2%.By the step identical with embodiment 1, Kaolinite Preparation of Catalyst is used.
Adopt the technological parameter of embodiment 1, process the waste water identical with embodiment 1, after treatment, water outlet COD is 35mg/L, and COD clearance is 76.7%.
Embodiment 4
The step Kaolinite Preparation of Catalyst precursor that adopts embodiment 1, the ratio that is 7:2:1:1 according to mass ratio, evenly mixes each catalyst precarsor of above-mentioned preparation, as the catalyst use of catalytic and oxidative electrolysis technology waste water difficult for biological degradation.
Adopt the technological parameter of embodiment 1, process the waste water identical with embodiment 1, after treatment, water outlet COD is 35mg/L, and COD clearance is 76.7%.
Embodiment 5
The step Kaolinite Preparation of Catalyst precursor that adopts embodiment 1, the ratio that is 7:2:1.5:1 according to mass ratio, evenly mixes each catalyst precarsor of above-mentioned preparation, as the catalyst use of catalytic and oxidative electrolysis technology waste water difficult for biological degradation.
Adopt the technological parameter of embodiment 1, process the waste water identical with embodiment 1, after treatment, water outlet COD is 36mg/L, and COD clearance is 76%.
Embodiment 6
Adopt the catalyst preparation step identical with embodiment 1 and identical catalyst precarsor mass mixing ratio, the catalyst of preparation is used as the catalyst of catalytic and oxidative electrolysis technology waste water difficult for biological degradation.
Certain steam power plant's chemistry water generator regenerative wastewater: COD is 120mg/L, pH=4.1.The technological parameter that adopts embodiment 1, it is stainless steel polar plate that catalytic and oxidative electrolysis technology reaction unit is selected pole plate, and after this waste water is processed, water outlet COD is 25mg/L, and COD clearance is 79.2%.
Embodiment 7
Adopt after the catalyst precarsor mass mixing ratio that the catalyst preparation step identical with embodiment 1 is identical with embodiment 4, the catalyst making is used as the catalyst of catalytic and oxidative electrolysis technology waste water difficult for biological degradation.
Adopt the technological parameter of embodiment 1, process the waste water identical with embodiment 6, after treatment, water outlet COD is 27mg/L, and COD clearance is 77.5%.
Claims (9)
1. an electrolytic oxidation Industrial Wastewater Treatment composite catalyst, comprises catalyst carrier and active component, it is characterized in that take that sulfonated polystyrene ion exchange resin is as carrier, with metal cations Fe
2+, Mn
2+, Cr
3+and Cu
2+for active component, adopt ion-exchange, by activity component metal ion, be carried on respectively on described sulfonated polystyrene ion exchange resin carrier, make respectively catalyst precarsor A, catalyst precarsor B, catalyst precarsor C and catalyst precarsor D, the load capacity of described each active component on described carrier is 1%～20% of described each catalyst precarsor quality; Electrolytic oxidation Industrial Wastewater Treatment composite catalyst is by forming according to the catalyst precarsor of mass percent meter as follows:
2. electrolytic oxidation Industrial Wastewater Treatment composite catalyst according to claim 1, is characterized in that electrolytic oxidation Industrial Wastewater Treatment composite catalyst is by forming according to the catalyst precarsor of mass percent meter as follows:
3. electrolytic oxidation Industrial Wastewater Treatment composite catalyst according to claim 1 and 2, is characterized in that described catalyst carrier sulfonated polystyrene ion exchange resin, and selecting diameter is 0.25～1.0mm, and specific surface is 100～600m
2the macropore polystyrene resin (ps) particle of/g, processes and obtains through sulfonation; The real density of the sulfonated polystyrene ion exchange resin obtaining after sulfonation is 1.30～1.50g/cm
3.
4. electrolytic oxidation Industrial Wastewater Treatment composite catalyst according to claim 3, is characterized in that described catalyst carrier sulfonated polystyrene ion exchange resin, and selecting diameter is 0.5～0.75mm, and specific surface is 300～550m
2the macropore polystyrene resin (ps) particle of/g, processes and obtains through sulfonation.
5. electrolytic oxidation Industrial Wastewater Treatment composite catalyst according to claim 1, is characterized in that described activity component metal ion Fe
2+, Mn
2+, Cr
3+, Cu
2+, by the aqueous solution of water soluble salt separately, being provided, in the aqueous solution, the mass percent concentration of metal ion is respectively:
6. electrolytic oxidation Industrial Wastewater Treatment composite catalyst according to claim 5, is characterized in that the mass percent concentration of metal ion in the described aqueous solution is respectively:
7. electrolytic oxidation Industrial Wastewater Treatment composite catalyst according to claim 1, is characterized in that the load capacity of described active component on described carrier is 5%～7% of described each catalyst precarsor quality.
