CN106746006B - Membrane-method Fenton-like process for wastewater treatment - Google Patents
Membrane-method Fenton-like process for wastewater treatment Download PDFInfo
- Publication number
- CN106746006B CN106746006B CN201611244230.8A CN201611244230A CN106746006B CN 106746006 B CN106746006 B CN 106746006B CN 201611244230 A CN201611244230 A CN 201611244230A CN 106746006 B CN106746006 B CN 106746006B
- Authority
- CN
- China
- Prior art keywords
- membrane
- wastewater
- reactor
- fenton
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 18
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 69
- 239000012528 membrane Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000012530 fluid Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000008213 purified water Substances 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- 230000000149 penetrating effect Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract 2
- 239000000919 ceramic Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 238000004043 dyeing Methods 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910002321 LaFeO3 Inorganic materials 0.000 claims description 2
- 229910002328 LaMnO3 Inorganic materials 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 22
- 239000003054 catalyst Substances 0.000 abstract description 22
- 238000006731 degradation reaction Methods 0.000 abstract description 22
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000011949 solid catalyst Substances 0.000 description 15
- 230000002572 peristaltic effect Effects 0.000 description 11
- 238000004364 calculation method Methods 0.000 description 6
- 238000001223 reverse osmosis Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a membrane method Fenton process for wastewater treatment, which comprises the following specific steps: (1) the wastewater after biochemical treatment is continuously introduced into a reactor containing a catalystIn the reactor (2); (2) using a membrane distributor to mix H2O2Introducing the mixture into a reactor at a certain speed, and carrying out Fenton-like reaction under the action of a catalyst; (3) after a certain time of reaction, feeding the papermaking wastewater containing the catalyst into a membrane separation system for solid-liquid separation; (4) the separated membrane penetrating fluid is purified water reaching the standard, and the trapped fluid returns to the reactor for continuous reaction. In one aspect of the invention control H2O2The feed concentration is distributed, the local concentration is prevented from being overhigh, and the H is improved2O2Utilization rate; on the other hand, the method solves the problems of separation and cyclic utilization of the nano catalyst, has the advantages of simple operation, mild conditions, no generation of solid waste, high COD degradation efficiency, capability of ensuring that the treated water can reach the discharge standard or the reclaimed water reuse standard, meeting the resource recycling of the wastewater and having great development potential and application prospect in the industrial wastewater treatment.
Description
Technical Field
The invention relates to a membrane Fenton process for wastewater treatment, which has the advantages of high COD (chemical oxygen demand) degradation efficiency and high H (hydrogen) yield2O2High utilization rate and no solid waste.
Background
The harm of industrial wastewater to the environment increases day by day, and along with the further improvement of the environmental protection standard, the COD of the wastewater after biochemical treatment is often higher than the national specified discharge standard, and the wastewater can reach the discharge standard or be recycled industrially after further advanced treatment. At present, the main advanced treatment methods comprise a Fenton method, a photocatalysis method, activated carbon adsorption, an ozone oxidation method, an electrochemical method, a wet oxidation method and the like, and the methods have some problems, such as the Fenton method generates a large amount of solid waste and increases the salt content in water; the catalytic efficiency of the photocatalytic method is not high; the electrode prepared by the electrochemical method is complicated and the electric energy consumption is high(ii) a The ozone oxidation method has high degradation efficiency, high energy consumption, low ozone solubility and low utilization rate; the wet oxidation method has high treatment efficiency, but requires a large temperature and pressure for the reaction. A Fenton-like process (also called heterogeneous Fenton method) has been developed in recent years, and has the advantages of high oxidation rate, high catalyst activity, good stability, no generation of a large amount of precipitates in the reaction process and the like, but H also exists2O2Low utilization rate, difficult catalyst recycling and separation and the like.
Chinese patent CN 104923229A discloses an active carbon catalyst for treating refractory organic wastewater by a Fenton-like method, and preparation and application thereof, wherein the active carbon catalyst is used for treating wastewater H at room temperature2O2(mg/L) COD (mg/L) is 0.3-1.5, and space velocity is 0.5-2.0h-1COD removal rate was greater than 50%, but H2O2The utilization rate of the catalyst needs to be improved, and the problem of recycling of the catalyst exists. Chinese patent CN 105731624A discloses a method for catalyzing and oxidizing reverse osmosis concentrated water by utilizing heterogeneous Fenton-like reaction, a catalyst and H in a reaction system2O2Simultaneously reacts with reverse osmosis concentrated water in the presence of hydroxyl radicals, organic pollutants in the reverse osmosis concentrated water are oxidized and degraded in an unselective way through the generated hydroxyl radicals, so that the reverse osmosis concentrated water is stably discharged up to the standard, but H is directly added in the reaction2O2It can result in excessive local concentration, causing H2O2The utilization rate is not high.
