CN113998764A - Composite oil removal agent and method for treating crude oil electric desalting wastewater - Google Patents
Composite oil removal agent and method for treating crude oil electric desalting wastewater Download PDFInfo
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- 238000002156 mixing Methods 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims abstract description 29
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- 239000000571 coke Substances 0.000 claims abstract description 24
- 239000002244 precipitate Substances 0.000 claims abstract description 24
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims abstract description 23
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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
-
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/547—Tensides
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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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention relates to a composite oil removal agent and a method for treating crude oil electric desalting wastewater. The composite oil removing agent comprises the following components: and (2) component A: a cationic reverse demulsifier; and (B) component: one or more of anthracite, lignite activated coke and lignite activated carbon; and a component C: polyaluminium sulfate. The method for treating the crude oil electric desalting wastewater comprises the following steps: mixing crude oil electric desalting wastewater with the composite oil removal agent to obtain a first mixture; and carrying out solid-liquid separation on the first mixture to obtain first treated wastewater and first precipitate. By adopting the composite oil removing agent and the method, the oil removing efficiency of the crude oil electric desalting wastewater is improved.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a composite oil removing agent for treating crude oil electric desalting wastewater and a method for treating the crude oil electric desalting wastewater by using the composite oil removing agent.
Background
The crude oil electric desalting device can be used for simultaneously desalting and dehydrating crude oil, provides high-quality raw materials for all downstream devices, is a 'tap' process of an oil refinery, and is also an essential crude oil pretreatment unit for the oil refining industry. The wastewater generated after the electric desalting treatment process is the electric desalting wastewater. The electric desalting wastewater is high-temperature saline oily wastewater, and contains high content of suspended matters and organic matters, crude oil, sulfides, demulsifiers and other pollutants. The total discharge amount of the electric desalting wastewater of each refinery in China is thousands of tons every year, and the salt-containing and oil-containing high-pollution load sewage is difficult to directly recycle or cascade recycle, and can not be directly discharged into a sewage treatment plant of an oil refinery without any pretreatment, otherwise, the impact on a drainage facility can be caused. In recent years, along with the annual increase of the proportion of high-acid and heavy crude oil processed in China, the difficulty of oil-water separation of electric desalted sewage is increased continuously, the emulsification phenomenon of the electric desalted sewage is increasingly serious, the phenomenon that the oil content is increased and even exceeds the standard is more frequent, and great pressure is caused on the sewage treatment and environmental standard reaching of a refinery.
At present, crude oil electric desalting wastewater pretreatment is generally adopted by oil refining enterprises to reach the standard and then discharged into a sewage treatment plant of an oil refinery for further treatment to reach the standard, but the requirements on the demulsification and oil removal capacity and effect of an electric desalting sewage treatment process are also obviously increased due to the results of serious emulsification and increased oil content of electric desalting sewage caused by crude oil deterioration and heaviness, and the conventional crude oil electric desalting wastewater pretreatment technology cannot meet the actual requirements.
The conventional crude oil electric desalting wastewater treatment technology comprises the following steps: 1) the hydrocyclone separation technology: the density difference of oil and water is utilized, the oil and the water are forced to be separated by centrifugal force when the liquid flow rotates highly, the requirement on the flow rate of inflow water is high, the energy consumption is large, and the method is not suitable for emulsified oil; 2) chemical demulsification and oil removal technology: one or more chemical substances are added to react with oil substances in water to perform demulsification, flocculation, precipitation, even catalytic oxidation and the like so as to achieve the aim of removing the oil substances from the water, and the defects that the requirements on reaction conditions are high, the pH value needs to be adjusted in advance, the types of added medicaments are more, the price of a demulsifier is high, the using amount is large, and secondary pollution is easily caused to sewage to influence the downstream process are overcome; 3) electrochemical oil removal technology: the physical action of an electric field and the electrochemical electrocoagulation action are utilized to achieve the purpose of oil-water stratification, and the defects are that the salinity and hardness of the electric desalting wastewater are high, dirt is easily formed on a polar plate, the treatment effect is influenced, the impact resistance of an electrochemical method is relatively weak, and the control requirement on the process is high.
Therefore, it is necessary to provide a method for treating crude oil electric desalting wastewater to solve the problems of low oil removal efficiency and the like in the prior art.
Disclosure of Invention
The invention aims to provide a method for treating crude oil electric desalting wastewater, which aims to solve the problem of low oil removal efficiency in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a composite oil remover for treating crude oil electric desalting wastewater, the composite oil remover comprising the following components: and (2) component A: a cationic reverse demulsifier; and (B) component: one or more of anthracite, lignite activated coke and lignite activated carbon; and (3) component C: polyaluminium sulfate.
