CN110092461A - One kind being based on Cu2+For active component catalyst to the processing method of bisphenol-A waste water - Google Patents
One kind being based on Cu2+For active component catalyst to the processing method of bisphenol-A waste water Download PDFInfo
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- CN110092461A CN110092461A CN201910265981.5A CN201910265981A CN110092461A CN 110092461 A CN110092461 A CN 110092461A CN 201910265981 A CN201910265981 A CN 201910265981A CN 110092461 A CN110092461 A CN 110092461A
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The invention belongs to water pollution processing technology fields, disclose a kind of based on Cu2+For the catalyst of active component the catalyst of optimal catalyzing oxidizing degrading bisphenol-A is filtered out to the processing method of bisphenol-A waste water by homogeneous CWPO reaction system, and has analyzed the CWPO performance of bisphenol-A under the conditions of differential responses；Obtain the reaction condition of best degradation removal bisphenol-A are as follows: the initial concentration of bisphenol-A simulated wastewater is 152mg/L, CuSO4Catalyst amount is 1g/L, H2O2Dosage is 78mmol/L, under the conditions of 75 DEG C, reacts 65min.The removal rate of bisphenol-A of the present invention is up to 95.4%, can efficiently catalyzing and oxidizing degrade bisphenol-A simulated wastewater, reaction process is not required to adjust the pH value of reaction solution, operation of the present invention is simple, reaction is fast, at low cost, and the pretreatment of the organic wastewater for toxic, difficult for biological degradation containing phenyl ring or advanced treating provide new approaches.
Description
Technical field
The invention belongs to water pollution processing technology fields, more particularly to one kind to be based on Cu2+For the catalyst pair of active component
The processing method of bisphenol-A waste water.
Background technique
Bisphenol-A is one of current industrial compound most popular in the world.It is industrially mainly as industrialization
The intermediate for closing object is the important source material for manufacturing the various kinds of resin such as epoxy resin, polycarbonate and phenol-formaldehyde resin modified, also uses
In preparing antioxidant, stabilizer, plasticizer, can coating, heat-sensitive paper, dental filling, paint and pesticide etc., it mainly passes through
The process of manufacture of the raw material containing bisphenol-A, not exclusively thoroughly wastewater treatment, landfill leachate and the ingredient containing bisphenol-A it is discarded
The leaching of object and move in environment.It has been examined in lake, river, drinking water, food, beverage, soil and air at present
Measure bisphenol-A.Bisphenol-A is determined as incretion interferent by Environmental Protection Agency (EPA) and World Wildlife Fund.Mesh
Before have been shown to have estrogen action, in 1000-10,000 μ g/L concentration range, have acute poison to aquatile
Property, a small amount of intake can also destroy the endocrine system of human body, be likely to result in infertility, monster and breast cancer etc., to the ecosystem
Safety and human health have potential hazard.Therefore the minimizing technology of research bisphenol-A is very necessary.
It mainly include in recent years physics, chemistry, biology and advanced oxidization method to the minimizing technology of bisphenol-A, such as adsorb,
Membrane technology, biodegrade, photocatalysis, ozonisation, ultrasonic wave, Fenton method, catalytic wet oxidation and electrocatalytic oxidation.?
In the processing method of bisphenol-A, physical method, e.g., and activated carbon adsorption, although absorption can quickly and effectively remove bisphenol-A,
It is that absorption method removes bisphenol-A not by the mode of degradation, but bisphenol-A is transferred in solid phase from water phase, mainly
As a kind of emergency processing method, and absorption method such as active carbon, general expenses are higher, and regenerative system processing difficulty is big.Bioanalysis
Processing bisphenol-A waste water has a extensive future, but also has very big disadvantage, and e.g., strain requirement is high, the domestication used time of sludge is longer, land occupation
Big and processing is not thorough, simultaneously because bisphenol-A may to microorganism generation toxicity, cause its biodegrade may need compared with
For a long time, it while being also possible to by many such environmental effects such as nutrition, temperature and salinity to limit its application.It is catalyzed wet
Formula oxidizing process, needs condition progress at high temperature and pressure, and device requires high, the pressure resistance of equipment needs and corrosion-resistant, service condition
It is harsh.In the prior art, Fenton method treatment effeciency is relatively high, but be directed to bisphenol-A, using Fenton method handle, exist as
Lower technical difficulty: bisphenol-A removal rate is lower, and only 50% or so；Reaction process has the floccule Fe (OH) of colloidal3It is raw
At centrifugal separating effect is poor, and natural subsidence needs 3 days or so time, than relatively time-consuming, low efficiency；Reaction process needs to adjust reaction
The pH value of liquid is under the conditions of 2-4；It is partially yellow to be discharged color.