Disclosure of Invention
The invention aims to improve H in the Fenton-like process2O2The utilization rate and the simplified separation of the solid catalyst in the system provide a membrane method Fenton process for wastewater treatment; the invention provides a membrane module for dispersing H in a Fenton-like process2O2Further increase H2O2The utilization rate is improved, the generation of hydroxyl free radicals is promoted, and the COD degradation efficiency is improved; and the membrane separation technology is used for realizing the recycling of the catalyst, so that the purified water reaches the discharge standard or the reclaimed water standard, the resource recycling of the wastewater is met, and the application prospect in the industrial wastewater treatment of papermaking, chemical industry, pharmacy, printing and dyeing and the like is good.
The technical scheme of the invention is as follows: a membrane method Fenton process for wastewater treatment comprises the following specific steps:
(1) continuously introducing the wastewater after biochemical treatment into a reactor containing a nano catalyst;
(2) using a membrane distributor to mix H2O2Introducing into a reactor at a certain speed, and performing the action of a nano catalyst
Carrying out Fenton-like reaction by using the following components;
(3) after a certain time of reaction, the wastewater containing the nano catalyst enters a membrane separation system for carrying out
Solid-liquid separation;
(4) the separated membrane penetrating fluid is purified water reaching the standard, and the trapped fluid containing the nano catalyst returns to the reactor
The reaction was continued.
Preferably, the nano-catalyst in the step (1) is one or more of metal oxide or composite oxide; the ratio of the added mass of the catalyst in the reactor to the volume of the wastewater is 0.5g/L-3 g/L. More preferably, the nanocatalyst is MnO2、Cu2O、LaMnO3Or LaFeO3One or more of (a).
Preferably, the membrane in the membrane distributor in the step (2) is an external pressure membrane, and the pore diameter of the membrane is 50-500 nm; the material is one of ceramic film or metal film. More preferably alumina, zirconia or stainless steel.
Preferably H as described in step (2)2O2The amount H added in the reactor2O2(mg/L):CODInflow water(mg/L) is 0.35-1.25, or is H2O2(mol/L):CDye material(mmol/L) is 0.2-1.5.
The reaction time in the step (3) is preferably 40min to 120 min.
Preferably, the pore diameter of the membrane for the membrane separation system in the step (3) is 20-500 nm; the material is one of an organic film, a ceramic film or a metal film.
The waste water mainly comes from pulping and papermaking industry, printing and dyeing industry or chemical and pharmaceutical industry and the like.
Has the advantages that:
(1) the invention adopts the membrane technology to be coupled with the advanced oxidation technology, and utilizes the membrane technology to distribute H2O2Feeding the raw materials into a feeding device,
avoid over high local concentration and improve H2O2Utilization rate, mass transfer effect in reaction process and reaction
The efficiency is high;
(2) the membrane is used as a separation medium to separate the nano solid catalyst after reaction, the operation is simple,
the cost is reduced;
(3) the reaction is carried out at normal temperature and normal pressure, no phase change exists, the treatment efficiency is high, the energy consumption is low, and the method is environment-friendly and economical.
Drawings
FIG. 1 is a process flow diagram of a wastewater treatment membrane method Fenton-like process with membrane tubes in a reactor according to an embodiment of the invention; wherein 1 is H2O2A raw material barrel; 2 is a waste water material liquid barrel; 3, 4 is a peristaltic pump; 5 is a membrane module (distribution H)2O2) (ii) a 6 is a membrane module (separating catalyst); 7 is a centrifugal pump; 8 is reuse water;
FIG. 2 is a process flow diagram of a Fenton-like process of wastewater treatment membrane with a distributor in a reactor and a separator outside the reactor according to an embodiment of the invention; wherein 1 is H2O2A raw material barrel; 2 is a waste water material liquid barrel; 3, 4 is a peristaltic pump; 5 is a membrane module (distribution H)2O2) (ii) a 6 is a membrane module (separating catalyst); 7 is a centrifugal pump; 8 is reuse water.
FIG. 3 is an SEM photograph of a solid catalyst in example 1 of the present invention;
FIG. 4 is an SEM photograph of a solid catalyst in example 4 of the present invention;
FIG. 5 is an SEM photograph of a solid catalyst in example 2 of the present invention;
FIG. 6 is an SEM photograph of the solid catalyst in example 3 of the present invention.
Detailed Description
The invention is further illustrated by way of the following examples.
