A kind of crude oil demulsifier and preparation method thereof
Technical field
The present invention relates to a kind of crude oil demulsifier and preparation method thereof.
Background technology
Crude oil at first makes its water ratio up to standard through joint station or treatment plant's dehydration after oil well produced, could outer be passed to refinery refining processing.At present, for oil increasing precipitation, realize the volume increase stable yields of crude oil high moisture period during domestic most of oil field has entered, polymer displacement of reservoir oil tech has become chemical flooding and has improved one of dominant technology of recovery ratio, has obtained huge technology, economic and social benefit.Meanwhile, the existence of polymkeric substance has increased the difficulty of crude oil demulsification dehydration, particularly to the viscous crude of high gum asphaltic content, adopts hydrophobic associated polymer as oil-displacing agent, and the breaking emulsion and dewatering difficulty of its extraction crude oil is just bigger.
The crude oil demulsifier of present commercial applications, polyethers has occupied the share of absolute majority, and in the polyethers emulsion splitter, major part is after utilizing initiator and oxyethane and propylene oxide reaction, improve the molecular weight of emulsion splitter again by chainextender, realize the performance synergy of emulsion splitter.In research, production and the application of crude oil demulsifier, about the existing great mass of data report in aspects such as initiator, raw material type, polymerization methods and synthetic method.It is less that yet the research work of the chainextender aspect of one of important source material is paid close attention to, in emulsion splitter is synthetic, the chemical reagent of chainextender many commodities in useization, as: CN 1544117A uses linking agents (chainextender) such as tolylene diisocyanate and Vanadium Pentoxide in FLAKES, EP 0141585 and DE 3319788 use chainextenders such as tolylene diisocyanate and organosilicon, CN 1101238C uses tolylene diisocyanate and multi-aryl polyisocyanate chainextender, (Speciality Petrochemicals such as Gong Huijuan, 2000,4:1-4) use tolylene diisocyanate and many alkylenes polyisocyanates chainextender, (petroleum journal (refining of petroleum) such as Xu Jiaye, 2002,18 (2): 48-52) use the hexanodioic acid chainextender, WOP 9213933A1 uses tetrapropylene succinyl oxide chainextender, in addition, also has diprotic acid, dimer (fatty acid) yl, dibasic acid anhydride etc.This shows that the polyfunctional group class chainextender of specialized designs synthetic macromolecule amount is rare report still, corresponding crude oil demulsifier research is not seen and is delivered.
Summary of the invention
The purpose of this invention is to provide a kind of crude oil demulsifier and preparation method thereof.
The preparation method of crude oil demulsifier provided by the present invention, be made up of following steps:
(1) be solvent with toluene or dimethylbenzene, add initiator polyethylene polyamine or nonyl phenol urea formaldehyde, adding mass ratio then is 1: the mean polymerisation degree of 1-3 is that polyethylene oxide and the mean polymerisation degree of 23-30 is the poly(propylene oxide) of 15-38, add catalyzer sodium hydroxide or potassium hydroxide again, 100-140 ℃, 0.2-0.5MPa, reacted 1.5-4 hour, obtain polyethers; Described polyethers has following structural formula, and wherein n is 23-30, and m is 15-38;
(2) polyethers in the step (1) and chainextender are pressed 1: the mixed in molar ratio of 0.06-0.15 is even, and the pyridine of mole numbers such as adding and described chainextender, and 90-100 ℃ was reacted 1-3 hour, vacuumized the back release, obtained crude oil demulsifier;
Described chainextender is the structural unit of being represented by following formula I, formula II and formula III, and with 1: 0.01-0.04: the weight-average molecular weight that the mol ratio of 0.01-0.09 is formed is the random copolymers of 600-2800; The structural formula of formula I, formula II and formula III is as follows:
Formula I formula II formula III
R among the formula I
1Expression H or CH
3, R
2Expression CH
3Or C
4H
9
In the described method, described polyethylene polyamine can be diethylenetriamine, triethylene tetramine, tetraethylene pentamine and five ethene hexamines.