Based on this, the present invention will provide technical support to solve the above problems, firstly, the catalyst that the present invention selects is urged
It is good, it can be achieved that the efficiently catalyzing and oxidizing of bisphenol-A is degraded to change effect；Secondly, catalytic component is simple, from a wealth of sources, at low cost；
Again, reaction condition is mild, is not required to adjust that the pH value of reaction solution, easily separated, effluent quality is limpid.The present invention can be practical high
It pre-processes early period of the organic wastewater of concentration or difficult for biological degradation or advanced treating provides technical support, to realize such have
The qualified discharge of machine waste water or biochemical processing have important ecology and social benefit.
Summary of the invention
In view of the problems of the existing technology, the present invention provides one kind to be based on Cu2+For active component catalyst to double
The processing method of phenol A waste water.The present invention enters from the screening of catalyst activity component first using Fenton reaction as theoretical direction
Hand, catalysis of the cheap transistion metal compound of analysis cost under homogeneous CWPO reaction system, to bisphenol-A organic pollutant
Oxidative degradation situation, and influence of the differential responses condition to homogeneous CWPO degradation property is analyzed, to filter out optimum catalyst
And optimum reaction condition, the processing for the practical waste water containing bisphenol-A provide Technical Reference.
The invention is realized in this way one kind is with Cu2+Oxygen is catalyzed for the embryonic stem-like cells system of catalyst activity component
Change the method for degradation treatment bisphenol-A waste water, it is described with Cu2+Oxygen is catalyzed for the Fenton-like reaction system of catalyst activity component
Change degradation treatment bisphenol-A waste water method include:
The first step is based on Fenton reaction theory, respectively with CuSO4、CuCl2、Cu(NO3)2、C4H6CuO4·H2O、
MnSO4、FeSO4、Fe2(SO4)3Or CoSO4As catalyst, simulation bisphenol-A waste water is carried out under homogeneous CWPO reaction system
Catalyzing oxidizing degrading filters out optimum catalyst active component Cu2+；
Second step, with optimum activity component Cu2+Compound CuSO4For catalyst, in catalyst amount 0.2g/L~2g/
L, bisphenol-A simulated wastewater initial concentration 40.1mg/L~152mg/L, H2O2Dosage 78mmol/L~470mmol/L, reaction temperature
Under 55 DEG C~85 DEG C, reaction time 15min~95min and pH value 3.0-7.9 reaction condition, to homogeneous CWPO reaction system
Bisphenol-A carries out catalyzing oxidizing degrading, the best catalyzing oxidizing degrading condition of optimization.
Further, catalyst CuSO4。
Further, catalyst amount 0.8g/L.
Further, bisphenol-A initial concentration is 152mg/L.
Further, H2O2Dosage is 78mmol/L；Reaction temperature is 75 DEG C；Reaction time is 65min.
Further, H2O2For dosage using the theory demands amount of bisphenol-A as foundation, foundation is C15H16O2+36H2O2→15CO2+
44H2O。
Another object of the present invention is to provide described in a kind of implementation with Cu2+For the Fenton-like of catalyst activity component
The pharmaceutical industry that reaction system catalyzing oxidizing degrading handles the method for bisphenol-A waste water is based on Cu2+For the catalyst pair of active component
The processing equipment of bisphenol-A waste water.
Another object of the present invention is to provide described in a kind of implementation with Cu2+For the Fenton-like of catalyst activity component
The petrochemical industry that reaction system catalyzing oxidizing degrading handles the method for bisphenol-A waste water is based on Cu2+For the catalyst pair of active component
The processing equipment of bisphenol-A waste water.
Another object of the present invention is to provide described in a kind of implementation with Cu2+For the Fenton-like of catalyst activity component
The chemical field that reaction system catalyzing oxidizing degrading handles the method for bisphenol-A waste water is based on Cu2+For the catalyst pair of active component
The processing equipment of bisphenol-A waste water.
Another object of the present invention is to provide described in a kind of implementation with Cu2+For the Fenton-like of catalyst activity component
The dyeing that reaction system catalyzing oxidizing degrading handles the method for bisphenol-A waste water is based on Cu2+For the catalyst pair of active component
The processing equipment of bisphenol-A waste water.