Preferably, the content of the component A is 0.5-3%, the content of the component B is 92-96% and the content of the component C is 1-5% based on the total weight of the composite oil removing agent.
Preferably, the cationic reverse demulsifier comprises one or more of polyquaternium salts, linear alkyl amine salts, alkyl pyridinium cationic reverse demulsifiers.
According to another aspect of the present invention, there is provided a method for treating crude oil electric desalting wastewater, the method comprising: mixing crude oil electric desalting wastewater with a composite oil removal agent to obtain a first mixture; carrying out solid-liquid separation on the first mixture to obtain first treatment wastewater and first precipitate; the composite oil removing agent is the composite oil removing agent according to the above aspect of the invention.
Preferably, the dosage of the composite oil removing agent is 1-10g/L based on the volume of the crude oil electric desalting wastewater.
Preferably, the mode for mixing the crude oil electric desalting wastewater and the composite oil removing agent comprises one or more of hydraulic mixing, aeration mixing and mechanical stirring.
Preferably, the time for mixing the crude oil electric desalting wastewater with the composite oil removing agent is 15-60 minutes.
Preferably, the mode of carrying out solid-liquid separation on the first mixture comprises one or more of inclined tube inclined plate sedimentation, corrugated inclined plate oil separation and coalescence inclined plate oil removal, and the time for carrying out solid-liquid separation on the first mixture is 60-120 minutes.
Preferably, the method further comprises: and filtering the first treated wastewater to obtain second treated wastewater, preferably, the filtering process is medium filtering, and more preferably, the filtering material adopted by the medium filtering is one or more of anthracite, lignite activated coke and lignite activated carbon.
Preferably, the method further comprises: and collecting the first precipitate by adopting a grid mud discharge hopper, a mud discharge pipe and a mud discharge valve.
Aiming at the problem of low oil removal efficiency in the prior art, the invention adopts the composite oil removal agent comprising the component A-cation reverse demulsifier, one or more of the component B-anthracite, lignite activated coke and lignite activated carbon and the component C-polyaluminium sulfate to replace the existing chemical oil removal agent to carry out chemical oil removal treatment on the crude oil electric desalting wastewater, thereby improving the oil removal efficiency of the crude oil electric desalting wastewater.
The component B in the composite oil removal agent, namely one or more of anthracite, lignite activated coke and lignite activated carbon, can not only destroy the interface structure of emulsion droplets in the emulsified wastewater and realize the demulsification effect, but also can adsorb impurities such as suspended matters, organic matters (COD) and the like in the wastewater. The component B is matched with two demulsifiers, namely a cation reverse demulsifier and a polyaluminium sulfate salt, and is commonly applied to the treatment of crude oil electric desalting wastewater, so that the oil content in the wastewater can be reduced to less than or equal to 150mg/L, and the requirement of related indexes of inlet water quality of a sewage treatment field of an oil refinery is met.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a process flow diagram for treating crude oil electric desalting wastewater provided by the invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to improve the oil removal efficiency of the crude oil electric desalting wastewater, according to one aspect of the invention, a composite oil remover for treating the crude oil electric desalting wastewater is provided, and the composite oil remover comprises the following components: component a-a cationic reverse demulsifier; the component B is one or more of anthracite, lignite activated coke and lignite activated carbon; and component C-polyaluminium sulfate.
The invention innovatively provides a method for treating crude oil electric desalting wastewater by adopting a three-component composite oil removal agent, and the demulsification and adsorption effects of the composite oil removal agent are utilized to destroy the emulsion droplet interface structure in the wastewater, adsorb and remove impurities such as suspended matters, organic matters (COD) and the like in the wastewater, so that the purpose of separating oil from water in the wastewater is achieved, and the composite oil removal agent has an efficient oil removal effect.
