CN113121001A - Cross-linked modified water clarifier for oilfield sewage treatment and preparation method and application thereof - Google Patents
Cross-linked modified water clarifier for oilfield sewage treatment and preparation method and application thereof Download PDFInfo
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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Abstract
The invention provides a crosslinking modified water cleaning agent for oilfield sewage treatment and a preparation method and application thereof, wherein polyethylene polyamine, 1, 6-hexanediamine, dodecahexadecyl dimethyl tertiary amine and water are mixed and placed at 25-40 ℃ to be stirred and react for 0.1-0.3h, then epoxy chloropropane is dripped into a reaction container, and the reaction is continued for 1-5h after the dripping is finished; continuously heating to 40-55 ℃, dropwise adding a cross-linking agent aqueous solution into the reaction vessel, and continuously reacting for 0.5-3h after dropwise adding is finished; and continuously heating to 65-80 ℃, and continuously reacting for 2-5h at the temperature to obtain the crosslinking modified water cleaning agent for the oilfield sewage treatment. The water purifier not only has the water purifying function, but also has the flotation function, is very suitable for the treatment of oil field sewage, and has the characteristics of small dosage, large water purifying range and the like.
Description
Technical Field
The invention relates to the technical field of oil-gas-water treatment, in particular to a cross-linking modified water clarifier for oilfield sewage treatment and a preparation method and application thereof.
Background
And the comprehensive water content of the produced liquid gradually rises along with the offshore oil field exploitation in the middle and later periods, the water yield gradually rises under the condition of ensuring the stable oil yield and the yield, and the treatment capacity of the treatment facility is close to saturation. The yield of crude oil in offshore oil fields is increased, and the discharge amount of water production and oil-containing pollutants is increased rapidly. According to statistics, the total amount of the sewage produced in 2018 exceeds 1.5 hundred million. The problems of short sewage treatment time, different characteristics, large treatment capacity and the like of the offshore oil field are solved, and the problem puzzling the offshore oil field production to be solved urgently is solved. China general offshore oil companies have always paid attention to the protection of the marine environment and the reasonable development of marine resources, and in our marine oil exploitation process, the oil content of discharged seawater is strictly controlled, so that the qualified treatment of oil field sewage is ensured.
Oilfield wastewater treatment is one of the important contents in offshore oilfield production. Crude oil recovery and treatment is a continuous, uninterrupted process, limited by the specificity of offshore operations, and oily wastewater from oil production and treatment processes must be qualified and utilized within a specified time and space. If the oily sewage can not be effectively treated in time, the result is that the production is stopped, the production is limited to strive for time to carry out emergency treatment, or the marine environment is polluted due to unqualified discharge, and the method is unacceptable no matter normal petroleum production is influenced, or the blue national soil is damaged. Therefore, the water purifier for oilfield sewage treatment is systematically researched to improve the water purifying capacity, and has important practical significance.
At present, the water purifiers at home and abroad mainly comprise:
(1) polyacrylamides: the water clarifier is widely applied to oil fields and has good effect, is composed of acrylamide and other groups, and has excellent water solubility, thickening property, flocculating property, chemical reaction activity and product diversity. Since the 50 s of the last century, research and development related to the production of industrial products, such as hydrosols, powders, emulsions (water-in-oil emulsions), water-dispersed (also called water-in-water emulsions), etc., have been actively conducted. The polymerization method has also been developed from the initial aqueous solution polymerization to the inverse emulsion polymerization, the inverse microemulsion polymerization, and the aqueous dispersion polymerization.
(2) Poly (meth) acrylates: the composite material has a cross-linked network structure, can selectively absorb oil substances dissolved or mixed in water, and is particularly suitable for recovery of floating oil on water surface and separation and purification treatment of oily sewage. When oil is absorbed, the lipophilic chain segment in the molecule and the oil molecule are subjected to solvation to expand the oil molecule, when the crosslinking degree is proper, the resin is only swelled and not dissolved, and the oil is wrapped in a macromolecular network structure to achieve the purpose of oil absorption. The water clarifier has the characteristics of high oil absorption, good oil-water selectivity, strong oil retention, good thermal stability, small density and the like, is widely concerned by people, and is a water clarifier with great development prospect.