In conclusion advantages of the present invention and good effect are as follows:
The present invention can realize the catalyzing oxidizing degrading of bisphenol-A in a short time, it can be made to be degraded in 1 hour
H2O and CO2.In addition the invention realizes the open loop of the compound containing benzene ring structure, can provide for the degradation of the type organic containing phenyl ring
Technical Reference.
Catalyst of the present invention all has higher degradation efficiency in 3.0~7.9 range of pH value, compares biography
The Fenton method of system is generally required to run in the range of pH value 2~4 and be had great advantages, simultaneously because at the beginning of bisphenol-A waste water
Beginning pH value is generally 6.6 or so, and reaction process is not required to additionally adjust the pH value of waste water.
Used catalyst of the present invention only has one kind, and is transition metal, low in cost.
The present invention can for manufacture and design a poisonous organic wastewater processing equipment technical support be provided, it can be achieved that amount it is small,
The quick processing of toxic, dispersion organic wastewater can promote waste water treatment and equip the development of industry.
Detailed description of the invention
Fig. 1 is provided in an embodiment of the present invention with Cu2+Oxygen is catalyzed for the embryonic stem-like cells system of catalyst activity component
Change the method flow diagram of degradation treatment bisphenol-A waste water.
Fig. 2 is that metallic compound provided in an embodiment of the present invention CWPO performance homogeneous on bisphenol-A influences.
Fig. 3 is that catalyst amount provided in an embodiment of the present invention CWPO performance homogeneous on bisphenol-A influences (solid line-bisphenol-A；
Dotted line-H2O2) shown in.
Fig. 4 is H provided in an embodiment of the present invention2O2Dosage CWPO performance homogeneous on bisphenol-A influences (solid line-bisphenol-A；It is empty
Line-H2O2)。
Fig. 5 is that reaction temperature provided in an embodiment of the present invention CWPO performance homogeneous on bisphenol-A influences (solid line-bisphenol-A；It is empty
Line-H2O2)。
Fig. 6 is that initial concentration provided in an embodiment of the present invention CWPO performance homogeneous on bisphenol-A influences (solid line-bisphenol-A；It is empty
Line-H2O2)。
Fig. 7 is that initial pH provided in an embodiment of the present invention CWPO performance homogeneous on bisphenol-A influences (solid line-bisphenol-A；It is empty
Line-H2O2)。
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to this hair
It is bright to be further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
In the physical treatment method of bisphenol-A, e.g., activated carbon adsorption, although absorption can quickly and effectively remove bis-phenol
A, but absorption method removes bisphenol-A not by the mode of degradation, but bisphenol-A is transferred in solid phase from water phase,
Mainly as a kind of emergency processing method, and absorption method such as active carbon, general expenses are higher, and regenerative system processing difficulty is big.
Biochemical method bisphenol-A waste water has a extensive future, but also has very big disadvantage, and e.g., strain requires high, sludge domestication
Used time is longer, land occupation is big and processing is not thorough, simultaneously because bisphenol-A may generate toxicity to microorganism, leads to its biology drop
Solution may need the long period, while be also possible to by many such environmental effects such as nutrition, temperature and salinity to limit it
Using.Catalytic wet air oxidation, needs condition progress at high temperature and pressure, and device requires high, the pressure resistance of equipment needs and corrosion resistant
Erosion, service condition are harsh.
Fenton method treatment effeciency is relatively high, but is directed to bisphenol-A, is handled using Fenton method, and it is tired that there are following technologies
Difficult: bisphenol-A removal rate is lower, and only 50% or so；Reaction process has the floccule Fe (OH) of colloidal3It generates, centrifugation point
Poor from effect, natural subsidence needs 3 days or so time, than relatively time-consuming, low efficiency；Reaction process needs to adjust the pH value of reaction solution
Under the conditions of 2-4；It is partially yellow to be discharged color.
To solve the above problems, below with reference to concrete scheme, the present invention is described in detail.
