CN102372820A - Long branched chain polymer used for tertiary oil recovery and synthesis method thereof - Google Patents
Long branched chain polymer used for tertiary oil recovery and synthesis method thereof Download PDFInfo
- Publication number
- CN102372820A CN102372820A CN2010102635364A CN201010263536A CN102372820A CN 102372820 A CN102372820 A CN 102372820A CN 2010102635364 A CN2010102635364 A CN 2010102635364A CN 201010263536 A CN201010263536 A CN 201010263536A CN 102372820 A CN102372820 A CN 102372820A
- Authority
- CN
- China
- Prior art keywords
- azo
- monomer
- oil recovery
- tertiary oil
- long chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a polymerizable functional monomer shown in a formula (11) and a synthesis method thereof. The prepared polymerizable functional monomer can be used for synthesizing a long branched chain polymer used for tertiary oil recovery, thus finally preparing a binary composite oil displacement agent for tertiary oil recovery. The binary composite oil displacement agent for tertiary oil recovery obtained in the invention can be used for greatly improving the viscosity of a single polymer oil displacement agent under the conditions of high salinity and high temperature, thereby being beneficial to the application in tertiary oil recovery.
Description
Technical field
The present invention relates to the TOR field, relate in particular to synthetic, long chain branched polymers synthetic of polymerizable functional monomer, can be applicable to fields such as TOR binary combination flooding finish.
Background technology
Radical polymerization is one of effective means of preparation vinyl polymer.Obtain through radical polymerization more than 70% in the vinyl polymer that uses at present.Radical polymerization has many advantages, and is many like suitable monomers, polymerizing condition is gentle, polymerization technique is simple etc.Because many monomers can carry out radical polymerization, can water be that medium suspends and letex polymerization, polymerization technique is easy and simple to handle, its favorable reproducibility, thereby since the fifties in last century, become the important technology of industrial production macromolecule product.
General free radical polymerisation process mainly contains compound methods such as substance law, aqua-solution method, emulsion method and suspension method.Whether add other monomers according to polymerization, can be divided into two kinds of homopolymerization and copolymerization again, of many uses in industries such as oil, mining, papermaking, water treatment, weaving, its demand is also in continuous increase.
What free yl polymerizating monomer was commonly used has: vinylbenzene, and vinylchlorid, vinyl acetate between to for plastic, vinyl cyanide, acrylic amide, vinylformic acid and ester class for improving polymer properties, often need have the functional monomer of various performances.As has a polymerization single polymerization monomer of emulsification function.
Polymerization single polymerization monomer with emulsification function; Claim polymerisable emulsifier again, except that the emulsifying agent group that contains hydrophilic and oleophilic, also contain the functional group that to participate in Raolical polymerizable in its molecular structure; Can be bonded in the latex particle surface with the mode of chemical bond; Become the part of polymkeric substance, so the emulsifying agent molecule desorb can not occur again, thereby make polymer particle in agglomeration process, receive electrostatic repulsion and bigger steric restriction effect; Make the be improved kind of polymerisable emulsifier of the stability of latex a lot, Malaysia acids polymerisable emulsifier have reactive behavior moderate, be difficult for distinct advantages such as homopolymerization.
The product that obtains the industrialization promotion application at oilfield polymer flooding mainly is a partially hydrolyzed polyacrylamide, but in the practice process that uses POLYACRYLAMIDE FLOODING, has also found some problems.The degraded of SEPIGEL 305 is one of more serious problem, comprises shear degradation, thermal destruction and oxidative degradation.Sampling analysis before and after the injection pump of partially hydrolyzed polyacrylamide can be found its viscosity degradation 10～30% in order to solve this shear degradation problem, and can adopt increases implantation concentration, adds linking agent or underground method such as synthetic.Present developing direction is through process for copolymerization, in the polyacrylamide amine molecule, introduces branched chain link, improves its rigidity, thereby improves its anti-shear ability.When SEPIGEL 305 surpasses 93 ℃ in temperature, serious thermal destruction can take place, therefore at the unsuitable SEPIGEL 305 that uses of high-temperature stratum.Also can in the polyacrylamide amine molecule, introduce ring texture and sulfonic group, improve its thermostability through the method for copolymerization.Oxygenizement also can cause the degraded of partially hydrolyzed polyacrylamide.