The invention firstly proposes that the cation reverse demulsifier, the polyaluminium sulfate and one or more substances selected from anthracite, lignite activated coke and lignite activated carbon are compounded for treating the crude oil electric desalting wastewater, and compared with the conventional demulsifier for removing oil from the wastewater, the invention can realize the high-efficiency removal of oil and other pollutants in the crude oil electric desalting wastewater. Particularly, the component B in the composite oil removal agent, namely one or more of anthracite, lignite activated coke and lignite activated carbon, can not only destroy the interface structure of emulsion droplets in the emulsified wastewater and realize the demulsification effect, but also can adsorb impurities such as suspended matters, organic matters (COD) and the like in the wastewater. The component B is matched with two demulsifiers, namely a cation reverse demulsifier and a polyaluminium sulfate salt, and is commonly used for oil removal treatment of crude oil electric desalted wastewater, so that the oil content in the wastewater can be reduced to be less than or equal to 150mg/L, the requirements of related indexes of water inlet quality of a sewage treatment field of an oil refinery are met, the impact of emulsified oil-containing electric desalted water on the sewage treatment field of the oil refinery is solved, the effluent is ensured to be discharged up to the standard, and the oil removal and flotation processes in the traditional 'three sets' treatment process 'oil removal-flotation-biochemistry' of the sewage treatment field of the oil refinery can be saved.
In addition, compared with the existing oil removal technology, the composite oil removal agent provided by the invention can not cause secondary pollution to wastewater, and the effluent meets the relevant indexes of inlet water quality of a sewage treatment plant of an oil refinery, so that the composite oil removal agent is an effective scheme for realizing pretreatment of crude oil electric desalting wastewater and improving the standard reaching rate of environmental treatment of oil refining enterprises. By adopting the composite oil removing agent, demulsification can be well carried out without too much power equipment and power consumption, the equipment is simple and reliable, and the oil removing effect can be ensured. The invention provides a new approach for reducing the load of sewage treatment facilities of oil refineries and improving the standard reaching rate of environmental treatment of oil refining enterprises, and can be applied to the field of oily sewage treatment such as crude oil electric desalting sewage pretreatment in the oil refining industry.
The composite oil removing agent can be suitable for the conventional crude oil electric desalting wastewater, and especially has more remarkable effect when the oil content of the crude oil electric desalting wastewater is 150-1000 mg/L and the COD is 600-5000 mg/L.
The cation reverse demulsifier adopted by the invention preferably comprises one or more of polyquaternium, linear alkyl amine salt and alkyl pyridinium cation reverse demulsifier, more preferably adopts polyquaternium cation reverse demulsifier, and more preferably adopts polyquaternium cation reverse demulsifier which is mainly synthesized by epichlorohydrin, dimethylamine, tertiary amine and cross-linking agent. For example, the demulsifier LS _ PR-02 from Guangdong blue-win environmental protection technology, Inc. may be used.
In the invention, the content of the component A, the content of the component B and the content of the component C are respectively 0.5 to 3 percent, 92 to 96 percent and 1 to 5 percent based on the total weight of the composite oil removing agent. In the composite oil removing agent, the main component B accounts for 92-96% of the total weight, the component B can fully play a demulsification and adsorption role in the weight percentage range, the component A and the component C are contained in the composite oil removing agent in smaller amount, and the component A and the component C are used as auxiliary demulsifiers and are matched with the component B to realize the high-efficiency oil removal of the crude oil electric desalting wastewater.
As the component B, any one of anthracite, lignite activated coke, or lignite activated carbon may be used alone, or two or more of anthracite, lignite activated coke, and lignite activated carbon may be used in combination. When used in combination, the use amount ratio between the anthracite coal, the lignite activated coke and the lignite activated carbon is not particularly limited.
According to another aspect of the present invention, there is provided a method for treating crude oil electric desalting wastewater, the method comprising: mixing crude oil electric desalting wastewater with a composite oil removal agent to obtain a first mixture; and carrying out solid-liquid separation on the first mixture to obtain first treated wastewater and first precipitate, wherein the composite oil removing agent is the composite oil removing agent according to one aspect of the invention.
By mixing the crude oil electric desalting wastewater with the composite oil removal agent, the demulsification and adsorption effects on the wastewater can be realized. Specifically, the electric desalting wastewater and the composite oil removing agent are stirred and mixed, so that oil in the wastewater can be separated from water through demulsification and adsorbed into the composite oil removing agent through adsorption; meanwhile, other pollutants in the wastewater, such as suspended matters and organic matters (COD) in the wastewater are also adsorbed into the composite oil removing agent. These adsorbates (including oil and other contaminants) form a solid precipitate with the composite degreaser that precipitates out of the wastewater. Subsequently, a physical separation of the treated wastewater (i.e., the first treated wastewater) from the solid precipitate (i.e., the first precipitate, including the composite degreaser, oil, and possibly other contaminants) is achieved using a solid-liquid separation means.
The composite oil removing agent is used for treating crude oil electric desalting wastewater, and the high-efficiency oil removal of the crude oil electric desalting wastewater can be realized through the steps of mixing, solid-liquid separation and the like.
