CN114437699A - Oil washing agent and preparation method and application thereof - Google Patents
Oil washing agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a washing oil agent for oil washing of oil sand and a preparation method and application thereof. The oil washing agent comprises at least two of a structural unit shown in a formula (1), a structural unit shown in a formula (2) and a structural unit shown in a formula (3), a structural unit shown in a formula (4) and a structural unit shown in a formula (5):
R1is one of C1-C12 alkyl groups, R2Is phenyl, trimethylsilyl or acetate radical, R3Is composed of
Description
Technical Field
The invention relates to the field of oil sand washing and thick oil exploitation research in oil fields, in particular to a washing agent for oil sand washing and a preparation method and application thereof.
Background
Oil sands are a mixture of bitumen, water, sand, and clay. With the development of conventional petroleum and the continuous rising of international oil price, oil sand is increasingly paid attention by governments of various countries as an important unconventional petroleum resource. The countries in the world with abundant oil sand resources are: canada, venezuela, usa, russia and china, most of which are concentrated in Alberta, canada. After years of research, the canadian oil sand development enters an industrialization stage, and the process mainly applied at present is ground excavation combined with hot water washing separation.
China has rich oil sand resources, and is mainly distributed in Xinjiang and Qinghai in the northwest region, Tibet, Sichuan and Guizhou in the southwest region, Guangxi in the southwest region, Zhejiang in the east China and inner Mongolia in the north China. The oil-bearing rate is high, the buried area is shallow, and the method has great development potential. The research on oil sand is still in the beginning stage in China, and large-scale industrialization cannot be realized. The selection of the proper mining technology has very important practical significance.
The oil contained in oil sands is usually heavy oil, and the density of the heavy oil (bitumen) is usually more than lg/cm3Viscosity of more than 10000mPa.s (viscosity is usually more than 1X 10)4m Pa.s thick oil is called asphalt), the mobility is extremely poor, so that the thick oil in the oil sand can not be obtained by a method of extracting crude oil and thick oil by using a common well.
Oil sand is very different from conventional oil and natural gas, is difficult to produce by a common oil exploitation method in the original state, and needs special treatment. The mining of oil sands can be classified into an in-situ mining method and a surface mining method according to the difference of the oil sands storage depth.
In-situ mining, hot mining, cold mining and chemical agent methods are commonly used, wherein the hot mining method is subdivided into methods such as steam huff and puff, steam flooding, in-situ combustion and the like, and the method mainly reduces the viscosity of asphalt by heating or using chemical agents and other special ways to enable the asphalt to flow and be collected and pumped out, and mainly relates to a hot mining process, a chemical process and a cold mining technology; the surface mining method is to mine oil sand by an open-pit mining method, and then recover thick oil from the oil sand by using the processes of hot water washing, solvent extraction, coking treatment and the like, and the surface mining method relates to the processes of hot alkaline water extraction, hot alkaline water combined surfactant extraction, organic solvent extraction, coking method and the like. The combination of the thermal recovery method and the chemical oil displacement method can improve the oil recovery speed and the oil recovery rate, and is a promising oil recovery method, and the hot alkaline water extraction method is the most widely applied method in surface recovery, but causes serious environmental pollution; the method can improve the asphalt recovery rate, reduce the production cost and reduce the environmental pollution by combining the surfactant.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a washing agent for oil sand washing, and a preparation method and application thereof. The oil washing agent takes an acrylate copolymer as a main body, and introduces a nonionic polyether long branched chain, an oleophilic branched chain, an anionic branched chain and other side groups with high activity on a long vinyl main chain, so that the surface activity, the thick oil emulsifying and dispersing performance and the emulsion stability of the copolymer are greatly improved, and the copolymer is dispersed in an aqueous solution system in the preparation process under the action of a composite surfactant. The oil washing agent is alkali-free, strong in salt resistance and strong in surface activity, can effectively reduce the viscosity of crude oil, and has high oil washing efficiency.