On polymer molecular chain, introduce the monomeric unit of some high thermal stability monomeric units, big skeleton and the group of strong hydratability; Thereby strengthen polymer thermostable property and molecule chain rigidity; Strengthen the polymer hydration ability; Make polymer molecule in the high salinity aqueous solution, can keep bigger ydrodynamics size, this has strengthened the polymkeric substance salt resistance ability to a certain extent.Simultaneously, the introducing of function monomer is restricted polymkeric substance hydrolysis under high salinity water quality condition, can not occur with calcium ions and magnesium ions sedimentary phenomenon taking place, thereby reach the purpose of anti-salt.
Summary of the invention
The technical problem that the present invention will solve:
The objective of the invention is to above-mentioned weak point; A kind of polymerizable functional monomer and compound method thereof are provided; Prepared polymerizable functional monomer can be used as polymeric emulsifiers, and is used for the synthetic of used for tertiary oil recovery long chain branched polymers; Use polymer properties to improve the displacement of reservoir oil, can be used as TOR binary combination flooding finish.
The product technology scheme of polymerizable functional monomer of the present invention is:
A kind of polymerizable functional monomer, its molecular structural formula are like (11) formula:
(11) in the formula: n is 2 or 6, and m is 4,6 or 8.
First kind of compound method technical scheme of polymerizable functional monomer of the present invention is:
The first step is mixed diamines with binary lipid acid, diamines structural formula NH
2-(CH
2)
n-NH
2, binary fatty acid structure formula HOOC-(CH
2)
m-COOH, n are 2 or 6, and m is 4,6 or 8, are heated to 110 ℃～160 ℃, react 2～6 hours, obtain midbody M, and the structural formula of midbody M is (12) formula:
In molar ratio, diamines: binary lipid acid=1: 1～1.2;
Second step in gained midbody M, added organic solvent, added cis-butenedioic anhydride again, under 80 ℃～110 ℃ of temperature of reaction, and back flow reaction 4～8 hours;
Described organic solvent is one or more the mixture in following: ethanol, acetone, ETHYLE ACETATE, benzene,toluene,xylene, methylene dichloride and trichloromethane; In molar ratio,
Diamines: organic solvent=1: 20～30;
Diamines: cis-butenedioic anhydride=1: 1～1.2;
The 3rd step, will go up the step product and steam organic solvent, drying obtains polymerizable functional monomer product;
Can further carry out recrystallization to product purifies.
Second kind of compound method technical scheme of polymerizable functional monomer of the present invention is:
The first step in organic solvent, is mixed diamines with binary lipid acid, be heated to 110 ℃～156 ℃, reacts 2～6 hours, obtains the solution of midbody M; The structural formula of midbody M is (12) formula:
Described organic solvent is one or more the mixture in following: ethanol, acetone, ETHYLE ACETATE, benzene,toluene,xylene, methylene dichloride and trichloromethane;
In molar ratio, diamines: organic solvent=1: 20～30;
Diamines: lipid acid=1: 1～1.2;
Second step in gained midbody M solution, added cis-butenedioic anhydride again, under 80 ℃～110 ℃ of temperature of reaction, and back flow reaction 4～8 hours,
In molar ratio, diamines: cis-butenedioic anhydride=1: 1～1.2;
The 3rd step, will go up the step product and steam organic solvent, drying obtains polymerizable functional monomer product;
Can further carry out recrystallization to product purifies.
Polymerizable functional monomer product of the present invention is used to prepare the used for tertiary oil recovery long chain branched polymers.Used for tertiary oil recovery long chain branched polymers of the present invention is under action of evocating, accomplishes through at least two kinds of monomeric polyreactions, shown in reaction formula (21):
Used for tertiary oil recovery long chain branched polymers of the present invention prepares through following method:
The first step takes by weighing monomer A, monomers B (polymerizable functional monomer) is made into the aqueous solution, and using alkali to regulate the pH value is 4～11; Preferred bases is a sodium hydroxide, or yellow soda ash.
Described monomer A is at least a in the following free yl polymerizating monomer:
Acrylic amide, vinylformic acid, esters of acrylic acid, vinylbenzene, 2-acrylamido-2-methyl propane sulfonic acid and N-vinyl pyrrolidone (NVP); Can be wherein a kind of separately, also can be multiple mixture.
Described polymerizable functional monomer B is that at least a formula is the compound shown in (11).
