CN104877706A - Demulsification method of oil-in-water type crude oil emulsion - Google Patents
Demulsification method of oil-in-water type crude oil emulsion Download PDFInfo
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- CN104877706A CN104877706A CN201410068677.9A CN201410068677A CN104877706A CN 104877706 A CN104877706 A CN 104877706A CN 201410068677 A CN201410068677 A CN 201410068677A CN 104877706 A CN104877706 A CN 104877706A
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Abstract
The invention discloses a demulsification method of an oil-in-water type crude oil emulsion. The method employs oxidized graphene as de-emulsifier to carry out dehydration treatment to the oil-in-water type crude oil emulsion at the room temperature. The de-oiling rate of the oil-in-water emulsion is more than 96%. The demulsification method of the invention can be applied to the dehydration treatment of oil-water emulsion with high water content in the petroleum industry.
Description
Technical field
The invention belongs to the Oil extraction particularly treatment technology of Produced Liquid in tertiary oil recovery, be specifically related to the breaking method of oil-in-water emulsion in rapid damage crude oil under a kind of normal temperature.
Background technology
In the process of the process for processing of crude oil, all face this important step, namely the processed of water-oil emulsion, is also called breakdown of emulsion.In the process of Oil extraction, water-oil emulsion, after the mechanically mixing of oil nozzle and gathering line, very easily forms stable milk sap.Crude oil emulsion greatly can increase accumulating burden and reduce the life-span of pipe laying.In addition, in the process of crude refining, owing to containing a large amount of inorganic salt in water, usually can cause the heavy corrosion of the poisoning of catalyzer and distillation plant.Therefore, crude oil must carry out breaking emulsion and dewatering process before entering refining.
Water-oil emulsion why can stable existence, mainly because crude oil studies on asphaltene, colloid and organic acid isopolarity material define the protective membrane of firmly crossover network structure at water-oil interface.The existence of protective membrane, makes cannot carry out gathering layering between drop, and the key therefore destroying water-oil emulsion stability is to destroy water-oil interface protective membrane.
In the process of oil-gas field development, primary oil recovery and secondary oil recovery Produced Liquid are mainly Water in Oil emulsion, adopt the mode of electricity-chemical combined breakdown of emulsion to realize oily water separation.At present, each elephant of China enters the high water-cut development stage in succession.Tertiary oil recovery technology is widely used, and oil field mining liquid mostly is the compound milk sap of oil-in-water emulsion or complexity.This Produced Liquid contains a large amount of water and causes the inefficacy of ordinary method.Specifically, this milk sap enters destructible electric field in electrical dehydrator, causes tripping operation, and continuous seepage is difficult to carry out smoothly.Therefore, the breaking method developing efficient fast processing oil-in-water emulsion is badly in need of.
Summary of the invention
The object of this invention is to provide and a kind ofly to Produced Liquid in Oil extraction particularly tertiary oil recovery, there is the breaking method of good demulsification.
A breaking method for oil-in-water-type crude oil emulsion, is characterized in that the method adopts graphene oxide as emulsion splitter, carries out processed at normal temperatures to oil-in-water-type crude oil emulsion.
The present invention adopts a small amount of graphene oxide can destroy the protective membrane of water-oil interface consumingly, thus the stability of water-oil emulsion is declined, through fully shaking; assembled rapidly by collision between oil droplet; with water sharp separation, and be suspended in the water surface, thus achieve the object of oily water separation.
A breaking method for oil-in-water-type crude oil emulsion, is characterized in that the method comprises the following steps:
A, graphite oxide is mixed with suspension, and abundant ultrasonic disperse, obtain graphene oxide emulsion splitter;
B, join in oil-in-water-type crude oil emulsion by graphene oxide dispersion, add-on is 1mg/L ~ 200mg/L, stirs, and carries out oily water separation after leaving standstill.
1 kilogram of graphene oxide emulsion splitter of the present invention can process oil-in-water-type crude oil emulsion 15-30 ton.
Water content in oil-in-water-type crude oil emulsion of the present invention is 80-99.5%.
We test with reference to People's Republic of China (PRC) oil and gas industry standard SY/T 5797-93 " demulsifier for oil in water emulsion use properties assessment method (bottle examination method) " in the experiment of concrete breakdown of emulsion.The oleaginousness of water is gone out with reference to People's Republic of China (PRC) oil and gas standard SY/T5329-2012 " petroclastic rock oil injection water quality fertilizer index and analytical procedure " quantitative assay.