An object of the present invention is to provide a water-soluble oil washing agent comprising at least two of a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3), a structural unit represented by formula (4), and a structural unit represented by formula (5):
wherein R is1Is one of C1-C12 alkyl groups, R2Is phenyl, trimethylsilyl or acetate radical, R3Is composed of
a＞0，b＞0。
The oil washing agent of the invention introduces nonionic polyether long-chain branch monomer, lipophilic monomer and hydrophilic monomer on a vinyl main chain of an acrylate copolymer.
In the oil-washing agent of the present invention,
the weight percentage of the structural units shown in the formula (1) in all the structural units is 30-65%, preferably 30-50%;
the weight percentage of the structural units shown in the formulas (2) and (3) in all the structural units is 10-20%, preferably 15-20%;
the weight percentage of the structural unit shown in the formula (4) in all the structural units is 20-40%, preferably 30-40%;
the weight percentage of the structural unit shown in the formula (5) in all the structural units is 5-10%, and preferably 8-10%.
Further, a combination of at least one of the structural unit represented by formula (2) and the structural unit represented by formula (3) is selected, wherein the weight ratio of the structural unit represented by formula (2) to the structural unit represented by formula (3) is (1:0.5) to (1:1.5), preferably (1:0.8) to (1: 1.2).
In the technical scheme of the invention, the structural unit shown in the formula (1) is derived from an acrylate monomer, the structural units shown in the formulae (2) and (3) are derived from a hydrophobic monomer, the structural unit shown in the formula (4) is derived from a long-chain branched monomer, and the structural unit shown in the formula (5) is derived from a hydrophilic monomer.
The second purpose of the invention is to provide a preparation method of the oil washing agent, which comprises the step of carrying out free radical polymerization on components comprising an acrylate monomer, a long-chain branched monomer, a hydrophobic monomer and a hydrophilic monomer to obtain the polymer.
In the technical scheme, the acrylate monomer has a structure shown in a formula (5),
wherein R is1Is one of C1-C12 alkyl groups,
preferably, the acrylate monomer is at least one of methyl acrylate, butyl acrylate and dodecyl acrylate; more preferably, the acrylate monomer is butyl acrylate.
The long-chain branched monomer is polyoxyethylene polyoxypropylene ether with a double bond at the end group, and preferably, the long-chain branched monomer is allyl polyoxyethylene polyoxypropylene ether with a structure shown in the following formula (6):
wherein a is more than 0 and b is more than 0.
The hydrophobic monomer is preferably at least two of methyl methacrylate, styrene, propenyl trimethylsilane and vinyl acetate; more preferably, the hydrophobic monomer is a combination of methyl methacrylate and at least one of styrene, propenyl trimethylsilane, vinyl acetate; most preferably, the hydrophobic monomers are methyl methacrylate and styrene.
The hydrophilic monomer is a hydrophilic monomer with a carboxyl group, and acrylic acid is preferred.
In the technical scheme, by taking the total mass of the acrylate monomer, the long-chain branched chain monomer, the hydrophobic monomer and the hydrophilic monomer as the basis,
the acrylate monomer accounts for 30-65%, and preferably 30-50%;
the long-chain branched chain monomer accounts for 20-40 wt%, preferably 30-40 wt%;
10-20 wt% of the hydrophobic monomer, preferably 15-20 wt%;
the hydrophilic monomer accounts for 5-10 wt%, and preferably 8-10 wt%.
In the hydrophobic monomer, the weight ratio of methyl methacrylate to at least one monomer selected from styrene, propenyl trimethylsilane and vinyl acetate is (1:0.5) to (1:1.5), preferably (1:0.8) to (1: 1.2).
Preferably, the preparation method of the oil washing agent comprises the following steps:
step 1, adding a long-chain branched monomer and a surfactant into water;
step 2, adding an acrylate monomer and a hydrophobic monomer, and adding a part of initiator under an inert atmosphere to perform reaction;
and 3, adding a hydrophilic monomer and the rest of initiator, and continuing to react to obtain the oil washing agent.
