CN114212869A - Preparation method of polycation polymer, compound oil removal agent and oil removal process - Google Patents
Preparation method of polycation polymer, compound oil removal agent and oil removal process Download PDFInfo
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- CN114212869A CN114212869A CN202111498512.1A CN202111498512A CN114212869A CN 114212869 A CN114212869 A CN 114212869A CN 202111498512 A CN202111498512 A CN 202111498512A CN 114212869 A CN114212869 A CN 114212869A
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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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
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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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
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Abstract
The invention relates to a preparation method of polycation polymer, the polycation polymer prepared by the method and polyaluminium chloride can be mutually dissolved in any weight fraction ratio, and both belong to cationic type, so that a novel compound oil removal agent can be prepared, the strong electric neutralization performance is realized, oil-in-water missible oil can be destroyed, oil drops quickly float upwards, the ideal oil-water separation effect can be achieved, and the excellent technical effect is realized when the polycation polymer is applied to oil-containing wastewater treatment.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a preparation method of a polycation polymer, a compound degreasing agent and a degreasing process.
Background
The oil field determines the size of an oil field area by the oil layer surface, the oil field generally occupies a large area, and for example, the Daqing city is built according to the oil field foundation. The traditional treatment method of the oil field industrial wastewater is to find a low-lying area for direct discharge after simple treatment, however, with high environmental requirements, the nation has clear indexes for the discharge of various polluted wastes or waste liquid, the current oil field industrial wastewater treatment technology is not mature, and the discharge of the industrial wastewater in the domestic oil field area becomes a big problem.
In the prior art, the agent for treating the oily wastewater is polyferric chloride, which is generally added before secondary air floatation, and the polyferric chloride mainly serves as a flocculating agent and can only flocculate suspended matters in the oily wastewater, so that the oil removal effect is not obvious. Therefore, a new process or a new medicament needs to be developed to treat the oily wastewater so as to reach the national oily wastewater discharge standard (less than or equal to 30 mg/L).
Disclosure of Invention
The application mainly solves the problems that the oil removing effect of the oily wastewater treated by the traditional technology is not obvious and the national emission standard cannot be reached.
In order to solve the above problems, the present application is implemented by the following technical solutions:
the application provides a preparation method of a polycation polymer, which comprises the following steps: s1, mixing dimethylamine and caustic soda liquid in equal molar ratio, and cooling to obtain a first mixed solution; s2, adding chloropropene dropwise into the first mixed solution in the step S1, and fully reacting to obtain dimethyl diallyl ammonium chloride; s3, carrying out polymerization reaction on the dimethyl diallyl ammonium chloride in the step S2 under the action of a redox initiator to prepare the polycation polymer.
As a further improvement of the present application, in step S2, the dropping temperature of the chloropropene is less than or equal to 45 ℃, preferably, the dropping temperature of the chloropropene is 10 ℃ to 45 ℃.
As a further improvement of this application, in step S2, before the full reaction, a part of the first mixed solution reacts with chloropropene to form an intermediate system, and liquid alkali is added to the intermediate system.
As a further improvement of the present application, in step S3, the redox initiator is an azo combination initiator.
As a further improvement of the present application, in step S3, the temperature of the polymerization reaction is 50 ℃ to 70 ℃ to obtain a high molecular weight polycationic polymer; the temperature of the polymerization reaction is 75-90 ℃, and polycation polymer with medium molecular weight is obtained; the temperature of the polymerization reaction is 95-120 ℃, and the low molecular weight polycation polymer is obtained.
In order to achieve the purpose, the application also provides a compound degreasing agent which is composed of polyaluminium chloride and a polycation polymer, wherein the polycation polymer is prepared by the preparation method of the polycation polymer.
As a further improvement of the application, the weight fraction ratio of the polyaluminium chloride to the polycationic polymer is 3: 1-20: 1; preferably, the weight fraction ratio of the polyaluminium chloride to the polycationic polymer is 4: 1-8: 1.
In order to achieve the above object, the present application further provides an oil removing process, comprising the steps of: the method comprises the following steps of treating oily wastewater by an oil separation tank, a first air flotation tank and a biochemical aeration tank in sequence and then discharging the oily wastewater, arranging a first dosing device at the first air flotation tank, and adding a compound degreasing agent into the first air flotation tank by the first dosing device, wherein the compound degreasing agent is the compound degreasing agent.