Above-mentioned monomer A and the monomers B total mass concentration in the aqueous solution is 10%～40%, and wherein the quality of polymerizable functional monomer B is 0.008%～16% of a monomer A;
In second step, under 0 ℃～20 ℃ temperature, under nitrogen protection, add initiator C, polymerization 1 to 8 hour;
Described initiator C is any two kinds in the following radical polymerization initiator system: azo initiator system, peroxide initiator system or redox initiation system;
Described azo initiator system is at least a in following: azo-bis-iso-dimethyl (trade(brand)name AIBME, V601); Azo-bis-isobutyrate hydrochloride (trade(brand)name AIBA, V50); Cellmic C 121 (trade(brand)name ADC whipping agent); Azo di-isopropyl imidazoline salt hydrochlorate (trade(brand)name AIBI, VA044), azo isobutyl cyanic acid methane amide (trade(brand)name CABN, V30), azo dicyclohexyl formonitrile HCN (trade(brand)name ACCN, V40); Azo dicyano valeric acid (trade(brand)name ACVA, V501); Azo di-isopropyl tetrahydroglyoxaline (trade(brand)name AIP, VA061), Diisopropyl azodicarboxylate (trade(brand)name AIBN, V60), AMBN (trade(brand)name AMBN, V59) and ABVN (trade(brand)name ABVN, V65);
Described peroxide initiator system is at least a in following: hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, the Lucidol and the Lucidol tert-butyl ester;
Described redox initiation system is at least a in following: vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide;
Preferred described ammonium persulphate-aliphatic amide is at least a in following: ammonium persulphate-N, N-Tetramethyl Ethylene Diamine and ammonium persulphate-diethylamine.
The quality of initiator C is 0.01%～0.1% of a monomer total mass;
The 3rd step was warmed up to 40 ℃～80 ℃, continued polymerization 1～4 hour;
The 4th step, the gained colloid is taken out, granulation, drying is pulverized, and obtains the used for tertiary oil recovery long chain branched polymers product of white granular.
In the above method, through a preferred scheme, the used for tertiary oil recovery long chain branched polymers that obtains, its structural formula are like (22) formula:
(22) in the formula; N is 2 or 6; M is 6,8 or 10; X is the polymerization degree of acrylic amide (monomer A), x=10 ten thousand～500,000; Y is the polymerization degree of 2-acrylamido-2-methyl propane sulfonic acid (monomer A), y=5 ten thousand～150,000; Z is the polymerization degree of polymerizable functional monomer B, z=1 ten thousand～50,000.
With used for tertiary oil recovery long chain branched polymers of the present invention and surfactant compound, form the binary combination flooding finish, to improve the temperature resistant antisalt performance of oil-displacing agent.
TOR binary combination flooding finish of the present invention is made up of following component: structural formula fully obtains the binary combination flooding finish after the stirring and dissolving like used for tertiary oil recovery long chain branched polymers, tensio-active agent, the salt brine solution of (22).
Described tensio-active agent is one or more a mixture of following compound: alkylaryl sulphonate, alkylaryl sulfonate, polyethenoxy ether sulphonate, sulphosuccinates, sulfonated petro-leum, petroleum carboxylate, amido-carboxylic acid salt, polyethenoxy ether carboxylate and T 46155 phosphoric acid salt;
Described salt brine solution is the aqueous solution that contains calcium ion, mg ion and NaCl;
The mass ratio of described used for tertiary oil recovery long chain branched polymers in total mass is 0.05%～0.3%; The mass ratio of described tensio-active agent quality in total mass is 0.05%～0.1%; Surplus is a salt solution.
In the described salt brine solution, the calcium ion quality is 0.004%～0.05% of a total mass, and the mg ion quality is 0.004%～0.05% of a total mass, and the NaCl quality is 0.1%～5% of a total mass;
Preparing method's technical scheme of binary combination flooding finish of the present invention is:
The first step takes by weighing described used for tertiary oil recovery long chain branched polymers, adds salt brine solution, stirs 1～2 hour, and it is fully dissolved; Described used for tertiary oil recovery long chain branched polymers is a kind of polymkeric substance in the structural formula (22);
Second step took by weighing tensio-active agent, joined in the above-mentioned solution, stirred 0.5～1 hour, and it is fully dissolved, and obtained the binary combination flooding finish.