In the above technical solution, the surfactant is preferably a composite surfactant obtained by compounding one or more of a cationic surfactant (such as Cetyl Trimethyl Ammonium Bromide (CTAB), octadecyl dimethyl benzyl quaternary ammonium chloride, and the like), an anionic surfactant (such as Sodium Dodecyl Benzene Sulfonate (SDBS), alkylbenzene sulfonate, alkyl glyceryl ether sulfonate, and the like), and polyoxyethylene octyl phenol ether-10 (OP-10) according to a certain proportion, and is preferably a composite surfactant.
The initiator is selected from at least one of 2,2 '-azobisisobutylamidine dihydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid and azobisisopropylimidazoline, and is preferably 2,2' -azobisisobutylamidine dihydrochloride.
In the technical scheme, the dosage of the surfactant is 3-8% of the total mass of the reaction emulsion, and preferably 5-8%.
In the above technical scheme, in the step 2, the initiator is 0.1-0.8% of the total mass of the monomers, and preferably 0.3-0.6%.
In the above technical scheme, in the step 3, the initiator is 0.025-0.2%, preferably 0.1-0.2% of the total mass of the monomers.
In the above technical scheme, in the step 2, the reaction temperature is 60-80 ℃, and the reaction time is 2-3 hours.
In the above technical scheme, in the step 3, the reaction temperature is 60-80 ℃, and the reaction time is 4-8 hours.
In the technical scheme, the total mass concentration of the acrylate monomer, the long-chain branched monomer, the hydrophobic monomer and the hydrophilic monomer in the reaction emulsion is 20-30%.
According to a preferred embodiment of the present invention, the method for preparing the water-soluble oil washing agent may comprise the steps of:
step 1, weighing a certain amount of long-chain branched monomer and surfactant, adding into distilled water, and stirring for 10 minutes until the monomers are completely dissolved.
And 2, weighing a certain amount of acrylate monomer and hydrophobic monomer, adding the acrylate monomer and the hydrophobic monomer into a three-neck flask, introducing nitrogen, stirring for 30min, adding a certain amount of initiator, and reacting for a certain time (2-3 hours) at the temperature of 60-80 ℃.
And 3, after reacting for a certain time, adding a hydrophilic monomer, supplementing and adding a certain amount of initiator, and continuously reacting for a certain time (4-8 hours) at the temperature of 60-80 ℃.
And 4, finishing the reaction to obtain the water-soluble oil washing agent.
On the basis of the technical scheme, the composite surfactant in the step 1 is preferably a mixture of CTAB and SDBS, preferably, the mass ratio of CTAB to SDBS is 1: 1-1: 3, preferably, the addition amount is 3-8% of the total mass of the synthesized emulsion, and preferably 5-8%.
On the basis of the technical scheme, the initiator in the steps 2 and 3 is preferably 2, 2-azodiisobutylaminidine dihydrochloride; preferably, the total amount of the initiator used in the 2 nd step and the initiator used in the 3 rd step are 0.125-1.0%, the amount used in the 2 nd step is 0.1-0.8%, and the amount used in the 3 rd step is 0.025-0.2%, based on the total mass of the acrylate monomer, the long-chain branched monomer, the hydrophobic monomer and the hydrophilic monomer.
The third purpose of the invention is to provide the application of the oil washing agent or the oil washing agent obtained by the preparation method in the fields of oil sand oil washing exploitation, production increase of silicate oil reservoir exploitation, viscosity reduction of thick oil and the like.