8. the preparation method of the electrolytic oxidation Industrial Wastewater Treatment composite catalyst of claim 1, is characterized in that comprising the steps:
1. the preparation of carrier-sulfonated polystyrene ion exchange resin
In the flask of stirring is housed, drop into chloroform 100ml, macropore polystyrene resin (ps) particle 10g, under room temperature, stirring, slowly adds the oleum 50ml of 30%-50%; Then, at 60～80 ℃ of temperature, sulfonation 160～200 minutes; After sulfonation finishes, slowly add absolute ethanol washing 3 times, suction filtration; Again with deionized water wash in cleaning solution without SO
4 2～, dry, make catalyst carrier-sulfonated polystyrene ion exchange resin;
2. the preparation of catalyst precarsor:
A. activity component metal ion Fe
2+, Mn
2+, Cr
3+, Cu
2+the preparation of the aqueous solution
According to drafting formula, take respectively and contain metal cations Fe
2+, Mn
2+, Cr
3+, Cu
2+water soluble salt, be dissolved in gauge water, make the activity component metal solion of desired concn, standby;
B. ion-exchange
Take catalyst carrier-sulfonated polystyrene ion exchange resin that 1. quantitative step is prepared, drop into respectively catalyst precarsor A, B prepared by wish, C, D the metal cations Fe prepared of step a separately
2+, Mn
2+, Cr
3+, Cu
2+in the aqueous solution, be controlled at 15 ℃～45 ℃ temperature, carry out ion-exchange, the reaction time is 60min～1200min, then, and through filtering and washing, the dry catalyst precarsor that makes;
3.. the preparation of electrolytic oxidation Industrial Wastewater Treatment composite catalyst
According to drafting formula, take each component of catalyst precarsor, mix, obtain electrolytic oxidation Industrial Wastewater Treatment composite catalyst product.
9. the preparation method of electrolytic oxidation Industrial Wastewater Treatment composite catalyst according to Claim 8, the reaction time that it is characterized in that the ion-exchange in step b is 90min～120min, reaction temperature is 25 ℃～30 ℃.
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| CN105293643A (en) * | 2014-07-11 | 2016-02-03 | 中国石油化工股份有限公司 | Method for treating sewage through electrolytic catalysis oxidation |
| CN105854938A (en) * | 2015-07-02 | 2016-08-17 | 江苏新淮河医药科技有限公司 | Polystyrene supported type catalyst and application method thereof in synthesis of dihydrocoumarin |
| CN106630345A (en) * | 2016-11-18 | 2017-05-10 | 浙江荣凯科技发展股份有限公司 | Electrolytic oxidation treatment process of intermediate 2-chloronicotinic acid production wastewater |
| CN107572716A (en) * | 2016-07-05 | 2018-01-12 | 中国石油化工股份有限公司 | Amine liquid regenerating unit produces the advanced treatment process of spent lye |
| CN107774328A (en) * | 2016-08-27 | 2018-03-09 | 中国石油化工股份有限公司 | electrolytic catalyst and preparation method thereof |
| CN107774327A (en) * | 2016-08-27 | 2018-03-09 | 中国石油化工股份有限公司 | Electrolytic sewage catalyst and preparation method thereof |
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| CN105293643A (en) * | 2014-07-11 | 2016-02-03 | 中国石油化工股份有限公司 | Method for treating sewage through electrolytic catalysis oxidation |
| CN105854938A (en) * | 2015-07-02 | 2016-08-17 | 江苏新淮河医药科技有限公司 | Polystyrene supported type catalyst and application method thereof in synthesis of dihydrocoumarin |
| CN105854938B (en) * | 2015-07-02 | 2018-03-09 | 江苏新淮河医药科技有限公司 | Loaded by polystyrene type catalyst and its application process in dihydrocoumarin synthesis |
| CN107572716A (en) * | 2016-07-05 | 2018-01-12 | 中国石油化工股份有限公司 | Amine liquid regenerating unit produces the advanced treatment process of spent lye |
| CN107572716B (en) * | 2016-07-05 | 2020-10-27 | 中国石油化工股份有限公司 | Advanced treatment process for waste alkali liquor generated by amine liquor regeneration device |
| CN107774328A (en) * | 2016-08-27 | 2018-03-09 | 中国石油化工股份有限公司 | electrolytic catalyst and preparation method thereof |
| CN107774327A (en) * | 2016-08-27 | 2018-03-09 | 中国石油化工股份有限公司 | Electrolytic sewage catalyst and preparation method thereof |
| CN107774326A (en) * | 2016-08-27 | 2018-03-09 | 中国石油化工股份有限公司 | Fluid bed electrolytic catalyst and preparation method thereof |
| CN107774328B (en) * | 2016-08-27 | 2020-07-10 | 中国石油化工股份有限公司 | Electrolytic catalyst |
| CN107774327B (en) * | 2016-08-27 | 2020-07-10 | 中国石油化工股份有限公司 | Sewage electrolysis catalyst and preparation method thereof |
| CN107774326B (en) * | 2016-08-27 | 2020-09-08 | 中国石油化工股份有限公司 | Fluidized bed electrolytic catalyst |
| CN106630345A (en) * | 2016-11-18 | 2017-05-10 | 浙江荣凯科技发展股份有限公司 | Electrolytic oxidation treatment process of intermediate 2-chloronicotinic acid production wastewater |
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