The invention has the beneficial effects as follows:
Polymerizable functional monomer product of the present invention can be used as polymeric emulsifiers, and is used for the synthetic of used for tertiary oil recovery long chain branched polymers, improves the used for tertiary oil recovery polymer properties, as the oil-displacing agent of TOR, can improve heatproof, the salt resistant character of oil-displacing agent.
Description of drawings
Fig. 1 is the structured testing figure of radical polymerization functional monomer.
Embodiment
Embodiment 1-6 [synthesizing of polymerizable functional monomer]
Embodiment 1
Press first kind of synthetic technology scheme of polymerizable functional monomer, the quadrol of getting 0.1mol mixes with the 0.1mol sebacic acid, is heated to 130 ℃, reacts 2～6 hours, obtains midbody.In the gained midbody, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol, under 80 ℃～110 ℃, back flow reaction steamed solvent after 4～8 hours, and drying gets polymerizable functional monomer product, is designated as monomer 1.
Fig. 1 is seen in structured testing, 2848.3cm
-1, 2916.8cm
-1Be the symmetry and the asymmetric stretching vibration absorption peak of methyl, methylene radical, 1377.5cm
-1, 1406.0cm
-1, 1467.5cm
-1In-plane bending vibration peak for methyl, methylene radical; 1709.3cm
-1Stretching vibration peak for C=O; 1642.5cm
-1, 1588.5cm
-1Stretching vibration peak for the two keys of C=C; 3073.1cm
-1Be the stretching vibration peak of the last c h bond of C=C-H, these have proved the existence of two keys.3241.2cm
-1Be the stretching vibration peak of N-H key, 1524.8cm
-1It then is the in-plane bending vibration of N-H.These charateristic avsorption bands have proved that the product that obtains is the radical polymerization functional monomer of structural formula (11).
Embodiment 2
Press first kind of synthetic technology scheme of polymerizable functional monomer, the hexanediamine of getting 0.1mol mixes with the 0.1mol sebacic acid, is heated to 130 ℃, reacts 2～6 hours, obtains midbody.In the gained midbody, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol, under 80 ℃～110 ℃, back flow reaction steamed solvent after 4～8 hours, and drying gets polymerizable functional monomer product, is designated as monomer 2.
Press second kind of synthetic technology scheme of polymerizable functional monomer, measure 150 milliliters of p-Xylol, the quadrol that adds 0.1mol mixes with the 0.1mol suberic acid, is heated to 130 ℃～150 ℃; Reacted 2～6 hours, and steamed solvent, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol again; Under 80 ℃～110 ℃, back flow reaction steamed solvent after 4～8 hours; Drying gets polymerizable functional monomer product, is designated as monomer 3.
Embodiment 4
Press second kind of synthetic technology scheme of polymerizable functional monomer, measure 150 milliliters of p-Xylol, the hexanediamine that adds 0.1mol mixes with the 0.1mol suberic acid, is heated to 130 ℃～150 ℃; Reacted 2～6 hours, and steamed solvent, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol again; Under 80 ℃～110 ℃, back flow reaction steamed solvent after 4～8 hours; Drying gets polymerizable functional monomer product, is designated as monomer 4
Embodiment 5
Press first kind of synthetic technology scheme of polymerizable functional monomer, get the quadrol and 0 of 0.1mol, the 1mol hexanodioic acid mixes, and is heated to 130 ℃, reacts 2～6 hours, obtains midbody.In the gained midbody, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol, under 80 ℃～110 ℃, back flow reaction steamed solvent after 4～8 hours, and drying gets polymerizable functional monomer product, is designated as monomer 5.
Embodiment 6
Press first kind of synthetic technology scheme of polymerizable functional monomer, the hexanediamine of getting 0.1mol mixes with the 0.1mol hexanodioic acid, is heated to 130 ℃, reacts 2～6 hours, obtains midbody.In the gained midbody, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol, under 80 ℃～110 ℃, back flow reaction steamed solvent after 4～8 hours, and drying gets polymerizable functional monomer product, is designated as monomer 6.
Embodiment 7-12 [synthesizing of used for tertiary oil recovery long chain branched polymers]
Embodiment 7 synthetic used for tertiary oil recovery long chain branched polymers
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 1 back and add azo-bis-isobutyrate hydrochloride (AIBA) 1.0 milligrams; Under nitrogen protection, add 2.0 milligrams of Ammonium Persulfate 98.5s, select 20 ℃ of temperature earlier, polymerization is after 8 hours; Be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out granulation; Drying is pulverized, and obtains white granular used for tertiary oil recovery long chain branched polymers product, is designated as polymkeric substance 1; The test polymer molecular weight is 2,800 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 35.5mPas.