As shown in Figure 1, provided in an embodiment of the present invention with Cu2+For the embryonic stem-like cells system of catalyst activity component
Catalyzing oxidizing degrading processing bisphenol-A waste water method include:
S101 is based on Fenton reaction theory, respectively with CuSO4、CuCl2、Cu(NO3)2、C4H6CuO4·H2O、 MnSO4、
FeSO4、Fe2(SO4)3Or CoSO4It as catalyst, investigates under homogeneous CWPO reaction system, simulation bisphenol-A waste water is urged
Change oxidative degradation situation, filters out optimum catalyst active component Cu2+。
S102, with optimum activity component Cu2+Compound CuSO4For catalyst, investigate catalyst amount 0.2g/L~
2g/L, bisphenol-A simulated wastewater initial concentration 40.1mg/L~152mg/L, H2O2Dosage 78mmol/L~470mmol/L, reaction
55 DEG C~85 DEG C of temperature, reaction time 15min~95min and pH value 3.0-7.9 differential responses condition are reacted in homogeneous CWPO
To the catalyzing oxidizing degrading performance of bisphenol-A, the best catalyzing oxidizing degrading condition of optimization under system.
In embodiments of the present invention, catalyst amount range is 0.2g/L~2g/L, bisphenol-A simulated wastewater initial concentration
Range is 40.1mg/L~152mg/L, H2O2Amount ranges are 78mmol/L~470mmol/L, and range of reaction temperature is 55 DEG C
~85 DEG C, react 65min.
In embodiments of the present invention, catalyst can be CuSO4、CuCl2、Cu(NO3)2、C4H6CuO4·H2O、 MnSO4、
FeSO4、Fe2(SO4)3Or CoSO4, wherein optimum catalyst is CuSO4。
As the preferred embodiment of the present invention, it is 152mg/L, at 75 DEG C of reaction temperature in bisphenol-A initial concentration, most preferably urges
Agent dosage is 0.8g/L.
In embodiments of the present invention, hydrogen peroxide use is using the theory demands amount of bisphenol-A as foundation: C15H16O2+36H2O2
→15CO2+44H2O。
In embodiments of the present invention, bisphenol-A initial concentration is 152mg/L, 75 DEG C of reaction temperature, catalyst amount are
Under 0.8g/L, best H2O2Dosage is 78mmol/L.
As the preferred embodiment of the present invention, optimal reaction temperature is 75 DEG C.
As the preferred embodiment of the present invention, catalyst has wider pH adaptability, right within the scope of pH value 3.0-7.9
Bisphenol-A all has higher catalyzing oxidizing degrading ability.
Below with reference to specific attached drawing and related experiment analysis, the invention will be further described.
1. in the present invention, bisphenol-A is incretion interferent, have toxicity big and difficult for biological degradation, to the mankind and aquatic
Object all has biggish harm, therefore is of great significance to this its progress degradation treatment.It is traditional in high-level oxidation technology
Wet oxidation process has many advantages, such as that reaction rate is fast and salinity is high, but must carry out at high temperature under high pressure, needs a large amount of high pressures
Power-equipment or air separation equipment, operating cost are higher.In order to reduce above-mentioned unfavorable conditions, urged by being added in the reaction
Agent, grown up CWAO method, rear by improving, with H2O2Instead of air or oxygen as oxidant, grow up
CWPO method, to reduce resistance to mass tranfer, has mitigated technique item its main feature is that oxidant can be made directly to mix with reactant
Part can be such that reaction carries out under room temperature and condition of normal pressure.Based on this, the present invention is first using Fenton reaction as theoretical direction
First start with from the screening of catalyst activity component, the cheap transistion metal compound of analysis cost is in homogeneous CWPO reaction system
Under, to the catalyzing oxidizing degrading situation of bisphenol-A, and influence of the differential responses condition to homogeneous CWPO degradation property is analyzed, thus
Optimum catalyst and optimum reaction condition are filtered out, the processing for the practical waste water containing bisphenol-A provides Technical Reference.
2. catalyst activity component screening test:
As shown in Figure 2, degrade to the CWPO of bisphenol-A, copper acetate almost without effect, cobaltous sulfate because after reaction solution be in
Weak aubergine, it is impacted using spectrophotometry, it is unable to correct response degradation effect, manganese sulfate has bisphenol-A certain
Degradation effect, removal rate is 52.6% after reacting 65min.Water quality reacts latter with quinoline after ferrous sulfate and ferric sulfate reaction
Sample, equally in isabelline, and it is muddy, water quality is still partially yellow after centrifuge separation, and water quality improves after precipitating 3 days.Come from test result
It sees, copper nitrate, copper chloride and three kinds of copper class compounds of copper sulphate homogeneous CWPO degradation capability with higher to bisphenol-A, i.e., it is living
Property group is divided into Cu2+, since copper chloride is there are chloride ion, may there is secondary pollution to water quality, copper nitrate there are nitrate ion,
There is certain oxidability in acid condition, therefore selects copper sulphate as the homogeneous CWPO method of evaluation to bisphenol-A catalysis oxidation
The catalyst of degradation capability.
