CN103723816B - A kind of continuous degradation AES vacuum removal water Zhong diox method and treatment unit - Google Patents
A kind of continuous degradation AES vacuum removal water Zhong diox method and treatment unit Download PDFInfo
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- CN103723816B CN103723816B CN201310728769.0A CN201310728769A CN103723816B CN 103723816 B CN103723816 B CN 103723816B CN 201310728769 A CN201310728769 A CN 201310728769A CN 103723816 B CN103723816 B CN 103723816B
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- ozone
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Abstract
The present invention relates to a kind of continuous degradation AES vacuum removal water Zhong diox method and treatment unit.The method that object is to provide can be degraded high density diox when producing AES in the vacuum removal water that produces; The treatment unit provided has structure feature simple and easy to use.Technical scheme is: a kind of method of continuous degradation AES vacuum removal water Zhong diox, comprises the following steps: 1) mixed with hydrogen peroxide by the vacuum removal water that AES vacuum removal diox produces, and pass into ozone and carry out pre-oxidation; 2) mixing water after step 1) process is passed in mixing tank, and pass into ozone and carry out initial breakdown reaction; 3) to through step 2) add catalyzer in degradation water after process, and pass into the further catalytic oxidation of ozone.A treatment unit for continuous degradation AES vacuum removal water Zhong diox, this treatment unit comprises preoxidation device, static mixer, catalytic oxidizer, and ozone source.
Description
Technical field
The present invention relates to a kind of using metal or metal oxide as the method for catalyzer continuous catalysis ozone degradation diox and treatment unit.
Background technology
In the production process of tensio-active agent fatty alcohol polyoxyethylene ether sulfate (hereinafter referred to as AES), include the processing step of vacuum removal diox, waste water (diox content containing high density diox can be produced up to 200-500mg/L).
Diox (Isosorbide-5-Nitrae-dioxane) is a kind of colourless volatile liquid, and molecular formula is C
4h
80
2, relative molecular mass is 88.11, and another name dioxane or Isosorbide-5-Nitrae-dioxane, has ethereal odor, inflammable, fusing point 11.8 DEG C, boiling point 101.3 DEG C, can with water, arene and most of immiscible organic solvent.Diox wetting ability is strong, and in water, solvability is good and stable, does not have facile hydrolysis group, does not absorb natural light, not facile hydrolysis or photodissociation in physical environment in molecular structure.Diox is volatile, easily transfers in underground water from soil, diox is directly entered the easy atmosphere pollution of sewage lagoon process, soil and water.
The degradation method of diox mainly comprises biological degradation method; Biological degradation method is consuming time for a long time and run not easily, is therefore badly in need of a kind of quickness and high efficiency more and can the method for serialization degraded diox and treatment unit.
Summary of the invention
The object of this invention is to provide a kind of method of continuous treatment diox, the method can be degraded high density diox when producing AES in the vacuum removal water that produces, and has the high and simple feature of technique of degradation rate;
The present invention also provides a kind for the treatment of unit of continuous treatment diox, and this treatment unit has structure feature simple and easy to use.
Technical scheme of the present invention is:
A method for continuous degradation AES vacuum removal water Zhong diox, comprises the following steps:
1) mixed with hydrogen peroxide by the vacuum removal water that AES vacuum removal diox produces, and pass into ozone and carry out pre-oxidation, process air pressure is 0.02-0.05MPa;
2) mixing water after step 1) process is passed in mixing tank, and pass into ozone and carry out initial breakdown reaction;
3) to through step 2) add catalyzer in degradation water after process, and pass into the further catalytic oxidation of ozone.
The charging capacity of described hydrogen peroxide is 50-100mg/L.
Ozone charging capacity in described three steps is followed successively by 10-20mg/L, 20-60mg/L and 10-20mg/L.
Described catalyzer is metal or metallic compound.
Described catalyzer is TiO2, Al
2o
3, Mn or Fe.
A kind for the treatment of unit of continuous degradation AES vacuum removal water Zhong diox, it is characterized in that: this treatment unit comprises to be connected the preoxidation device, static mixer, the catalytic oxidizer that communicate and the ozone source be communicated with the inlet mouth of these three reactor bottoms of preoxidation device, static mixer and catalytic oxidizer respectively successively by material pipe.
The described discharge port of preoxidation device is communicated with the opening for feed of static mixer and the discharge port of static mixer is communicated with the opening for feed of catalytic oxidizer.
Described preoxidation device, static mixer and catalytic oxidizer, the top vent of these three reactors is communicated with ozone breaker respectively.
Described ozone source is ozonizer.