Embodiment 8 synthetic used for tertiary oil recovery long chain branched polymers
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 2 backs and add azo-bis-isobutyrate hydrochloride (AIBA) 1.0 milligrams; Under nitrogen protection, add 2.0 milligrams of Ammonium Persulfate 98.5s, select 20 ℃ of temperature earlier, polymerization is after 8 hours; Be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out granulation; Drying is pulverized, and obtains white granular used for tertiary oil recovery long chain branched polymers product, is designated as polymkeric substance 2; The test polymer molecular weight is 2,600 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 33.8mPas.
Embodiment 9 synthetic used for tertiary oil recovery long chain branched polymers
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 3 backs and add azo-bis-isobutyrate hydrochloride (AIBA) 1.0 milligrams; Under nitrogen protection, add 2.0 milligrams of Ammonium Persulfate 98.5s, select 20 ℃ of temperature earlier, polymerization is after 8 hours; Be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out granulation; Drying is pulverized, and obtains white granular used for tertiary oil recovery long chain branched polymers product, is designated as polymkeric substance 3; The test polymer molecular weight is 2,500 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 30.2mPas.
Embodiment 10 synthetic used for tertiary oil recovery long chain branched polymers
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 4 backs and add azo-bis-isobutyrate hydrochloride (AIBA) 1.0 milligrams; Under nitrogen protection, add 2.0 milligrams of Ammonium Persulfate 98.5s, select 20 ℃ of temperature earlier, polymerization is after 8 hours; Be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out granulation; Drying is pulverized, and obtains white granular used for tertiary oil recovery long chain branched polymers product, is designated as polymkeric substance 4; The test polymer molecular weight is 2,400 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 29.4mPas.
Embodiment 11 synthetic used for tertiary oil recovery long chain branched polymers
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 5 backs and add azo-bis-isobutyrate hydrochloride (AIBA) 1.0 milligrams; Under nitrogen protection, add 2.0 milligrams of Ammonium Persulfate 98.5s, select 20 ℃ of temperature earlier, polymerization is after 8 hours; Be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out granulation; Drying is pulverized, and obtains white granular used for tertiary oil recovery long chain branched polymers product, is designated as polymkeric substance 5; The test polymer molecular weight is 2,000 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 20.6mPas.
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 6 backs and add azo-bis-isobutyrate hydrochloride (AIBA) 3.0 milligrams; Under nitrogen protection, add 6.0 milligrams of Ammonium Persulfate 98.5s, select 20 ℃ of temperature earlier, polymerization is after 8 hours; Be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out granulation; Drying is pulverized, and obtains white granular used for tertiary oil recovery long chain branched polymers product, is designated as polymkeric substance 6; The test polymer molecular weight is 1,900 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 18.2mPas.
Embodiment 13-18 [preparation of TOR binary combination flooding finish]
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 1 joins in the 200 gram salt brine solutions of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9%; Under magnetic stirring apparatus, stir after 1.5 hours; Add 0.1 gram alkylaryl sulphonate again; Stir and it was fully dissolved in 0.5 hour, obtain TOR binary combination flooding finish 1.
Embodiment 14 preparation TOR binary combination flooding finishes
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 2 joins in the 200 gram salt brine solutions of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9%; Under magnetic stirring apparatus, stir after 1.5 hours; Add 0.1 gram alkylaryl sulfonate again; Stir and it was fully dissolved in 0.5 hour, obtain TOR binary combination flooding finish 2.
Embodiment 15 preparation TOR binary combination flooding finishes
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 3 joins in the 200 gram salt brine solutions of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9%; Under magnetic stirring apparatus, stir after 1.5 hours; Add 0.1 gram polyethenoxy ether sulphonate again; Stir and it was fully dissolved in 0.5 hour, obtain TOR binary combination flooding finish 3.
Embodiment 16 preparation TOR binary combination flooding finishes
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 4 joins in the 200 gram salt brine solutions of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9%; Under magnetic stirring apparatus, stir after 1.5 hours; Add 0.1 gram sulfonated petro-leum again; Stir and it was fully dissolved in 0.5 hour, obtain TOR binary combination flooding finish 4.