As a further improvement of the application, a second air flotation tank is further arranged in front of the first air flotation tank, a second dosing device is arranged at the position of the second air flotation tank, and the second dosing device adds the compound degreasing agent into the second air flotation tank.
As a further improvement of the application, the dosage of the compound oil remover is 40 mg/L-120 mg/L.
The preparation method has the beneficial effects that the polycation polymer prepared by the method and the polyaluminium chloride can be mutually soluble in any weight fraction ratio, both belong to cationic types, and are compounded into a novel oil removal agent, so that the oil-in-water emulsion oil can be destroyed due to strong electric neutralization performance, oil droplets float up rapidly, and the ideal oil-water separation effect can be achieved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the specific embodiments of the present application. It should be understood that the described embodiments are only a few embodiments of the present application, not all embodiments, and are not intended to limit the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a preparation method of a polycation polymer, which comprises the following steps: s1, mixing dimethylamine and caustic soda liquid in equal molar ratio, and cooling to obtain a first mixed solution; s2, adding chloropropene dropwise into the first mixed solution in the step S1, and fully reacting to obtain dimethyl diallyl ammonium chloride; s3, carrying out polymerization reaction on the dimethyl diallyl ammonium chloride in the step S2 under the action of a redox initiator to prepare the polycation polymer. In the specific step S2, chloropropene and dimethylamine (nucleophilic agent) react under an alkaline (acid-binding agent) condition to generate dimethylallylamine (nucleophilic agent), and then react with the remaining chloropropene to generate dimethyldiallylammonium chloride, and the two reactions are completed in the same kettle.
Specifically, in step S2, the dropping temperature of the chloropropene is less than or equal to 45 ℃, and preferably, the dropping temperature of the chloropropene is 10 ℃ to 45 ℃. In step S2, before sufficient reaction, a part of the first mixed solution reacts with chloropropene to form an intermediate system, and since the intermediate system contains a byproduct dimethylamine hydrochloride, the reaction is affected, so that an alkali is added into the intermediate system to hydrolyze the byproduct dimethylamine hydrochloride until no dimethylamine salt taste occurs, thereby promoting the reaction, and specifically, the mass molar ratio of the alkali solution to the dimethylamine is 0.1: 1-0.4: 1. In step S3, the redox initiator is an azo initiator combination. In step S3: the temperature of the polymerization reaction is 50-70 ℃, and a high molecular weight polycation polymer is obtained, wherein the molecular weight of the high molecular weight polycation polymer is not less than 30 ten thousand; the polymerization reaction temperature is 75-90 ℃, and polycation high polymer with medium molecular weight is obtained, and the molecular weight of the polycation high polymer with medium molecular weight is 10-30 ten thousand; the polymerization temperature is 95-120 ℃, and the low molecular weight polycation polymer is obtained, and the molecular weight of the low molecular weight polycation polymer is less than or equal to 1 ten thousand. Further, when a polycationic polymer having a high molecular weight is produced, temperature compensation is continuously performed to the polymerization system at the latter stage of the polymerization because: the monomer molecule has a large space, and needs a certain amount of energy from the outside to activate the molecular activity, so the initiation is carried out at 55-70 ℃ and further 55-65 ℃, but the polymerization reaction is an exothermic reaction, so the temperature needs to be kept stable in the initiation period, and the temperature is controlled to be 65 ℃ for carrying out the polymerization reaction, so the molecular chain connection can be effectively improved, the higher the molecular weight is obtained, the longer the time for keeping the temperature stable is, and the temperature needs to be increased to 80 ℃ in the later period of the reaction, thereby ensuring the complete reaction. The high molecular weight polycationic polymer, the medium molecular weight polycationic polymer and the low molecular weight polycationic polymer prepared in the application are all homopolymers, and the polymers are generally classified into homopolymers and copolymers.
The application also provides a compound degreasing agent, which consists of the polyaluminium chloride and the polycation polymer, wherein the polycation polymer is prepared by the method, and the polycation polymer and the polyaluminium chloride can be mutually soluble in any proportion. Preferably, the weight percentage ratio of the polyaluminium chloride to the polycationic polymer is 3: 1-20: 1. Furthermore, the weight percentage ratio of the polyaluminium chloride to the polycationic polymer is 4: 1-8: 1. The polycation polymer in the embodiment is a hydrophilic agent and an oleophilic agent, and both the polycation polymer and the polyaluminium chloride belong to cationic compounds, so that the polycation polymer and the aqueous solution of the polyaluminium chloride can be mutually dissolved in any proportion to form a true solution. The compound oil removing agent has strong electric neutralization performance, so that the oil-in-water emulsion oil can be damaged, and oil droplets can quickly float upwards, thereby achieving the ideal oil-water separation effect. The compound oil removing agent is prepared by neutralizing, adsorbing and bridging macromolecular chains with strong positive charges to complete flocculation demulsification. In addition, the polycation copolymer contains amino and hydroxyl, and cannot be mutually dissolved and compounded with the inorganic salt flocculant in any proportion, so that an antagonistic state can be generated, and two medicine adding ports are required in production; the polycation polymer prepared by the method is a homopolymer, and the polycation polymer of the homopolymer and the polyaluminium chloride can be mutually dissolved in any proportion, so long as one medicine adding port is provided.
Specifically, with two kinds of medicaments of polyaluminium chloride and polycation polymer in proportion throw in the tank of dispensing, add water and dilute to the use concentration, adopt the automatic medicine equipment that has in the workshop of adding medicine, add the medicine measurement and throw in air supporting elevator pump entry negative pressure suction pump in, through the rotation of centrifuge impeller, make medicament and oily waste water intensive mixing.
In some specific examples, the conventional treatment scheme for oily wastewater is as follows: the oily wastewater is discharged after sequentially passing through an oil separation tank, an air floatation tank and a biochemical aeration tank, polyferric chloride is added as a flocculating agent before air floatation, the polyferric chloride flocculates suspended matters in the oily wastewater, and the treated oily wastewater cannot reach the national oily wastewater discharge standard (less than or equal to 30 mg/L). In order to save cost and ensure that the discharged oily wastewater reaches the national standard under the condition of not changing the existing treatment device, the application also provides an oil removing process aiming at the existing treatment device, which comprises the following steps: the method comprises the following steps of treating oily wastewater by an oil separation tank, a first air flotation tank and a biochemical aeration tank in sequence and then discharging the oily wastewater, arranging a first dosing device at the first air flotation tank, and adding a compound degreasing agent into the first air flotation tank by the first dosing device, wherein the compound degreasing agent is the compound degreasing agent. Furthermore, the dosage of the compound oil removing agent is 40 mg/L-120 mg/L.
Specifically, a second air flotation tank is further arranged in front of the first air flotation tank, a second dosing device is arranged at the second air flotation tank, and the compound degreasing agent is added into the second air flotation tank through the second dosing device. Furthermore, the oil particles in the oily wastewater from the oil separation tank of the oil refinery have a smaller dielectric constant than water and therefore have negative charges. The surface activity of oil refining byproducts such as naphthenic acid, long-chain condensed ring aromatic acid and the like is dissolved in water, and the oil refining byproducts and oil particles are combined into a stable oil-in-water emulsion, which brings great difficulty to oil-water separation. Generally, the oil concentration in the oily wastewater discharged from an oil separation tank of an oil refinery is 100-150 mg/L, while the oil concentration in the oily wastewater discharged by national regulations cannot be higher than 30 mg/L. Adding 20% of the measured compound degreasing agent into a second air flotation tank, performing pretreatment, then adding 80% of the measured compound degreasing agent into the first air flotation tank, reducing the oil content of the oily wastewater to be less than or equal to 30mg of oil/L to reach the oil refining wastewater discharge standard through two-stage air flotation, reducing the oil content of the oily wastewater to be 6.8mg/L at the lowest time, removing suspended matters in water to reach the standard, basically removing water-soluble substances, discharging colorless and transparent water, and controlling the medicament cost to be 0.6 yuan/T of water.
To demonstrate the technical solution of the present application, the present application provides the following examples
Preparatory example 1
Fully mixing dimethylamine and liquid alkali in an equimolar manner, cooling to obtain a first mixed solution, dropwise adding chloropropene at 10 ℃ into the first mixed solution, reacting part of the first mixed solution with chloropropene to form an intermediate system, and fully adding alkali into the intermediate system for purification reaction to obtain dimethyldiallylamine chloride; and (2) carrying out polymerization reaction on the dimethyldiallylamine chloride under the action of an azo combination initiator, wherein the temperature of the polymerization reaction is 60 ℃, and continuously carrying out temperature compensation in a polymerization reaction system in the polymerization reaction process, so that the temperature of the reaction system is maintained at 60 ℃, and preparing the high-molecular-weight polycation high-molecular homopolymer.
