CN108408919B - Method for removing refractory pollutants in water body based on rape straw pretreatment waste gas - Google Patents
Method for removing refractory pollutants in water body based on rape straw pretreatment waste gas Download PDFInfo
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- CN108408919B CN108408919B CN201810098829.8A CN201810098829A CN108408919B CN 108408919 B CN108408919 B CN 108408919B CN 201810098829 A CN201810098829 A CN 201810098829A CN 108408919 B CN108408919 B CN 108408919B
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
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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
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2101/40—Organic compounds containing sulfur
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
Abstract
The invention provides a method for removing refractory pollutants in a water body based on rape straw pretreatment waste gas, which comprises the following steps: collecting waste gas generated by rape straw pretreatment, introducing the waste gas into a closed container filled with waste liquid of pollutants difficult to degrade in a water body, and performing degradation reaction at 30-80 ℃. The method has excellent removal effect on common water body pollutants difficult to degrade, overcomes the defect that complex equipment is needed in the prior art, avoids the defect that the raw materials need to be subjected to special modification treatment in the prior solid-based treatment technology, realizes the high-efficiency degradation effect on the water pollutants difficult to degrade, truly realizes the technical purpose of directly treating waste with waste, and realizes the organic combination of two industries of bioethanol preparation and wastewater treatment.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for removing refractory pollutants in a water body based on rape straw pretreatment waste gas.
Background
China is a traditional textile large country, and in recent years, along with the requirement for transformation of an economic structure, the improvement of a textile production waste treatment technology will be more and more emphasized. The dye is one of main pollutants in the textile production process, has complex components, much biotoxicity and difficult degradability, and is waste water which is difficult to treat.
At this stage, the conventional methods for treating pollution are adsorption, membrane separation, ozone oxidation and photocatalytic methods.
However, the existing water treatment technology for pollutants with difficult degradability (such as potassium perfluorooctanesulfonate, bisphenol A, atrazine and tetracycline) is not mature enough, and complex technical means are often needed for treating the pollutants.
The application publication No. CN 105668921A of Chinese patent realizes the treatment of difficultly degradable bisphenol A by using a complex instrument and combining three technologies of electrochemical reaction, magnetic strengthening technology and biodegradation. Chinese patent application publication No. CN 107459234A provides a three-dimensional electro-fenton-like water treatment system for tetracycline. However, the above patent depends on its special equipment, which is not suitable for popularization and application.
The Chinese patent with application publication number CN 106334559A is improved on the basis of the traditional Fenton catalyst, and the treatment efficiency of bisphenol A is improved
The Chinese patent with the publication number of CN 102659235B provides a method for treating dye wastewater, overcomes the defects of common homogeneous Fenton oxidation by a multiphase Fenton catalytic oxidation mode, and greatly improves the efficiency of treating organic wastewater. Chinese patent application publication No. CN 107051388A realizes efficient removal of tetracycline by using modified activated carbon fiber. The Chinese patent with application publication number CN 107376891 discloses a catalyst of double-rare earth co-doped titanium dioxide for treating tetracycline in wastewater, and realizes efficient degradation of tetracycline under visible light. However, like other solid-phase treating agents, the above-mentioned treatment techniques face problems of reusability and solid waste treatment.
In summary, the current treatment technology for the water pollutants with difficult degradability is complex in treatment technology or is based on a solid treatment agent. Although the water treatment by depending on the equipment has the advantages of scale and automation, the particularity of the equipment makes the popularization of the technology unsuitable. The solid treating agent has the advantages of rapidness and convenience, some solid treating agents can be prepared by using waste raw materials even, and have the function of treating wastes with processes of wastes against one another, but the solid treating agent also has the problem of environmental protection which cannot be ignored in the subsequent solid waste treatment. More importantly, the existing preparation technology of the solid treating agent of treating wastes with wastes still faces the problem of production cost, so that the cost pressure is faced when the solid treating agent is used for treating difficultly-degradable pollutants in wastewater. Therefore, it is the subject of the next stage of intensive research to develop a method for treating difficultly degradable pollutants by "directly treating wastes with wastes" with direct wastes generated by the current production activities.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for removing refractory pollutants in a water body based on rape straw pretreatment waste gas, which comprises the following steps: collecting waste gas generated by rape straw pretreatment, introducing the waste gas into a closed container filled with waste liquid of pollutants difficult to degrade in a water body, and performing degradation reaction at 30-80 ℃;
the refractory pollutants in the water body comprise potassium perfluorooctanesulfonate, bisphenol A, atrazine or tetracycline;
the rape straw pretreatment method comprises the following steps:
placing rape straws into a reaction kettle, and adding a concentrated phosphoric acid-hydrogen peroxide mixed reagent for pretreatment reaction, wherein the mass fraction of concentrated phosphoric acid is 62.0-68.0%, and the mass fraction of hydrogen peroxide is 6.0-7.0%.