In the present invention, in order to screen optimal catalyst activity component, Main Analysis transistion metal compound is with molten
State is solved in homogeneous CWPO reaction to the Degrading experiment of bisphenol-A.Test carries out in reaction flask, weighs the 1g/L (difference of 1g/L
Transition metal compound catalyst is obtained by conversion, i.e. Cu2+Concentration is 0.4mol/L, same as below) transition metal
Compound is dissolved in the bisphenol-A simulated wastewater that initial concentration is 152mg/L respectively as catalyst, 196mmol/L is added
H2O2(mass fraction, 30%) reacts 65min under the conditions of 75 DEG C, and partial results such as Fig. 3 catalyst amount is equal to bisphenol-A
Shown in phase CWPO performance influences.
3. homogeneous CWPO test
The influence of 3.1 catalyst amounts, as Fig. 3 catalyst amount CWPO performance homogeneous on bisphenol-A influences (solid line-bis-phenol
A；Dotted line-H2O2) shown in.
Before analysis differential responses condition CWPO degradation property homogeneous on bisphenol-A simulated wastewater influences, analyze respectively double
The volatilization of phenol solution A, independent Ni metal2+Ion and independent H2O2Oxidation contributes the degradation of simulated wastewater, the results showed that
After reacting 2h, the volatilization of simulated wastewater is all not above 8.9% to the contribution of removal rate, independent Ni metal2+Ion pair removal
The contribution of rate is not above 8.6%, independent H2O2Oxidation 8.5% is not above to the contribution of removal rate, illustrate catalyst and
The synergistic effect of hydrogen peroxide is only the key of CWPO method degradation bisphenol-A simulated wastewater.
Test carries out in tool plug reaction flask, reaction condition are as follows: in the simulation bis-phenol for the 152mg/L that initial pH value is 6.6
The CuSO of various concentration is added in A waste water4The H of 78mmol/L is added in catalyst in bisphenol-a reaction bottle2O2(mass fraction,
30%) it, is then reacted the regular hour under 75 DEG C of waters bath with thermostatic control, as a result as shown in Fig. 3.From the figure 3, it may be seen that when catalyst is used
Amount is in 0.4g/L or less, and after reacting 15min, the removal rate of bisphenol-A all only has 75% or so；Reach after reacting 65min
90% or so.It is found that catalyst amount is in 0.8g/L from Fig. 3, effect is best, under the same reaction time, urges than other
Removal rate is high by 4% or so under the conditions of agent dosage, and bisphenol-A removal rate is respectively 95.4% He after reacting 65min and 95min
96.6%, TOC removal rate are respectively 86% and 85.9%.
The influence of 3.2 hydrogen peroxide uses, H2O2Dosage CWPO performance homogeneous on bisphenol-A influences (solid line-bisphenol-A；It is empty
Line-H2O2)。
As shown in Figure 4, in H2O2When dosage is 78mmol/L, bisphenol-A removal rate highest, after reacting 15min, removal rate
For 77%, H2O2Consumption rate is 60.1%；Work as H2O2When dosage is 470mmol/L, within the same time, removal rate is
16.3%, H2O2Consumption rate is 45.5%.Continue to increase with the reaction time, the removal rate and H of bisphenol-A2O2Consumption rate
Also with raising, after reacting 65min, under the conditions of dioxygen water consumption is 78mmol/L and 470mmol/L, the removal of bisphenol-A
Rate is respectively 98% and 68.8%, H2O2Consumption rate is respectively 82.1% and 75.2%, is illustrated with the extension of reaction time, instead
More strong oxidizing property OH free radical, CWPO improved efficiency can should be gradually generated in the process.It is indicated above that H2O2Dosage is to double
The degradation of phenol A is most important.Work as H2O2When dosage excess, homogeneous CWPO effect sharp fall will lead to, this may mainly return
Because in excessive H2O2Itself consumption has occurred with OH free radical to react.
The influence of 3.3 reaction temperatures
In the CuSO for simulating addition 0.2g/L in bisphenol-A waste water for the 152mg/L that initial pH value is 6.64Catalyst and
The H2O2 (mass fraction, 30%) of 78mmol/L, then reacts the regular hour under different waters bath with thermostatic control, as a result as Fig. 5 is anti-
Temperature CWPO performance homogeneous on bisphenol-A is answered to influence (solid line-bisphenol-A；Dotted line-H2O2) shown in.