(3) Cationic copolymers: the compound is a linear high molecular compound with wide application, and has the advantages of high positive charge density, good water solubility, easy control of relative molecular mass, high efficiency, no toxicity and the like. In addition, the positive charge groups contained in the flocculant can perform electric neutralization on the negative charge organic colloid in water and have excellent bridging coagulation function of macromolecules, so that colloidal particles are promoted to aggregate into massive floccules which are separated from the suspension, and compared with nonionic and anionic polyacrylamide, the flocculant has more obvious flocculation effect and less dosage. Therefore, the method is suitable for treating the wastewater with higher organic colloid content in industries such as oil fields, dyeing, paper making, food, metallurgy, mineral separation, coal dust, aquatic product processing, fermentation and the like.
(4) Dithiocarbamates (DTC) type: the oil remover is a compound generated by the reaction of organic primary amine or secondary amine and carbon disulfide under the alkaline condition, is a novel oil remover developed in the United states in the 90 s of the 20 th century, has high oil removing speed and good effect, and has the performances of sterilization, corrosion inhibition and scale prevention.
(5) Polyethers: the polymer is widely used in crude oil demulsification and oily sewage treatment, and the main products at present are polyoxyethylene and polyoxypropylene block or random copolymers, which are nonionic surfactants with the molecular weight of 1000 to millions, and the demulsification effect tends to increase along with the increase of the molecular weight.
(6) Natural high molecular compounds: the esterified substance of amylose, dextrin, sucrose and the like after being treated by organic acid has certain water purification effect.
However, the above water purifiers can not meet the requirements of oil-containing sewage treatment of offshore oil fields:
(1) the polyacrylamide and cationic copolymer water purifiers have certain effect on oil-containing sewage treatment of oil fields under the condition of higher dosage, but the water purifiers of the type have poor water purification effect under the condition of lower dosage. The higher dosage of the water clarifier can generate a large amount of floccules, which causes difficult subsequent treatment.
(2) The poly (methyl) acrylate and Dithiocarbamate (DTC) water clarifier has good treatment effect on oil field oily sewage with the oil content of less than 1000mg/L, and generally has poor treatment effect on oil field oily sewage with the oil content of more than 1000 mg/L.
(3) The polyether water clarifier is generally matched with a crude oil demulsifier to treat crude oil, and has poor treatment effect on oily sewage in an oil field, particularly on oily sewage in the oil field with the oil content of more than 1000 mg/L.
(4) The natural high molecular compound water clarifier is generally used together with inorganic salt, has poor treatment effect on oily sewage of an oil field when being used alone, and can breed a large amount of bacteria and influence the use of the water clarifier because the natural high molecular compound takes vegetable gum and starch as main raw materials.
Disclosure of Invention
The invention overcomes the defects in the prior art, and the problems that the water yield and the discharge amount of oil-containing pollutants rapidly rise after the offshore oil field is lifted and the oil content of the treated produced water exceeds the standard cannot be better met by the existing water purifying agent. The preparation method has simple process, easy control of the reaction process, safety, reliability, environmental protection and stronger universal applicability.
The purpose of the invention is realized by the following technical scheme.
A crosslinking modified water clarifier for oilfield sewage treatment and a preparation method thereof are carried out according to the following steps:
step 1, mixing polyethylene polyamine, 1, 6-hexamethylene diamine, dodecahexadecyl dimethyl tertiary amine and water, placing the mixture at a temperature of between 25 and 40 ℃, stirring the mixture for reaction for 0.1 to 0.3 hour, dropwise adding epoxy chloropropane into the reaction container, and continuing the reaction for 1 to 5 hours after the dropwise adding is finished, wherein the molar ratio of the polyethylene polyamine to the 1, 6-hexamethylene diamine to the dodecahexadecyl dimethyl tertiary amine is (8-10) to (12-15) to (6-9), the adding amount of the water is 25 to 30 times of the mass of the polyethylene polyamine, and the molar ratio of the epoxy chloropropane to the 1, 6-hexamethylene diamine is (9-12) to 1;
and 2, after the reaction in the step 1 is finished, continuously heating to 40-55 ℃, dropwise adding a cross-linking agent aqueous solution into the reaction container, and continuously reacting for 0.5-3h after dropwise adding is finished, wherein the mass ratio of the cross-linking agent to the 1, 6-hexamethylene diamine in the cross-linking agent aqueous solution is (2-4):1, and the mass ratio of the cross-linking agent to water is 1: (1-4);
and 3, after the reaction in the step 2 is finished, continuously heating to 65-80 ℃, and continuously reacting for 2-5 hours at the temperature to obtain the crosslinking modified water clarifier for the oilfield sewage treatment.
In the step 1, dodecyl dimethyl tertiary amine or tetradecyl dimethyl tertiary amine is adopted as the dodecyl dimethyl tertiary amine, the molar ratio of polyethylene polyamine, 1, 6-hexamethylene diamine and long-chain alkyl dimethyl tertiary amine is 9:14 (7-8), the adding amount of water is 26-27 times of the mass of polyethylene polyamine, the mixture is placed at 30-35 ℃ for reaction for 0.2h, the molar ratio of epoxy chloropropane to 1, 6-hexamethylene diamine is (10-11):1, the dropping speed of epoxy chloropropane is 3-5 drops/s, and after the dropping is finished, the mixture is placed at 30-35 ℃ for continuous reaction for 2-4 h.
In the step 2, the cross-linking agent adopts ethylenediamine or diethylenetriamine, the mass ratio of the cross-linking agent to 1, 6-hexanediamine in the cross-linking agent aqueous solution is 3:1, and the mass ratio of the cross-linking agent to water is 1: (2-3), the dropping rate of the cross-linking agent aqueous solution is 3-5 drops/s, and after the dropping is finished, the reaction is continued for 1-2 hours at the temperature of 40-55 ℃.
And in the step 3, continuously heating to 70-75 ℃, and continuously reacting for 3-4h at the temperature to obtain the cross-linked modified water clarifier for treating the oilfield sewage.
The oil removal rate of the obtained crosslinking modified water clarifier is 90-97% when the crosslinking modified water clarifier is used for treating oil field oily sewage with the oil content of 200-2500 mg/L.
The invention has the beneficial effects that: the crosslinking modified water clarifier is a novel polyammonium polymer water clarifier product which is developed aiming at the field working condition and the oily sewage property of offshore oil fields, and is modified by crosslinking, so that the product has the advantages of large water clarifying range, less dosage, large water clarifying amplitude, low self viscosity, medicament timeliness which cannot be achieved by water clarifier products sold in the market, and can be generally suitable for various oil and gas fields, particularly offshore oil and gas fields; the preparation method of the crosslinking modified water clarifier for oilfield sewage treatment has the advantages of simple process, easily controlled reaction process, safety, reliability, environmental protection and strong universal applicability.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Polyethylene polyamines were purchased from the majoram chemical industries of Tianjin.
Example 1
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1, 6-hexamethylene diamine and 3.06g of dodecyl dimethyl tertiary amine, adding 130.0g of distilled water, adding the mixed solution into a reaction kettle with a stirring and reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 26.41g of epoxy chloropropane into the reaction kettle at the speed of 3 drops/s, continuously reacting for 2-4h after all dripping is finished, and keeping the temperature in the reaction kettle controlled at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 5.17g of ethylenediamine with 10.34g of distilled water, slowly dropping the mixed solution into the reaction kettle at the rate of 3 drops/s, continuously reacting for 1-2h after all the mixed solution is dropped, and keeping the temperature in the reaction kettle to be 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Example 2
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1, 6-hexamethylene diamine and 3.06g of dodecyl dimethyl tertiary amine, adding 130.0g of distilled water, adding the mixed solution into a reaction kettle with a stirring and reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 26.41g of epoxy chloropropane into the reaction kettle at the speed of 5 drops/s, continuously reacting for 2-4h after all dripping is finished, and keeping the temperature in the reaction kettle controlled at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 8.87g of diethylenetriamine with 17.74g of distilled water, slowly dripping the mixed solution into the reaction kettle at the speed of 5 drops/s, continuously reacting for 1-2h after all the mixed solution is dripped, and keeping the temperature in the reaction kettle to be controlled at 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Example 3
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1,6 hexamethylene diamine and 3.46g of tetradecyl dimethyl tertiary amine, adding 130.0g of distilled water, adding the mixed solution into a reaction kettle with a stirring and reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 26.41g of epoxy chloropropane into the reaction kettle at the speed of 4 drops/s, continuously reacting for 2-4h after all dripping is finished, and keeping the temperature in the reaction kettle controlled at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 5.17g of ethylenediamine with 10.34g of distilled water, slowly dropping the mixed solution into the reaction kettle at the rate of 4 drops/s, continuously reacting for 1-2h after all the mixed solution is dropped, and keeping the temperature in the reaction kettle to be 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Example 4
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1, 6-hexanediamine and 3.46g of tetradecyl dimethyl tertiary amine, adding 132.5g of distilled water, adding the mixed solution into a reaction kettle with a stirring and reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 26.41g of epoxy chloropropane into the reaction kettle at the speed of 2 drops/s, continuously reacting for 2-4h after all dripping is finished, and keeping the temperature in the reaction kettle controlled at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 8.87g of diethylenetriamine with 17.74g of distilled water, slowly dropping the mixed solution into the reaction kettle at the rate of 2 drops/s, continuously reacting for 1-2h after all the mixed solution is dropped, and keeping the temperature in the reaction kettle to be controlled at 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Example 5
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1, 6-hexamethylene diamine and 3.27g of dodecyl dimethyl tertiary amine, adding 132.5g of distilled water, adding the mixed solution into a reaction kettle with a stirring reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 27.73g of epoxy chloropropane into the reaction kettle at the speed of 6 drops/s, continuously reacting for 2-4h after all the epoxy chloropropane is dripped into the reaction kettle, and keeping the temperature in the reaction kettle at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 5.17g of ethylenediamine with 12.93g of distilled water, slowly dropping the mixed solution into the reaction kettle at the rate of 6 drops/s, continuously reacting for 1-2h after all the mixed solution is dropped, and keeping the temperature in the reaction kettle to be 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Example 6
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1, 6-hexamethylene diamine and 3.27g of dodecyl dimethyl tertiary amine, adding 132.5g of distilled water, adding the mixed solution into a reaction kettle with a stirring reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 27.73g of epoxy chloropropane into the reaction kettle at the speed of 4 drops/s, continuously reacting for 2-4h after all the epoxy chloropropane is dripped into the reaction kettle, and keeping the temperature in the reaction kettle at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 8.87g of diethylenetriamine with 22.18g of distilled water, slowly dropping the mixed solution into the reaction kettle at the rate of 4 drops/s, continuously reacting for 1-2h after all the mixed solution is dropped, and keeping the temperature in the reaction kettle to be controlled at 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Example 7
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1, 6-hexanediamine and 3.71g of tetradecyl dimethyl tertiary amine, adding 132.5g of distilled water, adding the mixed solution into a reaction kettle with a stirring and reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 27.73g of epoxy chloropropane into the reaction kettle at the speed of 5 drops/s, continuously reacting for 2-4h after all the epoxy chloropropane is dripped into the reaction kettle, and keeping the temperature in the reaction kettle at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 5.17g of ethylenediamine with 12.93g of distilled water, slowly dropping the mixed solution into the reaction kettle at the rate of 5 drops/s, continuously reacting for 1-2h after all the mixed solution is dropped, and keeping the temperature in the reaction kettle to be 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Example 8
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1, 6-hexanediamine and 3.71g of tetradecyl dimethyl tertiary amine, adding 132.5g of distilled water, adding the mixed solution into a reaction kettle with a stirring and reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 27.73g of epoxy chloropropane into the reaction kettle at the speed of 3 drops/s, continuously reacting for 2-4h after all the epoxy chloropropane is dripped into the reaction kettle, and keeping the temperature in the reaction kettle at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 8.87g of diethylenetriamine with 22.18g of distilled water, slowly dripping the mixed solution into the reaction kettle at the speed of 3 drops/s, continuously reacting for 1-2h after all the mixed solution is dripped, and keeping the temperature in the reaction kettle to be controlled at 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Example 9
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1, 6-hexamethylene diamine and 3.49g of dodecyl dimethyl tertiary amine, adding 135.0g of distilled water, adding the mixed solution into a reaction kettle with a stirring and reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 29.05g of epoxy chloropropane into the reaction kettle at the speed of 2 drops/s, continuously reacting for 2-4h after all the epoxy chloropropane is dripped into the reaction kettle, and keeping the temperature in the reaction kettle at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 5.17g of ethylenediamine with 15.51g of distilled water, slowly dropping the mixed solution into the reaction kettle at the rate of 2 drops/s, continuously reacting for 1-2h after all the mixed solution is dropped, and keeping the temperature in the reaction kettle to be 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Example 10
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1, 6-hexamethylene diamine and 3.49g of dodecyl dimethyl tertiary amine, adding 135.0g of distilled water, adding the mixed solution into a reaction kettle with a stirring and reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 29.05g of epoxy chloropropane into the reaction kettle at the speed of 6 drops/s, continuously reacting for 2-4h after all the epoxy chloropropane is dripped into the reaction kettle, and keeping the temperature in the reaction kettle at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 8.87g of diethylenetriamine with 26.61g of distilled water, slowly dropping the mixed solution into the reaction kettle at the rate of 6 drops/s, continuously reacting for 1-2h after all the mixed solution is dropped, and keeping the temperature in the reaction kettle to be 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Example 11
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1, 6-hexanediamine and 3.95g of tetradecyl dimethyl tertiary amine, adding 135.0g of distilled water, adding the mixed solution into a reaction kettle with a stirring and reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 29.05g of epoxy chloropropane into the reaction kettle at the speed of 5 drops/s, continuously reacting for 2-4h after all the epoxy chloropropane is dripped into the reaction kettle, and keeping the temperature in the reaction kettle at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 5.17g of ethylenediamine with 15.51g of distilled water, slowly dropping the mixed solution into the reaction kettle at the rate of 5 drops/s, continuously reacting for 1-2h after all the mixed solution is dropped, and keeping the temperature in the reaction kettle to be 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Example 12
(1) Mixing 5.0g of polyethylene polyamine, 3.33g of 1, 6-hexanediamine and 3.95g of tetradecyl dimethyl tertiary amine, adding 135.0g of distilled water, adding the mixed solution into a reaction kettle with a stirring and reflux condenser, starting a stirrer, opening cooling water of the reflux condenser, heating to 30-35 ℃, and stirring for 0.2 h;
(2) slowly dripping 29.05g of epoxy chloropropane into the reaction kettle at the speed of 4 drops/s, continuously reacting for 2-4h after all the epoxy chloropropane is dripped into the reaction kettle, and keeping the temperature in the reaction kettle at 30-35 ℃ in the whole process;
(3) heating to 45-50 ℃, mixing 8.87g of diethylenetriamine with 26.61g of distilled water, slowly dropping the mixed solution into the reaction kettle at the rate of 4 drops/s, continuously reacting for 1-2h after all the mixed solution is dropped, and keeping the temperature in the reaction kettle to be 45-50 ℃ in the whole process;
(4) heating to 70-75 deg.C, and reacting for 3-4h to obtain the aqua.
Evaluation test one
Experiment raw materials: certain offshore oilfield wastewater (high oil content wastewater, oil content 2460mg/L)
Evaluation criteria: SY/T0530-2011 spectrophotometry for measuring oil content in oil field produced water
SY/T5797-93 & lt & ltmethod for evaluating demulsification usability of oil-in-water emulsion & gt
Experiment temperature: 68 deg.C
The concentration of the medicament: 600mg/L
The evaluation method comprises the following steps: adding 600mg/L of water clarifier into 80mL of sewage at the high oily sewage temperature of 68 ℃, oscillating and mixing uniformly, observing an oil-water interface and water color, and measuring the oil content of the lower-layer sewage after 10 minutes.
The test results were as follows:
TABLE 1 high oil-contaminated water test data
Remarking: water color: a. the-、A、A+-Qing B-、B、B+General C-、C、C+-difference
Interface: a. the-、A、A+-is not substituted by B-、B、B+General C-、C、C+-irregularity
Oil droplet floating speed: slow, normal, fast and fast
Evaluation test two
Experiment raw materials: certain offshore oilfield wastewater (middle oil-containing wastewater, oil content 820mg/L)
Evaluation criteria: SY/T0530-2011 spectrophotometry for measuring oil content in oil field produced water
SY/T5797-93 & lt & ltmethod for evaluating demulsification usability of oil-in-water emulsion & gt
Experiment temperature: 70 deg.C
The concentration of the medicament: 200mg/L
The evaluation method comprises the following steps: and (3) adding 200mg/L of water clarifier into 80mL of sewage at the high oily sewage temperature of 70 ℃, oscillating and uniformly mixing, observing an oil-water interface and water color, and measuring the oil content of the lower-layer sewage after 10 minutes.
The test results were as follows:
oily wastewater test data in Table 2
Remarking: water color: a. the-、A、A+-Qing B-、B、B+General C-、C、C+-difference
Interface: a. the-、A、A+-is not substituted by B-、B、B+General C-、C、C+-irregularity
Oil droplet floating speed: slow, normal, fast and fast
Evaluation test three
Experiment raw materials: certain offshore oilfield wastewater (Low oil content wastewater, oil content 200mg/L)
Evaluation criteria: SY/T0530-2011 spectrophotometry for measuring oil content in oil field produced water
SY/T5797-93 & lt & ltmethod for evaluating demulsification usability of oil-in-water emulsion & gt
Experiment temperature: 65 deg.C
The concentration of the medicament: 50mg/L
The evaluation method comprises the following steps: adding 50mg/L of water clarifier into 80mL of sewage at the temperature of 65 ℃ of the high-oil-content sewage, oscillating and uniformly mixing, observing an oil-water interface and water color, and measuring the oil content of the lower-layer sewage after 10 minutes.
The test results were as follows:
TABLE 3 Low oily wastewater test data
Remarking: water color: a. the-、A、A+-Qing B-、B、B+General C-、C、C+-difference
Interface: a. the-、A、A+-is not substituted by B-、B、B+General C-、C、C+-irregularity
Oil droplet floating speed: slow, normal, fast and fast
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A crosslinking modified water clarifier for oilfield sewage treatment is characterized in that: the method comprises the following steps:
step 1, mixing polyethylene polyamine, 1, 6-hexamethylene diamine, dodecahexadecyl dimethyl tertiary amine and water, placing the mixture at a temperature of between 25 and 40 ℃, stirring the mixture for reaction for 0.1 to 0.3 hour, dropwise adding epoxy chloropropane into the reaction container, and continuing the reaction for 1 to 5 hours after the dropwise adding is finished, wherein the molar ratio of the polyethylene polyamine to the 1, 6-hexamethylene diamine to the dodecahexadecyl dimethyl tertiary amine is (8-10) to (12-15) to (6-9), the adding amount of the water is 25 to 30 times of the mass of the polyethylene polyamine, and the molar ratio of the epoxy chloropropane to the 1, 6-hexamethylene diamine is (9-12) to 1;
and 2, after the reaction in the step 1 is finished, continuously heating to 40-55 ℃, dropwise adding a cross-linking agent aqueous solution into the reaction container, and continuously reacting for 0.5-3h after dropwise adding is finished, wherein the mass ratio of the cross-linking agent to the 1, 6-hexamethylene diamine in the cross-linking agent aqueous solution is (2-4):1, and the mass ratio of the cross-linking agent to water is 1: (1-4);
and 3, after the reaction in the step 2 is finished, continuously heating to 65-80 ℃, and continuously reacting for 2-5 hours at the temperature to obtain the crosslinking modified water clarifier for the oilfield sewage treatment.
2. The crosslinking modified water clarifier of claim 1, which is characterized in that: in the step 1, dodecyl dimethyl tertiary amine or tetradecyl dimethyl tertiary amine is adopted as the dodecyl dimethyl tertiary amine, the molar ratio of polyethylene polyamine, 1, 6-hexamethylene diamine and long-chain alkyl dimethyl tertiary amine is 9:14 (7-8), the adding amount of water is 26-27 times of the mass of polyethylene polyamine, the mixture is placed at 30-35 ℃ for reaction for 0.2h, the molar ratio of epoxy chloropropane to 1, 6-hexamethylene diamine is (10-11):1, the dropping speed of epoxy chloropropane is 3-5 drops/s, and after the dropping is finished, the mixture is placed at 30-35 ℃ for continuous reaction for 2-4 h.
3. The crosslinking modified water clarifier of claim 1, which is characterized in that: in the step 2, the cross-linking agent adopts ethylenediamine or diethylenetriamine, the mass ratio of the cross-linking agent to 1, 6-hexanediamine in the cross-linking agent aqueous solution is 3:1, and the mass ratio of the cross-linking agent to water is 1: (2-3), the dropping rate of the cross-linking agent aqueous solution is 3-5 drops/s, and after the dropping is finished, the reaction is continued for 1-2 hours at the temperature of 40-55 ℃.
4. The crosslinking modified water clarifier of claim 1, which is characterized in that: and in the step 3, continuously heating to 70-75 ℃, and continuously reacting for 3-4h at the temperature to obtain the cross-linked modified water clarifier for treating the oilfield sewage.
5. A preparation method of a crosslinking modified water clarifier for oilfield sewage treatment is characterized by comprising the following steps: the method comprises the following steps:
step 1, mixing polyethylene polyamine, 1, 6-hexamethylene diamine, dodecahexadecyl dimethyl tertiary amine and water, placing the mixture at a temperature of between 25 and 40 ℃, stirring the mixture for reaction for 0.1 to 0.3 hour, dropwise adding epoxy chloropropane into the reaction container, and continuing the reaction for 1 to 5 hours after the dropwise adding is finished, wherein the molar ratio of the polyethylene polyamine to the 1, 6-hexamethylene diamine to the dodecahexadecyl dimethyl tertiary amine is (8-10) to (12-15) to (6-9), the adding amount of the water is 25 to 30 times of the mass of the polyethylene polyamine, and the molar ratio of the epoxy chloropropane to the 1, 6-hexamethylene diamine is (9-12) to 1;
and 2, after the reaction in the step 1 is finished, continuously heating to 40-55 ℃, dropwise adding a cross-linking agent aqueous solution into the reaction container, and continuously reacting for 0.5-3h after dropwise adding is finished, wherein the mass ratio of the cross-linking agent to the 1, 6-hexamethylene diamine in the cross-linking agent aqueous solution is (2-4):1, and the mass ratio of the cross-linking agent to water is 1: (1-4);
and 3, after the reaction in the step 2 is finished, continuously heating to 65-80 ℃, and continuously reacting for 2-5 hours at the temperature to obtain the crosslinking modified water clarifier for the oilfield sewage treatment.
6. The preparation method of the crosslinking modified water clarifier for oilfield sewage treatment according to claim 5, characterized in that: in the step 1, dodecyl dimethyl tertiary amine or tetradecyl dimethyl tertiary amine is adopted as the dodecyl dimethyl tertiary amine, the molar ratio of polyethylene polyamine, 1, 6-hexamethylene diamine and long-chain alkyl dimethyl tertiary amine is 9:14 (7-8), the adding amount of water is 26-27 times of the mass of polyethylene polyamine, the mixture is placed at 30-35 ℃ for reaction for 0.2h, the molar ratio of epoxy chloropropane to 1, 6-hexamethylene diamine is (10-11):1, the dropping speed of epoxy chloropropane is 3-5 drops/s, and after the dropping is finished, the mixture is placed at 30-35 ℃ for continuous reaction for 2-4 h.
7. The preparation method of the crosslinking modified water clarifier for oilfield sewage treatment according to claim 5, characterized in that: in the step 2, the cross-linking agent adopts ethylenediamine or diethylenetriamine, the mass ratio of the cross-linking agent to 1, 6-hexanediamine in the cross-linking agent aqueous solution is 3:1, and the mass ratio of the cross-linking agent to water is 1: (2-3), the dropping rate of the cross-linking agent aqueous solution is 3-5 drops/s, and after the dropping is finished, the reaction is continued for 1-2 hours at the temperature of 40-55 ℃.
8. The preparation method of the crosslinking modified water clarifier for oilfield sewage treatment according to claim 5, characterized in that: and in the step 3, continuously heating to 70-75 ℃, and continuously reacting for 3-4h at the temperature to obtain the cross-linked modified water clarifier for treating the oilfield sewage.
9. The use of the cross-linked modified water-cleaning agent as claimed in any one of claims 1 to 4 for treating oily sewage in oil field.
10. Use according to claim 9, characterized in that: the oil removal rate of the obtained crosslinking modified water clarifier is 90-97% when the crosslinking modified water clarifier is used for treating oil field oily sewage with the oil content of 200-2500 mg/L.
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