The inventors of the present invention conducted a study of pretreatment of a lignocellulosic raw material with concentrated phosphoric acid in combination with hydrogen peroxide for enzymatic hydrolysis in CN 103555774B, and achieved excellent technical effects. The inventor surprises that when the inventor uses the method in the patent to introduce the waste gas generated in the pretreatment process by taking the rape straws as the raw material into the waste water containing pollutants, the pollutants which are difficult to degrade (potassium perfluorooctanesulfonate, bisphenol A, atrazine or tetracycline) in the waste water are rapidly degraded.
Furthermore, the inventor tests the degradation degree of the pollutants, and finds that the removal efficiency of the pollutants which are difficult to degrade reaches more than 80%, and the removal efficiency of the bisphenol A reaches more than 95.8%. That is, the invention has better effect of removing the pollutants than the prior general treatment equipment and solid-based materials for the pollutants of the refractory water.
As can be seen by those skilled in the art, the present invention undoubtedly opens up a new way of wastewater treatment. For example, in the wastewater treatment of farmlands and livestock farms, the pretreatment of straws and the efficient removal of pollutants (such as tetracycline for livestock) in wastewater can be realized at one time. In this example, no additional treatment agent preparation is required, greatly reducing the cost of water pollutant treatment.
Although the conversion rate of sugar is remarkably improved in CN 103555774B, the method makes an important contribution to the bioethanol industry. However, in practical application, some waste gas is inevitably generated, which causes pollution to some extent. Therefore, the significance of the present invention is also to solve the problem of recycling of the exhaust gas in CN 103555774B.
At present, the inventor of the invention still tests the gas components in the gas components and explores the pollutant removal mechanism in the gas components, and simultaneously carries out corresponding scale application improvement.
The weight volume ratio of the rape straws to the waste liquid of the pollutants difficult to degrade in the water body is 1: 0.5-2. Unless otherwise specified, the weight-to-volume ratio referred to in the present invention is g/mL, or kg/L.
As a preferable scheme of the invention, the weight-volume ratio of the rape straws to the waste liquid of the pollutants difficult to degrade in the water body is 8:7.5
In a preferred embodiment of the present invention, the mass fraction of the concentrated phosphoric acid is 65.0% and the mass fraction of the hydrogen peroxide is 7.0%.
In a preferred embodiment of the present invention, the degradation reaction is carried out at a reaction temperature of 50 to 80 ℃.
In a preferred embodiment of the present invention, the degradation reaction is carried out at a reaction temperature of 50 ℃. Since the removal rate of contaminants is already excellent at 50 ℃, it is economical to perform the contaminant removal treatment at this temperature from the viewpoint of saving the reaction cost.
The degradation reaction is carried out synchronously with the pretreatment, and the waste gas generated by the pretreatment is synchronously introduced into the closed container for the degradation reaction, namely the pretreatment time is the degradation reaction time.
Generally speaking, when rape straw pretreatment is carried out, the pretreatment reaction time is 3-5 h.
As a preferable scheme of the invention, when the rape straw is pretreated, the time of the pretreatment reaction is 4 hours.
According to the description of the embodiment of the present invention, the treatment technique of the present invention has an excellent effect of removing the contaminants having a concentration of 100 ppm. It will be appreciated by those skilled in the art that the present invention is also suitable for removing other concentrations of contaminants based on this.
The invention has the beneficial effects that:
the method has excellent removal effect on common water body pollutants difficult to degrade, overcomes the defect that complex equipment is needed in the prior art, avoids the defect that the raw materials need to be subjected to special modification treatment in the prior solid-based treatment technology, realizes the high-efficiency degradation effect on the water pollutants difficult to degrade, truly realizes the technical purpose of directly treating waste with waste, and realizes the organic combination of two industries of bioethanol preparation and wastewater treatment.
Detailed Description
The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
Crushing rape straws, and sieving the crushed rape straws with a 40-mesh sieve to obtain rape straw powder; putting 8g of rape straw powder into a reaction kettle, adding 80g of mixed solution of phosphoric acid and hydrogen peroxide into the reaction kettle according to the solid-to-liquid ratio of 1:10, wherein the mass fraction of concentrated phosphoric acid is 65.0%, the mass fraction of hydrogen peroxide is 7.0%, the pretreatment temperature is 50 ℃, and the pretreatment time is 4 hours; collecting gas generated during pretreatment, synchronously introducing the gas into a closed container (50ml specification) filled with 7.5ml of water body degradation-resistant pollutant waste liquid, and performing degradation reaction at 50 ℃.
Perfluorooctanesulfonic acid potassium salt, bisphenol A, atrazine and tetracycline with the concentration of 100ppm are respectively used as the pollutants difficult to degrade in the water body to carry out 4 groups of corresponding experiments.