And mutually dissolving the polyaluminium chloride and the prepared high-molecular-weight polycation polymer homopolymer according to the weight ratio of 3:1 to form the compound degreasing agent.
Preparatory example 2
Fully mixing dimethylamine and liquid alkali in an equimolar manner, cooling to obtain a first mixed solution, dropwise adding chloropropene at 30 ℃ into the first mixed solution, reacting part of the first mixed solution with chloropropene to form an intermediate system, and fully adding alkali into the intermediate system for purification reaction to obtain dimethyldiallylamine chloride; and (3) carrying out polymerization reaction on the dimethyldiallylamine chloride under the action of an azo combination initiator, wherein the temperature of the polymerization reaction is 85 ℃, and preparing the polycation high-molecular homopolymer with medium molecular weight.
And mutually dissolving the polyaluminium chloride and the prepared polycation polymer homopolymer with the medium molecular weight according to the weight ratio of 5:1 to form the compound degreasing agent.
Preparatory example 3
Fully mixing dimethylamine and liquid alkali in an equimolar manner, cooling to obtain a first mixed solution, dropwise adding chloropropene at 45 ℃ into the first mixed solution, reacting part of the first mixed solution with chloropropene to form an intermediate system, and fully adding alkali into the intermediate system for purification reaction to obtain dimethyldiallylamine chloride; and (3) carrying out polymerization reaction on the dimethyldiallylamine chloride under the action of an azo combination initiator, wherein the polymerization reaction temperature is 100 ℃, and preparing the polycation high-molecular homopolymer with medium molecular weight.
And mutually dissolving the polyaluminium chloride and the prepared polycation polymer homopolymer with the medium molecular weight according to the weight ratio of 3:1 to form the compound degreasing agent.
Example 1
Selecting oily wastewater with the oil content of 150mg/L discharged from an oil refinery in Daqing city as a sample for treatment, firstly, enabling the oily wastewater to pass through an oil separation tank, adding polyferric chloride before entering a first air flotation tank, and flocculating suspended matters in the oily wastewater; secondly, enabling the oily wastewater to enter a first flotation tank, adding the compound degreasing agent prepared in the preparation example 2 into the first flotation tank through a first dosing device according to the concentration of 120mg/L, and fully reacting the oily wastewater; and finally, the oily wastewater enters a biochemical aeration tank for treatment and then is discharged. Through detection, the oil content of the oily wastewater treated by the steps is 30 mg/L.
Example 2
Selecting oily wastewater with the oil content of 150mg/L discharged from an oil refinery in Daqing city as a sample for treatment, firstly enabling the oily wastewater to pass through an oil separation tank, adding polyferric chloride before entering a second air floatation tank, flocculating suspended matters in the oily wastewater, adding the compound degreasing agent of preparation example 2 into the second air floatation tank through a second medicine adding device according to the concentration of 24mg/L, and fully reacting the oily wastewater; secondly, enabling the oily wastewater to enter a first flotation tank, adding the compound degreasing agent prepared in the preparation example 2 into the first flotation tank through a first dosing device according to the concentration of 96mg/L, and fully reacting the oily wastewater; and finally, the oily wastewater enters a biochemical aeration tank for treatment and then is discharged. Through detection, the oil content of the oily wastewater treated by the steps is 10 mg/L.
Example 3
Selecting oily wastewater with the oil content of 150mg/L discharged from an oil refinery in Daqing city as a sample for treatment, firstly enabling the oily wastewater to pass through an oil separation tank, adding the compound degreasing agent of preparation example 2 into a second air floatation tank through a second medicine adding device according to the concentration of 24mg/L, fully reacting the oily wastewater, adding polyferric chloride before entering a first air floatation tank, and flocculating suspended matters in the oily wastewater; secondly, enabling the oily wastewater to enter a first flotation tank, adding the compound degreasing agent prepared in the preparation example 2 into the first flotation tank through a first dosing device according to the concentration of 96mg/L, and fully reacting the oily wastewater; and finally, the oily wastewater enters a biochemical aeration tank for treatment and then is discharged. Through detection, the oil content of the oily wastewater treated by the steps is 10 mg/L.