Fig. 5 is it is found that influence of the reaction temperature to bisphenol-A is also very big, when reaction temperature is increased to 85 DEG C from 55 DEG C, reaction
After 15min, the removal rate of bisphenol-A is increased to 86.6%, H from 33%2O2Consumption rate be increased to 84% from 37%.It is reacting
After 65min, under 55,65,75 and 85 DEG C of reaction temperatures, the removal rate of bisphenol-A is respectively 65.5,81,98 and 98.6%, H2O2
Consumption rate be respectively 52.3,67.3,82.1 and 96.9%.It follows that removal and H of the reaction temperature to bisphenol-A2O2Disappear
Consumption influences very big.It can also illustrate that reaction temperature influences very the removal of bisphenol-A from the point of view of the variation of solution colour in reaction process
Greatly, only add catalyst or H at room temperature2O2When solution colour will not change, when both be added after, solution can rather
Inside become pale yellow, then gradually becoming shallower as greenish-yellow, shallow brown yellow, brown and black can shoal at once after being put into 75 DEG C of water-baths
Purplish red, rear thin out rapidly, solution colour disappears after 15min.By observing the color of solution under other three reaction temperatures, hair
When present reaction temperature is 55 DEG C, entire solution is in light violet magenta；It is molten in preceding 25min when reaction temperature is 65 DEG C
Liquid is in light violet magenta, rear bleach；Under 85 DEG C of reaction temperatures, entire solution is transparent, occurs without color.
By Arrhenius formula(in formula, A is pre-exponential factor, and Ea is activation energy, and R is gas constant, T
For thermodynamic temperature) it is found that reaction temperature and reaction rate constant k are proportional, therefore reaction temperature more high reaction rate more
Greatly.Any chemical reaction require certain activation energy, only when the energy of reaction system meets or exceeds the reaction
When required activation energy, reactant molecule just can be activated to form anakmetomeres.Under low reaction temperature, reaction system energy
Measure it is lower so that without enough energy be used for reactant molecule activation, the anakmetomeres negligible amounts resulted in,
Reaction progress is insufficient, therefore bisphenol-A oxidation removal rate is lower under lower reaction temperature.With the raising of reaction temperature, instead
Answer H in system2O2The quantity of activation generation OH free radical and pollutant are converted into the number of anakmetomeres under catalyst
The increase of amount or concentration, enables oxidation reaction adequately to be carried out, to mention the removal rate of bisphenol-A.
On the other hand, the bisphenol-A molecule and OH number of free radicals activated in reaction system with the raising of reaction temperature and
While increase, molecular motion rate can also aggravate with the raising of reaction temperature, can directly improve reactant in reaction system
The intermolecular probability that effective collision occurs, thus the probability to react between improving reactant molecule；Meanwhile high temperature also can be
Reaction system provides higher energy, can greatly shorten catalysis induction period, and organic matter CWPO reaction is made to enter quickly oxidation quickly
Phase reduces intermediate product and aoxidizes transformation time, therefore the homogeneous CWPO transformation efficiency of bisphenol-A is higher under high reaction temperature, instead
Answer rate fast.
The CuSO of 0.2g/L is added in the influence of 3.4 bisphenol-A initial concentrations in the simulation bisphenol-A waste water of various concentration4
The H of catalyst and 78mmol/L2O2(mass fraction, 30%), adjusting its pH value is 6.6, then respectively in 75 DEG C of waters bath with thermostatic control
The lower reaction regular hour, as a result as Fig. 6 initial concentration CWPO performance homogeneous on bisphenol-A influences (solid line-bisphenol-A；Dotted line-
H2O2) shown in.
It will be appreciated from fig. 6 that removal rate has large change with the increase of bisphenol A concentration, after reacting 65min, work as bisphenol-A
When concentration increases to 331mg/L from 40.1mg/L, the removal rate of bisphenol-A drops to 99% from 97.4%, illustrates bisphenol A concentration
Increase, the increase in demand to strong oxidizing property OH free radical, in same catalyst, H2O2Concentration and in the reaction time, generation
Strong oxidizing property OH free radical is not enough to aoxidize enough bisphenol-As.It will be appreciated from fig. 6 that H2O2Consumption rate is changed by bisphenol A concentration
It influences significantly, after reacting 65min, H2O2Consumption rate drops to 82.7% from 96.7%, it may be possible to since bisphenol A concentration is higher,
Intermediate product or the bubble etc. for reacting generation form space steric effect and hinder Cu2+With H2O2Come into full contact with, cause
Its decomposition is slack-off, and the speed decline of OH free radical is generated so as to cause system.