The composite oil removing agent can be suitable for the conventional crude oil electric desalting wastewater, and especially has more remarkable effect when the oil content of the crude oil electric desalting wastewater is 150-1000 mg/L and the COD is 600-5000 mg/L.
In the mixing step of the crude oil electric desalting wastewater and the composite oil removing agent, in order to improve the utilization efficiency and optimize the treatment effect, the composite oil removing agent can be added into the crude oil electric desalting wastewater according to a quantitative proportion, and the dosage of the composite oil removing agent is preferably 1-10g/L based on the volume of the crude oil electric desalting wastewater. Within the dosage range, the composite oil removing agent can effectively realize the demulsification and adsorption of the wastewater. If the amount is less than 1g/L, demulsification and adsorption may be insufficient, resulting in inefficient separation of oil and other contaminants; if the amount is more than 10g/L, there is a possibility that the composite oil removing agent is unnecessarily wasted.
In the method of the present invention, it is preferable to stir and mix the crude oil electric desalting wastewater and the composite oil removing agent. The process means of the stirring and mixing is not particularly limited, but it is preferable to mix the crude oil electric desalting wastewater with the composite degreasing agent by one or more processes of hydraulic mixing, aeration mixing and mechanical stirring.
Demulsification and adsorption require a certain amount of time to be fully completed. In the present invention, the time for mixing the crude oil electro-desalting wastewater with the composite oil removing agent is preferably 15 to 60 minutes. In this time quantum, can realize the breakdown of emulsion adsorption effect of preferred.
According to the method, the solid-liquid separation mode of the first mixture comprises one or more of inclined tube inclined plate sedimentation, corrugated inclined plate oil separation and coalescence inclined plate oil removal. By adopting the technical means, the precipitation efficiency can be improved, and the precipitation time can be greatly shortened. The solid-liquid separation time for the first mixture is preferably 60 to 120 minutes, and in this time period, sufficient solid-liquid separation can be achieved. The solid-liquid separation of the wastewater, the composite oil removing agent and oil and other pollutants by the precipitation process can avoid the secondary pollution of the oil removing agent to the subsequent process.
In the method of the present invention, a small amount of small particle precipitates (mainly, residual small particle precipitates of oil and organic matter) may be present in the first treated wastewater obtained by mixing with the composite oil removal agent and performing solid-liquid separation. Therefore, the treatment method of the present invention preferably further comprises the steps of: and filtering the first treated wastewater to obtain second treated wastewater. Preferably, the filtering process adopts medium filtering, and more preferably, the filtering material adopted by the medium filtering is one or more of anthracite, lignite activated coke and lignite activated carbon. By utilizing the adsorption and molecular interception functions of the filter material, small particle precipitated pollutants can be further removed from the first treated wastewater, so that second treated wastewater is obtained.
Furthermore, in the process of the present invention, the first precipitate obtained by solid-liquid separation can be collected for subsequent use. The first precipitate can be collected using means and devices conventional in the art. The invention preferably adopts a grid mud discharging hopper, a mud discharging pipe and a mud discharging valve to collect the first precipitate. After the first precipitate is collected, if the composite oil removing agent in the precipitate is not saturated, the first precipitate can be directly recycled to the mixing step of the method, and if the composite oil removing agent in the precipitate is completely saturated, the first precipitate can be recycled after being regenerated, or can be directly used as combustion.
The process of the present invention is described below with reference to FIG. 1. In fig. 1, crude oil electro-desalting wastewater from a crude oil electro-desalting plant or a conditioning tank is discharged into a mixing tank. The oil content of the wastewater is 150mg/L-1000mg/L, and the COD is 600mg/L-5000 mg/L. And (3) adding the composite oil removal agent into a mixing tank by using a composite oil removal agent adding system to be mixed with the wastewater. Based on the volume of the crude oil electric desalting wastewater, the dosage of the composite oil removing agent is 1-10 g/L. The composite oil removing agent comprises the following components: component a-a cationic reverse demulsifier; the component B is one or more of anthracite, lignite activated coke and lignite activated carbon; component C-polymeric aluminum sulfate. Based on the total weight of the composite oil removing agent, the content of the component A is 0.5-3%, the content of the component B is 92-96%, and the content of the component C is 1-5%. And fully mixing the wastewater and the composite degreaser for 15-60 minutes in a mixing pool by adopting a mechanical stirring mode and the like. Discharging the mixture from the mixing tank to a sedimentation tank for sedimentation. In the sedimentation tank, the composite oil removal agent, the adsorbed oil and other pollutants are precipitated by adopting an inclined plate sedimentation method, so that solid-liquid separation is realized with the treated wastewater (first treated wastewater), and the solid-liquid separation time is 60-120 minutes. After solid-liquid separation, the treated wastewater from the sedimentation tank is discharged into a filter for filtration treatment, thereby removing small-particle precipitates in the wastewater. The filter is preferably a multi-media filter, and the filter media are one or more of anthracite, lignite activated coke and lignite activated carbon. The effluent from the filter may be sent to a biochemical process for further treatment. On the other hand, after solid-liquid separation, the solid precipitate from the sedimentation tank is discharged into a sedimentation collection tank, wherein a grid mud discharge hopper, a mud discharge pipe and a mud discharge valve are adopted to collect the solid precipitate. The solid precipitate is mainly a composite degreasing agent adsorbed with oil, and can be directly recycled into the mixing tank if the composite degreasing agent is not saturated, or can be subjected to regeneration treatment if the composite degreasing agent is saturated, and then can be recycled into wastewater treatment, or can be directly used as fuel.