Example 1:
taking reverse osmosis concentrated water of a certain factory, wherein the COD of the wastewater is 350 mg/L. An amount of 5L of papermaking wastewater was fed into the reactor of FIG. 1, and 0.5g/L of MnO as a solid catalyst was added2As shown in FIG. 3, wastewater and H were continuously fed into the reactor by a peristaltic pump2O2Using ZrO with a pore size of 50nm in the reactor2Single channel ceramic membrane distribution H2O2Control H2O2(mg/L):CODInflow water(mg/L) is 1.25; reacting at 30 ℃ under normal pressure for 40min, continuously separating the catalyst from the 50nm zirconium oxide ceramic membrane in the reactor by a centrifugal pump, measuring the COD degradation rate of the wastewater, and calculating to obtain the COD degradation rate of the papermaking wastewater of 52.57%.
Example 2:
taking biochemical wastewater of a certain factory, wherein the COD of the wastewater is 318 mg/L. 5L of papermaking wastewater is added into the reactor of figure 2, and 0.5g/L of solid catalyst LaMnO is added3As shown in FIG. 5, wastewater and H were continuously fed into the reactor by a peristaltic pump2O2By using a reactor with a pore diameter of 200nm ZrO2Single channel ceramic membrane distribution H2O2Control H2O2(mg/L):CODInflow water(mg/L) 0.78; reacting at 30 ℃ under normal pressure for 60min, feeding the wastewater from the reactor into a 20nm polysulfone organic membrane outside the reactor through a pipeline by using a centrifugal pump, continuously separating the catalyst, and measuring the COD degradation rate of the wastewater, wherein the COD degradation rate of the papermaking wastewater is calculated to be 55.97%.
Example 3:
taking biochemical wastewater of a certain factory, wherein the COD of the wastewater is 318 mg/L. A quantity of 5L of papermaking wastewater is added into the reactor of figure 1, and 1.2g/L of solid catalyst LaFeO is added3As shown in FIG. 6, wastewater and H were continuously fed into the reactor by a peristaltic pump2O2By using a reactor with a pore diameter of 200nmAl2O3Single channel ceramic membrane distribution H2O2Control H2O2(mg/L):CODInflow water(mg/L) is 0.45; reacting at 30 ℃ under normal pressure for 120min, continuously separating the catalyst from the 500nm alumina ceramic membrane in the reactor by a centrifugal pump, measuring the COD degradation rate of the wastewater, and calculating the COD degradation rate of the papermaking wastewater to be70.88％。
Example 4:
taking biochemical wastewater of a certain factory, wherein the COD of the wastewater is 318 mg/L. 5L of papermaking wastewater is added into the reactor of the figure 2, and 1.5g/L of solid catalyst Cu is added2O, as shown in FIG. 4, wastewater and H were continuously fed into the reactor by a peristaltic pump2O2Using a reactor with a pore diameter of 500nmAl2O3Single channel ceramic membrane distribution H2O2Control H2O2(mg/L):CODInflow water(mg/L) is 0.45; reacting at 30 ℃ under normal pressure for 120min, making the wastewater enter a 200nm stainless steel metal film outside the reactor through a pipeline by using a centrifugal pump, continuously separating the catalyst, and measuring the COD degradation rate of the wastewater, wherein the COD degradation rate of the papermaking wastewater is 73.90% by calculation.
Example 5:
taking pharmaceutical wastewater of a certain factory, wherein the COD of the wastewater is 54 mg/L. 5L of papermaking wastewater is added into the reactor of the figure 1, and 2.5g/L of solid catalyst Cu is added2O, as shown in FIG. 4, wastewater and H were continuously fed into the reactor by a peristaltic pump2O2Using a reactor with a pore diameter of 500nmAl2O3Single channel ceramic membrane distribution H2O2Control H2O2(mg/L):CODInflow water(mg/L) 0.35; reacting at 30 ℃ under normal pressure for 40min, continuously separating the catalyst from the 50nm alumina ceramic membrane in the reactor by a centrifugal pump, and measuring the COD degradation rate of the wastewater, wherein the COD degradation rate of the papermaking wastewater is 59.14 percent by calculation.
Example 6:
taking pharmaceutical wastewater of a certain factory, wherein the COD of the wastewater is 54 mg/L. 5L of papermaking wastewater is added into the reactor of the figure 2, and 1.8g/L of solid catalyst Cu is added2O, as shown in FIG. 4, wastewater and H were continuously fed into the reactor by a peristaltic pump2O2Using a reactor with a pore diameter of 500nmAl2O3Single channel ceramic membrane distribution H2O2Control H2O2(mg/L):CODInflow water(mg/L) is 0.5; reacting at 30 deg.C under normal pressure for 120min, and introducing waste water from the reactor by centrifugal pumpThe catalyst is continuously separated after entering a stainless steel metal film with the thickness of 500nm outside the reactor through a pipeline, and the COD degradation rate of the wastewater is measured, and the COD degradation rate of the papermaking wastewater is 73.22 percent by calculation.
Example 7:
taking pharmaceutical wastewater of a certain factory, wherein the COD of the wastewater is 54 mg/L. 5L of papermaking wastewater is added into the reactor of the figure 2, and 2g/L of solid catalyst Cu is added2O, as shown in FIG. 4, wastewater and H were continuously fed into the reactor by a peristaltic pump2O2Using a reactor with a pore diameter of 500nmAl2O3Single channel ceramic membrane distribution H2O2Control H2O2(mg/L):CODInflow water(mg/L) is 0.45; reacting at 40 ℃ under normal pressure for 60min, feeding the wastewater from the reactor into a 500nm alumina ceramic membrane outside the reactor through a pipeline by using a centrifugal pump, continuously separating the catalyst, and measuring the COD degradation rate of the wastewater, wherein the COD degradation rate of the papermaking wastewater is 79.22 percent by calculation.
Example 8:
preparing the simulated printing and dyeing wastewater, wherein the concentration of methyl orange is 130 mg/L. An amount of 5L of the dye solution was placed in the reactor of FIG. 1, and 0.5g/L of the solid catalyst Cu was added2O, as shown in FIG. 4, wastewater and H were continuously fed into the reactor by a peristaltic pump2O2And the distribution H is carried out by utilizing a stainless steel membrane with the aperture of 50nm in the reactor2O2Control H2O2(mol/L):CDye material(mmol/L) is 1.5; reacting at 50 ℃ under normal pressure for 120min, continuously separating the catalyst from the 50nm alumina ceramic membrane in the reactor by a centrifugal pump, and measuring the dye degradation rate, wherein the dye degradation rate is 90% by calculation.
Example 9:
preparing simulated printing and dyeing wastewater, wherein the concentration of rhodamine B is 130 mg/L. An amount of 5L of the dye solution was placed in the reactor of FIG. 2, and 0.5g/L of the solid catalyst Cu was added2O, as shown in FIG. 4, wastewater and H were continuously fed into the reactor by a peristaltic pump2O2And the distribution H is carried out by utilizing a stainless steel membrane with the aperture of 500nm in the reactor2O2Control H2O2(mol/L):CDye material(mmol/L)Is 0.2; reacting at 25 ℃ under normal pressure for 120min, feeding the wastewater from the reactor into a 200nm alumina ceramic membrane through a pipeline by using a centrifugal pump, continuously separating the catalyst, and measuring the dye degradation rate, wherein the dye degradation rate is 71.76 percent by calculation.
Claims (7)
1. A membrane method Fenton process for wastewater treatment is characterized by comprising the following specific steps:
(1) continuously introducing the wastewater after biochemical treatment into a reactor containing a nano catalyst; wherein the nano catalyst is MnO2、Cu2O、LaMnO3Or LaFeO3One or more of;
(2) using a membrane distributor to mix H2O2Introducing the mixture into a reactor, and carrying out Fenton-like reaction under the action of a nano catalyst; wherein the membrane in the membrane distributor is an external pressure membrane, and the pore diameter of the membrane is 50-500 nm; the material is one of ceramic film or metal film;
(3) after a certain time of reaction, the wastewater containing the nano catalyst enters a membrane separation system for solid-liquid separation;
(4) the separated membrane penetrating fluid is purified water reaching the standard, and the trapped fluid containing the nano catalyst returns to the reactor for continuous reaction.
2. The membrane-process Fenton-like process according to claim 1, wherein the volume ratio of the added mass of the nano-catalyst in the reactor to the wastewater in step (1) is 0.5g/L-3 g/L.
3. The membrane-process Fenton-like process according to claim 1, wherein the membrane in the membrane distributor in step (2) is made of alumina, zirconia or stainless steel.
4. The membrane-process Fenton-like process according to claim 1, wherein said H in step (2)2O2Amount added in the reactor: mg per liter H2O2And milligram per liter CODInflow waterThe ratio of the hydrogen to the oxygen is 0.35-1.25, or the mol ratio of the hydrogen to the oxygen is H2O2To millimoles per liter of CDye materialThe ratio of the ratio is 0.2-1.5.
