CN111153512A - Method and device for treating wastewater containing benzene series and application thereof - Google Patents
Method and device for treating wastewater containing benzene series and application thereof Download PDFInfo
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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
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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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
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
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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
- C02F2103/08—Seawater, e.g. for desalination
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- Water Treatment By Sorption (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the field of wastewater treatment, and discloses a method and a device for treating wastewater containing benzene series and application thereof. The method for treating the wastewater containing the benzene series comprises the step of sequentially carrying out gravity separation, membrane separation and adsorption separation on the wastewater containing the benzene series. The treatment method and the device have the advantages of simple operation, low energy consumption and low equipment requirement, and can effectively solve the problem of in-situ rapid separation of the seawater of the offshore emergency benzene series hazardous chemical represented by the dimethylbenzene.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a method and a device for treating wastewater containing benzene series and application thereof.
Background
With the development of the chemical industry, the quantity and trade volume of hazardous chemicals are greatly increased, so that the transportation volume of the hazardous chemicals on the sea is rapidly increased, the leakage accidents of the hazardous chemicals are occasionally caused, and the hazardous chemicals are very serious in result once leaking due to the characteristics of flammability, explosiveness, toxicity, harm and corrosiveness of the hazardous chemicals. At present, offshore hazardous chemicals are leaked, an adsorbing material is used for recovering to a great extent, then the hazardous chemicals are separated by an oil-water separation device, or the hazardous chemicals are recovered on a ship and then brought back for treatment, so that the weight load on an emergency ship is greatly increased, and the emergency treatment capacity of the whole accident is also reduced due to the fact that the oil-water separation device is used for separating hazardous chemicals from seawater without being aligned. Therefore, an in-situ treatment process aiming at the separation of hazardous chemical seawater is urgently needed, polluted seawater is treated in time and then discharged after reaching the standard, the load of an emergency ship is reduced, and the treatment efficiency is improved
The existing emergency technical research aiming at the leakage of the marine hazardous chemical substances mainly focuses on the marine recovery problem of the floating hazardous chemical substances, and no patent is published on the in-situ rapid separation process of the seawater polluted by the hazardous chemical substances. And the oil-water separation process which is similar to the hazardous chemical seawater separation process is researched more. Patent CN106045088A introduces a combined multi-stage oil-water separation process, which adopts a self-cleaning filter, a pollution-resistant oil-water separator and a multi-stage high-precision oil-water separator to carry out multi-stage combined treatment on oily sewage, and realizes the recycling of oil products by pure physical separation. But the physical and chemical properties of different oil products and hazardous chemicals are greatly different, and the high toxicity and volatility of the hazardous chemicals determine that the hazardous chemicals must be separated with pertinence to improve the emergency capacity of the leakage of the offshore hazardous chemicals. Therefore, a process capable of realizing rapid in-situ separation of hazardous chemical seawater is urgently needed to be researched to meet the offshore emergency requirement.
Disclosure of Invention
The invention aims to overcome the problems in the prior art, and provides a method and a device for treating wastewater containing benzene series and application thereof.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for treating benzene-containing wastewater, comprising subjecting the benzene-containing wastewater to gravity separation, membrane separation and adsorption separation in this order.
Preferably, the benzene series-containing wastewater is benzene series-containing seawater.
Preferably, the benzene series is a xylene compound and/or a toluene compound.
Preferably, the residence time of the gravity separation is above 5 min.
Preferably, the filter membrane used for the membrane separation is a cellulose membrane.
Preferably, the adsorptive separation is performed using activated carbon.
Preferably, the activated carbon is activated carbon particles and/or activated carbon fibers;
preferably, the particle size of the activated carbon particles is 12-40 mm.
Preferably, the activated carbon particles have a specific surface area of 1500m2More than 1300m of specific surface area of the activated carbon fiber2More than g.
