CN104231257A - Aryl alkyl alcohol-polypropylene oxide-polyoxyethylene block copolymer as well as preparation method and application of block polymer - Google Patents
Aryl alkyl alcohol-polypropylene oxide-polyoxyethylene block copolymer as well as preparation method and application of block polymer Download PDFInfo
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Abstract
The invention discloses an aryl alkyl alcohol-polypropylene oxide-polyoxyethylene block copolymer, which has a structure in a general formula I. The preparation method comprises the following steps: alkylating alkenyl carboxylate and aromatic hydrocarbon to obtain aryl alkyl carboxylic acid; esterifying aryl alkyl carboxylic acid and methanol to obtain aryl alkyl carboxylic methyl ether; alkylating alkyl carboxylic methyl ether and aromatic hydrocarbon to obtain aryl alkyl carboxylic methyl ether; carrying out hydrogenation reduction on the aryl alkyl carboxylic methyl ether to form aryl alkyl alcohol; carrying out ring-opening reaction on the aryl alkyl alcohol and epoxypropane to obtain aryl alkyl alcohol polyoxypropylene ether; and carrying out ethoxylation reaction on the aryl alkyl alcohol polyoxypropylene ether and ethylene oxide to obtain the aryl alkyl alcohol-polypropylene oxide-polyoxyethylene block copolymer. The aryl alkyl alcohol-polypropylene oxide-polyoxyethylene block copolymer can be applied to the fields such as residual oil emulsification, thickened oil viscosity reduction, heavy oil pour point depression, nano emulsion preparation, tertiary oil recovery, daily-use chemical industry and the like.
Description
Technical field
The present invention relates to a kind of arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer, belong to tensio-active agent science and technology field.
Background technology
Fatty alcohol polyoxypropylene polyoxyethylene block copolymer is the novel nonionogenic tenside of a class, and oxypropylene block is oil soluble, and this makes the hydrophobic group of active agent molecule relatively add a lot, and oily molten effect strengthens greatly; Simultaneously due to the increase of molecular weight, under finite concentration, micelle is close to each other and in reticulated structure or assemble the possibility forming rod-shaped micelle and increase, solution can become very thickness.Due to these characteristics of fatty alcohol polyoxypropylene polyoxyethylene block copolymer, at some specific area, there is good application prospect.
The fatty alcohol preparing fatty alcohol polyoxypropylene polyoxyethylene block copolymer used is mainly derived from animal-plant oil, is with C
12to C
18fatty alcohol be main.
The chemical composition of usual crude oil is alkane, aromatic hydrocarbon, resin and asphalt.List the fractions consisting of Daqing crude oil and some crude oil of China below, in table 1 and table 2.
Table 1 Daqing oil field crude oil forms
Some crude oil fractions consistings of table 2 China
There is the polyoxyethylene polyoxypropylene segmented copolymer of arylalkyl hydrophobic group structure, because hydrophobic group structure forms similar to crude oil, can be stronger to the solublization of crude oil, especially residual oil and viscous crude etc.; Oxypropylene block makes active agent molecule larger, and in the emulsification, viscosity reduction, pour point depression etc. of crude oil, viscous crude, residual oil, performance also can be more outstanding; Simultaneously due to more outstanding to the viscosifying action of solution, in tertiary oil recovery field, viscosity time composite with polymkeric substance comparatively polymer viscosity can increase greatly, low permeability oil field exploitation field, because the molecular weight of polymkeric substance is very large, be difficult to enter low-permeability oil deposit duct, there is the polyoxyethylene polyoxypropylene segmented copolymer tackifying liquid of arylalkyl structure, the effect controlling mobility can be played.
Therefore, there is the polyoxyethylene polyoxypropylene segmented copolymer of arylalkyl hydrophobic group structure, there is very important application and development prospect.