Described chainextender prepares in accordance with the following methods:
A) be 1 with mol ratio: the acrylate of 0.01-0.12 and hydroxyethyl methylacrylate are dissolved in toluene or the dimethylbenzene, add the dibenzoyl peroxide of 0.02-0.6% of described acrylate and hydroxyethyl methylacrylate total mass or following any chain-transfer agent of 1-9% of Diisopropyl azodicarboxylate and described acrylate and hydroxyethyl methylacrylate total mass: Resorcinol, phenol, antioxidant 1010, Virahol or mercaptoethanol, at 70-100 ℃ of copolyreaction 2-6 hour, obtain the multipolymer of acrylate and hydroxyethyl methylacrylate;
B) adding in the acrylate that obtains in step a) and the multipolymer of hydroxyethyl methylacrylate is the phosphorus tribromide of described hydroxyethyl methylacrylate 1/3rd mole numbers, 90-110 ℃ following bromine substitution reaction 4-8 hour, 90 ℃ of underpressure distillation promptly get chainextender.
The present invention specifically provides following three kinds of preferred preparation emulsion splitter methods:
First method is: among the preparation method of described crude oil demulsifier, in the described step (1), initiator is a tetraethylene pentamine, the mean polymerisation degree of described polyethylene oxide and poly(propylene oxide) is respectively 30 and 19, their mass ratio is 1: 3, described temperature of reaction is 130 ℃, and the reaction times is 2.5 hours; In the described step (2), the mol ratio of polyethers and chainextender is 1: 0.10, and temperature of reaction is 90 ℃, and the reaction times is 3 hours;
Among the preparation method of described chainextender, described acrylate is a methyl methacrylate, and the mol ratio of described methyl methacrylate and hydroxyethyl methylacrylate is 1: 0.08; Described dibenzoyl peroxide is 0.5% of described methyl methacrylate and a hydroxyethyl methylacrylate total mass; Described chain-transfer agent is a mercaptoethanol, and described mercaptoethanol is 2% of described methyl methacrylate and a hydroxyethyl methylacrylate total mass; Described copolyreaction temperature is 100 ℃, and the copolyreaction time is 2 hours; Described bromine substitution reaction temperature is 105 ℃, and the bromine substitution reaction time is 4 hours.
Second method is: among the preparation method of described crude oil demulsifier, in the described step (1), described initiator is the nonyl phenol urea formaldehyde, the mean polymerisation degree of described polyethylene oxide and poly(propylene oxide) is respectively 23 and 15, their mass ratio is 1: 2, described temperature of reaction is 123 ℃, and the reaction times is 3.5 hours; In the described step (2), the mol ratio of described polyethers and chainextender is 1: 0.07, and temperature of reaction is 100 ℃, and the reaction times is 1 hour;
Among the preparation method of described chainextender, described acrylate is a butyl acrylate, and the mol ratio of described butyl acrylate and hydroxyethyl methylacrylate is 1: 0.04; Described dibenzoyl peroxide is 0.07% of described butyl acrylate and a hydroxyethyl methylacrylate total mass; Described chain-transfer agent is a Virahol, and described Virahol is 9% of described butyl acrylate and a hydroxyethyl methylacrylate total mass; Described copolyreaction temperature is 80 ℃, and the copolyreaction time is 6 hours; Described bromine substitution reaction temperature is 95 ℃, and the bromine substitution reaction time is 5 hours.
The third method is: among the preparation method of described crude oil demulsifier, described initiator is five ethene hexamines, the mean polymerisation degree of described polyethylene oxide and poly(propylene oxide) is respectively 23 and 38, their mass ratio is 1: 1.5, temperature of reaction in the described step (1) is 115 ℃, and the reaction times is 4 hours; In the described step (2), the mol ratio of polyethers and chainextender is 1: 0.12, and temperature of reaction is 100 ℃, and the reaction times is 1.5 hours;
Among the preparation method of described chainextender, described acrylate is a methyl methacrylate, and the mol ratio of described methyl methacrylate and hydroxyethyl methylacrylate is 1: 0.12; Described dibenzoyl peroxide is 0.42% of described methyl methacrylate and a hydroxyethyl methylacrylate total mass; Described chain-transfer agent is a mercaptoethanol, and described mercaptoethanol is 4% of described methyl methacrylate and a hydroxyethyl methylacrylate total mass; Described copolyreaction temperature is 95 ℃, and the copolyreaction time is 3 hours; Described bromine substitution reaction temperature is 90 ℃, and the bromine substitution reaction time is 8 hours.
Emulsion splitter by above-mentioned any method preparation also belongs to protection scope of the present invention.
Emulsion splitter of the present invention has the high and rational characteristics of the degree of branching of molecular weight, and its preparation method is simple, and the crude oil demulsifier consumption is few, and breaking emulsion and dewatering is effective, and cost is low, is specially adapted to the efficient breaking emulsion and dewatering of viscous crude association polymer repelling crude oil; The present invention can effectively solve the problem that the viscous crude association polymer drives extraction dehydrating of crude oil difficulty.In addition, crude oil demulsifier of the present invention not only can be used for viscous crude association polymer repelling crude oil breaking emulsion and dewatering, also can be used for the processed that conventional polymer is driven extraction crude oil.
Embodiment
Experimental technique among the following embodiment if no special instructions, is ordinary method.
Embodiment 1, weight-average molecular weight are the preparation of 710 chainextender.
With dimethylbenzene is solvent, methyl methacrylate and hydroxyethyl methylacrylate are rendered in the there-necked flask by 1: 0.08 mol ratio, mechanical stirring, 2% the chain-transfer agent mercaptoethanol that adds 0.5% initiator dibenzoyl peroxide of methyl methacrylate and hydroxyethyl methylacrylate total mass and methyl methacrylate and hydroxyethyl methylacrylate total mass, 100 ℃ were reacted 2 hours, can obtain the multipolymer of methyl acrylate and hydroxyethyl methylacrylate; Adding in this multipolymer is the phosphorus tribromide of hydroxyethyl methylacrylate mole number 1/3rd, mechanical stirring, and 105 ℃ of reactions 4 hours, 90 ℃ of underpressure distillation 2 hours promptly get the random copolymers chainextender.Wherein: the mol ratio of methyl methacrylate, hydroxyethyl methylacrylate and methacrylic acid bromine ethyl ester structural unit is 0.78: 0.022: 0.036, and the weight-average molecular weight of this chainextender is 710.
Embodiment 2, weight-average molecular weight are the preparation of 2580 chainextender.
With dimethylbenzene is solvent, butyl acrylate and hydroxyethyl methylacrylate are rendered in the there-necked flask by 1: 0.04 mol ratio, mechanical stirring, 9% the chain-transfer agent Virahol that adds 0.07% initiator dibenzoyl peroxide of butyl acrylate and hydroxyethyl methylacrylate total mass and butyl acrylate and hydroxyethyl methylacrylate total mass, 80 ℃ were reacted 6 hours, can obtain the multipolymer of butyl acrylate and hydroxyethyl methylacrylate; Adding in this multipolymer is the phosphorus tribromide of hydroxyethyl methylacrylate mole number 1/3rd, mechanical stirring, and 95 ℃ of reactions 5 hours, 90 ℃ of underpressure distillation 2 hours promptly get the random copolymers chainextender.Wherein: the mol ratio of butyl acrylate, hydroxyethyl methylacrylate and methacrylic acid bromine ethyl ester structural unit is 0.82: 0.014: 0.02, and the weight-average molecular weight of this chainextender is 2580.
Embodiment 3, weight-average molecular weight are the preparation of 1090 chainextender.
With toluene is solvent, methyl methacrylate and hydroxyethyl methylacrylate are rendered in the there-necked flask by 1: 0.12 mol ratio, mechanical stirring, 4% the chain-transfer agent mercaptoethanol that adds 0.42% initiator dibenzoyl peroxide of methyl methacrylate and hydroxyethyl methylacrylate total mass and methyl methacrylate and hydroxyethyl methylacrylate total mass, 95 ℃ were reacted 3 hours, can obtain the multipolymer of methyl methacrylate and hydroxyethyl methylacrylate; Adding in this multipolymer is the phosphorus tribromide of hydroxyethyl methylacrylate mole number 1/3rd, mechanical stirring, and 90 ℃ of reactions 8 hours, 90 ℃ of underpressure distillation 2 hours promptly get the random copolymers chainextender.Wherein: the mol ratio of methyl methacrylate, hydroxyethyl methylacrylate and methacrylic acid bromine ethyl ester structural unit is 0.94: 0.016: 0.087, and the weight average branch output of this chainextender is 1090.
Embodiment 4, prepare emulsion splitter with the chainextender of embodiment 1
With dimethylbenzene is solvent, add the initiator tetraethylene pentamine, the mean polymerisation degree that adds total mass then and be 100 times of quality of initiator is that 30 polyethylene oxide and mean polymerisation degree are that 19 poly(propylene oxide)s mix, wherein, mean polymerisation degree is that 30 polyethylene oxide and mean polymerisation degree are that the mass ratio of 19 poly(propylene oxide) is 1: 3; Add is that described mean polymerisation degree is that 6% sodium hydroxide of 30 polyethylene oxide quality is as catalyzer again, 130 ℃, pressure is 0.5MPa, reacted 2.5 hours, and obtained polyethers, the chainextender of preparation among polyethers and the embodiment 1 is even by 1: 0.10 mixed in molar ratio, and the pyridine of mole numbers such as adding and chainextender, 90 ℃ were reacted 3 hours, vacuumized the back release, obtained crude oil demulsifier.
With above-mentioned emulsion splitter Bohai SZ 36-1 oil field association polymer repelling crude oil is dewatered, concrete grammar is as follows: add the above-mentioned emulsion splitter of 9mg in 100ml crude oil, mixing, left standstill 2 hours by 70 ℃; Other gets 100ml heating crude oil to 70 ℃, leaves standstill 2 hours as blank, and the result shows that neater through the crude oil water-oil interface that emulsion splitter was handled, water colour is more clear, and the dehydration rate of emulsion splitter is 88%; And blank does not have water-oil interface, and water colour muddiness, dehydration rate are 10%.
Embodiment 5, prepare emulsion splitter with the chainextender of embodiment 2
With toluene is solvent, add initiator nonyl phenol urea formaldehyde, the mean polymerisation degree that adds total mass then and be 200 times of quality of initiator is that 23 polyethylene oxide and mean polymerisation degree are 15 poly(propylene oxide), mix, wherein, mean polymerisation degree is that 23 polyethylene oxide and mean polymerisation degree are that the mass ratio of 15 poly(propylene oxide) is 1: 2; Add is that described mean polymerisation degree is that 11% potassium hydroxide of 23 polyethylene oxide quality is as catalyzer again, 123 ℃, pressure is 0.4MPa, react after 3.5 hours, obtain polyethers, the chainextender of preparation among polyethers and the embodiment 2 is even by 1: 0.07 mixed in molar ratio, and the pyridine of mole numbers such as adding and chainextender, 100 ℃ were reacted 1 hour, vacuumized the back release, obtained crude oil demulsifier.
With above-mentioned emulsion splitter Bohai SZ 36-1 oil field association polymer repelling crude oil is dewatered, concrete grammar is as follows: add the above-mentioned emulsion splitter of 9mg in 100ml crude oil, 70 ℃, mixing left standstill 2 hours, other gets the heating crude oil to 70 ℃ that 100ml does not contain polymkeric substance, leave standstill 2 hours as blank, the result shows, and is neater through the crude oil water-oil interface that emulsion splitter was handled, water colour is clear, and the dehydration rate of emulsion splitter is 80%; And blank does not have water-oil interface, and the muddy dehydration rate of water colour is 10%.
Embodiment 6, prepare emulsion splitter with the chainextender of embodiment 3
With toluene is solvent, add initiator five ethene hexamines, the mean polymerisation degree that adds total mass then and be 260 times of quality of initiator is that 23 polyethylene oxide and mean polymerisation degree are 38 poly(propylene oxide), mix, wherein, mean polymerisation degree is that 23 polyethylene oxide and mean polymerisation degree are that the mass ratio of 38 poly(propylene oxide) is 1: 1.5; Add is that described mean polymerisation degree is that 4% potassium hydroxide of 23 polyethylene oxide quality is as catalyzer again, 115 ℃, pressure is 0.3MPa, react after 4 hours, obtain polyethers, the chainextender of preparation among polyethers and the embodiment 3 is even by 1: 0.12 mixed in molar ratio, and the pyridine of mole numbers such as adding and chainextender, 100 ℃ were reacted 1.5 hours, vacuumized the back release, obtained crude oil demulsifier.
With above-mentioned emulsion splitter Bohai SZ 36-1 oil field association polymer repelling crude oil is dewatered, concrete grammar is as follows: add the above-mentioned emulsion splitter of 8mg in 100ml crude oil, 70 ℃, mixing left standstill 2 hours, other gets 100ml heating crude oil to 70 ℃, leave standstill 2 hours as blank, the result shows, and is neat through the crude oil water-oil interface that emulsion splitter was handled, water colour is more clear, and the dehydration rate of emulsion splitter is 78%; And blank does not have water-oil interface, and water colour muddiness, dehydration rate are 10%.