Embodiment 17 preparation TOR binary combination flooding finishes
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 5 joins in the 200 gram salt brine solutions of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9%; Under magnetic stirring apparatus, stir after 1.5 hours; Add 0.1 gram petroleum carboxylate again; Stir and it was fully dissolved in 0.5 hour, obtain TOR binary combination flooding finish 5.
Embodiment 18 preparation TOR binary combination flooding finishes
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 6 joins in the 200 gram salt brine solutions of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9%; Under magnetic stirring apparatus, stir after 1.5 hours; Add 0.1 gram T 46155 phosphoric acid salt again; Stir and it was fully dissolved in 0.5 hour, obtain TOR binary combination flooding finish 6.
In order to further specify effect of the present invention, the AV of long chain branched polymers oil-displacing agent and TOR binary combination flooding finish is tested and comparison, see table 31
Table 31
Use BROOKFIELD DV-III viscosity apparatus to be: 7.34S at rotating speed
-1, the AV of mensuration aqueous solutions of polymers under 85 ℃ the condition, test condition: 7.34s
-1, 85 ℃, polymer concentration: 1500mg/L, the solution total mineralization is 32868mg/L.
By above interpretation of result, gained TOR binary combination flooding finish of the present invention has improved the viscosity of single polymers oil-displacing agent greatly under high salinity (32868mg/L) and high temperature (85 ℃), help the application in TOR.
Claims (8)
1. used for tertiary oil recovery long chain branched polymers, its structural formula are like (22) formula:
(22) in the formula: n is 2 or 6; M is 6,8 or 10; X=10 ten thousand～500,000; Y=5 ten thousand～150,000; Z=1 ten thousand～50,000.
2. used for tertiary oil recovery long chain branched polymers, through following method preparation:
The first step takes by weighing monomer A, monomers B (polymerizable functional monomer) is made into the aqueous solution, and using alkali to regulate the pH value is 4～11;
Described monomer A is one or more the arbitrary proportion mixture in the following free yl polymerizating monomer: acrylic amide, vinylformic acid, esters of acrylic acid, vinylbenzene, 2-acrylamido-2-methyl propane sulfonic acid and N-vinyl pyrrolidone (NVP);
Described polymerizable functional monomer B is that at least a formula is the compound shown in (11), and n is 2 or 6 in (11) formula, and m is 4,6 or 8:
Above-mentioned monomer A and the monomers B total mass concentration in the aqueous solution is 10%～40%, and wherein the quality of polymerizable functional monomer B is 0.008%～16% of a monomer A;
In second step, under 0 ℃～20 ℃ temperature, under nitrogen protection, add initiator C, polymerization 1 to 8 hour;
Described initiator C is any two kinds in the following radical polymerization initiator system: azo initiator system, peroxide initiator system or redox initiation system; The quality of initiator C is 0.01%～0.1% of a monomer total mass;
The 3rd step was warmed up to 40 ℃～80 ℃, continued polymerization 1～4 hour;
The 4th step, the gained colloid is taken out, granulation, drying is pulverized, and obtains the used for tertiary oil recovery long chain branched polymers product of white granular.
3. used for tertiary oil recovery long chain branched polymers according to claim 2 adopts sodium hydroxide or yellow soda ash to regulate the pH value in preparing method's the first step.
4. according to claim 2 or 3 described used for tertiary oil recovery long chain branched polymers, in the preparation method in second step,
Described azo initiator system is at least a in following: azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121; Azo di-isopropyl imidazoline salt hydrochlorate, azo isobutyl cyanic acid methane amide, azo dicyclohexyl formonitrile HCN; Azo dicyano valeric acid; Azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, AMBN and ABVN;
Described peroxide initiator system is at least a in following: hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, the Lucidol and the Lucidol tert-butyl ester;
Described redox initiation system is at least a in following: vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide.
5. used for tertiary oil recovery long chain branched polymers according to claim 4, in preparation method second in the step, described ammonium persulphate-aliphatic amide is at least a in following: ammonium persulphate-N, N-Tetramethyl Ethylene Diamine and ammonium persulphate-diethylamine.
6. the preparation method of a used for tertiary oil recovery long chain branched polymers comprises the steps:
The first step takes by weighing monomer A, monomers B (polymerizable functional monomer) is made into the aqueous solution, and using alkali to regulate the pH value is 4～11;
Described monomer A is one or more the arbitrary proportion mixture in the following free yl polymerizating monomer: acrylic amide, vinylformic acid, esters of acrylic acid, vinylbenzene, 2-acrylamido-2-methyl propane sulfonic acid and N-vinyl pyrrolidone (NVP);
Described polymerizable functional monomer B is that at least a formula is the compound shown in (11), and n is 2 or 6 in (11) formula, and m is 4,6 or 8:
Above-mentioned monomer A and the monomers B total mass concentration in the aqueous solution is 10%～40%, and wherein the quality of polymerizable functional monomer B is 0.008%～16% of a monomer A;
In second step, under 0 ℃～20 ℃ temperature, under nitrogen protection, add initiator C, polymerization 1 to 8 hour;
Described initiator C is any two kinds in the following radical polymerization initiator system: azo initiator system, peroxide initiator system or redox initiation system; The quality of initiator C is 0.01%～0.1% of a monomer total mass;
Described azo initiator system is at least a in following: azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121; Azo di-isopropyl imidazoline salt hydrochlorate, azo isobutyl cyanic acid methane amide, azo dicyclohexyl formonitrile HCN; Azo dicyano valeric acid; Azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, AMBN and ABVN;
Described peroxide initiator system is at least a in following: hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, the Lucidol and the Lucidol tert-butyl ester;
Described redox initiation system is at least a in following: vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide.
The 3rd step was warmed up to 40 ℃～80 ℃, continued polymerization 1～4 hour;
The 4th step, the gained colloid is taken out, granulation, drying is pulverized, and obtains the used for tertiary oil recovery long chain branched polymers product of white granular.
7. the preparation method of used for tertiary oil recovery long chain branched polymers according to claim 6 adopts sodium hydroxide or yellow soda ash to regulate the pH value in the first step.
8. according to the preparation method of claim 6 or 7 described used for tertiary oil recovery long chain branched polymers, be at least a in following at the ammonium persulphate-aliphatic amide described in second step: ammonium persulphate-N, N-Tetramethyl Ethylene Diamine and ammonium persulphate-diethylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010263536 CN102372820B (en) | 2010-08-26 | 2010-08-26 | Long branched chain polymer used for tertiary oil recovery and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010263536 CN102372820B (en) | 2010-08-26 | 2010-08-26 | Long branched chain polymer used for tertiary oil recovery and synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102372820A true CN102372820A (en) | 2012-03-14 |
| CN102372820B CN102372820B (en) | 2013-07-03 |
Family
ID=45792086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010263536 Active CN102372820B (en) | 2010-08-26 | 2010-08-26 | Long branched chain polymer used for tertiary oil recovery and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102372820B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103320113A (en) * | 2013-06-27 | 2013-09-25 | 西南石油大学 | Water-soluble AM-AA-NVP-BEMA quadripolymer oil-displacing agent and synthetic method thereof |
| CN103320111A (en) * | 2013-06-25 | 2013-09-25 | 西南石油大学 | AM(acrylamide) /AA(acrylic acid)/NVP(N-vinyl pyrrolidinone)/YEML quadripolymer oil-displacing agent and synthetic method thereof |
| CN103788295A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Two-step preparation method of acrylamide copolymer |
| CN104250217A (en) * | 2013-06-27 | 2014-12-31 | 中国石油化工股份有限公司 | Polymerizable functional monomer and preparation method and application thereof |
| CN104250340A (en) * | 2013-06-27 | 2014-12-31 | 中国石油化工股份有限公司 | Polymerizable functional monomer and preparation method and application thereof |
| CN104558400A (en) * | 2013-10-14 | 2015-04-29 | 中国石油化工股份有限公司 | Random copolymer, method for preparing random copolymer and application of random copolymer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397491A (en) * | 2008-10-27 | 2009-04-01 | 中国科学院长春应用化学研究所 | Multi-element co-polymerization oil well cement fluid loss additive and preparation method thereof |
-
2010
- 2010-08-26 CN CN 201010263536 patent/CN102372820B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397491A (en) * | 2008-10-27 | 2009-04-01 | 中国科学院长春应用化学研究所 | Multi-element co-polymerization oil well cement fluid loss additive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 许家友等: "防垢剂AM-AA-MA三元共聚物的合成", 《化学世界》, no. 10, 31 December 1996 (1996-12-31), pages 541 - 545 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788295A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Two-step preparation method of acrylamide copolymer |