The invention has the beneficial effects as follows:
1, the present invention by adding hydrogen peroxide to improve the oxidation capacity of ozone in vacuum removal water, and using metal or metallic compound as catalyzer, more than 95% can be reached by Shi diox degradation rate, not only alleviate environmental protection treatment pressure, and the lower and technique of cost simple (cost more with high investment that biological degradation method needs and run difficulty larger);
2, the present invention uses ozone as oxygenant, not only less expensive, degradation treatment speed, and the product generated after ozone reduction is that oxygen ， diox is finally converted into carbonic acid gas and water, can alleviate the burden of follow-up environmental protection treatment;
3, diox is a kind of cyclic ether compounds, not easily decomposition, needs to use oxidation potential to be greater than the oxygenant of 2.0eV; And UV+H
2o
2and O
3+ H
2o
2oxidation potential higher, may be used for degrade diox; In the present invention, the oxidation potential of ozone and hydrogen peroxide is 2.7eV, and the effect of degraded diox is higher;
4, according to the difference of used catalyzer, two class catalytic ozonations can be divided into: a class is homogeneous catalysis ozone oxidation, catalyzer is generally transition metal ion, as Fe (II), Mn (II), Ni (II), Co (II), Cd (II), Cu (II), Ag (I), Cr (III), Zn (II) etc.; Another kind of be use solid metal, metal oxide or load on carrier metal or metal oxide as catalyzer, carry out heterogeneous catalysis ozone oxidation; The present invention with metal or metal oxide for catalyzer, can adsorb ozone Yu diox carries out DeR, the catalytic decomposition efficiency of ozone and the generation of hydroxyl radical free radical can be improved simultaneously;
5, preoxidation device can increase the concentration of ordinary dissolution of ozone in water, thus improves the utilization ratio of ozone;
6, static mixer can make ozone fully contact Yu diox, thus improves the degradation efficiency of diox in catalyst-free situation, extends the work-ing life of catalyzer in catalytic oxidizer;
7, treatment unit of the present invention not only small volume, and be combined to form by maturing appts, can continuous treatment be realized, and combine simple and convenient, can also regulate according to wastewater treatment capacity and arrange, save processing cost.
Accompanying drawing explanation
Fig. 1 is the main TV structure schematic diagram for the treatment of unit of the present invention.
Embodiment
Chemical oxidization method is a kind of method of effective degraded diox, but in the process using ozonize diox, there is the problems such as the low and ozone oxidation of ozone utilization rate is not thorough; For this reason, the present invention adds H simultaneously
2o
2and catalyzer, significantly improve the degradation efficiency of Dui diox.
The invention will be further described below, but the present invention is not limited to following examples.
One, a method for continuous degradation diox, comprises the following steps:
The first step, by AES vacuum removal diox produce vacuum removal water mix with hydrogen peroxide (50-100mg/L), then pass into the ozone (10-20mg/L) produced by ozone source and carry out pre-oxidation; During process, air pressure remains on 0.02-0.05MPa;
Second step, the mixing water after the first step process to be mixed (preferably adopting static mixer) further, pass into the ozone (20-60mg/L) that produced by ozone source to carry out initial breakdown reaction simultaneously; Keep normal pressure in described static mixer and temperature is 40-60 DEG C;
3rd step, in the degradation water after second step process, add catalyzer, and pass into the ozone (10-20mg/L) that produced by ozone source to carry out catalytic oxidation; Normal pressure and temperature is 40-60 DEG C is kept during described catalysis; This catalyzer is metal or metallic compound; Catalyzer preferred TiO2, Al
2o
3, Mn or Fe.
Two, a treatment unit for continuous degradation diox, as shown in Figure 1, is comprised and to be connected successively the preoxidation device 1, static mixer 2, the catalytic oxidizer 3 that communicate by material pipe, and ozonizer 4 and ozone breaker 5;
The side-lower of described preoxidation device is shaped with opening for feed 1-1, and bottom is shaped with inlet mouth 1-3, is shaped with discharge port 1-2 above side, and top is shaped with venting port 1-4; The side-lower of described static mixer is shaped with opening for feed 2-1, and bottom is shaped with inlet mouth 2-3, is shaped with discharge port 2-2 above side, and top is shaped with venting port 2-4; The side-lower of described catalytic oxidizer is shaped with opening for feed 3-1, and bottom is shaped with inlet mouth 3-3, is shaped with discharge port 3-2 above side, and top is shaped with venting port 3-4;
The opening for feed input vacuum removal water A and hydrogen peroxide B of preoxidation device; The discharge port of preoxidation device is communicated with the opening for feed of static mixer by material pipe (omitting in figure) and the discharge port of static mixer is communicated with the opening for feed of catalytic oxidizer by material pipe; The discharge port of catalytic oxidizer then exports treated vacuum removal water;
Described ozone source is ozonizer; Described ozonizer is communicated with inlet mouth, the inlet mouth of static mixer, the inlet mouth of catalytic oxidizer of preoxidation device respectively by pipeline;
Described ozone breaker is communicated with venting port, the venting port of static mixer, the venting port of catalytic oxidizer of preoxidation device respectively by pipeline; Tail gas after ozone breaker process can directly discharge;
The wastewater treatment capacity of described treatment unit is preferably 1m
3/ h, and can by parallel for multiple treatment unit to increase waste treatment capacity;
Described pre-oxidation reactor, static mixer and catalytic oxidizer are prior art, and buyable obtains.
Three, experimental data
Check the effect of continuous degradation diox of the present invention, need utilising efficiency and the catalytic ozonation processing cost of comprehensive consideration ozone; Measure below by way of parameters such as change hydrogen peroxide dosage, ozone concn, metal or metallic compounds;
1, test case one
Keep ozone always throwing amount Yu the constant rate of diox concentration, keep the ozone feed ratio of preoxidation device, static mixer and catalytic oxidizer constant, with TiO
2as catalyzer, repeatedly adjust hydrogen peroxide Yu after diox concentration ratio, obtain diox degradation rate (shown in table 1):
Table 1: hydrogen peroxide concentration is on the impact of diox degradation rate
Visible: after adding hydrogen peroxide while ozonize, increase substantially diox degradation rate.
2, test case two
Keep hydrogen peroxide concentration Yu the constant rate of diox concentration, with TiO
2for catalyzer, repeatedly adjust ozone always throwing amount Yu diox concentration ratio also adjusts the ozone feed ratio of preoxidation device, static mixer and catalytic oxidizer simultaneously, obtain diox degradation rate (shown in table 2):
Table 2: ozone concn is on the impact of diox degradation rate
Visible: under different diox concentration levels, the feed intake impact of comparison diox degradation rate of ozone always throwing amount and ozone is little.
3, test case three
Keep hydrogen peroxide concentration Yu the constant rate of diox concentration, keep ozone always throwing amount Yu the constant rate of diox concentration, keep the ozone feed ratio of preoxidation device, static mixer and catalytic oxidizer constant, repeatedly adjust catalyzer, obtain diox degradation rate (shown in table 3):
Table 3: catalyzer is on the impact of diox degradation rate
Visible: metal oxide is as diox degradation rate during catalyzer, and outline is higher than diox degradation rate during using metal as catalyzer.
Claims (2)
1. the method for diox in continuous degradation AES vacuum removal water, comprises the following steps:
1) mixed with hydrogen peroxide by the vacuum removal water that the vacuum removal diox in AES production process produces, and pass into ozone and carry out pre-oxidation, process air pressure is 0.02-0.05MPa;
2) by through step 1) mixing water after process passes in mixing tank, and pass into ozone and carry out initial breakdown reaction;
3) to through step 2) add catalyzer in degradation water after process, and pass into the further catalytic oxidation of ozone;
The charging capacity of described hydrogen peroxide is 50-100mg/L;
Ozone charging capacity in described three steps is followed successively by 10-20mg/L, 20-60mg/L and 10-20mg/L;
Described catalyzer is metal or metallic compound;
Described catalyzer is TiO
2, Al
2o
3, Mn or Fe.
2. the treatment unit of a continuous degradation diox, it is characterized in that: this treatment unit comprises to be connected the preoxidation device (1), static mixer (2), the catalytic oxidizer (3) that communicate and the ozone source be communicated with the inlet mouth of these three reactor bottoms of preoxidation device, static mixer and catalytic oxidizer respectively successively by material pipe;
The described discharge port of preoxidation device is communicated with the opening for feed of static mixer and the discharge port of static mixer is communicated with the opening for feed of catalytic oxidizer;
Described preoxidation device, static mixer, catalytic oxidizer, the top vent of these three reactors is communicated with ozone breaker (5) respectively;
Described ozone source is ozonizer (4).
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| CN103723816B true CN103723816B (en) | 2015-07-29 |
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Address after: Hangzhou City, Zhejiang province 310009 City Shangcheng District No. 128 Lane Patentee after: Praise Technology Group Limited by Share Ltd Patentee after: Jiaxing Zanyu Technology Co., Ltd. Address before: Hangzhou City, Zhejiang province 310009 City Shangcheng District No. 128 Lane Patentee before: Zhejiang Zanyu Technology Co., Ltd. Patentee before: Jiaxing Zanyu Technology Co., Ltd. |