Compared with the prior art, the oil washing agent for oil washing of oil sand and the preparation method thereof have the following advantages and effects in molecular design and synthesis:
the invention takes acrylic ester copolymer as a main body, introduces side groups with high activity, such as nonionic polyether long branched chain, lipophilic branched chain, anionic branched chain and the like, on a long vinyl main chain, greatly improves the surface activity, the emulsifying and dispersing performance of thick oil and the emulsion stability of the copolymer, and disperses the copolymer in an aqueous solution system in the preparation process under the action of a composite surfactant. The oil washing agent is alkali-free, strong in salt resistance and strong in surface activity, can effectively reduce the viscosity of crude oil, and has high oil washing efficiency. In addition, the formula system contains various active groups and has the performances of dispersion, wetting, oil washing and the like, so that the formula system also has high application value in the oil field chemical fields of crude oil emulsion breaking, sewage sludge treatment and the like.
The substantial difference between the present invention and the prior art is:
the main body of the oil washing agent for oil sand washing is an acrylate polymer, and the polymer introduces a nonionic polyether long-chain branch group, a lipophilic group and a hydrophilic group with high activity on a vinyl main chain, so that the surface activity, the thick oil emulsifying and dispersing performance and the oil sand washing performance of the copolymer are greatly improved. In addition, the acrylate polymer is an oil-soluble polymer, has better affinity with crude oil, is dispersed in a water system through a composite surfactant system, improves the oil washing performance, reduces the application cost, and simultaneously improves the convenience and safety of field operation.
The invention has the beneficial effects that:
the oil-soluble acrylate polymer containing polyether long-chain branch groups, lipophilic groups and hydrophilic groups is dispersed in a water system through a composite surfactant system to prepare the water-soluble oil washing agent for oil sand oil washing, and the oil washing agent can effectively reduce the viscosity of crude oil and improve the oil washing efficiency.
Detailed Description
While the present invention will be described in conjunction with specific embodiments thereof, it is to be understood that the following embodiments are presented by way of illustration only and not by way of limitation, and that numerous insubstantial modifications and adaptations of the invention may be made by those skilled in the art in light of the teachings herein.
The starting materials used in the embodiments of the present invention are commercially available.
The effect evaluation adopts the evaluation tests of viscosity reduction of common thick oil and static oil washing:
the oil sample used in the test is an oil sample (viscosity of 734mPa.s at 50 ℃) of a certain block of a victory oil field island, and the density of the oil sample is 0.94g/cm3And the water content is 38.1 percent, and the viscosity reduction rate and the oil washing rate of different oil washing agents are determined by carrying out a viscosity reduction test and a static oil washing test.
The synthesized oil detergent and comparative samples (commercially available oil detergent KB-3 and commercially available heavy oil displacement agent QU-02) were mixed with mineralized water (degree of mineralization TDS 100000mg/L) to prepare a solution with a concentration of 1000 ppm.
The viscosity reduction test method comprises the following steps: initial viscosity μ of the test oil sample at 50 ℃ was measured with an Anton Paar MCR301 rheometer0Taking 35g of crude oil, putting the crude oil into a 100ml beaker, pouring 15g of the prepared viscosity reducer solution, heating the mixture at a constant temperature of 50 ℃ for 30min, then stirring the mixture by using a stirrer for 5min at a stirring speed of 50rpm, and testing the viscosity mu of the emulsion under an Anton Paar MCR301 rheometer, wherein the viscosity reduction rate is calculated according to the formula (1):
f＝(μ0﹣μ)/μ0×100％ (1)，
in the formula:
f-viscosity reduction rate,%;
μ0-initial viscosity of crude oil at 50 ℃, mPa · s;
mu-viscosity of crude oil after viscosity reduction, mPas.
The static oil washing performance evaluation method comprises the following steps: oil sand was prepared using the selected oil samples as the base oil samples, with an oil-to-sand ratio of 1:4, and aged at 80 ℃ for 7 days. Other procedures were performed according to the method in Q/SLCG 5370-1999.
Example 1
In step 1, 8g of allyl polyoxyethylene polyoxypropylene ether (40% of the total mass of the monomers, 100g of the total amount of the solution, and 20% of the total concentration of the monomers in the solution), 6g of a complex surfactant (6% of the total mass of the solution, 2g and 4g of CTAB: SDBS ═ 1:2, respectively) were weighed out and added to distilled water, and stirred for 10 minutes until complete dissolution.
Step 2, 6g of butyl acrylate (accounting for 30 percent of the total mass of the monomers), 2g of methyl methacrylate and 2g of styrene (accounting for 20 percent of the total mass of the monomers) are weighed and added into a three-neck flask, nitrogen is introduced, and the mixture is stirred for 30 min. 0.06g of 2, 2-azobisisobutylamidine dihydrochloride (0.3% by mass based on the total mass of the monomers) was added and reacted at 80 ℃ for 3 hours.
In step 3, after a certain reaction time, 2g of acrylic acid (10% by weight based on the total mass of the monomers) was added, and 0.02g of 2, 2-azobisisobutylamidine dihydrochloride (0.1% by weight based on the total mass of the monomers) was additionally added, and the reaction was continued at 80 ℃ for 8 hours.
And step 4, finishing the reaction to obtain the water-soluble oil washing agent which is semitransparent milky white liquid in appearance.
Example 2
In step 1, 12g of allyl polyoxyethylene polyoxypropylene ether (40% by mass of the total monomer, 100g of the total solution, and 30% by mass of the total solution monomer), 8g of a complex surfactant (8% by mass of the total solution, 4g and 4g of CTAB: SDBS ═ 1:1, respectively) were weighed and added to distilled water, and stirred for 10 minutes until complete dissolution.
Step 2, 9g of butyl acrylate (accounting for 30 percent of the total mass of the monomers), 3g of methyl methacrylate and 3g of styrene (accounting for 20 percent of the total mass of the monomers) are weighed and added into a three-neck flask, nitrogen is introduced, and the mixture is stirred for 30 min. 0.18g of 2, 2-azobisisobutylamidine dihydrochloride (0.6% by mass based on the total mass of the monomers) was added and reacted at 80 ℃ for 3 hours.
Step 3, after reacting for a certain time, 3g of acrylic acid (10% of the total mass of the monomers) was added, and 0.06g of 2, 2-azobisisobutylamidine dihydrochloride (0.2% of the total mass of the monomers) was additionally added, and the reaction was continued at 80 ℃ for 8 hours.
And step 4, finishing the reaction to obtain the water-soluble oil washing agent which is semitransparent milky white liquid in appearance.
Example 3
In step 1, 5g of allyl polyoxyethylene polyoxypropylene ether (20% of the total mass of the monomers, 100g of the total amount of the solution, 25% of the total concentration of the monomers in the solution), 6g of a complex surfactant (6% of the total mass of the solution, 2g and 4g of CTAB: SDBS ═ 1:2, respectively) were weighed out and added to distilled water, and stirred for 10 minutes until complete dissolution.
Step 2, weighing 12.5g of butyl acrylate (accounting for 50 percent of the total mass of the monomers), 2g of methyl methacrylate and 3g of styrene (accounting for 20 percent of the total mass of the monomers), adding into a three-neck flask, introducing nitrogen, and stirring for 30 min. 0.075g of 2, 2-azobisisobutylamidine dihydrochloride (0.3% based on the total mass of the monomers) was added and reacted at 80 ℃ for 2 hours.
In step 3, after a certain reaction time, 2.5g of acrylic acid (10% by mass of the total monomer) was added, and 0.025g of 2, 2-azobisisobutylamidine dihydrochloride (0.1% by mass of the total monomer) was additionally added, and the reaction was continued at 80 ℃ for 6 hours.
And step 4, finishing the reaction to obtain the water-soluble oil washing agent which is semitransparent milky white liquid in appearance.
Example 4
In step 1, 5g of allyl polyoxyethylene polyoxypropylene ether (20% of the total mass of the monomers, 100g of the total amount of the solution, and 25% of the total concentration of the monomers in the solution), 8g of a complex surfactant (8% of the total mass of the solution, 4g and 4g of CTAB: SDBS ═ 1:1, respectively) were weighed out and added to distilled water, and stirred for 10 minutes until complete dissolution.
Step 2, 16.25g of butyl acrylate (accounting for 65 percent of the total mass of the monomers), 1.5g of methyl methacrylate and 1g of styrene (accounting for 10 percent of the total mass of the monomers) are weighed and added into a three-neck bottle, nitrogen is introduced, and the mixture is stirred for 30 min. 0.075g of 2, 2-azobisisobutylamidine dihydrochloride (0.3% based on the total mass of the monomers) was added and reacted at 80 ℃ for 3 hours.
In step 3, after a certain reaction time, 1.25g of acrylic acid (5% by mass of the total monomer) was added, and 0.025g of 2, 2-azobisisobutylamidine dihydrochloride (0.1% by mass of the total monomer) was additionally added, and the reaction was continued at 80 ℃ for 8 hours.
And step 4, finishing the reaction to obtain the water-soluble oil washing agent which is semitransparent milky white liquid in appearance.
Example 5
In step 1, 7.5g of allyl polyoxyethylene polyoxypropylene ether (30% of the total mass of the monomers, 100g of the total amount of the solution, 25% of the total concentration of the monomers in the solution), 6g of a complex surfactant (6% of the total mass of the solution, 2g and 4g of CTAB: SDBS ═ 1:2, respectively) were weighed out and added to distilled water, and stirred for 10 minutes until complete dissolution.
Step 2, weighing 10g of butyl acrylate (accounting for 40 percent of the total mass of the monomers), 2.5g of methyl methacrylate and 2.5g of styrene (accounting for 20 percent of the total mass of the monomers) and adding the mixture into a three-neck bottle, introducing nitrogen and stirring for 30 min. 0.075g of 2, 2-azobisisobutylamidine dihydrochloride (0.3% based on the total mass of the monomers) was added and reacted at 80 ℃ for 2 hours.
In step 3, after a certain reaction time, 2.5g of acrylic acid (10% by mass of the total monomer) was added, and 0.025g of 2, 2-azobisisobutylamidine dihydrochloride (0.1% by mass of the total monomer) was additionally added, and the reaction was continued at 80 ℃ for 6 hours.
And step 4, finishing the reaction to obtain the water-soluble oil washing agent which is semitransparent milky white liquid in appearance.
Example 6
In step 1, 7.5g of allyl polyoxyethylene polyoxypropylene ether (30% of the total mass of the monomers, 100g of the total amount of the solution, 25% of the total concentration of the monomers in the solution), 6g of a complex surfactant (6% of the total mass of the solution, 2g and 4g of CTAB: SDBS ═ 1:2, respectively) were weighed out and added to distilled water, and stirred for 10 minutes until complete dissolution.
Step 2, weighing 10g of dodecyl acrylate (accounting for 40 percent of the total mass of the monomers), 2.5g of methyl methacrylate and 2.5g of styrene (accounting for 20 percent of the total mass of the monomers) and adding the materials into a three-neck bottle, introducing nitrogen and stirring for 30 min. 0.075g of 2, 2-azobisisobutylamidine dihydrochloride (0.3% based on the total mass of the monomers) was added and reacted at 80 ℃ for 2 hours.
In step 3, after a certain reaction time, 2.5g of acrylic acid (10% by mass of the total monomer) was added, and 0.025g of 2, 2-azobisisobutylamidine dihydrochloride (0.1% by mass of the total monomer) was additionally added, and the reaction was continued at 80 ℃ for 6 hours.
And step 4, finishing the reaction to obtain the water-soluble oil washing agent which is semitransparent milky white liquid in appearance.
Example 7
In step 1, 7.5g of allyl polyoxyethylene polyoxypropylene ether (30% of the total mass of the monomers, 100g of the total amount of the solution, 25% of the total concentration of the monomers in the solution), 6g of a complex surfactant (6% of the total mass of the solution, 2g and 4g of CTAB: SDBS ═ 1:2, respectively) were weighed out and added to distilled water, and stirred for 10 minutes until complete dissolution.
Step 2, weighing 10g of butyl acrylate (accounting for 40 percent of the total mass of the monomers), 2.5g of methyl methacrylate and 2.5g of vinyl trimethylsilane (accounting for 20 percent of the total mass of the monomers) and adding the mixture into a three-neck flask, introducing nitrogen and stirring for 30 min. 0.075g of 2, 2-azobisisobutylamidine dihydrochloride (0.3% based on the total mass of the monomers) was added and reacted at 80 ℃ for 2 hours.
In step 3, after a certain reaction time, 2.5g of acrylic acid (10% by mass of the total monomer) was added, and 0.025g of 2, 2-azobisisobutylamidine dihydrochloride (0.1% by mass of the total monomer) was additionally added, and the reaction was continued at 80 ℃ for 6 hours.
And step 4, finishing the reaction to obtain the water-soluble oil washing agent which is semitransparent milky white liquid in appearance.
Comparative example 1
In step 1, 7.5g of allyl polyoxyethylene polyoxypropylene ether (30% of the total mass of the monomers, 100g of the total amount of the solution, 25% of the total concentration of the monomers in the solution), 6g of a complex surfactant (6% of the total mass of the solution, 2g and 4g of CTAB: SDBS ═ 1:2, respectively) were weighed out and added to distilled water, and stirred for 10 minutes until complete dissolution.
Step 2, weighing 10g of butyl acrylate (accounting for 40 percent of the total mass of the monomers) and 5g of methyl methacrylate (accounting for 20 percent of the total mass of the monomers), adding into a three-necked bottle, introducing nitrogen, and stirring for 30 min. 0.075g of 2, 2-azobisisobutylamidine dihydrochloride (0.3% based on the total mass of the monomers) was added and reacted at 80 ℃ for 2 hours.
In step 3, after a certain reaction time, 2.5g of acrylic acid (10% by mass of the total monomer) was added, and 0.025g of 2, 2-azobisisobutylamidine dihydrochloride (0.1% by mass of the total monomer) was additionally added, and the reaction was continued at 80 ℃ for 6 hours.
And step 4, finishing the reaction to obtain the water-soluble oil washing agent which is semitransparent milky white liquid in appearance.
Application example:
the synthesized oil detergents (examples 1 to 5) and comparative samples (commercially available oil detergents KB-3 and commercially available heavy oil displacement agent QU-02) were mixed with mineralized water (degree of mineralization TDS: 100000mg/L) to prepare solutions having a concentration of 1000 ppm.
TABLE 1 Low dynamic viscosity reduction and static wash oil test results for different wash oil agents
The experimental results show that: examples 1-8 of the water-soluble oil washing agent for oil washing of oil sand disclosed by the invention have good oil washing and viscosity reduction effects, and the comprehensive performance of the water-soluble oil washing agent is superior to that of a commercially available oil washing agent KB-3 and a commercially available heavy oil displacement agent QU-02.
Claims (11)
1. An oil washing agent comprising at least two of a structural unit represented by formula (1), a structural unit represented by formula (2) and a structural unit represented by formula (3), a structural unit represented by formula (4) and a structural unit represented by formula (5):
wherein R is1Is one of C1-C12 alkyl groups, R2Is phenyl, trimethylsilyl or acetate radical, R3Is composed of
a＞0，b＞0。
2. The oil washing agent according to claim 1, characterized in that:
the weight percentage of the structural units shown in the formula (1) in all the structural units is 30-65%, preferably 30-50%;
the weight percentage of the structural units shown in the formulas (2) and (3) in all the structural units is 10-20%, preferably 15-20%;
the weight percentage of the structural units shown in the formula (4) in all the structural units is 20-40%, and preferably 30-40%;
the weight percentage of the structural unit shown in the formula (5) in all the structural units is 5-10%, and preferably 8-10%.
3. An oil washing agent according to claim 2, characterized in that:
the weight ratio of the structural unit represented by formula (2) to the structural unit represented by formula (3) is (1:0.5) to (1:1.5), and preferably (1:0.8) to (1: 1.2).
4. A method for preparing the oil washing agent according to any one of claims 1 to 3, comprising subjecting components including an acrylate monomer, a long-chain branched monomer, a hydrophobic monomer and a hydrophilic monomer to radical polymerization to obtain the oil washing agent.
5. The method for producing an oil washing agent according to claim 4, characterized in that:
the acrylate monomer is at least one of methyl acrylate, butyl acrylate and dodecyl acrylate; and/or the presence of a gas in the gas,
the long-chain branched monomer is polyoxyethylene polyoxypropylene ether with a double bond at the end group, preferably allyl polyoxyethylene polyoxypropylene ether; and/or the presence of a gas in the gas,
the hydrophobic monomer is at least two of methyl methacrylate, styrene, propenyl trimethylsilane and vinyl acetate; and/or the presence of a gas in the gas,
the hydrophilic monomer is acrylic acid.
6. The method for producing an oil washing agent according to claim 4, characterized in that:
based on the total mass of the acrylate monomer, the long-chain branched monomer, the hydrophobic monomer and the hydrophilic monomer,
the acrylate monomer accounts for 30-65%, and preferably 30-50%;
the long-chain branched chain monomer accounts for 20-40 wt%, preferably 30-40 wt%;
10-20 wt% of the hydrophobic monomer, preferably 15-20 wt%;
the hydrophilic monomer accounts for 5-10 wt%, and preferably 8-10 wt%.
7. A method for producing an oil washing agent according to any one of claims 4 to 6, characterized by comprising the steps of:
step 1, adding a long-chain branched monomer and a surfactant into water;
step 2, adding an acrylate monomer and a hydrophobic monomer, and adding a part of initiator under an inert atmosphere to perform reaction;
and 3, adding a hydrophilic monomer and the rest of initiator, and continuing to react to obtain the oil washing agent.
8. The method for producing an oil washing agent according to claim 7, characterized in that:
the surfactant is at least one selected from cetyl trimethyl ammonium bromide, octadecyl dimethyl benzyl quaternary ammonium chloride, sodium dodecyl benzene sulfonate, alkylbenzene sulfonate, alkyl glycerol ether sulfonate and polyoxyethylene octyl phenol ether-10; and/or the presence of a gas in the gas,
the initiator is selected from at least one of 2,2' -azobisisobutylamidine dihydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid and azobisisopropylimidazoline.
9. The method for producing an oil washing agent according to claim 7, characterized in that:
the dosage of the surfactant is 3-8% of the total mass of the reaction emulsion, and preferably 5-8%; and/or the presence of a gas in the atmosphere,
in the step 2, the initiator accounts for 0.1-0.8% of the total mass of the monomers, and preferably 0.3-0.6%; and/or the presence of a gas in the gas,
in the step 3, the initiator accounts for 0.025-0.2% of the total mass of the monomers, and preferably accounts for 0.1-0.2%.
10. The method for producing an oil washing agent according to claim 7, characterized in that:
in the step 2, the reaction temperature is 60-80 ℃, and the reaction time is 2-3 hours; and/or the presence of a gas in the gas,
in the step 3, the reaction temperature is 60-80 ℃, and the reaction time is 4-8 hours.
11. The application of the oil washing agent as defined in any one of claims 1 to 3 or the oil washing agent obtained by the preparation method as defined in any one of claims 4 to 10 in the fields of oil sand oil washing exploitation, production increase of silicate oil reservoir exploitation and viscosity reduction of thick oil.
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