| CN103788295B (en) * | 2012-10-30 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of two-step method prepares the method for acrylamide based copolymer |
| CN103320111A (en) * | 2013-06-25 | 2013-09-25 | 西南石油大学 | AM(acrylamide) /AA(acrylic acid)/NVP(N-vinyl pyrrolidinone)/YEML quadripolymer oil-displacing agent and synthetic method thereof |
| CN103320111B (en) * | 2013-06-25 | 2015-08-05 | 西南石油大学 | A kind of AM/AA/NVP/YEML quadripolymer oil-displacing agent and synthetic method thereof |
| CN103320113A (en) * | 2013-06-27 | 2013-09-25 | 西南石油大学 | Water-soluble AM-AA-NVP-BEMA quadripolymer oil-displacing agent and synthetic method thereof |
| CN104250217A (en) * | 2013-06-27 | 2014-12-31 | 中国石油化工股份有限公司 | Polymerizable functional monomer and preparation method and application thereof |
| CN104250340A (en) * | 2013-06-27 | 2014-12-31 | 中国石油化工股份有限公司 | Polymerizable functional monomer and preparation method and application thereof |
| CN103320113B (en) * | 2013-06-27 | 2015-08-12 | 西南石油大学 | A kind of water-soluble AM-AA-NVP-BEMA tetrapolymer oil-displacing agent and synthetic method thereof |
| CN104250340B (en) * | 2013-06-27 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of polymerizable functional monomer and its preparation method and application |
| CN104250217B (en) * | 2013-06-27 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of polymerizable functional monomer and its preparation method and application |
| CN104558400A (en) * | 2013-10-14 | 2015-04-29 | 中国石油化工股份有限公司 | Random copolymer, method for preparing random copolymer and application of random copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102372820B (en) | 2013-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102372820B (en) | Long branched chain polymer used for tertiary oil recovery and synthesis method thereof | |
| CN104448125B (en) | Amphoteric hydrophobically-associating polymer and preparation method thereof | |
| CN104448128B (en) | Polymer mobility control agent suitable for high-temperature and high-salinity harsh reservoir and preparation method of polymer mobility control agent | |
| CN102031101B (en) | Heat-resistant and salt-resistant polymer thickening agent and preparation method thereof | |
| CN104448127B (en) | Polymer mobility control agent suitable for special high salinity reservoirs and preparation method thereof | |
| CN106866878B (en) | Polymer-type profile control agent and preparation method thereof suitable for high temperature and high salt harshness oil reservoir | |
| CN102050913B (en) | Temperature and salt resistant grafted polyacrylamide and preparation method thereof | |
| CN103146372A (en) | Inverse emulsion polymer thickener for fracturing fluid and preparation method thereof | |
| CN106496411B (en) | A kind of purposes of the hydrophobic associated polymer with a variety of ring structure side chains and preparation method thereof with it | |
| CN102391417A (en) | Hydrophobically associating water-soluble polymer (HAWSP) oil displacement agent and preparation method thereof | |
| CN103435750B (en) | Hydrophobic associated polymer containing capsaicine activity monomer and preparation method thereof | |
| CN104672408B (en) | A kind of water-soluble flooding polymers for having rigid core shell structure and preparation method thereof | |
| CN101157741A (en) | Synthesis technology of high molecular weight temperature-tolerant anti-salt polyacrylamide | |
| CN102746441B (en) | Acrylamide terpolymer and polymer and preparation method and application thereof | |
| CN102372647B (en) | Free radical polymerization functional monomer and synthesis method thereof | |
| CN102373051B (en) | Binary composite oil displacement agent and preparation method thereof | |
| CN102373052B (en) | Binary composite oil displacement agent for tertiary oil recovery and preparation method thereof | |
| CN102372648B (en) | Polymerizable functional monomer and synthesis method thereof | |
| CN103483216B (en) | Polymerizable monomer, and preparation method and application thereof | |
| CN102372819B (en) | Long branched chain polymer used for oil displacement and synthesis method thereof | |
| CN106478869B (en) | A kind of temperature-resistant anti-salt reversed-phase emulsion transfer drive system and its preparation method and application | |
| CN103304465B (en) | A kind of N-alkylsulphonic acid base maleimide monomer and its preparation method and application | |
| CN1137146C (en) | Process for the production of acrylamide polymer dispersion | |
| CN104250343B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN103304729B (en) | A kind of random copolymers and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |