CN109929584B - Clay mineral demulsifier, and preparation method, application and recycling method thereof - Google Patents
Clay mineral demulsifier, and preparation method, application and recycling method thereof Download PDFInfo
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Abstract
The invention relates to a novel clay mineral demulsifier, a preparation method thereof, and a demulsification treatment and recycling method for an oil-in-water crude oil emulsion. The demulsifier is prepared by mixing pretreated clay mineral with ferric chloride, sodium citrate, ethylene glycol and polyethylene glycol, ultrasonically dispersing uniformly, then placing the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining, heating the reaction temperature of the reaction kettle to 200-240 ℃, reacting for 20-28 h at a constant temperature, and cooling. The novel clay mineral demulsifier prepared by the invention is used for demulsification and dehydration treatment of oil-in-water type crude oil emulsion, the demulsification efficiency of the water-in-oil type crude oil emulsion is up to more than 99.0 percent, the oil content of the dehydrated crude oil emulsion is lower than 10mg/L, and the secondary water discharge standard is basically reached. Therefore, the invention provides a cheap and efficient method for demulsification and dehydration treatment of the oil-in-water type crude oil emulsion, and has good application prospect.
Description
Technical Field
The invention belongs to the demulsification and dehydration treatment technology of crude oil emulsion in the fields of crude oil exploitation and heavy oil emulsification and viscosity reduction, and particularly relates to a novel clay mineral demulsifier, a preparation method thereof, and a demulsification treatment and recycling method of oil-in-water type emulsion.
Background
Water or steam is used in large quantities in the processes of water/steam flooding extraction of crude oil, emulsification and viscosity reduction of heavy oil, water-based extraction of oil sands, and hydraulic fracturing or steam injection extraction of oil shale. Water treatment processes are becoming one of the most important strategies for enhanced recovery of traditional crude oil and unconventional oil and gas resources. However, a large amount of oil-water emulsion is inevitably generated in the water treatment method and the subsequent gathering and transportation process. The existence of oil-water emulsion, firstly, increases the storage and transportation burden; second, since the oil-water emulsion contains a large amount of inorganic salts, it often causes poisoning of the catalyst, causing severe corrosion of oil pipelines and high-temperature distillation equipment, thereby reducing the life of transportation pipelines and refinery equipment. Therefore, the emulsified crude oil must be subjected to a demulsification dehydration treatment before transporting and refining the oil.
Although the densities of the oil phase and the water phase in the crude oil emulsion are different, the crude oil emulsion is difficult to destroy, and the main reason is that the crude oil contains a large amount of natural surface active substances, such as asphaltene, colloid, paraffin, fatty acid, clay fine particles and the like, which play the role of a natural emulsifier. Among them, asphaltenes and gums are believed to play a major role in the formation of oil and water emulsions. Currently, the structure of asphaltenes is thought to be the core of a single or multiple fused aromatic ring system, with several aliphatic and aromatic rings attached around it. The asphaltene molecule contains polar hydrophilic groups such as hydroxyl, carboxyl, amino, nitro, sulfydryl and the like, and also contains nonpolar oleophilic groups such as alkyl, polycyclic aromatic hydrocarbon and the like, so the asphaltene is a natural surface active substance with amphiphilic property and plays a role of a natural emulsifier in the formation process of the oil-water emulsion. Under the combined action of weak acting forces such as dipole interaction, charge transfer, hydrogen bonds and the like, asphaltene molecules form aggregates with various special structures, under the synergistic action of colloid, clay and other natural surface active substances, the asphaltene aggregates form a firm cortex protection layer with a viscoelastic cross network structure on an oil-water interface, and water drops are mutually isolated by a cortex layer and cannot mutually agglomerate and settle.
The chemical demulsification method is the most widely applied demulsification method in China at present, and mainly changes the interface property of an emulsion system by adding a demulsifier, thereby destroying the stability of oil-water emulsion and achieving the purpose of oil-water separation. The traditional demulsifier plays an important role in the process of oil field development, but still has a plurality of defects which are difficult to overcome, such as serious environmental pollution; the universality of the demulsifier is poor, and the demulsifier is only suitable for specific crude oil emulsion; the manufacturing cost of part of demulsifiers is very expensive, which is not beneficial to large-scale industrial use, etc. In recent years, the crude oil extraction in China enters secondary and tertiary oil extraction stages, the extracted crude oil contains a large amount of surfactants, solid particles and the like, the yield of high-stable extracted liquid is greatly increased, the usage amount of a chemical demulsifier is increased day by day, the demulsification temperature is increased continuously, and the dehydration difficulty is increased day by day. When a large amount of energy is consumed, a large amount of extremely stable and difficultly treated flocculent transition layers appear in the settling tank, and the normal and stable operation of a crude oil dehydration system is seriously influenced. Although many important research progresses at home and abroad currently, under a new situation, the development of a demulsification technology with strong universality (crude oil with different water contents, different pH values, different impurities and different production places), high efficiency, rapidness, economy and practicability is still a long-standing and difficult task.
In recent years, clay minerals (such as attapulgite, montmorillonite, etc.) have attracted attention and been widely used in the fields of petroleum, chemical engineering, medicine, environmental protection, paint, etc. because of their excellent physicochemical properties. According to the invention, based on the special physical and chemical properties of clay minerals, the surface of the clay minerals is modified and decorated, so that the novel clay mineral demulsifier which has the advantages of good demulsification effect, simple process, low cost and repeated use is prepared.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel clay mineral demulsifier, a preparation method thereof and a method for demulsifying and recycling oil-in-water type emulsion.
In order to achieve the purpose, the clay mineral is firstly purified, acidified and aminated and modified in sequence, and then the modified clay mineral, ferric chloride, sodium citrate, ethylene glycol and polyethylene glycol are used as raw materials to carry out solvothermal reaction to prepare a novel clay mineral demulsifier, so that the crude oil-in-water emulsion is subjected to demulsification and dehydration treatment. According to the invention, a small amount of novel clay mineral demulsifier is added to strongly destroy the protective film layer on the interface of the crude oil emulsion, so that the stability of the oil-water emulsion is reduced, oil drops can be rapidly agglomerated by collision after full oscillation, and the oil drops are rapidly separated from a water phase, thereby achieving the purpose of rapid demulsification and dehydration of the oil-water emulsion under the conditions of normal temperature, low temperature and the like. After the demulsification treatment is finished, the demulsifier is recovered, washed and dried, and then can be continuously recycled.
One of the above objects of the present invention is achieved by the following technical solutions:
a preparation method of a novel clay mineral demulsifier comprises the following steps:
(1) sieving the clay mineral, and sequentially performing purification, acidification and amination modification treatment to obtain a modified clay mineral;
(2) mixing the modified clay mineral obtained in the step (1) with ferric chloride, sodium citrate, ethylene glycol and polyethylene glycol according to a ratio, placing the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining after ultrasonic dispersion is uniform, then heating the reaction temperature of the reaction kettle to 200-240 ℃, carrying out constant temperature reaction for 20-28 h at the temperature of 200-240 ℃, and cooling to room temperature after the reaction is finished, thus obtaining the novel clay mineral demulsifier.
Further, according to the technical scheme, the clay mineral in the step (1) is any one or more of attapulgite clay, montmorillonite or bentonite.
Further, in the above technical solution, the acid used in the acidification treatment in step (1) is any one of hydrochloric acid or nitric acid.
Further, in the above technical scheme, the modifier used in the amination modification treatment in the step (1) is an amino coupling agent, and the amino coupling agent is any one of 3-aminopropyltriethoxysilane or dimethyldimethylaminochlorosilane.
Further, according to the technical scheme, the mass ratio of the modified clay mineral in the step (2) to the ferric chloride is 1: 1-2, preferably 1: 1.35; the mass ratio of the modified clay mineral to the sodium citrate is 1: 3-4, preferably 1: 3.6; the mass ratio of the modified clay mineral to the polyethylene glycol is 1: 0.5-2, preferably 1: 1; the dosage ratio of the modified clay mineral to the ethylene glycol is 1 part by mass: 20-60 parts by volume, preferably 1 part by mass: 40 parts by volume, wherein: the mass part and the volume part are as follows: mL was used as a reference.
Further, in the above technical scheme, the reaction temperature in the step (2) is preferably 220 ℃, and the reaction time is preferably 24 h.
The second purpose of the invention is to provide the novel clay mineral demulsifier prepared by the preparation method of the novel clay mineral demulsifier.
The third purpose of the invention is to provide a method for demulsifying the oil-in-water crude oil emulsion by using the novel clay mineral demulsifier prepared by the method, which comprises the following steps:
(1) adjusting the pH value of the crude oil emulsion to 1.0-10.0;
(2) preparing a novel clay mineral demulsifier into a suspension, and fully performing ultrasonic dispersion to obtain a demulsifier dispersion liquid;
(3) and (3) adding the emulsion breaker dispersion liquid obtained in the step (2) into the emulsion liquid obtained in the step (1), uniformly stirring, then shaking for 2-10 min at normal temperature to enable the emulsion breaker and an emulsion interface to fully act, and standing for oil-water separation.
Further, according to the technical scheme, the water content of the crude oil emulsion obtained in the step (1) is 80-99.5%.
Further, in the above technical solution, the pH value of the crude oil emulsion in the step (1) is preferably 5.5.
Further, in the above technical scheme, the normal temperature in the step (3) is a natural room temperature condition in four seasons, no additional cooling or heating treatment is performed, and the normal temperature is generally controlled to be 10-30 ℃, preferably 15-25 ℃.
Further, in the above technical solution, the oscillation time in step (3) is preferably 2 min.
Further, according to the technical scheme, the addition amount of the demulsifier in the step (3) is 1 mg/L-5000 mg/L.
The fourth purpose of the invention is to provide a method for recycling the demulsifier after demulsification treatment, which comprises the following steps:
after the demulsification treatment is finished, the separated oil phase floats on the surface of water, the demulsifier is settled at the bottom of the water, the oil phase and the separated water phase are discharged, the demulsifier is recovered, then a small amount of toluene is used for washing, and the demulsifier is dried and then continuously recycled.
Further, according to the technical scheme, the baking temperature of the demulsifier is 60-80 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the novel clay mineral demulsifier prepared by the invention is used for demulsification and dehydration treatment of oil-in-water type crude oil emulsion, the demulsification efficiency of the oil-in-water type crude oil emulsion is up to more than 99.0 percent, the oil content of dehydrated water is lower than 10mg/L, and the secondary water discharge standard and reinjection standard are basically reached. And the floating oil phase has low water content and is easy for subsequent treatment.
2. The novel clay mineral demulsifier disclosed by the invention is stable in property, and is non-toxic and harmless. The raw materials for preparing the demulsifier are cheap and easy to obtain, and the preparation method is simple and mature. After demulsification, the demulsifier can be recycled by simple sedimentation and washing methods, and has good application prospect in the demulsification and dehydration treatment of crude oil-in-water type emulsion.
3. The crude oil emulsion treated by the method has low temperature dependence. The test is carried out at normal temperature, and the demulsification effect is good at low temperature and high temperature. The demulsification effect is better under the working condition higher than the normal temperature.
4. The method of the invention is adopted to dehydrate the oil-in-water crude oil emulsion, and has high dehydration efficiency and short demulsification time. The emulsion can be broken rapidly in as little as a few minutes. And the longer the standing time is, the better the quality of the removed water is.
5. The method for treating the oil-in-water type emulsion has strong universality and is widely suitable for common oil-in-water type crude oil emulsion and heavy crude oil-in-water type emulsion.
6. The invention can be used for dehydration treatment of high water content oil-water emulsion in petroleum industry, and provides a new approach for demulsification treatment of oil-in-water emulsion.
Drawings
FIG. 1 is a graph comparing the effect of pH on oil content and demulsification efficiency in an aqueous phase in example 4 of the present invention.
FIG. 2 is a graph comparing the effect of different dosages of demulsifier on oil content and demulsification efficiency in the aqueous phase in example 5 of the present invention.
FIG. 3 is a graph comparing the effect of the standing time after demulsification on the oil content and the demulsification efficiency in the aqueous phase in example 6 of the present invention.
FIG. 4 is a graph comparing the effect of demulsification temperature on oil content in the aqueous phase and demulsification efficiency in example 7 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments and accompanying drawings. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The specific demulsification experiment of the invention is tested by referring to a method for evaluating the service performance of an oil-in-water emulsion demulsifier (bottle test method) of standard SY/T5797-93 of the oil and gas industry of the people's republic of China. And quantitatively measuring the oil content of the dehydrated water by referring to the oil and gas standard SY/T5329-2012 recommendation index and analysis method for water quality of clastic rock oil flooding of the people's republic of China.
The oil-in-water crude oil emulsion demulsification method of the following embodiment of the invention adopts attapulgite clay as a demulsifying agent. Generally, the higher the concentration of the aqueous emulsion breaker dispersion, the less water is brought into the emulsion. However, the concentration of the demulsifying agent dispersion liquid is prepared by taking the dispersion degree of the attapulgite clay into consideration. The dosage of the demulsifier can be determined according to the requirements of oil content and dehydrated water index in the emulsion or determined by an demulsifier concentration optimization experiment. Generally, the higher the oil content in an oil-in-water emulsion, the lower the oil content of the dehydrated water, and the greater the amount of demulsifier required. It should be noted that when the attapulgite clay dosage exceeds the optimum use range, the cleanliness of the dehydrated water and the oil content will be affected. The reason is that the attapulgite clay is yellow brown in color and absorbs partial compounds in oil in the demulsification process. After demulsification, excessive attapulgite clay is suspended in the water phase to make the water phase yellow, and the oil content of the dehydrated water is slightly higher than that of the water in the optimal dosage range. When oil and water are layered, the standing time is 5 min-2 h.
The 1kg attapulgite clay demulsifier can treat 15-30 tons of oil-in-water crude oil emulsion.
Example 1
The preparation method of the novel attapulgite clay demulsifier comprises the following steps:
(1) purifying the attapulgite clay: the attapulgite crude ore is crushed and sieved by a 200-mesh sieve. Adding 1kg of attapulgite clay into 50L of water, adding 6g of sodium hexametaphosphate, and mechanically stirring for 2h at 3000 rpm; standing for 2-8 h, taking out the clay mineral at the upper layer by a siphon method, centrifuging at 5000rpm, and freeze-drying. Obtaining the purified attapulgite clay with quartz and other impurities removed.
(2) Acidizing the attapulgite clay: adding 100g of purified attapulgite clay mineral into 500mL of deionized water, ultrasonically scattering for 1h, adding the dispersed suspended matters into a reaction container, adding 1mol/L of dilute hydrochloric acid, reacting for 1h at 60 ℃, centrifuging the attapulgite after the reaction is finished, washing with the deionized water for three times, and freeze-drying to obtain the acidized and modified attapulgite clay.
(3) Amination modification of attapulgite: adding 20g of acidified and modified attapulgite clay into absolute ethyl alcohol, adding 10mL of 3-aminopropyltriethoxysilane, reacting for 2h at 80 ℃, centrifuging, and washing with absolute ethyl alcohol for three times to obtain the aminated and modified attapulgite clay.
(4) Solvent thermal synthesis of the novel clay mineral demulsifier: dissolving 1.35g of ferric chloride in 40ml of ethylene glycol solution, adding 1g of the modified attapulgite clay obtained in the step (3), 3.6g of sodium citrate and 1.0g of polyethylene glycol, stirring for two minutes, ultrasonically dispersing for 10min by using an ultrasonic cleaning instrument, uniformly stirring, transferring the mixture into a hydrothermal synthesis reaction kettle, reacting for 24h at a constant temperature of 220 ℃, taking out a product, centrifuging and washing to obtain the novel attapulgite clay demulsifier.
Example 2
The preparation method of the novel attapulgite clay demulsifier of the embodiment is basically the same as that of embodiment 1, and the differences are only that: step (4), solvent thermal synthesis of the novel clay mineral demulsifier: dissolving 1g of ferric chloride in 20ml of ethylene glycol solution, adding 1g of the modified attapulgite clay obtained in the step (3), 3g of sodium citrate and 0.5g of polyethylene glycol, stirring for two minutes, ultrasonically dispersing for 10min by using an ultrasonic cleaner, uniformly stirring, transferring the mixture into a hydrothermal synthesis reaction kettle, reacting at a constant temperature of 200 ℃ for 28h, taking out the product, centrifuging and washing to obtain the novel attapulgite clay demulsifier.
Example 3
The preparation method of the novel attapulgite clay demulsifier of the embodiment is basically the same as that of embodiment 1, and the differences are only that: step (4), solvent thermal synthesis of the novel clay mineral demulsifier: dissolving 2g of ferric chloride in 60ml of ethylene glycol solution, adding 1g of the modified attapulgite clay obtained in the step (3), 4g of sodium citrate and 2g of polyethylene glycol, stirring for two minutes, ultrasonically dispersing for 10min by using an ultrasonic cleaner, uniformly stirring, transferring the mixture into a hydrothermal synthesis reaction kettle, reacting at constant temperature of 240 ℃ for 20h, taking out the product, centrifuging and washing to obtain the novel attapulgite clay demulsifier.
Example 4
The novel clay demulsifier is used for the demulsification and dehydration treatment of crude oil-in-water type emulsion, and the method comprises the following steps:
40g and 360g of victory island crude oil were placed in plastic containers, respectively. After mixing the oil and water, dispersing for 3min at 28000rpm by a high shear dispersion emulsifier to obtain a uniformly dispersed oil-in-water crude oil emulsion with an oil content of 10%. Before emulsification, the pH of the distilled water is adjusted to 1, 2, 3, 4 and 5 respectively to prepare emulsions with the same concentration and different pH values. A plurality of demulsifying reagent bottles are taken and numbered in sequence.
Ultrasonically dispersing a certain amount of the novel attapulgite clay demulsifier prepared in example 1 by using deionized water, respectively adding the novel attapulgite clay demulsifier into emulsions in a demulsification reagent bottle, violently shaking for 3min, observing a demulsification effect, standing for 2h, and then measuring the oil content in water and calculating the demulsification efficiency by using kerosene as an extraction solvent according to a standard method described in SY/T5329-2012. The demulsification efficiency under different pH conditions when the demulsifier is added at a dosage of 400mg/L is shown in figure 1: the novel clay demulsifier has demulsification efficiency of more than 98% in emulsions with different pH values, wherein the demulsification efficiency is the lowest when the pH value is 4, and the demulsification effect is better when the pH value is under strong acid (pH value is 1) and neutral conditions (pH value is 5). After demulsification, the oil content of the dehydrated water is lower than 10mg/L under the optimal condition, and the oil content reaches the secondary water discharge standard. Thus, the optimal emulsion breaking pH can be selected to be neutral.
Example 5
The novel clay demulsifier is used for the demulsification and dehydration treatment of crude oil-in-water type emulsion, and the method comprises the following steps:
40g and 360g of victory island crude oil were placed in plastic containers, respectively. After mixing the oil and water, dispersing for 3min at 28000rpm by a high shear dispersion emulsifier to obtain a uniformly dispersed oil-in-water crude oil emulsion with an oil content of 10%. Before emulsification, the emulsion pH was adjusted to neutral. A plurality of demulsifying reagent bottles are taken and numbered in sequence.
The novel attapulgite clay demulsifier prepared in example 1 with different dosages is ultrasonically dispersed by deionized water, and is respectively added into emulsion of a demulsification reagent bottle, is violently vibrated for 3min, the demulsification effect is observed, and after standing for 2h, kerosene is adopted as an extraction solvent, the oil content in water is measured, and the demulsification efficiency is calculated according to a standard method described in SY/T5329-2012. The demulsification efficiency with different demulsifier dosages added is shown in figure 2: the novel attapulgite clay demulsifier is added into the emulsion, the oil content of the water phase after demulsification is obviously reduced from-700 mg/L to-10 mg/L, and the demulsification efficiency is obviously increased (from 99.3 percent to 99.9 percent) along with the increase of the dosage. When the dosage of the demulsifier is 400mg/L, the demulsification efficiency basically does not change along with the increase of the dosage. Therefore, the optimal demulsifier dosage of the crude oil-in-water emulsion with water content and the novel attapulgite demulsifier is 400 mg/L.
Example 6
The novel clay demulsifier is used for the demulsification and dehydration treatment of crude oil-in-water type emulsion, and the method comprises the following steps:
40g and 360g of victory island crude oil were placed in plastic containers, respectively. After mixing the oil and water, dispersing for 3min at 28000rpm by a high shear dispersion emulsifier to obtain a uniformly dispersed oil-in-water crude oil emulsion with an oil content of 10%. Before emulsification, the emulsion pH was adjusted to neutral. A plurality of demulsifying reagent bottles are taken and numbered in sequence.
And ultrasonically dispersing novel clay demulsifiers with different dosages by using deionized water, respectively adding the novel clay demulsifiers into emulsions in a demulsification reagent bottle, violently shaking for 3min, observing a demulsification effect, standing for 10min, 20min, 30min, 60min, 90min, 120min and 150min, and measuring the oil content in water and calculating the demulsification efficiency by using kerosene as an extraction solvent according to the standard method of SY/T5329-2012. The demulsification efficiency with different demulsifier dosages added is shown in figure 3: under the conditions of optimal demulsifying agent amount and pH, after demulsification, the oil content of the dehydrated water is obviously reduced along with the change of standing time, and when the standing time is 10min, the oil content in the water is up to 120 mg/L; when the standing time is prolonged to 120min, the oil content in the water is reduced to 10mg/L, the standing time is continuously prolonged, the oil content is slightly reduced, but the influence on the demulsification efficiency is small. The optimal standing time for dewatering is 120min after the novel attapulgite clay demulsifier demulsifies.
Example 7
The novel clay demulsifier is used for the demulsification and dehydration treatment of crude oil-in-water type emulsion, and the method comprises the following steps:
40g and 360g of victory island crude oil were placed in plastic containers, respectively. After mixing the oil and water, dispersing for 3min at 28000rpm by a high shear dispersion emulsifier to obtain a uniformly dispersed oil-in-water crude oil emulsion with an oil content of 10%. Before emulsification, the emulsion pH was adjusted to neutral. A plurality of demulsifying reagent bottles are taken and numbered in sequence.
The novel attapulgite clay demulsifier prepared in example 1 with the same dosage is ultrasonically dispersed by deionized water, and is respectively added into the emulsion of a demulsification reagent bottle, and is violently vibrated for 3min, the demulsification effect is observed, and the standing time is 120 min. Demulsification experiments were performed at 10 deg.C, 25 deg.C and 60 deg.C, respectively. Referring to the standard method described in SY/T5329-2012, kerosene was used as the extraction solvent and the oil content in the water was determined and the demulsification efficiency was calculated. The demulsification efficiency with different demulsifier doses was shown in figure 4: demulsification is carried out at 10 ℃, 25 ℃ and 60 ℃, the oil content in water is respectively 21.61mg/L, 12.93mg/L and 4.25mg/L, although the oil content in water is slightly reduced along with the temperature change, the demulsification efficiency is basically not greatly influenced, and the demulsification is carried out at the normal temperature (25 ℃) to the optimal demulsification temperature under the condition of reducing energy consumption.