In summary, the application provides a preparation method of a polycation polymer, the polycation polymer prepared by the method and polyaluminium chloride can be mutually soluble in any weight fraction ratio, because the polycation polymer is a homopolymer and both belong to cationic type, and the polycation polymer and the cationic type are compounded into a novel oil removal agent, the oil-in-water emulsion oil can be damaged due to strong electric neutralization performance, oil droplets can quickly float upwards, and therefore an ideal oil-water separation effect can be achieved.
Although the description is given in terms of embodiments, not every embodiment includes only a single embodiment, and such description is for clarity only, and those skilled in the art will recognize that the embodiments described herein may be combined as a whole to form other embodiments as would be understood by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing polycation high polymer is characterized by comprising the following steps:
s1, mixing dimethylamine and caustic soda liquid in equal molar ratio, and cooling to obtain a first mixed solution;
s2, adding chloropropene dropwise into the first mixed solution in the step S1, and fully reacting to obtain dimethyl diallyl ammonium chloride;
s3, carrying out polymerization reaction on the dimethyl diallyl ammonium chloride in the step S2 under the action of a redox initiator to prepare the polycation polymer.
2. The method for producing a polycationic polymer according to claim 1, wherein in step S2, the dropping temperature of chloropropene is not more than 45 ℃, preferably 10 ℃ to 45 ℃.
3. The method of claim 1, wherein in step S2, before the reaction is completed, a part of the first mixed solution is reacted with chloropropene to form an intermediate system, and a liquid alkali is added to the intermediate system.
4. The method for producing a polycationic polymer according to claim 1, wherein in step S3, said redox initiator is an azo initiator.
5. The method for producing a polycationic polymer according to claim 1, wherein in step S3, the polymerization temperature is 50 to 70 ℃ to obtain a high molecular weight polycationic polymer; the temperature of the polymerization reaction is 75-90 ℃, and polycation polymer with medium molecular weight is obtained; the temperature of the polymerization reaction is 95-120 ℃, and the low molecular weight polycation polymer is obtained.
6. A compound degreasing agent, which is characterized by consisting of polyaluminium chloride and a polycation polymer, wherein the polycation polymer is prepared by the preparation method of the polycation polymer according to any one of claims 1 to 5.
7. The compound degreasing agent as claimed in claim 6, wherein the weight fraction ratio of the polyaluminum chloride to the polycationic polymer is 3: 1-20: 1; preferably, the weight fraction ratio of the polyaluminium chloride to the polycationic polymer is 4: 1-8: 1.
8. An oil removing process is characterized by comprising the following steps: the oily wastewater is discharged after being sequentially treated by an oil separating tank, a first air flotation tank and a biochemical aeration tank, a first chemical adding device is arranged at the first air flotation tank, a compound degreasing agent is added into the first air flotation tank through the first chemical adding device,
the compound oil remover is the compound oil remover in claim 7.
9. The oil removing process according to claim 8, wherein a second flotation tank is further arranged in front of the first flotation tank, a second dosing device is arranged at the second flotation tank, and the compound oil removing agent is added into the second flotation tank through the second dosing device.
10. The oil removing process according to claim 8, wherein the dosage of the compound oil removing agent is 40mg/L to 120 mg/L.
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| CN101323473A (en) * | 2007-06-15 | 2008-12-17 | 南京理工大学 | Polyaluminium chloride e-poly-dimethyl-diallyl-ammonium chloride composite flocculent, preparation and use method thereof |
| CN101269903A (en) * | 2008-04-25 | 2008-09-24 | 北京世纪华扬能源科技有限公司 | Further advanced treatment technique and apparatus for sewage water of oil refining |
| CN101591110A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | A kind of oil refining sewage treatment technology |
| CN101704571A (en) * | 2009-11-16 | 2010-05-12 | 常州友邦净水材料有限公司 | Preparation method and application of efficient composite coagulant |
| CN101870544A (en) * | 2010-07-16 | 2010-10-27 | 大庆市新中瑞环保有限公司 | Method for treating petroleum refining waste water |
| CN102260025A (en) * | 2011-06-24 | 2011-11-30 | 上海亚同环保实业有限公司 | Biochemical pretreatment process of oily wastewater |
| CN104230055A (en) * | 2014-09-19 | 2014-12-24 | 陕西华陆化工环保有限公司 | Refinery wastewater treatment method |
| CN106986959A (en) * | 2017-03-29 | 2017-07-28 | 中国海洋石油总公司 | The preparation method of flocculant for sewage treatment PDDA |
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