CN111170528A - Purification treatment method of organic wastewater with difficultly-degraded oil sludge - Google Patents
Purification treatment method of organic wastewater with difficultly-degraded oil sludge Download PDFInfo
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- CN111170528A CN111170528A CN202010117931.5A CN202010117931A CN111170528A CN 111170528 A CN111170528 A CN 111170528A CN 202010117931 A CN202010117931 A CN 202010117931A CN 111170528 A CN111170528 A CN 111170528A
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- organic wastewater
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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
- C02F9/00—Multistage 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a purification treatment method of organic wastewater with difficultly degraded oil sludge, which uses a flocculating agent to remove solid and colloid in the organic wastewater with difficultly degraded oil sludge; adjusting the pH value of the wastewater to 4.5-8.5, and treating the wastewater by using an iron-carbon micro-electrolysis filler; purifying with organically modified attapulgite clay accounting for 1.0-5.0% of the mass of the organic wastewater with difficultly degraded oil sludge, and performing solid-liquid separation after adsorption; and the adsorbed oil sludge degradation-resistant organic wastewater directly enters a biochemical system for biochemical treatment, so that the standard-reaching discharge of the oil sludge degradation-resistant organic wastewater is realized. The invention reduces the toxicity of the organic wastewater with the oil sludge difficult to degrade to the microorganisms through the iron-carbon micro-electrolysis, and improves the biodegradability of the organic wastewater with the oil sludge difficult to degrade; the low-cost organic attapulgite clay is adopted for adsorption, so that the use of high-cost active carbon or resin is avoided, and the cost for treating the organic wastewater with oil sludge difficult to degrade is reduced; provides a new method for realizing the recycling of the organic wastewater with the oil sludge difficult to degrade.
Description
Technical Field
The invention relates to a treatment method of organic wastewater, in particular to a purification treatment method of organic wastewater with difficultly degraded oil sludge.
Background
Lubricating oil is one of four major petroleum products, and is blood for maintaining normal operation of machinery. The lubricating oil gradually loses its original performance due to normal loss, oxidation, temperature, moisture, dust pollution and the like in the using process and becomes waste lubricating oil. In China, which is the second major lubricating oil consumption country in the world, the consumption of lubricating oil reaches 641 ten thousand tons only in 2016, and if the generated waste lubricating oil is calculated to be about 50% of new oil, the consumption of the waste lubricating oil in 2016 is close to 350 ten thousand tons. If the waste lubricating oil cannot be well treated, not only is valuable energy wasted, but also the environment is seriously polluted.
Because of the wide source of the used lubricating oil, a large amount of oil sludge is generated in the regeneration process of the used lubricating oil, the oil sludge contains a certain amount of waste water, and a certain amount of waste water is generated in the oil sludge cleaning and deoiling process. The organic wastewater difficult to degrade by the oil sludge is actually a multiphase system integrating suspended solid, oil, high molecular compound and dissolved substance, has poor biodegradability (BOD/COD), is difficult to biodegrade organic wastewater, has very complex components, contains various acids, aldehydes, ketones, esters, ethers, benzene, sulfur, phenol, amine and the like, and has very high COD (chemical oxygen demand) of the organic wastewater difficult to degrade by the oil sludge, even up to tens of thousands to hundreds of thousands of mg/L; among them, the aromatic compounds, sulfur, amine (nitrile) and other substances in the wastewater have strong biological toxicity and cannot be treated by the conventional sewage treatment means. If the organic wastewater with the oil sludge difficult to degrade is discharged without being treated, the organic wastewater can pollute the surrounding environment, especially crops, the surface water and the underground water system, damage the crops and influence the growth of aquatic organisms.
Combining with the increasingly severe environmental protection situation and environmental protection requirement in China at present, the recycling or standard discharge of organic wastewater generated by the waste lubricating oil regeneration industry becomes the key work of each manufacturer, and the comprehensive treatment of three wastes is directly related to whether an enterprise can normally produce the waste lubricating oil.
Disclosure of Invention
The invention aims to: the method can effectively reduce the content of harmful organic matters in the organic wastewater difficult to degrade, improve the biodegradability of the organic wastewater difficult to degrade, enable the high-concentration harmful oil sludge organic wastewater difficult to degrade to be treated by a conventional biochemical method, reduce the treatment cost of the organic wastewater difficult to degrade, and obtain better social benefit and environmental benefit.