The CuSO of 0.2g/L is added in the influence of 3.5 initial pH values in the simulation bisphenol-A waste water of 152mg/L4Catalyst and
The H of 78mmol/L2O2(mass fraction, 30%), adjusts its pH value respectively, when then reacting certain under 75 DEG C of waters bath with thermostatic control
Between, as a result as the initial pH of Fig. 7 CWPO performance homogeneous on bisphenol-A influences (solid line-bisphenol-A；Dotted line-H2O2) shown in.
It as shown in Figure 7, is the homogeneous CWPO removal rate of bisphenol-A within the scope of 0-7.9 in pH value in entire reaction process
It is not much different.But in reaction early stage, have a certain impact, after reacting 15min, the removal rate of bisphenol-A is fallen after rising,
Respectively 70.2,79.5,77 and 73%, H2O2Consumption rate gap it is larger, respectively 18,64,60.2 and 70.6%.Initial
The stage of reaction, pH value have certain influence to be attributable to weak acid especially under mild acid conditions the homogeneous CWPO of bisphenol-A degradation
H under the conditions of property2O2Decomposition inhibited by certain, with the progress of reaction, system pH may be increased, H2O2Decomposition suppression
System releases；After reacting 65min, in addition under the conditions of pH value 0, the removal rate of bisphenol-A is slightly worse outer, under other pH value conditions all
91% or more, wherein under the conditions of pH7.9 bisphenol-A removal rate up to 96.6%, H2O2Consumption rate reach peak 98.1%.
In addition under the conditions of analyzing other pH, degradation effect of the bisphenol-A in homogeneous CWPO, the results showed that, in the condition of pH value 6 and 2.0
Under, bisphenol-A is hardly degraded, H2O2Consumption rate respectively only have 4.9% and 13%, illustrate under strongly acidic conditions, to be unfavorable for
H2O2It is decomposed into strong oxidizing property OH free radical.Also research thinks, transition metal ions is when pH value of solution changes, valence
State may change, and become hydrous oxide precipitating or become positively charged polyhydroxy complex polymerisation body, to easily inhale
Attached HO2 -, its activity is reduced, H is inhibited2O2Decomposition.Under the conditions of pH value is 10.1, after reacting 65min, bisphenol-A is gone
Except rate is still up to 86.6%, H2O2Reach 100% consumption；It is double after reacting 65min under the conditions of pH value is 14 and 12.0
Phenol A is hardly degraded, but H2O2It has been completely consumed that, and observe solution to have reddish-brown precipitation generation.Illustrate in strong basicity
Under the conditions of, H2O2It is extremely unstable, HO easy to form2 -, and HO2 -It is a kind of nucleopilic reagent, Yi Yinfa H2O2It decomposes and generates free radical,
And Cu2+It is also easier to and OH-Precipitation reaction occurs, therefore is unfavorable for the progress of homogeneous CWPO reaction under strongly alkaline conditions.
Below with reference to effect, the invention will be further described.
Catalyst activity component screening test the result shows that, copper acetate to bisphenol-A almost without effect, ferrous sulfate and
Ferric sulfate effect is poor, and copper nitrate, copper chloride and copper sulphate effect are preferable, and comprehensive each factor determines Cu2+(copper sulphate) is
Active component.
The test of homogeneous CWPO degradation bisphenol-A is obtained by carrying out differential responses condition:
1) in the early reaction stage, the quick progress that catalyst amount is conducive to reaction is improved, but reacts the later period, is urged
Agent dosage influences less, and under the conditions of this experimental concentration, the catalyst amount of best bisphenol-A of degrading is 0.8g/L, at this
Under part, after reacting 65min, the removal rate and TOC removal rate of bisphenol-A are respectively 95.4% and 85.9%.
2) reaction temperature has a significant impact to the catalyzing oxidizing degrading of bisphenol-A, removal rate and H2O2Consumption rate is with reaction
The raising of temperature and increase, 75 DEG C are proper reaction temperatures.In this experimental concentration range, the removal of bisphenol-A is with dense
The increase of degree has certain decline.