The following examples are provided to further illustrate the advantageous effects of the present invention.
Example 1
The refined raw oil of large-scale oil refining enterprises is mainly Daqing oil. The oil content of discharged water of the electric desalting device in normal operation is higher than 150mg/L, and the oil content of backwashing sewage of the electric desalting device can reach 5000 mg/L. The electric desalting wastewater is discharged into a conventional oil removal-flotation-biochemical oil refinery sewage treatment field after being pretreated. The crude oil with serious emulsification and high oil content still has the oil content higher than 200mg/L after the electro-desalting pretreatment. The oily wastewater which is not up to the standard after pretreatment is discharged into a sewage treatment field of an oil refinery, and the operation of the sewage treatment field is impacted, so that the COD (chemical oxygen demand) of the effluent of a biochemical unit is easily higher than 200mg/L, and the effluent is difficult to meet the standard of discharge.
The embodiment provides a treatment method of crude oil electric desalting wastewater refined by oil refining enterprises, which specifically comprises the following steps:
(1) the test raw water is taken from the normal operation drainage (water sample I) and the back flush drainage (water sample II) of the crude oil electric desalting device of the enterprise;
(2) the test raw water enters a mixing tank, and a composite degreasing agent is added, wherein the composite degreasing agent comprises 3% of polyquaternary ammonium salt cation reverse phase demulsifier (demulsifier LS _ PR-02, which is synthesized by epichlorohydrin, dimethylamine, tertiary amine and a cross-linking agent) serving as a component A, 96% of anthracite, lignite activated coke and lignite activated carbon serving as a component B (based on the total weight of the component B, the weight percentages of the anthracite, the lignite activated coke and the lignite activated carbon in the component B are respectively 10%, 80% and 10%) and 1% of polymerized aluminum sulfate serving as a component C. Based on the volume of the experimental raw water, the adding amount of the composite oil removing agent is 5 g/L. And (4) mechanically stirring to ensure that the composite degreasing agent is fully mixed and reacted with the test raw water. The retention time is 30 min;
(3) the effluent of the mixing tank enters an inclined plate sedimentation tank, and the retention time is 90 min;
the effluent of the sedimentation tank is used as the effluent of the embodiment, and is discharged to a sewage treatment plant for treatment after being checked to reach the standard. The solid separated by the sedimentation tank is sent to a sedimentation collecting tank and can be recycled or regenerated.
Under the optimized process or test conditions of the embodiment, the main indexes of the raw oil electric desalting wastewater inlet water and the treated outlet water are shown in table 1. Therefore, after the treatment by the method of the embodiment, the oil content and COD pollution load in the electric desalting wastewater are obviously reduced, the treated effluent can not only meet the requirements of relevant indexes of water quality of inlet water of a sewage treatment field of an oil refinery, but also can directly enter a biochemical process of the sewage treatment field of the oil refinery due to the low enough oil content of the effluent, so that the oil removal and flotation processes of oil removal, flotation and biochemistry of the conventional sewage treatment field of the oil refinery can be saved.
TABLE 1 crude oil electric desalting wastewater treatment test results
| Raw water sample | Detecting items | Unit of | Inflow water | Discharging water | Removal rate |
| Water sample I | Oil content | mg/L | 160 | <35 | >78％ |
| Water sample I | COD | mg/L | 960 | <370 | >61％ |
| Water sample II | Oil content | mg/L | 750 | <140 | >81％ |
| Water sample II | COD | mg/L | 2550 | <930 | >64％ |
Example 2
The experimental environment and the specific method steps of the enterprise in this example are the same as those in example 1. The only difference is that: the composite oil removal agent comprises 3% of cation reverse demulsifier as a component A, 92% of anthracite, lignite activated coke and lignite activated carbon as a component B and 5% of polymerized aluminum sulfate salt as a component C by weight.
Under the optimized process or test conditions of the embodiment, the main indexes of the raw oil electric desalting wastewater inlet water and the treated outlet water are shown in table 2.
TABLE 2 crude oil electric desalting wastewater treatment test results
Example 3
The experimental environment and the specific method steps of the enterprise in this example are the same as those in example 1. The only difference is that: the composite oil removal agent comprises 0.5% of cation reverse demulsifier as a component A, 95.5% of anthracite, lignite activated coke and lignite activated carbon as a component B, and 4% of polymerized aluminum sulfate salt as a component C.
Under the optimized process or test conditions of the embodiment, the main indexes of the raw oil electric desalting wastewater inlet water and the treated outlet water are shown in table 2.
TABLE 3 crude oil electric desalting wastewater treatment test results
| Raw water sample | Detecting items | Unit of | Inflow water | Discharging water | Removal rate |
| Water sample I | Oil content | mg/L | 160 | <38 | >76％ |
| Water sample I | COD | mg/L | 960 | <380 | >60％ |
| Water sample II | Oil content | mg/L | 750 | <160 | >78％ |
| Water sample II | COD | mg/L | 2550 | <990 | >61％ |
Example 4
The experimental environment and the specific method steps of the enterprise in this example are the same as those in example 1. The only difference is that: the composite oil removal agent comprises 10% of cation reverse demulsifier as a component A, 80% of anthracite, lignite activated coke and lignite activated carbon as a component B and 10% of polymerized aluminum sulfate salt as a component C by weight.
Under the optimized process or test conditions of the embodiment, the main indexes of the raw oil electric desalting wastewater inlet water and the treated outlet water are shown in table 4.
TABLE 4 crude oil electric desalting wastewater treatment test results
| Raw water sample | Detecting items | Unit of | Inflow water | Discharging water | Removal rate |
| Water sample I | Oil content | mg/L | 160 | <48 | >70％ |
| Water sample I | COD | mg/L | 960 | <480 | >50％ |
| Water sample II | Oil content | mg/L | 750 | <270 | >64％ |
| Water sample II | COD | mg/L | 2550 | <1200 | >53％ |
Example 5
The experimental environment and the specific method steps of the enterprise in this example are the same as those in example 1. The only difference is that: the dosage of the composite oil removing agent is 1 g/L.
Under the optimized process or test conditions of the embodiment, the main indexes of the raw oil electric desalting wastewater inlet water and the treated outlet water are shown in table 5.
TABLE 5 crude oil electric desalting wastewater treatment test results
| Raw water sample | Detecting items | Unit of | Inflow water | Discharging water | Removal rate |
| Water sample I | Oil content | mg/L | 160 | <75 | >53％ |
| Water sample I | COD | mg/L | 960 | <520 | >45％ |
| Water sample II | Oil content | mg/L | 750 | <370 | >51％ |
| Water sample II | COD | mg/L | 2550 | <1500 | >41％ |
Example 6
The experimental environment and the specific method steps of the enterprise in this example are the same as those in example 1. The only difference is that: the dosage of the composite oil removing agent is 10 g/L.
Under the optimized process or test conditions of the embodiment, the main indexes of the raw oil electric desalting wastewater inlet water and the treated outlet water are shown in table 6.
TABLE 6 crude oil electric desalting wastewater treatment test results
| Raw water sample | Detecting items | Unit of | Inflow water | Discharging water | Removal rate |
| Water sample I | Oil content | mg/L | 160 | <36 | >77％ |
| Water sample I | COD | mg/L | 960 | <350 | >63％ |
| Water sample II | Oil content | mg/L | 750 | <230 | >70％ |
| Water sample II | COD | mg/L | 2550 | <1200 | >53％ |
Example 7
The refined raw oil of large-scale oil refining enterprises is mainly Daqing oil. The oil content of discharged water of the electric desalting device in normal operation is higher than 150mg/L, and the oil content of backwashing sewage of the electric desalting device can reach 5000 mg/L. The electric desalting wastewater is discharged into a conventional oil removal-flotation-biochemical oil refinery sewage treatment field after being pretreated. The crude oil with serious emulsification and high oil content still has the oil content higher than 200mg/L after the electro-desalting pretreatment. The oily wastewater which is not up to the standard after pretreatment is discharged into a sewage treatment field of an oil refinery, and the operation of the sewage treatment field is impacted, so that the COD (chemical oxygen demand) of the effluent of a biochemical unit is easily higher than 200mg/L, and the effluent is difficult to meet the standard of discharge.
The embodiment provides a treatment method of crude oil electric desalting wastewater refined by oil refining enterprises, which specifically comprises the following steps:
(1) the test raw water is taken from the normal operation drainage (water sample I) and the back flush drainage (water sample II) of the crude oil electric desalting device of the enterprise;
(2) the test raw water enters a mixing tank, and a composite oil removal agent is added, wherein the composite oil removal agent comprises 2.5% of polyquaternary ammonium salt cation reverse phase demulsifier (synthesized by epichlorohydrin, dimethylamine, tertiary amine and a cross-linking agent) serving as a component A, 93% of anthracite, lignite activated coke and lignite activated carbon serving as a component B, and 4.5% of polyaluminium sulfate serving as a component C. Based on the volume of the experimental raw water, the adding amount of the composite oil removing agent is 5 g/L. And (4) mechanically stirring to ensure that the composite degreasing agent is fully mixed and reacted with the test raw water. The retention time is 30 min;
(3) the effluent of the mixing tank enters an inclined plate sedimentation tank, and the retention time is 90 min;
(4) the effluent of the sedimentation tank enters a multi-medium filter for filtration, the medium consists of anthracite, lignite activated coke and lignite activated carbon (based on the total weight of the filter material, the weight percentages of the anthracite, the lignite activated coke and the lignite activated carbon in the filter material are respectively 10%, 80% and 10%), and the retention time is 10 min.
The effluent of the multi-media filter is used as the effluent of the embodiment, and is discharged to a sewage treatment plant for treatment after being checked to reach the standard. The solid separated by sedimentation in the sedimentation tank is sent to a sludge collection tank and can be recycled or regenerated.
Under the optimized process or test conditions of the embodiment, the main indexes of the raw oil electric desalting wastewater inlet water and the treated outlet water are shown in table 7. Therefore, after the treatment by the method of the embodiment, the oil content and COD pollution load in the electric desalting wastewater are obviously reduced, the treated effluent can not only meet the requirements of relevant indexes of water quality of inlet water of a sewage treatment field of an oil refinery, but also can directly enter a biochemical process of the sewage treatment field of the oil refinery due to the low enough oil content of the effluent, so that the oil removal and flotation processes of oil removal, flotation and biochemistry of the conventional sewage treatment field of the oil refinery can be saved.
TABLE 7 crude oil electric desalting wastewater treatment test results
| Raw water sample | Detecting items | Unit of | Inflow water | Discharging water | Removal rate |
| Water sample I | Oil content | mg/L | 160 | <8 | >95％ |
| Water sample I | COD | mg/L | 960 | <230 | >77％ |
| Water sample II | Oil content | mg/L | 750 | <10 | >99％ |
| Water sample II | COD | mg/L | 2550 | <350 | >87％ |
Comparative example 1
The experimental environment and the specific method steps of the enterprise of this comparative example are the same as those of example 1. The only difference is that: a single polyquaternary ammonium cation reverse demulsifier (a demulsifier LS _ PR-02 synthesized by epichlorohydrin, dimethylamine, tertiary amine and a cross-linking agent) is adopted to replace a composite oil removal agent.
In comparative example 1, the main indices of the wastewater inlet and outlet of crude oil electric desalting are shown in Table 8.
TABLE 8 crude oil electric desalting wastewater treatment test results
| Raw water sample | Detecting items | Unit of | Inflow water | Discharging water | Removal rate |
| Water sample I | Oil content | mg/L | 160 | >105 | <35％ |
| Water sample I | COD | mg/L | 960 | >580 | <30％ |
| Water sample II | Oil content | mg/L | 750 | >500 | <40％ |
| Water sample II | COD | mg/L | 2550 | >1800 | <30％ |
Comparative example 2
The experimental environment and the specific method steps of the enterprise of this comparative example are the same as those of example 1. The only difference is that: the single polyaluminium sulfate salt is used to replace the composite degreasing agent.
In comparative example 2, the main indices of the wastewater inlet and outlet of crude oil electric desalting are shown in Table 9.
TABLE 9 crude oil electric desalting wastewater treatment test results
| Raw water sample | Detecting items | Unit of | Inflow water | Discharging water | Removal rate |
| Water sample I | Oil content | mg/L | 160 | >130 | <20％ |
| Water sample I | COD | mg/L | 960 | >645 | <23％ |
| Water sample II | Oil content | mg/L | 750 | >530 | <30％ |
| Water sample II | COD | mg/L | 2600 | >1900 | <27％ |
As can be seen from the above examples, the method for treating crude oil electric desalting wastewater of the invention has the following advantages:
1. the invention can realize the high-efficiency pretreatment of crude oil electric desalting wastewater, enhance the demulsification and oil removal efficiency, ensure that the oil content of the treated effluent meets the conventional requirement of the water quality of the inlet water of the sewage treatment field of the oil refinery, and because the oil removal effect is excellent, the pretreated effluent can directly enter the biochemical process of the sewage treatment field of the oil refinery, namely the oil removal and flotation processes in the combination of the oil removal, flotation and biochemical processes of the sewage treatment field of the conventional oil refinery can be saved.
2. The demulsification and oil removal effects are enhanced.
1) Compared with the hydraulic cyclone separation technology, the device has the function of demulsification and deoiling, and is more suitable for the actual production that the emulsification phenomenon of the electric desalting sewage is more frequent and serious due to the poor quality and the heavy quality of crude oil at present. And the requirement on the inflow velocity is not high as that of the hydrocyclone separation technology, and the operation energy consumption is reduced.
2) Compared with chemical demulsification and oil removal, the composite oil removal agent has the advantages that the consumption of the composite oil removal agent is less, secondary pollution to sewage is avoided, the composite oil removal agent can be repeatedly used, and the operation cost is lower.
3) Compared with the electrochemical oil removal technology, the process is simpler to control, the operation condition is not influenced by the high salt content and high hardness of the electric desalting wastewater, and the impact resistance is stronger.
3. The invention has the advantages of high efficiency of demulsification and oil removal, short process flow, compact operation space, simple and reliable operation control, less required medicament amount, no secondary pollution to sewage, capability of reducing the load of sewage treatment facilities of a refinery, reduction of the comprehensive sewage treatment cost of oil refining enterprises, improvement of the standard reaching rate of environmental treatment of the enterprises and powerful technical support.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The composite oil removing agent for treating crude oil electric desalting wastewater is characterized by comprising the following components:
and (2) component A: a cationic reverse demulsifier;
and (B) component: one or more of anthracite, lignite activated coke and lignite activated carbon;
and (3) component C: polyaluminium sulfate.
2. The composite oil remover according to claim 1, wherein the content of component A is 0.5-3%, the content of component B is 92-96%, and the content of component C is 1-5% based on the total weight of the composite oil remover.
3. The composite oil removal agent of claim 1, wherein the cationic reverse demulsifier comprises one or more of a polyquaternary ammonium salt ion reverse demulsifier, a linear alkyl amine salt ion reverse demulsifier, and an alkyl pyridinium salt cationic reverse demulsifier.
4. A method for treating crude oil electric desalting wastewater, which is characterized by comprising the following steps:
mixing the crude oil electric desalting wastewater with a composite oil removing agent to obtain a first mixture;
carrying out solid-liquid separation on the first mixture to obtain first treated wastewater and first precipitate;
the composite oil remover is the composite oil remover as defined in any one of claims 1 to 3.
5. The method according to claim 4, wherein the amount of the composite oil removal agent is 1-10g/L based on the volume of the crude oil electro-desalting wastewater.
6. The method according to claim 4, wherein the means for mixing the crude oil electro-desalting wastewater with the composite oil removing agent comprises one or more of hydraulic mixing, aeration mixing and mechanical stirring.
7. The method as claimed in claim 4, wherein the time for mixing the crude oil electro-desalting wastewater with the composite oil removing agent is 15-60 minutes.
8. The method of claim 4, wherein the means for performing solid-liquid separation on the first mixture comprises one or more of inclined tube inclined plate sedimentation, corrugated inclined plate oil separation and coalescence inclined plate oil removal, and preferably the time for performing solid-liquid separation on the first mixture is 60-120 minutes.
9. The method of claim 4, further comprising: and filtering the first treated wastewater to obtain second treated wastewater, preferably, the filtering process is medium filtering, and more preferably, the filtering material adopted by the medium filtering is one or more of anthracite, lignite activated coke and lignite activated carbon.
10. The method of claim 4, further comprising: and collecting the first precipitate by adopting a grid mud discharge hopper, a mud discharge pipe and a mud discharge valve.
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