Summary of the invention
Object of the present invention aims to provide a kind of arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer, has formula I structure:
Wherein:
M+n is 0,1,2 ... 28,29,30 positive integers;
P is 1,2 ... 4998,4999,5000 positive integers;
Q is 0,1,2 ... 4998,4999,5000 positive integers;
R is phenyl, tolyl, m-xylene base, p-Xylol base, o-Xylol base, ethylbenzene, n-propyl phenyl, isopropyl phenyl, n-butylphenyl, isobutyl phenenyl, tert-butyl-phenyl, naphthyl, methyl naphthyl, dimethyl naphthyl, ethyl naphthyl, propyl group naphthyl, butyl naphthyl, xenyl, the one in phenylol.
Further, in technique scheme, m+n is preferably 8,15,19, is more preferably 15.
Further, in technique scheme, p is preferably 5,6 ... 998, the positive integer of 999,1000, is more preferably 5,6 ... 49, the positive integer of 50.
Further, in technique scheme, q is preferably 5,6 ... 998, the positive integer of 999,1000, is more preferably 5,6 ... 49, the positive integer of 50.
Further, in technique scheme, R is preferably m-xylene base.
Another object of the present invention is to provide the preparation method of above-mentioned arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer, technical scheme of the present invention is under an acidic catalyst effect, by alkene-carboxylic acid and aromatic hydrocarbon alkylation, obtain arylalkyl carboxylic acids, arylalkyl carboxylic acids and methyl alcohol carry out esterification and obtain arylalkyl carboxylic acids's methyl esters: also alkene-carboxylic acid's methyl esters and aromatic hydrocarbon can be carried out alkylation, obtain arylalkyl carboxylic acids's methyl esters, arylalkyl carboxylic acids's methyl ester hydrogenation is reduced into arylalkyl alcohol, arylalkyl alcohol and propylene oxide carry out ring-opening reaction, obtain arylalkyl alcohol polyethenoxy ether, arylalkyl alcohol polyethenoxy ether carries out ethoxylation with oxyethane again, obtain arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer
Further, in technique scheme, synthesizing aryl alkyl carboxylic acid of the present invention and arylalkyl carboxylic acids's methyl esters an acidic catalyst used be selected from sulfuric acid, hydrofluoric acid, methylsulphonic acid, trifluoromethanesulfonic acid, the trifluoromethanesulfonic acid root of metal salts of trifluoromethane sulphonic acid or load, heteropolyacid, solid super-strong acid, acid zeolite, perfluorinated resin, ionic liquid any one or a few, the trifluoromethanesulfonic acid root of preferable methyl sulfonic acid, metal salts of trifluoromethane sulphonic acid or load, more preferably methylsulphonic acid.
Further, in technique scheme, in the present invention, arylalkyl methyl ester hydrogenation is reduced into arylalkyl alcohol, is the liquid-phase hydrogenatin technique under the effect of Cu-Cr/Cu-Zn/Cu-Si mixed catalyst.
Further, in technique scheme, the ring-opening reaction that in the present invention, arylalkyl alcohol and propylene oxide carry out, used catalyst is selected from BF
3, SbCI
5, SnCI
4, solid acid, heteropolyacid, one in carried molecular sieve catalyst; Or be selected from potassium hydroxide, sodium hydroxide, sodium methylate, sodium ethylate, Mg/AI composite oxides (MAO), the oxide compound of barium and the mixture of oxyhydroxide, aluminum alkoxide sulfonate, rare metal alcoxyl vitriol, alkaline earth metal oxide and phosphoric acid, the one in preferred potassium hydroxide, sodium methylate, Mg/AI composite oxides (MAO).
Further, in technique scheme, the ethoxylation that in the present invention, arylalkyl alcohol polyethenoxy ether and oxyethane carry out, used catalyst is selected from BF
3, SbCI
5, SnCI
4, solid acid, heteropolyacid, one in carried molecular sieve catalyst; Or the one be selected from potassium hydroxide, sodium hydroxide, sodium methylate, sodium ethylate, Mg/AI composite oxides (MAO), the oxide compound of barium and the mixture of oxyhydroxide, aluminum alkoxide sulfonate, rare metal alcoxyl vitriol, alkaline earth metal oxide and phosphoric acid, preferred potassium hydroxide, sodium methylate, Mg/AI composite oxides (MAO).