3)H2O2Dosage be affected to the degradation of bisphenol-A, with H2O2The increase of dosage, removal rate are substantially reduced.
The best H of degradation bisphenol-A2O2Dosage is 78mmol/L.
4) Cu is used2+Homogeneous CWPO method as catalyst, which is compared, uses Fe2+As the Fenton method of catalyst, have
Wider pH adaptability all has higher degradation efficiency in 3.0~7.9 range of pH value.In conclusion with active component
Cu2+Bisphenol-A waste water is handled in homogeneous CWPO reaction system as catalyst with very strong catalyzing oxidizing degrading ability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. one kind is with Cu2+Bisphenol-A waste water is handled for the embryonic stem-like cells system catalyzing oxidizing degrading of catalyst activity component
Method, which is characterized in that described with Cu2+It is double for the embryonic stem-like cells system catalyzing oxidizing degrading processing of catalyst activity component
The method of phenol A waste water includes:
The first step is based on Fenton reaction theory, respectively with CuSO4、CuCl2、Cu(NO3)2、C4H6CuO4·H2O、MnSO4、
FeSO4、Fe2(SO4)3Or CoSO4As catalyst, catalysis oxygen is carried out to simulation bisphenol-A waste water under homogeneous CWPO reaction system
Change degradation, filters out optimum catalyst active component Cu2+；
Second step, with optimum activity component Cu2+Compound CuSO4For catalyst, in catalyst amount 0.2g/L~2g/L, bis-phenol
A simulated wastewater initial concentration 40.1mg/L~152mg/L, H2O2Dosage 78mmol/L~470mmol/L, 55 DEG C of reaction temperature~
Under 85 DEG C, reaction time 15min~95min and pH value 3.0-7.9 reaction condition, to the bisphenol-A of homogeneous CWPO reaction system into
Row catalyzing oxidizing degrading, the best catalyzing oxidizing degrading condition of optimization.
2. as described in claim 1 with Cu2+At the embryonic stem-like cells system catalyzing oxidizing degrading of catalyst activity component
The method for managing bisphenol-A waste water, which is characterized in that catalyst CuSO4。
3. as described in claim 1 with Cu2+At the embryonic stem-like cells system catalyzing oxidizing degrading of catalyst activity component
The method for managing bisphenol-A waste water, which is characterized in that catalyst amount 0.8g/L.
4. as described in claim 1 with Cu2+At the embryonic stem-like cells system catalyzing oxidizing degrading of catalyst activity component
The method for managing bisphenol-A waste water, which is characterized in that bisphenol-A initial concentration is 152mg/L.
5. as described in claim 1 with Cu2+At the embryonic stem-like cells system catalyzing oxidizing degrading of catalyst activity component
The method for managing bisphenol-A waste water, which is characterized in that H2O2Dosage is 78mmol/L；Reaction temperature is 75 DEG C；Reaction time is
65min。
6. as described in claim 1 with Cu2+At the embryonic stem-like cells system catalyzing oxidizing degrading of catalyst activity component
The method for managing bisphenol-A waste water, which is characterized in that H2O2For dosage using the theory demands amount of bisphenol-A as foundation, foundation is C15H16O2+
36H2O2→15CO2+44H2O。
7. with Cu described in a kind of implementation claim 12+It is dropped for the embryonic stem-like cells system catalysis oxidation of catalyst activity component
The pharmaceutical industry of the method for solution processing bisphenol-A waste water is based on Cu2+The processing of bisphenol-A waste water is set for the catalyst of active component
It is standby.
8. with Cu described in a kind of implementation claim 12+It is dropped for the embryonic stem-like cells system catalysis oxidation of catalyst activity component
The petrochemical industry of the method for solution processing bisphenol-A waste water is based on Cu2+The processing of bisphenol-A waste water is set for the catalyst of active component
It is standby.
9. with Cu described in a kind of implementation claim 12+It is dropped for the embryonic stem-like cells system catalysis oxidation of catalyst activity component
The chemical field of the method for solution processing bisphenol-A waste water is based on Cu2+The processing of bisphenol-A waste water is set for the catalyst of active component
It is standby.
10. with Cu described in a kind of implementation claim 12+It is dropped for the embryonic stem-like cells system catalysis oxidation of catalyst activity component
The dyeing of the method for solution processing bisphenol-A waste water is based on Cu2+The processing of bisphenol-A waste water is set for the catalyst of active component
It is standby.
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