Preferably, the activated carbon is a mixture of activated carbon particles and activated carbon fibers, and the weight ratio of the activated carbon particles to the activated carbon fibers is 1: 0.5-1.
The invention provides a device for treating wastewater containing benzene series, which comprises a gravity separator, a membrane separator and an adsorption separator which are connected in sequence.
Preferably, the filter membrane used in the membrane separator is a cellulose membrane.
Preferably, the adsorbent material used in the adsorptive separator is activated carbon.
Preferably, the activated carbon is activated carbon granules and/or activated carbon fibers.
Preferably, the particle size of the activated carbon particles is 12-40 mm.
Preferably, the activated carbon particles have a specific surface area of 1500m2More than 1300m of specific surface area of the activated carbon fiber2More than g.
Preferably, the activated carbon is a mixture of activated carbon particles and activated carbon fibers, and the weight ratio of the activated carbon particles to the activated carbon fibers is 1: 0.5-1.
In a third aspect, the present invention provides a use of the treatment method or the treatment apparatus according to the present invention for treating seawater containing benzene compounds.
Through the technical scheme, the gravity separation, the membrane separation and the adsorption separation which are selected by the invention belong to the processes which have low requirements on equipment, low consumption and easy operation. Wherein, the gravity separation can rapidly reduce the high-concentration dimethylbenzene in the seawater to about 200 ppm; the membrane separation can further reduce the concentration of the dimethylbenzene to dozens of ppm, and the good impact resistance can also prevent the problem that the adsorption component is directly impacted by the high-concentration dimethylbenzene due to the fact that gravity separation cannot act in time under the condition of poor sea conditions; the adsorption separation can well ensure that the effluent reaches below 15ppm of the national standard, so that the treated seawater can be directly discharged. The combination of the three processes can quickly realize the separation of the dimethylbenzene and the seawater, has good application prospect for the offshore emergency treatment of the dimethylbenzene dangerous chemicals which are not easy to dissolve in water, and fills the blank of a mature in-situ dimethylbenzene dangerous chemical-water separation device and method in the existing market.
Drawings
FIG. 1 is a schematic view showing the construction of an apparatus for treating a waste water containing benzene series according to the present invention.
Description of the reference numerals
1. Gravity separator 2, membrane separator 3, adsorption separator
4. Waste water sample feeding bottle 5, diaphragm pump 6 and first valve
7. Second valve
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for treating wastewater containing benzene series, which comprises the steps of sequentially carrying out gravity separation, membrane separation and adsorption separation on the wastewater containing the benzene series.
The method can quickly finish the separation operation of the benzene series hazardous chemical substances and the wastewater, has simple treatment method, large flux and high treatment efficiency, and is particularly suitable for the requirements of in-situ operations such as offshore hazardous chemical substance leakage and the like. Preferably, the benzene-containing wastewater of the present invention is benzene-containing seawater, and more preferably, xylene-containing seawater.
The benzene-based compound to be separated in the present invention may be any benzene-based compound which is not easily soluble in water, and examples thereof include xylene-based compounds and/or toluene-based compounds, and specific examples thereof include xylene (o-xylene, m-xylene, and p-xylene), toluene, and styrene. The content of the benzene-based compound in the wastewater may be, for example, 1g/L or more, preferably 5g/L or more and 10g/L or more. The upper limit of the benzene-based compound content in the wastewater is not particularly limited, and may be, for example, 1000g/L or less, 800g/L or less, 500g/L or less, 200g/L or less, 100g/L or less, or the like. The method is particularly suitable for treating the wastewater with high benzene series content.
In the present invention, the gravity separation is used for the preliminary separation of benzene series. In the gravity separation, the benzene series and the wastewater are kept stand, and an organic phase containing the benzene series and a water phase from which most of the benzene series is separated are directly obtained due to the insolubility of the benzene series and the wastewater. For example, where the benzene-based compound is xylene, the aqueous phase is below and the organic phase is above. The organic phase can be directly discharged through a valve, thereby completing the primary separation operation.