Further, in technique scheme, the alkene-carboxylic acid described in the present invention is undecylenic acid: CH
2=CH (CH
2)
8cOOH, oleic acid: CH
3(CH
2)
7cH=CH (CH
2)
7cOOH, erucic acid: cis-13-docosenoic acid, preferred oleic acid.
Further, in technique scheme, alkene-carboxylic acid's methyl esters in the present invention is methyl undecylenate, Witconol 2301, methyl erucate, preferred Witconol 2301.
Further, in technique scheme, aromatic hydrocarbon of the present invention is benzene, toluene, m-xylene, p-Xylol, o-Xylol, ethylbenzene, n-propylbenzene, isopropyl benzene, n-butylbenzene, isobutyl-benzene, tert.-butylbenzene, naphthalene, methylnaphthalene, dimethylnaphthalene, ethyl naphthalene, propyl group naphthalene, dibutyl naphthalene, biphenyl, the one in phenol, preferred m-xylene.
Further, in technique scheme, liquid acid methylsulphonic acid is as catalyzer, the mol ratio of alkene-carboxylic acid or alkene-carboxylic acid's methyl esters and aromatic hydrocarbon, catalyzer is 1:1.5-3.5:1.15-2.0, temperature of reaction 100-135 DEG C, drips alkene-carboxylic acid or alkene-carboxylic acid's methyl esters, then react 5 hours, be washed to pH value neutrality, short-path distillation removes the raw material that do not reflect and saturated acid wherein, obtains arylalkyl carboxylic acids or arylalkyl carboxylic acids's methyl esters.
Further, in technique scheme, according to different application targets, the size of adjustment polyoxypropylene, polyoxyethylene blocks, can obtain suitable polyoxyethylene polyoxypropylene segmented copolymer.
Further, in technique scheme, the ring-opening reaction that arylalkyl alcohol of the present invention and propylene oxide carry out, preferred aryl groups alkyl alcohol and propylene oxide mol ratio are the reaction of 1:5 ~ 50.
Further, in technique scheme, the ring-opening reaction that arylalkyl alcohol polyethenoxy ether of the present invention and oxyethane carry out, preferred aryl groups alkyl alcohol polyethenoxy ether and molar are than the reaction for 1:10 ~ 50.
Beneficial outcomes of the present invention is:
1. aromatic yl alkyl group of the present invention and oxypropylene block are oil soluble, have very strong with crude oil, viscous crude, residual oil etc. the performance that mixes, by controlling the size of access ethylene oxide block, the oleophylic hydrophilic balance of arylalkyl alcohol polyoxyethylene polyoxypropylene block can be controlled, be widely used in the fields such as residual oil emulsification, reducing thick oil viscosity, emulsification of crude oil;
2. arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer of the present invention, has highly stable chemical property, is particularly suitable for the application in tertiary oil recovery chemical flooding, has emulsification, solubilising, the performance such as wetting;
3. arylalkyl alcohol polyoxyethylene polyoxypropylene block copolymer amount of the present invention is larger, easily rod-shaped micelle is formed in aqueous under finite concentration, there is good Efficient Adhesive Promotion, apply under being particularly suitable for low permeability oil field or the inapplicable situation of high temperature and high salt field polymers;
4. arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer preparation method transformation efficiency of the present invention is high, is applicable to industrialization and produces.
Accompanying drawing explanation
Accompanying drawing 5 width of the present invention,
Fig. 1 is the infrared spectrogram of the m-xylene base octadecane carboxylic acid that embodiment 1 prepares;
Fig. 2 is the m-xylene base octadecane carboxylate methyl ester infrared spectrogram that embodiment 1 prepares;
Fig. 3 is the m-xylene base Stearyl alcohol infrared spectrogram that embodiment 1 prepares;
Fig. 4 is m-xylene base Stearyl alcohol polyoxypropylene (15) the ether flight time mass spectrum figure that embodiment 1 prepares;
Fig. 5 is m-xylene base Stearyl alcohol polyoxypropylene (15) polyoxyethylene (15) the segmented copolymer flight time mass spectrum figure arrived prepared by embodiment 1.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but not as a limitation of the invention.
Embodiment 1:
1. Friedel-Crafts alkylation:
1. reaction formula
Wherein: m+n=15.
2. raw material specification
Technical grade high-purity oleic acid C18:1 content>=75.0%, iodine number (gI
2/ 100g) 80-100, moisture≤0.5%, peroxide value≤10 (mg/Kg).
Technical grade methyl sulfonic acid, clear, content >=98.0%, ion content≤100ppm.
Technical grade m-xylene, content >=99.0%.
3. proportioning raw materials
Oleic acid: methylsulphonic acid: m-xylene=1:1.5:3.0 (mol ratio).
4. synthesis technique
In sealing 2000 liters of enamel reaction stills; inflated with nitrogen displaced air; add 496.9 kilograms of m-xylenes and 225 kilograms of methylsulphonic acids; reactor inflated with nitrogen is protected, and stirs, is warming up to 125 DEG C; start constant speed and add industrial high-purity oleic acid; control temperature of reaction at 130 DEG C, within 5 hours, add 440.6 kilograms of high-purity oleic acid of industry altogether, oleic acid adds rear continuation reaction 2h.
5. post-treating method
Under being cooled to room temperature, material being proceeded in another 3000 liters of enamel reaction stills, under whipped state, slowly add 200 kilograms of deionized waters, the deionized water joining day is at about 60min, then continue to stir about 60min, static more than 2 hours, separate lower layer of water and methylsulphonic acid.
The water separated and methylsulphonic acid reclaim methylsulphonic acid by falling film evaporation thickening and rectifying, and the methylsulphonic acid of recovery recycles.
Reaction mass deionized water agitator treating three times, neutral to pH value.
Material after washing steams m-xylene and residual water through falling liquid film, and after natural layering, m-xylene recycles.
Material removes unreacted oleic acid (comprising saturated fatty acid) through molecular distillation, vacuum tightness 1Pa, temperature 150 DEG C.
Material, through molecular distillation decolouring (vacuum tightness 1Pa, temperature 210 DEG C), obtains m-xylene base octadecane carboxylic acid.
Gas-chromatography and liquid-phase chromatographic analysis, oleic acid conversion >=93%.
6. structural characterization and product property
M-xylene base octadecane carboxylic acid infrared spectrogram is shown in Fig. 1.
At Fig. 1, we can see 1710cm
-1(carboxylic acid dimerization C=O stretching vibration), 1614cm
-1(carboxylate radical COO antisymmetric stretching vibration), 1412cm
-1(carboxylate radical COO symmetrical stretching vibration), 1284cm
-1(carboxylic acid C-OH stretching vibration, 1047cm
-1(lactone C-O-C symmetrical stretching vibration), 938cm
-1(carboxylic acid COH out-of-plane deformation vibration); 1502cm
-1(phenyl ring skeleton C=C stretching vibration), 877cm
-1(phenyl ring having isolated hydrogen), 817cm
-1(phenyl ring skeleton C=C out-of-plane deformation vibration), 725cm
-1(between on phenyl ring disubstituted C-H out-of-plane deformation vibration); 2925cm
-1(CH
2alkane antisymmetric stretching vibration), 2853cm
-1(CH
2alkane symmetrical stretching vibration) 1463cm
-1(CH
2alkane angle vibrate), 1377cm
-1(CH
3symmetric deformation vibrates).
M-xylene base octadecane carboxylic acid indices: content>=95%, iodine number≤10 (gI
2/ 100g), pour point-21 DEG C, flash-point 238 DEG C (opening), density 0.923 (g/cm
2).
2. esterification: 1. reaction formula
Wherein: m+n=15
2. raw material specification
M-xylene base octadecane carboxylic acid is prepared by step 1: content>=95%, iodine number≤10 (gI
2/ 100g).
Methanol content >=99.0% moisture≤0.1%
Strongly-acid large pores cation exchange resin D061.
3. technique
Adopt three-stage fixed bed esterification technique
First step fixed bed: m-xylene base octadecane carboxylic acid: methyl alcohol=1:7 (mol ratio), temperature 90 DEG C, flow velocity is 0.3 times of resin volume, adopts falling-film evaporator to remove the water of generation and excessive methyl alcohol.
Second stage fixed bed: m-xylene base octadecane carboxylic acid: methyl alcohol=1:5 (mol ratio), temperature 90 DEG C, flow velocity is 0.5 times of resin volume, adopts falling-film evaporator to remove the water of generation and excessive methyl alcohol.
Third stage fixed bed: m-xylene base octadecane carboxylic acid: methyl alcohol=1:3 (mol ratio), temperature 90 DEG C, flow velocity is 0.5 times of resin volume, adopts falling-film evaporator to remove the water of generation and excessive methyl alcohol.
Material, through molecular distillation decolouring (vacuum tightness 1Pa, temperature 200 DEG C), obtains m-xylene base octadecane carboxylate methyl ester.
3. reduction reaction: 1. reaction formula, m-xylene base octadecane carboxylate methyl ester is prepared by step 2,
2. hydrogenation process conditions
Temperature of reaction 210 ~ 230 DEG C, reaction pressure 18 ~ 21MPa, hydrogen internal circulating load 150 ~ 175m
3/ h, the initial 30Kg/h of sample introduction speed, 60Kg/h when stablizing, transformation efficiency 98%.
3. structural characterization
M-xylene base Stearyl alcohol infrared spectrogram is shown in Fig. 3.
At Fig. 3, we can see 3333cm
-1(the OH stretching vibration of alcoholic extract hydroxyl group R-OH), 1056cm
-1(alcoholic extract hydroxyl group C-OH stretching vibration); 1502cm
-1(phenyl ring skeleton C=C stretching vibration), 877cm
-1(phenyl ring having isolated hydrogen), 817cm
-1(phenyl ring skeleton C=C out-of-plane deformation vibration), 722cm
-1(between on phenyl ring disubstituted C-H out-of-plane deformation vibration); 2927cm
-1(CH
2alkane antisymmetric stretching vibration), 2853cm
-1(CH
2alkane symmetrical stretching vibration) 1463cm
-1(CH
2alkane angle vibrate), 1377cm
-1(CH
3symmetric deformation vibrates).
4. ring-opening reaction: 1. reaction formula
2. synthesis technique
Take 111.8 grams of m-xylene base Stearyl alcohols and 2.0 grams of Mg/AI composite oxides (MAO) are dropped in 1 liter of synthesis reactor, synthesis reactor is sealed, with nitrogen replacement 3 times.Start and stir, be warming up to 140 DEG C, start vacuum pump evacuation, stop vacuumizing when being warming up to 170 DEG C.Open feed valve, be pressed into gradually in reactor by 261.36 grams of propylene oxide in storage tank with nitrogen, control temperature of reaction at 140 DEG C ~ 180 DEG C, pressure≤0.15MPa, reacts 5 hours.Cooling, discharging, obtains m-xylene base Stearyl alcohol polyoxypropylene (15) ether.
3. structural characterization
M-xylene base Stearyl alcohol polyoxypropylene (15) ether flight time mass spectrum figure is shown in Fig. 4.
By Fig. 4, we can see, it is in normal distribution form that propylene oxide adds to the polyoxypropylene ether structure that m-xylene base Stearyl alcohol obtains.
5. ethoxylation: 1. reaction formula
2. synthesis technique
Take 249 grams of m-xylene base Stearyl alcohol polyoxypropylene (15) ethers and 1.5 grams of sodium methylates drop in 1 liter of synthesis reactor, synthesis reactor is sealed, with nitrogen replacement 3 times.Start and stir, be warming up to 130 DEG C, start vacuum pump evacuation, stop vacuumizing when being warming up to 160 DEG C.Open feed valve, be pressed into gradually in reactor by 133 grams of oxyethane in storage tank with nitrogen, control temperature of reaction at 130 DEG C ~ 170 DEG C, pressure≤0.15MPa, reacts 6 hours.Cooling, discharging, obtains m-xylene base octadecane polyoxypropylene (15) polyoxyethylene (15) segmented copolymer.
3. structural characterization
M-xylene base octadecane polyoxypropylene (15) polyoxyethylene (15) segmented copolymer flight time mass spectrum figure is shown in Fig. 5.
By Fig. 5, we can see, ethyleneoxide addition to m-xylene base Stearyl alcohol polyoxypropylene ether structure are also normal distribution addition is gone, and the superposition of two normal distribution structures, obtains the flight time mass spectrum form of Fig. 5.
Embodiment 2: provide another to prepare the method for arylalkyl carboxylic acids's methyl esters, all the other steps are with embodiment 1.
Friedel-Crafts alkylation:
1. reaction formula
Wherein: m+n=15
2. raw material specification
The high-purity Witconol 2301 of technical grade: C18:1 content>=75.0%, iodine number (gI
2/ 100g) 80-100, moisture≤0.5%, acid number≤0.5 (mgKOH/g), peroxide value≤10 (mg/Kg).
Technical grade methyl sulfonic acid clear content >=98.0% ion content≤100ppm
Technical grade m-xylene content >=99.0%
3. proportioning raw materials
Witconol 2301: methylsulphonic acid: m-xylene=1:1.5:3.0 (mol ratio)
4. synthesis technique
In sealing 2000 liters of enamel reaction stills; inflated with nitrogen displaced air; add 496.9 kilograms of m-xylenes and 225 kilograms of methylsulphonic acids; reactor inflated with nitrogen is protected, and stirs, is warming up to 125 DEG C; start constant speed and add industrial high-purity Witconol 2301; control temperature of reaction at 130 DEG C, within 5 hours, add 462.5 kilograms of high-purity Witconol 2301s of industry altogether, Witconol 2301 adds rear continuation reaction 2h.
5. post-treating method
Under being cooled to room temperature, material being proceeded in another 3000 liters of enamel reaction stills, under whipped state, slowly add 200 kilograms of deionized waters, the deionized water joining day is at about 60min, then continue to stir about 60min, static more than 2 hours, separate lower layer of water and methylsulphonic acid.
The water separated and methylsulphonic acid reclaim methylsulphonic acid by falling film evaporation thickening and rectifying, and the methylsulphonic acid of recovery recycles.
Reaction mass deionized water agitator treating three times, neutral to pH value.
Material falling liquid film after washing steams m-xylene and residual water, and after natural layering, m-xylene recycles.
Material removes unreacted Witconol 2301 (comprising saturated fatty acid methyl ester) through molecular distillation, vacuum tightness 1Pa, temperature 140 DEG C.
Material, through molecular distillation decolouring (vacuum tightness 1Pa, temperature 200 DEG C), obtains m-xylene base octadecane carboxylate methyl ester.
Gas-chromatography and liquid-phase chromatographic analysis, Witconol 2301 transformation efficiency >=93%.
6. structural characterization and product property
M-xylene base octadecane carboxylate methyl ester infrared spectrogram is shown in Fig. 2.
At Fig. 2, we can see 1742cm
-1(carboxylicesters C=O stretching vibration), 1436cm
-1(carboxylate radical COO symmetrical stretching vibration), 1170cm
-1(high carboxylic acid's ester C-O-C antisymmetric stretching vibration, 1031cm
-1(fatty acid ester C-O-C symmetrical stretching vibration); 1502cm
-1(phenyl ring skeleton C=C stretching vibration), 873cm
-1(phenyl ring having isolated hydrogen), 817cm
-1(phenyl ring skeleton C=C out-of-plane deformation vibration), 723cm
-1(between on phenyl ring disubstituted C-H out-of-plane deformation vibration); 2925cm
-1(CH
2alkane antisymmetric stretching vibration), 2853cm
-1(CH
2alkane symmetrical stretching vibration) 1462cm
-1(CH
2alkane angle vibrate), 1376cm-1 (CH
3symmetric deformation vibrates).
M-xylene base octadecane carboxylate methyl ester indices: content>=95%, acid number≤0.5 (mgKOH/g), iodine number≤10 (gI
2/ 100g), pour point-24 DEG C, flash-point 226 DEG C (opening), density 0.895 (g/cm
2).
Application examples 1:
Arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer and polymkeric substance work in coordination with viscosifying action.