The invention is realized by adopting the following technical scheme: removing solid and colloid impurities in the organic wastewater with the oil sludge difficult to degrade by using a flocculating agent; then adjusting the pH value of the wastewater to 4.5-8.5, and then treating the wastewater by using an iron-carbon micro-electrolysis filler; finally, purifying the organic modified attapulgite clay which accounts for 1.0-5.0% of the mass of the organic wastewater with the difficultly-degradable oil sludge, and performing solid-liquid separation after adsorption; and the adsorbed oil sludge degradation-resistant organic wastewater directly enters a biochemical system for biochemical treatment, so that the standard-reaching discharge of the oil sludge degradation-resistant organic wastewater is realized.
Wherein the flocculating agent comprises one or more of polyaluminium chloride, polyferric chloride, cationic polyacrylamide, anionic polyacrylamide and amphoteric polyacrylamide flocculating agents; the dosage of the flocculant is 1 ppm-100 ppm of the oil sludge degradation-resistant organic wastewater.
Wherein the organically modified attapulgite clay is attapulgite clay modified by one or more organic modifiers; the organic modifier is: cationic surfactants such as octadecyl trimethyl ammonium chloride and hexadecyl trimethyl ammonium chloride, and anionic surfactants such as sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and sodium fatty alcohol-polyoxyethylene ether sulfate.
Wherein the modification method of the organically modified attapulgite clay comprises the following steps: mixing attapulgite raw ore 10 parts, sulfuric acid 5 parts and water 50 parts, stirring at constant temperature of 60 deg.C for 120 min, filtering, oven drying, grinding, and sieving to obtain acid modified attapulgite; preparing an organic modifier-toluene solution with the mass concentration of 10.0% by using an organic modifier, adding 5 parts of acid-modified attapulgite into 100 parts of the organic modifier solution, refluxing for 24 hours, filtering, drying, grinding and sieving to obtain the organic modified attapulgite.
The iron-carbon micro-electrolysis filler is prepared from reduced iron powder, graphite, activated carbon and clay.
Wherein the iron-carbon micro-electrolysis filler contains 30-70% of iron, 20-60% of carbon and 15-30% of clay by mass; the clay is one or more of attapulgite, sepiolite and montmorillonite.
Wherein, the solid-liquid separation method comprises one of centrifugation or filtration.
Compared with the prior art, the invention has the following advantages:
1) the flocculation, the iron-carbon micro-electrolysis, the activated clay adsorption and the like are combined, so that the comprehensive treatment of the organic wastewater which is difficult to degrade in the lubricating oil industry is realized, and the discharge reaching the standard is realized.
2) The organic modified attapulgite clay is used as an adsorbent to further adsorb organic substances of the iron-carbon filler which are difficult to micro-electrolyze, so that the biodegradability of the wastewater is further improved.
Detailed Description
The technical solution of the invention is further illustrated below with reference to specific examples, which are not to be construed as limiting the technical solution. In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention.
Example 1: taking 100 parts of oily sludge degradation-resistant organic wastewater, adjusting the pH value of the wastewater to 7, then adding 100ppm of polyaluminium chloride solution, stirring for 30min, standing for 1h, wherein the COD (chemical oxygen demand) of supernatant is 101975 mg/L, and the chroma is 800; transferring the supernatant into an iron-carbon packed tower (the mass fraction of iron in the iron-carbon packed tower is 30%, the mass fraction of active carbon is 50%, and the mass fraction of attapulgite clay is 20%) to perform micro-electrolysis reaction for 60-120 min, and reducing the COD (chemical oxygen demand) of the wastewater to about 65000 mg/L after the micro-electrolysis combined Fenton reaction; then adding 5% by mass of organic attapulgite clay (the organic modifier is hexadecyl trimethyl ammonium chloride) into the wastewater, and stirring and adsorbing for 3 hours; and finally, transferring the liquid to a biochemical system for biochemical treatment to realize standard discharge.
Example 2: taking 100 parts of oily sludge degradation-resistant organic wastewater, adjusting the pH value of the wastewater to 4.5, then adding 10ppm of cationic polyacrylamide, stirring for 30min, standing for 1h, wherein the COD (chemical oxygen demand) of supernatant is 111975mg/L, and the chroma is 860; transferring the supernatant into an iron-carbon packed tower (the mass fraction of iron in the iron-carbon packed tower is 70%, the mass fractions of graphite and activated carbon are respectively 10, and the mass fraction of montmorillonite clay is 10%) to perform micro-electrolysis reaction for 120 min, and reducing the COD (chemical oxygen demand) of the wastewater to about 53000 mg/L after the micro-electrolysis combined Fenton reaction; then adding 1% by mass of organic attapulgite clay (the organic modifier is octadecyl trimethyl ammonium chloride) into the wastewater, and stirring and adsorbing for 3 h; and finally, transferring the liquid to a biochemical system for biochemical treatment to realize standard discharge.