Adopt graphene oxide as emulsion splitter in oil-in-water-type crude oil emulsion breaking method of the present invention.Generally, water-soluble demulsifier dispersion liquid concentration is higher, and the water yield of bringing in milk sap is fewer.But, the degree of scatter of graphene oxide will be taken into account during preparation emulsion splitter dispersion liquid concentration.The consumption of emulsion splitter can be determined according to the oleaginousness in milk sap and the index request deviating from water or be determined by demulsifier concentration optimization experiment.In general, in oil-in-water emulsion, oleaginousness is higher, and the oleaginousness of deviating from water is lower, and the amount of required emulsion splitter is larger.It must be noted that, when the dosage of graphene oxide exceedes best use range, degree of cleaning and the oleaginousness of deviating from water will be affected.Reason is that graphene oxide is originally as tawny, and in the process of breakdown of emulsion, adsorbed the part of compounds in oil.After breakdown of emulsion, excessive graphene oxide is suspended in aqueous phase and makes aqueous phase be yellow, deviates from the oleaginousness of water also than slightly high during optimal dose scope.During profit layering, time of repose is 5 minutes ~ 2 hours.
The method process oil-in-water emulsion has the following advantages:
1, the de-oiling rate of water external emulsion of the present invention is greater than 96%.The oil phase water content floated is low, is easy to subsequent disposal.Deviate from water oleaginousness low, deviate from water base and reach three grades of emission standards and reinjection standard.
2, emulsion splitter of the present invention is graphene oxide dispersion.The stable in properties of this emulsion splitter, nontoxic.Cheaper starting materials is easy to get, and preparation method is simple, ripe.After breakdown of emulsion, emulsion splitter can carry out recycling by simple filtration method.
3, method process crude oil emulsion of the present invention is used, low to temperature-dependence.Test is carried out all at normal temperatures, and respond well.For higher than under the working conditions of normal temperature, demulsification is better.
4, adopt this method to carry out processed to oil-in-water-type crude oil emulsion, dewatering efficiency is high, the breakdown of emulsion time is short.Milk sap can rapid breakdown of emulsion in short several minutes.And time of repose is longer, it is better to deviate from water quality.
5, adopt this method process oil-in-water emulsion, universality is strong, is widely used in crude oil emulsion and the heavy crude oil-in-water emulsion of ortho-water oil-in.
The present invention can be used in the processed of the water-oil emulsion of high-moisture in petroleum industry.
Embodiment
In order to the superiority of more directly perceived, accurate understanding method of the present invention and this method, be explained by concrete example below.But the present invention is not limited to the following examples.
Embodiment 1:
With the graphite oxide suspension that deionized water compound concentration is 2mg/mL, ultrasonic disperse more than 90 minutes, to obtain graphene oxide dispersion, stand-by.
Respectively 40g Crude Oil in Tarim Basin and 360g deionized water are placed in plastic containers.Oil-water mixture disperses 3min by high-shear emulsion machine under 28000rpm condition, to obtain the oil-in-water-type crude oil emulsion that homodisperse oleaginousness is 10%.Get breakdown of emulsion reagent bottle some, and number consecutively.In breakdown of emulsion reagent bottle, add the milk sap of equivalent respectively, at ambient temperature, leave standstill 30min.
The graphene oxide dispersion of different volumes is joined concussion in breakdown of emulsion reagent bottle even, standing, observe and record aqueous phase, oil phase and state of interface.
After leaving standstill 60min, with reference to the standard method of analysis described in SY/T5329-2012, kerosene is adopted to be that extraction solvent measures the oleaginousness in water and calculates de-oiling rate.
The dosage and the breakdown of emulsion experimental result that add emulsion splitter refer to table 1.
Table 1
Embodiment 2:
With the graphite oxide suspension that deionized water compound concentration is 2mg/mL, ultrasonic disperse more than 90 minutes, to obtain graphene oxide dispersion, stand-by.
Respectively 20g Crude Oil in Tarim Basin and 380g deionized water are placed in plastic containers.Oil-water mixture disperses 3min by high-shear emulsion machine under 28000rpm condition, to obtain the oil-in-water-type crude oil emulsion that homodisperse oleaginousness is 5%.Get breakdown of emulsion reagent bottle some, and number consecutively.In breakdown of emulsion reagent bottle, add the milk sap of equivalent respectively, at ambient temperature, leave standstill 30min.
The graphene oxide dispersion of different volumes joined in breakdown of emulsion reagent bottle, concussion evenly.Leave standstill, observe and record aqueous phase, oil phase and state of interface.
After leaving standstill 60min, with reference to the standard method of analysis described in SY/T5329-2012, kerosene is adopted to be that extraction solvent measures the oleaginousness in water and calculates de-oiling rate.
The dosage and the breakdown of emulsion experimental result that add emulsion splitter refer to table 2.
Table 2
Embodiment 3:
With the graphite oxide suspension that deionized water compound concentration is 2mg/mL, ultrasonic disperse more than 90 minutes, to obtain graphene oxide dispersion, stand-by.
Respectively 2g Crude Oil in Tarim Basin and 398g deionized water are placed in plastic containers.Oil-water mixture disperses 3min by high-shear emulsion machine under 28000rpm condition, to obtain the oil-in-water-type crude oil emulsion that homodisperse oleaginousness is 0.5%.Get breakdown of emulsion reagent bottle some, and number consecutively.In breakdown of emulsion reagent bottle, add the milk sap of equivalent respectively, at ambient temperature, leave standstill 30min.
The graphene oxide dispersion of different volumes joined in breakdown of emulsion reagent bottle, concussion evenly.Leave standstill, observe and record aqueous phase, oil phase and state of interface.
After leaving standstill 60min, with reference to the standard method of analysis described in SY/T5329-2012, kerosene is adopted to be that extraction solvent measures the oleaginousness in water and calculates de-oiling rate.
The dosage and the breakdown of emulsion experimental result that add emulsion splitter refer to table 3.
Table 3
。
Claims (4)
1. a breaking method for oil-in-water-type crude oil emulsion, is characterized in that the method adopts graphene oxide as emulsion splitter, carries out processed at normal temperatures to oil-in-water-type crude oil emulsion.
2. the method for claim 1, is characterized in that the method comprises the following steps:
A, graphite oxide is mixed with suspension, and abundant ultrasonic disperse, obtain graphene oxide emulsion splitter;
B, join in oil-in-water-type crude oil emulsion by graphene oxide dispersion, add-on is 1mg/L ~ 200mg/L, stirs, and carries out oily water separation after leaving standstill.
3. method as claimed in claim 1 or 2, is characterized in that 1 kilogram of graphene oxide emulsion splitter process oil-in-water-type crude oil emulsion 15-30 ton.
4. method as claimed in claim 1 or 2, is characterized in that the water content in oil-in-water-type crude oil emulsion is 80-99.5%.
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| CN201410068677.9A CN104877706A (en) | 2014-02-27 | 2014-02-27 | Demulsification method of oil-in-water type crude oil emulsion |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106219669A (en) * | 2016-08-01 | 2016-12-14 | 山东交通学院 | A kind of preparation method of magnetic oxygenated Graphene demulsifier |
| CN106978995A (en) * | 2017-05-03 | 2017-07-25 | 中国石油天然气股份有限公司 | Fine and close oil meter face surfactant flooding is for experiment on-line metering device and method of handling up |
| CN109825331A (en) * | 2019-03-12 | 2019-05-31 | 吉林化工学院 | The preparation and application of emulsified crude oil solid demulsifier in microwave field |
| CN110639240A (en) * | 2019-09-24 | 2020-01-03 | 中国科学院兰州化学物理研究所 | Preparation and application of magnetic inorganic clay-graphene composite demulsification material |
| CN111394080A (en) * | 2019-12-30 | 2020-07-10 | 浙江工业大学 | Thick oil viscosity reducer and using method thereof |
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| JPS4991075A (en) * | 1972-12-30 | 1974-08-30 | ||
| CN101287679A (en) * | 2005-10-14 | 2008-10-15 | 普林斯顿大学理事会 | Thermally exfoliated graphite oxide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS4991075A (en) * | 1972-12-30 | 1974-08-30 | ||
| CN101287679A (en) * | 2005-10-14 | 2008-10-15 | 普林斯顿大学理事会 | Thermally exfoliated graphite oxide |
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| 丰华: "《石油加工助剂及石油产品添加剂加工配制与生产应用最新工艺技术操作手册 第一卷》", 30 June 2006, 中国科技文化出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106219669A (en) * | 2016-08-01 | 2016-12-14 | 山东交通学院 | A kind of preparation method of magnetic oxygenated Graphene demulsifier |
| CN106219669B (en) * | 2016-08-01 | 2019-03-29 | 山东交通学院 | A kind of preparation method of magnetic oxygenated graphene demulsifier |
| CN106978995A (en) * | 2017-05-03 | 2017-07-25 | 中国石油天然气股份有限公司 | Fine and close oil meter face surfactant flooding is for experiment on-line metering device and method of handling up |
| CN106978995B (en) * | 2017-05-03 | 2019-09-10 | 中国石油天然气股份有限公司 | Fine and close oil meter face surfactant flooding tests on-line metering device and method for handling up |
| CN109825331A (en) * | 2019-03-12 | 2019-05-31 | 吉林化工学院 | The preparation and application of emulsified crude oil solid demulsifier in microwave field |
| CN110639240A (en) * | 2019-09-24 | 2020-01-03 | 中国科学院兰州化学物理研究所 | Preparation and application of magnetic inorganic clay-graphene composite demulsification material |
| CN111394080A (en) * | 2019-12-30 | 2020-07-10 | 浙江工业大学 | Thick oil viscosity reducer and using method thereof |
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