In the gravity separation process, in order to achieve a better separation effect, the retention time of the gravity separation is preferably more than 5min, and more preferably 8-15 min. By setting the residence time of the gravity separation to the above range, it is possible to ensure that the concentration of the benzene series in the aqueous phase located at the interface between the two phases by 10cm or more is 160ppm or less, thereby ensuring the effect of the gravity separation.
In the present invention, the membrane separation is used for further separation of benzene series. The filter membrane that membrane separation used is the interception membrane, for example cellulose membrane, can pass through water promptly and with the material that water is mutually soluble, the material that does not mutually dissolve with water can't pass through, can effectual interception be difficult for the benzene series thing of water to can permeate through waste water and intercept benzene series thing, guarantee the separation effect of the benzene series thing that paraxylene is as representing. For achieving a good separation effect, it is preferable to use, for example, an HK brand cellulose film.
The membrane separation may be performed under normal pressure, or may be performed under a certain pressure or reduced pressure in order to improve the separation efficiency. The flow rate for separation can be 100-1000mL/min, preferably 300-640mL/min, so as to ensure that the flow rate of the whole process is within the maximum membrane flux range, thereby achieving the optimal separation effect and the longest service life.
According to the invention, the concentration of benzene series in the wastewater can be reduced to below 100mg/L through membrane separation.
In the present invention, the adsorption separation is used for still further separation of benzene series. The adsorption separation can be carried out by using any existing adsorption separation device which can be used for separating benzene series, and is preferably porous adsorption material with high selective adsorption and large specific surface area. Examples of the adsorbent used for adsorption and separation include activated carbon particles and activated carbon fibers.
According to a preferred embodiment of the present invention, the activated carbon used for the adsorptive separation may be activated carbon particles and/or activated carbon fibers. The particle diameter of the activated carbon particles may be, for example, 12 to 40mm, and more preferably 20 to 40 mm. The specific surface area of the activated carbon particles may be 1500m2More than/g, preferably 1500-2(ii)/g; the specific surface area of the activated carbon fiber can be 1300m2More than 1300-2(ii) in terms of/g. In a preferred embodiment of the present invention, the activated carbon is a mixture of activated carbon particles and activated carbon fibers, and the weight ratio of the activated carbon particles to the activated carbon fibers in the mixture may be, for example, 1: 0.5-1, preferably 1: 0.5-0.7. By using the mixture of the activated carbon particles and the activated carbon fibers, the large adsorption capacity of the activated carbon can be ensured, and the activated carbon is not compacted and abraded under the impact of high-flow-rate water flow, so that the service life of the adsorption material is ensured.
According to the invention, through the adsorption separation, the concentration of benzene series in the wastewater can be reduced to below 15mg/L, and the treated wastewater meets the national standard and can be directly discharged.
In a second aspect of the present invention, there is provided an apparatus for treating wastewater containing benzene series, which comprises a gravity separator 1, a membrane separator 2 and an adsorption separator 3 connected in this order, as shown in FIG. 1.
According to the present invention, the gravity separator 1 is not particularly limited, and may be, for example, a gravity separator tank. Preferably, a first valve 6 is arranged in the upper part of the gravity separator 1, and more preferably, the first valve 6 is a valve with a window, so that the separation process can be observed conveniently, and the obtained benzene series can be discharged from the gravity separator 1 at a proper time.
According to the invention, the membrane separator 2 can be used with any membrane separator known in the art for the separation of waste water. The filter membrane that uses in the membrane separator 2 is the interception membrane, can pass through promptly and with the material that water is mutually soluble, the material that does not mutually dissolve with water can't pass through, can effectual interception be difficult for the benzene series thing of water to can see through waste water and intercept benzene series thing, guarantee to the separation effect of benzene series thing. The filter membrane used in the membrane separator 2 is preferably a cellulose membrane. For achieving a good separation effect, it is preferable to use, for example, an HK brand cellulose film.