5. The membrane-process Fenton-like process according to claim 1, wherein the reaction time in step (3) is 40-120 min.
6. The membrane-method Fenton-like process according to claim 1, wherein the membrane for the membrane separation system in step (3) has a pore size of 20-500 nm; the material is one of an organic film, a ceramic film or a metal film.
7. The membrane-process Fenton-like process according to claim 1, wherein the wastewater is mainly wastewater of pulp and paper industry, printing and dyeing industry or chemical and pharmaceutical industry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611244230.8A CN106746006B (en) | 2016-12-29 | 2016-12-29 | Membrane-method Fenton-like process for wastewater treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611244230.8A CN106746006B (en) | 2016-12-29 | 2016-12-29 | Membrane-method Fenton-like process for wastewater treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106746006A CN106746006A (en) | 2017-05-31 |
| CN106746006B true CN106746006B (en) | 2021-02-19 |
Family
ID=58927587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611244230.8A Active CN106746006B (en) | 2016-12-29 | 2016-12-29 | Membrane-method Fenton-like process for wastewater treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106746006B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108083513A (en) * | 2018-01-31 | 2018-05-29 | 山东泰禾环保科技股份有限公司 | The method and its device of oxidation coupling ceramic membrane filter contaminant water |
| CN113479988B (en) * | 2021-08-16 | 2022-09-13 | 南京工业大学 | Visible light catalysis-Fenton membrane reactor for wastewater treatment |
| CN116081838A (en) * | 2021-10-31 | 2023-05-09 | 中国石油化工股份有限公司 | Method for treating organic phosphine wastewater by utilizing homogeneous catalysis wet oxidation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140134990A (en) * | 2013-05-15 | 2014-11-25 | 한국화학연구원 | A water treatment system including porous alumina membranes immobilized photocatalysts, operating method thereof, and purifying method of wastewater using thereby |
| CN104671502B (en) * | 2015-02-13 | 2017-06-30 | 滨州学院 | A kind of online chemical oxidation Dynamic Membrane Waste Water Treatment |
-
2016
- 2016-12-29 CN CN201611244230.8A patent/CN106746006B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106746006A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101020590B (en) | Process of treating refractory organic effluent with free radical | |
| CN107117690B (en) | Device and method for treating refractory pollutants through electrocatalytic oxidation | |
| Jaroszek et al. | Ion-exchange membranes in chemical synthesis–a review | |
| CN106746006B (en) | Membrane-method Fenton-like process for wastewater treatment | |
| CN105600909B (en) | The method of catalytic wet oxidation processing organic wastewater | |
| CN104445533B (en) | A kind of ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor | |
| CN101723533B (en) | Method for treating concentrated water produced by coking wastewater recycling process | |
| CN202465455U (en) | Novel membrane concentrated water treatment device | |
| CN204689706U (en) | A kind of Multistage external circulating formula ozone contact reaction device | |
| CN111499056B (en) | Advanced treatment system and method for recycling water in fine chemical tail water | |
| CN104925917A (en) | Merged propeller blade type electro-catalytic reactor for high-viscosity wastewater treatment | |
| CN103436910B (en) | The preparation method of a kind of gluconic acid and glucaric acid | |
| CN109264845A (en) | A kind of device and method of reverse osmosis concentrated water organic matter and ammonia nitrogen removal simultaneously | |
| CN203411383U (en) | Membrane tube catalyst | |
| CN104071873A (en) | Fixed bed three-dimensional electrocatalytic oxidation wastewater reactor | |
| CN106865736A (en) | A kind of processing method and processing device of industrial wastewater | |
| CN212199433U (en) | Resourceful treatment device for incineration fly ash of high-chlorine organic hazardous waste | |
| CN210438469U (en) | Catalytic oxidation reaction system for advanced wastewater treatment | |
| CN103232326A (en) | Continuous production process for preparing phenol with benzene through hydroxylation | |
| CN111186961B (en) | Electrochemical bubble-free aeration membrane bioreactor and application thereof | |
| CN107459124A (en) | COD method and device in a kind of hydrogen peroxide heterocatalysis oxidized waste water | |
| CN106007113A (en) | Treatment device and treatment method for circulating cooling water | |
| CN206843278U (en) | A kind of alkali decrement waste water handles equipment up to standard | |
| CN206553335U (en) | A kind of new photooxidation catalyzing deodorizing wastewater treatment equipment | |
| CN207210198U (en) | Multidimensional is electrolysed MBR sewage disposal devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 210009, 5 new model street, Gulou District, Jiangsu, Nanjing Applicant after: NANJING TECH University Address before: 211816 Puzhu South Road, Pukou District, Nanjing, Jiangsu Province, No. 30 Applicant before: NANJING TECH University |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |