CN105129961A - Method of treating chromium-containing organic waste water by virtue of microwave heating enhanced near-critical water oxidation - Google Patents
Method of treating chromium-containing organic waste water by virtue of microwave heating enhanced near-critical water oxidation Download PDFInfo
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- CN105129961A CN105129961A CN201510590136.7A CN201510590136A CN105129961A CN 105129961 A CN105129961 A CN 105129961A CN 201510590136 A CN201510590136 A CN 201510590136A CN 105129961 A CN105129961 A CN 105129961A
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Abstract
The invention relates to a method of treating leather manufacturing industrial chromium-containing organic waste water by virtue of microwave heating enhanced near-critical water oxidation, and belongs to the technical field of sewage treatment and recycling. The super (near) critical water oxidation is a novel high-efficiency and pollution-free top-grade oxidation treatment technology for organic pollutants difficult to degrade. An oxidation treatment process is enhanced by virtue of the microwave heating. The chromium-containing leather manufacturing industrial waste water and excessive hydrogen peroxide are added into a microwave kettle to react with each other; the hydrogen peroxide is rapidly decomposed at the temperature of 120 DEG C or above to generate oxygen to be used as an oxidant, wherein the reaction temperature is 180 to 220 DEG C; the reaction time is 0.5h to 2h; after the oxidation, solid chromium sesquioxide is obtained, and the particle size of the solid chromium sesquioxide is 500nm to 2 micrometers. The COD removal rate is 95 percent or above.
Description
Technical field
The present invention relates to a kind of microwave heating strengthening near-critical water oxidative degradation process containing the organic waste water of heavy metal obtains the method for ultrafine particle, belongs to sewage disposal and resource technology field.
Background technology
Along with socioeconomic fast development, industrial scale continues to increase, and the quantity discharged of waste water also increases thereupon.In the production processes such as plating, printing and dyeing and leather process, not only containing organic pollution materials in the waste water of discharge, usually also containing heavy metal.These are contained to the organic waste water of heavy metal, traditional treatment process is difficult to reach emission standard.Particularly after heavy metals emission, not only can polluted surface water and underground water, and constantly accumulate in the physical environment such as water body, soil, store, be detrimental to health directly or indirectly.Therefore to being major issue urgently to be resolved hurrily containing the process of heavy metal organic waste water.
Super (closely) critical oxidation technology is a kind of novel, efficient method for processing organic wastewater, has the advantage of uniqueness when processing poisonous, harmful, indegradable industrial effluent.Point out in one of listed by American National gordian technique six large fields " energy and environment " report, the most promising treatment technology is exactly supercritical Water Oxidation Technology.Super (closely) critical oxidation technology suitability is strong, efficiency is high, thorough, process closure is good, do not form secondary pollution, and the waste water after process can utilize by direct circulation.Utilize super (closely) critical oxide treatment containing the organic waste water of heavy metal, while organism Quick Oxidation destroys, in the water of High Temperature High Pressure, heavy metal is separated out fast by with the form of oxide compound or simple substance, and form superfine powder, the recycling of heavy metal high added value can be realized.
Supercritical water hydrogen bond greatly weakens and almost becomes non-polar solvent, thus salt is not dissolved in supercritical water, and the halogen existed in water will cause the strong corrosion of most of material.In addition, due to the critical temperature of water and pressure all higher, these unfavorable factors also counteracts that the practical application of supercritical water.Relative to supercritical water, near-critical water had both had some feature of supercritical water, had again the advantage of self.First be its as solvent, specific inductivity, between normality water and supercritical water, also has good solvability to nonpolar organism.Next is that the corrodibility of near-critical water to material itself is more much smaller than supercritical water, and near clinical water condition is relatively gentle, effectively can alleviate the potential safety hazard of supercritical water.
But because near-critical water is relatively gentle, oxide treatment speed is comparatively slow and oxidation is not thorough, therefore needs outer field action to be improved.Microwave is the hertzian wave of frequency greatly within the scope of 300MHz ~ 300GHz, and compared to traditional type of heating, microwave technology has unique advantage in the selectivity promoting chemical reaction course and speed of response and product etc.Under this heating condition, except heat effect, microwave field change of frequency can cause reactant molecule to pass through to move or rotate and produce torque and reach dynamic balance state, cause molecular motion on microcosmic, have certain orientation, improve effective collision probability, thus accelerate chemical reaction rate, raising reaction yield and selectivity.Therefore, microwave heating is adopted can to strengthen near-critical water oxidising process.
Leather-making industrial wastewater contains heavy metal chromium, is a kind of carcinogenic, sensitizing substance, can enters human body, serious harm human health by water etc.This patent adopts the oxidation of microwave heating strengthening near-critical water containing chromium process hides organic waste water, obtains the ultrafine particle of chromium, realize good social and economic effects while Quick Oxidation degradable organic pollutant.
Summary of the invention
The object of this invention is to provide the method for a kind of microwave heating strengthening near-critical water oxide treatment tanning industry containing chromium organic waste water.It is characterized in that there is following process and step:
A, mixes a certain amount of tanning industry with excessive hydrogen peroxide containing chromium organic waste water, both volume ratio 3:1; The mass concentration of hydrogen peroxide is 30%;
B, puts into microwave reaction kettle by above-mentioned mixed solution, and temperature of reaction is 180 ~ 220 DEG C, and the reaction times is 0.5 ~ 2h, and microwave frequency is 300 ~ 1000MHz; Electric power is 1.2 ~ 2Kw; Make to make full use of microwave heating near-critical water with oxidation containing chromium organic waste water; Obtain solids through suction filtration after reaction, obtain chromium sesquioxide oxide ultra fine particles, particle diameter is 500nm ~ 2 μm.
Accompanying drawing explanation
Fig. 1 is the XRD figure of solid sample after reaction, and its characteristic peak shows that solid matter is chromium sesquioxide.
Fig. 2 is the SEM figure that example 1 reacts rear solid sample.
Fig. 3 is the SEM figure that example 2 reacts rear solid sample.
Fig. 4 is the SEM figure that example 3 reacts rear solid sample.
Fig. 5 is the SEM figure that example 4 reacts rear solid sample.
Embodiment
After now specific embodiments of the invention being described in.
embodiment one
Take from the untreated waste water of Shanghai Xinhua tannery containing chromium leather-making industrial wastewater, its COD content is 1530mg/L, and chromium content is 85mg/L.240ml process hides plant effluent is joined in microwave reaction kettle together with the excessive hydrogen peroxide of 80ml, temperature of reaction and time are set as 180 DEG C, 2h respectively.Reaction terminates rear question response still and naturally cools to room temperature, and reaction solution is carried out decompress filter.The solid sample of suction filtration gained puts into the dry 24h of baking oven of 70 DEG C, and dried solid sample carries out SEM test, and granular size is about 1.5 μm.Filtrate carries out the mensuration of COD, and measuring the COD value obtaining processing rear water sample is 60.1mg/L.
embodiment two
Take from the untreated waste water of Shanghai Xinhua tannery containing chromium leather-making industrial wastewater, its COD content is 1530mg/L, and chromium content is 85mg/L.240ml process hides plant effluent is joined in microwave reaction kettle together with the excessive hydrogen peroxide of 80ml, temperature of reaction and time are set as 200 DEG C, 1h respectively.Reaction terminates rear question response still and naturally cools to room temperature, and reaction solution is carried out decompress filter.The solid sample of suction filtration gained puts into the dry 24h of baking oven of 70 DEG C, and dried solid sample carries out SEM test, and granular size is about 1 μm.Filtrate carries out the mensuration of COD, and measuring the COD value obtaining processing rear water sample is 60.7mg/L.
embodiment three
Take from the untreated waste water of Shanghai Xinhua tannery containing chromium leather-making industrial wastewater, its COD content is 1530mg/L, and chromium content is 85mg/L.240ml process hides plant effluent is joined in microwave reaction kettle together with the excessive hydrogen peroxide of 80ml, temperature of reaction and time are set as 200 DEG C, 1.5h respectively.Reaction terminates rear question response still and naturally cools to room temperature, and reaction solution is carried out decompress filter.The solid sample of suction filtration gained puts into the dry 24h of baking oven of 70 DEG C, and dried solid sample carries out SEM test, and granular size is about 900nm.Filtrate carries out the mensuration of COD, and measuring the COD value obtaining processing rear water sample is 51.6mg/L.
embodiment four
Take from the untreated waste water of Shanghai Xinhua tannery containing chromium leather-making industrial wastewater, its COD content is 1530mg/L, and chromium content is 85mg/L.240ml process hides plant effluent is joined in microwave reaction kettle together with the excessive hydrogen peroxide of 80ml, temperature of reaction and time are set as 220 DEG C, 1h respectively.Reaction terminates rear question response still and naturally cools to room temperature, and reaction solution is carried out decompress filter.The solid sample of suction filtration gained puts into the dry 24h of baking oven of 70 DEG C, and dried solid sample carries out SEM test, and granular size is about 800nm.Filtrate carries out the mensuration of COD, and measuring the COD value obtaining processing rear water sample is 49.6mg/L.
Claims (1)
1. microwave heating strengthening near-critical water oxide treatment is containing a method for chromium organic waste water, it is characterized in that having following process and step:
A, mixes a certain amount of tanning industry with excessive hydrogen peroxide containing chromium organic waste water, both volume ratio 3:1; The mass concentration of hydrogen peroxide is 30%;
B, puts into microwave reaction kettle by above-mentioned mixed solution, and temperature of reaction is 180 ~ 220 DEG C, and the reaction times is 0.5 ~ 2h, and microwave frequency is 300 ~ 1000MHz; Electric power is 1.2 ~ 2Kw; Make to make full use of microwave heating near-critical water with oxidation containing chromium organic waste water; Obtain solids through suction filtration after reaction, obtain chromium sesquioxide oxide ultra fine particles, particle diameter is 500nm ~ 2 μm.
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| CN201510590136.7A CN105129961A (en) | 2015-09-17 | 2015-09-17 | Method of treating chromium-containing organic waste water by virtue of microwave heating enhanced near-critical water oxidation |
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| CN201510590136.7A CN105129961A (en) | 2015-09-17 | 2015-09-17 | Method of treating chromium-containing organic waste water by virtue of microwave heating enhanced near-critical water oxidation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109231265A (en) * | 2018-10-16 | 2019-01-18 | 张静娟 | A kind of supercritical preparation process of hydrophobic type titanium dioxide |
| CN109867421A (en) * | 2019-04-08 | 2019-06-11 | 陕西科技大学 | A kind of chromium-bearing sludge processing method and system based on supercritical water oxidation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640822A (en) * | 2003-06-19 | 2005-07-20 | 关西涂料株式会社 | Method for clarifying waste water containing organic material |
| US20050155378A1 (en) * | 2004-01-19 | 2005-07-21 | Gershtein Vladimir Y. | System for supply and delivery of high purity and ultrahigh purity carbon dioxide |
| CN102010054A (en) * | 2010-10-27 | 2011-04-13 | 南京工业大学 | System and method for processing blue-green algae by using supercritical water oxidation (SCWO) |
-
2015
- 2015-09-17 CN CN201510590136.7A patent/CN105129961A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640822A (en) * | 2003-06-19 | 2005-07-20 | 关西涂料株式会社 | Method for clarifying waste water containing organic material |
| US20050155378A1 (en) * | 2004-01-19 | 2005-07-21 | Gershtein Vladimir Y. | System for supply and delivery of high purity and ultrahigh purity carbon dioxide |
| CN102010054A (en) * | 2010-10-27 | 2011-04-13 | 南京工业大学 | System and method for processing blue-green algae by using supercritical water oxidation (SCWO) |
Non-Patent Citations (1)
| Title |
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| 潘明华: "超临界水氧化处理铬鞣段废水实验研究", 《环境科学与技术》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109231265A (en) * | 2018-10-16 | 2019-01-18 | 张静娟 | A kind of supercritical preparation process of hydrophobic type titanium dioxide |
| CN109867421A (en) * | 2019-04-08 | 2019-06-11 | 陕西科技大学 | A kind of chromium-bearing sludge processing method and system based on supercritical water oxidation |
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