Preferably, a second valve 7 is provided in the upper part of the membrane separator 2, more preferably said second valve 7 is a valve with a window, to facilitate the observation of the separation process, and to discharge the resulting benzene series from the membrane separator 2 at the appropriate time.
According to the present invention, the adsorption separator 3 may use any adsorption separator 3 for separating waste water, such as an adsorption separation column, etc. The adsorbent used in the adsorption separator 3 may be, for example, activated carbon, and may be, for example, activated carbon granules or activated carbon fibers.
According to a preferred embodiment of the present invention, the activated carbon used in the adsorptive separator 3 is activated carbon granules and/or activated carbon fibers. The particle diameter of the activated carbon particles may be, for example, 12 to 40mm, and more preferably 20 to 40 mm. The specific surface area of the activated carbon particles may be 1500m2More than/g, preferably 1500-2(ii)/g; the specific surface area of the activated carbon fiber can be 1300m2More than 1300-2(ii) in terms of/g. In a preferred embodiment of the present invention, the activated carbon used in the adsorption separator 3 is a mixture of activated carbon particles and activated carbon fibers, and the weight ratio of the activated carbon particles to the activated carbon fibers in the mixture may be, for example, 1: 0.5-1, preferably 1: 0.5-0.7. By using the mixture of the activated carbon particles and the activated carbon fibers, the large adsorption capacity of the activated carbon particles can be ensured, and the activated carbon is not compacted and abraded under the impact of water flow with large flow velocity, so that the service life of the adsorption material is ensured。
The third aspect of the present invention provides the use of the above-mentioned treatment method or treatment apparatus of the present invention in the treatment of seawater containing benzene-based compounds.
The treatment device is convenient to arrange on a ship, so that the treatment process can be directly finished in offshore operation, the treated seawater is directly discharged, and the cost of recovery and transportation is reduced.
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.
Example 1
A treatment apparatus for xylene-containing wastewater as shown in FIG. 1 was used to treat seawater containing 40000ppm of xylene.
The treatment device comprises a gravity separator 1, a membrane separator 2 and an adsorption separator 3 which are connected in sequence; the gravity separator 1 is a gravity separation tank, and a first valve 6 with a window is arranged at the upper part of the gravity separator; the membrane separator 2 uses two-stage separation membranes which are commercially available from HK (high-k) of Nanjing Bidun environmental protection Limited company, and the upper part of the membrane separator 2 is provided with a second valve 7 with a window; the adsorption separator 3 is an adsorption separation column in which a mixture of activated carbon particles and activated carbon fibers is used as an adsorption material (0.8 kg in total, wherein the weight ratio of the activated carbon particles to the activated carbon fibers is 1: 0.5, the particle size of the activated carbon particles is 20mm, and the specific surface area is 1500m2(1300 m) of the specific surface area of the activated carbon fiber2/g)。
The xylene-containing seawater in the wastewater sample bottle 4 was pumped into the gravity separator 1 through the diaphragm pump 5 at a flow rate of 640mL/min, the retention time of gravity separation was 10min, the gravity separation process was observed through a window, and the separated xylene was led out through the first valve 6.
And the water phase at the lower part is sequentially sent to the membrane separator 2 and the adsorption separator 3 for separation, the membrane separation process is observed through a window, the separated dimethylbenzene is led out from the second valve 7, and the seawater separated in the adsorption separator 3 is directly discharged.
After each stage of treatment, seawater was sampled, xylene in the water was extracted with n-hexane, and the concentration of xylene was measured by gas chromatography (Agilent 7820A), and the data of the results are shown in table 1 below.
TABLE 1
Example 2
The apparatus and method of example 1 was used to perform a treatment of seawater containing xylene, except that the seawater containing xylene was pumped into the gravity separator 1 at a flow rate of 1000 mL/min. The xylene concentration after each stage of treatment was measured according to the method of example 1, and the results are shown in Table 2 below.
TABLE 2
Example 3
The apparatus and method of example 1 was used to perform a xylene-containing seawater treatment, except that only activated carbon particles were used as the adsorbent material. The xylene concentration after each stage of treatment was measured according to the method of example 1, and the results are shown in Table 3 below.
TABLE 3
As can be seen from the results in tables 1-3, the xylene and seawater can be rapidly separated by the treatment method of the invention, the xylene is not detected in the separated seawater, and the device of the invention has simple structure, low operation and maintenance cost and is convenient for direct operation on the sea.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The method for treating the wastewater containing the benzene series is characterized by comprising the step of sequentially carrying out gravity separation, membrane separation and adsorption separation on the wastewater containing the benzene series.
2. The method of claim 1, wherein the benzene-containing wastewater is benzene-containing seawater.
3. The method of claim 1, wherein the benzene-based compound is a xylene-based compound and/or a toluene-based compound.
4. A process according to any one of claims 1 to 3, wherein the residence time of the gravity separation is 5min or more.
5. The method according to any one of claims 1 to 3, wherein the membrane used for the membrane separation is a cellulose membrane.
6. The process of any one of claims 1-3, wherein the adsorptive separation is performed using activated carbon;
preferably, the activated carbon is activated carbon particles and/or activated carbon fibers;
preferably, the particle size of the activated carbon particles is 12-40 mm;
preferably, the activated carbon particles have a specific surface area of 1500m2More than 1300m of specific surface area of the activated carbon fiber2More than g;
preferably, the activated carbon is a mixture of activated carbon particles and activated carbon fibers, and the weight ratio of the activated carbon particles to the activated carbon fibers is 1: 0.5-1.
7. The device for treating the wastewater containing the benzene series is characterized by comprising a gravity separator, a membrane separator and an adsorption separator which are sequentially connected.
8. The device of claim 7, wherein the filter membrane used in the membrane separator is a cellulose membrane.
9. The apparatus of claim 7 or 8, wherein the adsorbent material used in the adsorptive separator is activated carbon;
preferably, the activated carbon is activated carbon particles and/or activated carbon fibers;
preferably, the particle size of the activated carbon particles is 12-40 mm;
preferably, the activated carbon particles have a specific surface area of 1500m2More than 1300m of specific surface area of the activated carbon fiber2More than g;
preferably, the activated carbon is a mixture of activated carbon particles and activated carbon fibers, and the weight ratio of the activated carbon particles to the activated carbon fibers is 1: 0.5-1.
10. Use of the treatment method according to any one of claims 1 to 6 or the treatment plant according to any one of claims 7 to 9 for the treatment of benzene-containing seawater.
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Cited By (3)
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| CN112250204A (en) * | 2020-10-26 | 2021-01-22 | 浙江海洋大学 | Offshore hazardous chemical leakage treatment method, recovery separation cabin, treatment platform and method |
| CN113511770A (en) * | 2021-09-13 | 2021-10-19 | 江苏飞亚化学工业集团股份有限公司 | Sewage treatment system in xylene course of working |
| CN113735288A (en) * | 2020-05-28 | 2021-12-03 | 中国石油化工股份有限公司 | Recovery and separation integrated treatment system for aquatic dangerous chemicals |
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| CN113735288A (en) * | 2020-05-28 | 2021-12-03 | 中国石油化工股份有限公司 | Recovery and separation integrated treatment system for aquatic dangerous chemicals |
| CN112250204A (en) * | 2020-10-26 | 2021-01-22 | 浙江海洋大学 | Offshore hazardous chemical leakage treatment method, recovery separation cabin, treatment platform and method |
| CN113511770A (en) * | 2021-09-13 | 2021-10-19 | 江苏飞亚化学工业集团股份有限公司 | Sewage treatment system in xylene course of working |
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