Example 3: taking 100 parts of oily sludge degradation-resistant organic wastewater, adjusting the pH value of the wastewater to 6.5, then adding 1ppm of amphoteric polyacrylamide, stirring for 30min, standing for 1h, wherein the COD (chemical oxygen demand) of supernatant is 91975 mg/L, and the chroma is 760; transferring the supernatant into an iron-carbon filler tower (the mass fraction of iron in the iron-carbon filler is 30%, the mass fractions of active carbon are 60% respectively, and the mass fraction of sepiolite clay is 10%) to perform micro-electrolysis reaction for 120 min, and reducing the COD (chemical oxygen demand) of the wastewater to about 64000 mg/L after the micro-electrolysis combined Fenton reaction; then adding organic attapulgite clay (the organic modifier is sodium dodecyl benzene sulfonate) with the mass fraction of 4% into the wastewater, stirring and adsorbing for 3 h; and finally, transferring the liquid to a biochemical system for biochemical treatment to realize standard discharge.
The technical solution of the present invention is not limited to the above embodiments, and other embodiments obtained according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (8)
1. The purification treatment method of the oily sludge degradation-resistant organic wastewater is characterized by comprising the following steps: removing solids and colloids in the organic wastewater with the oil sludge difficult to degrade by using a flocculating agent; adjusting the pH value of the wastewater to 4.5-8.5, and treating the wastewater with an iron-carbon micro-electrolysis filler; purifying by using organically modified attapulgite clay accounting for 1.0-5.0% of the mass of the organic wastewater with difficultly-degradable oil sludge, and performing solid-liquid separation after adsorption; and directly feeding the adsorbed organic wastewater difficult to degrade into a biochemical system for biochemical treatment, so that the organic wastewater difficult to degrade is discharged up to the standard.
2. The method for purifying hardly degradable organic wastewater containing sludge according to claim 1, wherein: the flocculant comprises one or more of polyaluminium chloride, polyferric chloride, cationic polyacrylamide, anionic polyacrylamide and amphoteric polyacrylamide.
3. The method for purifying hardly degradable organic wastewater containing sludge according to claim 1, wherein: the dosage of the flocculant is 1 ppm-100 ppm of the oil sludge degradation-resistant organic wastewater.
4. The method for purifying hardly degradable organic wastewater containing sludge according to claim 1, wherein: the organically modified attapulgite clay is attapulgite clay modified by one or more organic modifiers; the organic modifier is: cationic surfactants such as octadecyl trimethyl ammonium chloride and hexadecyl trimethyl ammonium chloride, and anionic surfactants such as sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and sodium fatty alcohol-polyoxyethylene ether sulfate.
5. The method for purifying and treating the hardly degradable organic wastewater containing oil sludge according to claim 4, wherein the method for preparing the organically modified attapulgite clay comprises the following steps: mixing attapulgite raw ore 10 parts, sulfuric acid 5 parts and water 50 parts, stirring at constant temperature of 60 deg.C for 120 min, filtering, oven drying, grinding, and sieving to obtain acid modified attapulgite; preparing an organic modifier-toluene solution with the mass concentration of 10.0% by using an organic modifier, adding 5 parts of acid-modified attapulgite into 100 parts of the organic modifier solution, refluxing for 24 hours, filtering, drying, grinding and sieving to obtain the organic modified attapulgite.
6. The method for purifying hardly degradable organic wastewater containing sludge according to claim 1, wherein: the iron-carbon micro-electrolysis filler is prepared from reduced iron powder, graphite, activated carbon and clay.
7. The method for purifying hardly degradable organic wastewater containing sludge according to claim 6, wherein: in the iron-carbon micro-electrolysis filler, the mass fraction of iron is 30-70%, the mass fraction of carbon is 20-60%, and the mass fraction of clay is 15-30%; the clay is one or more of attapulgite, sepiolite and montmorillonite.
8. The method for purifying hardly degradable organic wastewater containing sludge according to claim 1, wherein: the solid-liquid separation method comprises one of centrifugation or filtration.
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| CN202010117931.5A CN111170528A (en) | 2020-02-26 | 2020-02-26 | Purification treatment method of organic wastewater with difficultly-degraded oil sludge |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995158A (en) * | 2020-08-12 | 2020-11-27 | 广东省科学院资源综合利用研究所 | Method for treating emulsified oil sludge-containing wastewater in gem processing industry |
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| CN111995158A (en) * | 2020-08-12 | 2020-11-27 | 广东省科学院资源综合利用研究所 | Method for treating emulsified oil sludge-containing wastewater in gem processing industry |
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Application publication date: 20200519 |