Claims (9)
1. A preparation method of a clay mineral demulsifier is characterized by comprising the following steps: the method comprises the following steps:
(1) sieving the clay mineral, and sequentially performing purification, acidification and amination modification treatment to obtain a modified clay mineral;
(2) mixing the modified clay mineral obtained in the step (1) with ferric chloride, sodium citrate, ethylene glycol and polyethylene glycol according to a ratio, placing the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining after ultrasonic dispersion is uniform, then heating the reaction temperature of the reaction kettle to 200-240 ℃, carrying out constant temperature reaction for 20-28 h at the temperature of 200-240 ℃, and cooling to room temperature after the reaction is finished to obtain the clay mineral demulsifier; wherein: the mass ratio of the modified clay mineral to the ferric chloride is 1: 1-2; the mass ratio of the modified clay mineral to the sodium citrate is 1: 3-4; the mass ratio of the modified clay mineral to the polyethylene glycol is 1: 0.5 to 2; the dosage ratio of the modified clay mineral to the ethylene glycol is 1 part by mass: 20-60 parts by volume, wherein: the mass part and the volume part are as follows: mL was used as a reference.
2. The preparation method of the clay mineral demulsifier according to claim 1, wherein the clay mineral demulsifier comprises: the clay mineral in the step (1) is any one or more of attapulgite clay, montmorillonite or bentonite.
3. The preparation method of the clay mineral demulsifier according to claim 1, wherein the clay mineral demulsifier comprises: the acid adopted in the acidification treatment in the step (1) is any one of hydrochloric acid or nitric acid.
4. The preparation method of the clay mineral demulsifier according to claim 1, wherein the clay mineral demulsifier comprises: the modifier adopted in the amination modification treatment in the step (1) is an amino coupling agent, and the amino coupling agent is any one of 3-aminopropyl triethoxysilane or dimethyl dimethylamino chlorosilane.
5. The clay mineral demulsifier prepared by the method for preparing the clay mineral demulsifier of any one of claims 1 to 4.
6. The method for demulsifying an oil-in-water crude oil emulsion by using the clay mineral demulsifier prepared by the method of any one of claims 1 to 4 is characterized by comprising the following steps: the method comprises the following steps:
(1) adjusting the pH value of the crude oil emulsion to 1.0-10.0;
(2) preparing a clay mineral demulsifier into a suspension, and fully performing ultrasonic dispersion to obtain a demulsifier dispersion liquid;
(3) and (3) adding the emulsion breaker dispersion liquid obtained in the step (2) into the emulsion liquid obtained in the step (1), uniformly stirring, then shaking for 2-10 min at normal temperature to enable the emulsion breaker and an emulsion interface to fully act, and standing for oil-water separation.
7. The method for demulsifying an oil-in-water crude oil emulsion by using the clay mineral demulsifier according to claim 6, wherein the method comprises the following steps: the water content of the crude oil emulsion obtained in the step (1) is 80-99.5%.
8. The method for demulsifying an oil-in-water crude oil emulsion by using the clay mineral demulsifier according to claim 6, wherein the method comprises the following steps: the addition amount of the demulsifier in the step (3) is 1 mg/L-5000 mg/L.
9. The method for recycling the clay mineral demulsifier after demulsification treatment of any one of claims 6 to 8, which is characterized by comprising the following steps: the method comprises the following steps: after the demulsification treatment is finished, the separated oil phase floats on the surface of water, the demulsifier is settled at the bottom of the water, the oil phase and the separated water phase are discharged, the demulsifier is recovered, then a small amount of toluene is used for washing, and the demulsifier is dried and then continuously recycled.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103131462A (en) * | 2013-02-28 | 2013-06-05 | 滨州学院 | Method for demulsifying crude oil produced liquid through using SD-3 demulsifier |
| CN106630246A (en) * | 2015-11-02 | 2017-05-10 | 张家港格林台科环保设备有限公司 | Waste emulsion demulsification processing method |
| CN108002614A (en) * | 2018-01-10 | 2018-05-08 | 东莞市盛源石油化工有限公司 | A kind of oil-containing sewage treatment technique |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103131462A (en) * | 2013-02-28 | 2013-06-05 | 滨州学院 | Method for demulsifying crude oil produced liquid through using SD-3 demulsifier |
| CN106630246A (en) * | 2015-11-02 | 2017-05-10 | 张家港格林台科环保设备有限公司 | Waste emulsion demulsification processing method |
| CN108002614A (en) * | 2018-01-10 | 2018-05-08 | 东莞市盛源石油化工有限公司 | A kind of oil-containing sewage treatment technique |
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