And based on the change of the reaction concentration before and after the reaction, the removal rate of the pollutants was measured for the above 4 experiments, and the results are shown in table 1:
TABLE 1
Example 2
The mass fraction of concentrated phosphoric acid was adjusted to 60.0%, the mass fraction of hydrogen peroxide was adjusted to 8.8%, and the rest was kept the same as in example 1. The removal rate of 4 pollutants is still over 80 percent, wherein the removal rate of bisphenol A is 92.3 percent.
Example 3
The weight of the rape straw powder is adjusted to be 10g, the volume of the waste liquid of the pollutants which are difficult to degrade in the water body is 5ml, and the rest is kept consistent with that of the embodiment 1. The removal rate of 4 pollutants is still over 80 percent, wherein the removal rate of bisphenol A is 92.7 percent.
Example 4
The weight of the rape straw powder is adjusted to be 4g, the volume of the waste liquid of the pollutants which are difficult to degrade in the water body is 8ml, and the rest is kept consistent with that of the embodiment 1. The removal rate of 4 pollutants is still over 80 percent, wherein the removal rate of bisphenol A is 91.9 percent.
Example 5
The pretreatment time was adjusted to 3 hours, and the rest was the same as in example 2. The removal rate for bisphenol A was 90.3%.
Example 6
The pretreatment time was adjusted to 5 hours, and the rest was the same as in example 2. The removal rate for bisphenol A was 95.3%.
Comparative example 1
The rape straws are adjusted to be sorghum straws, and the rest is consistent with the embodiment 1. The removal rate of 4 pollutants is only 68-71%, wherein the removal rate of bisphenol A is only 70.6%.
Comparative example 2
The pretreatment time was adjusted to 1 hour, and the rest was the same as in example 2. The removal rate for bisphenol A was only 78.6%.
Claims (10)
1. The method for removing the pollutants difficult to degrade in the water body based on rape straw pretreatment waste gas is characterized by comprising the following steps:
collecting waste gas generated by rape straw pretreatment, introducing the waste gas into a closed container filled with waste liquid of pollutants difficult to degrade in a water body, and performing degradation reaction at 30-80 ℃;
the refractory pollutants in the water body comprise potassium perfluorooctanesulfonate, bisphenol A, atrazine or tetracycline;
the rape straw pretreatment method comprises the following steps:
placing rape straws into a reaction kettle, and adding a concentrated phosphoric acid-hydrogen peroxide mixed reagent for pretreatment reaction, wherein the mass fraction of concentrated phosphoric acid is 62.0-68.0%, and the mass fraction of hydrogen peroxide is 6.0-7.0%.
2. The method according to claim 1, wherein the weight-to-volume ratio of the rape straws to the waste liquid of the pollutants difficult to degrade in the water body is 1: 0.5-2.
3. The method of claim 2, wherein the weight-to-volume ratio of the rape straw to the waste liquid of the pollutants difficult to degrade in the water body is 8: 7.5.
4. The method of claim 1, wherein the mass fraction of concentrated phosphoric acid is 65.0% and the mass fraction of hydrogen peroxide is 7.0%.
5. The method according to claim 1, wherein the degradation reaction is carried out at a reaction temperature of 50 to 80 ℃.
6. The method according to claim 5, wherein the degradation reaction is carried out at a reaction temperature of 50 ℃.
7. The method according to any one of claims 1 to 6, wherein the degradation reaction is performed synchronously with the pretreatment, and the waste gas generated by the pretreatment is synchronously introduced into the closed container for the degradation reaction.
8. The method as claimed in claim 1, wherein the pretreatment reaction time is 3-5 h when the rape straw pretreatment is carried out.
9. The method as claimed in claim 8, wherein the pretreatment reaction time is 4 hours when the rape straw pretreatment is carried out.
10. The method of claim 1, wherein the concentration of refractory water pollutant is at least 100 ppm.
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| CN201810098829.8A CN108408919B (en) | 2018-01-31 | 2018-01-31 | Method for removing refractory pollutants in water body based on rape straw pretreatment waste gas |
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| CN108408919B true CN108408919B (en) | 2020-05-26 |
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| CN101100330A (en) * | 2006-07-07 | 2008-01-09 | 同济大学 | Method for manufacturing and using material for removing pollutant difficult to be degraded in water |
| CN106977045A (en) * | 2017-03-30 | 2017-07-25 | 中国环境科学研究院 | A kind of strenuous primary treatment method and device of refractory pharmaceutical park tail water |
| CN206767867U (en) * | 2017-03-31 | 2017-12-19 | 昆明理工大学 | A kind of persistent organic pollutant wastewater processing system |
| CN107117690B (en) * | 2017-06-22 | 2021-01-22 | 天津碧水源膜材料有限公司 | Device and method for treating refractory pollutants through electrocatalytic oxidation |
| CN107082519A (en) * | 2017-06-22 | 2017-08-22 | 吉林大学 | A kind of preprocessing system and method to the pollutant waste water of water soluble polymer containing difficult degradation |
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