Raw material specification:
Polymkeric substance (water-soluble polyacrylamide, Daqing Refinery company produces);
Promoting agent 1: octadecyl hydroxypropyl sultaine (18 tertiary amines and 3-chlorine-2-hydroxyl propanesulfonate press 1:1.1 mol ratio, and methyl alcohol makees solvent, and 125 DEG C are reacted 8 hours, and separating methanol obtains product);
Promoting agent 2: m-xylene base Stearyl alcohol polyoxypropylene (7) polyoxyethylene (20) segmented copolymer (synthetic method is with embodiment 1);
Water: sewage injects in grand celebration ten factory.
The composition of binary system composition:
The composition of ternary system composition:
Synergy viscosity number is in table 3.
Viscosity number during table 3 unitary, binary and ternary system 30 DEG C
Conclusion: 1. arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer and beet alkali surface activator are to the Efficient Adhesive Promotion of polymkeric substance clearly, relatively can reduce the consumption of polymkeric substance in actual applications according to this characteristic, reduces combination flooding cost; 2. in ternary system, the viscosity influence of sodium carbonate to polymkeric substance is very large, but with arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer and beet alkali surface activator as in the ternary system of promoting agent, for polymkeric substance, viscosity does not only reduce, and also increases to some extent on the contrary.
Application examples 2. arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer is to the application in tertiary oil recovery
Raw material specification:
(1) polymkeric substance: water-soluble polymers is partially hydrolyzed polyacrylamide HPAM, Daqing Refinery company produces, and molecular weight is 2,500 ten thousand.
(2) sulfonate surfactant: heavy alkylbenzene sulfonate is produced by Donghao Investment Co Ltd, Daqing.
(3) nonionogenic tenside: m-xylene base Stearyl alcohol polyoxypropylene (7) polyoxyethylene (20) ether (synthetic method is with embodiment 1).
Add the composition of arylalkyl alcohol polyoxyethylene polyoxypropylene block copolymer composition:
Comparative example 1
Ternary composite driving composition:
Berea core oil displacement experiment is carried out to above-mentioned interpolation arylalkyl alcohol polyoxyethylene polyoxypropylene block copolymer composition:
Berea core oil displacement experiment carries out according to People's Republic of China (PRC) oil and gas industry standard SY/T6424-2000.Experiment oil is grand celebration one factory simulated oil, and experimental water is grand celebration one factory Simulated Water.When water drive to moisture 100% time inject the interpolation arylalkyl alcohol polyoxyethylene polyoxypropylene block copolymer composition of 0.7 times of volume of voids (PV), then carry out water drive to moisture 100% time terminate.
Wherein Berea core parameter is as shown in table 4.
Table 4. adds the Berea core parameter of arylalkyl alcohol polyoxyethylene polyoxypropylene block copolymer composition experiment
Utilize above-mentioned interpolation arylalkyl alcohol polyoxyethylene polyoxypropylene block copolymer composition to carry out Berea core oil displacement experiment, result is as shown in table 5:
Table 5. adds the oil displacement experiment result of arylalkyl alcohol polyoxyethylene polyoxypropylene block copolymer composition
The ternary composite driving composition of Comparison study example 1 carries out Berea core oil displacement experiment
Berea core oil displacement experiment carries out according to People's Republic of China (PRC) oil and gas industry standard SY/T6424-2000.Experiment oil is grand celebration one factory simulated oil, and experimental water is grand celebration one factory Simulated Water.When water drive to moisture 100% time inject the ternary composite driving composition of 0.7 times of volume of voids (PV), then carry out water drive to moisture 100% time terminate.
Wherein Berea core parameter is as shown in table 6.
The Berea core parameter of the ternary composite driving composition experiment of table 6. comparative example 1
Utilize the ternary composite driving composition of comparative example 1 to carry out Berea core oil displacement experiment, result is as shown in table 7:
The oil displacement experiment result of the ternary composite driving composition of table 7. comparative example 1
Conclusion: add a small amount of arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer in ternary composite driving composition, owing to adding the emulsification of displacement system, the performance such as wetting, relatively improve microcosmic swept volume and displacement efficiency, improve recovery ratio amplitude and add 3.5%.
The application of application examples 3 arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer in emulsification, viscosity reduction:
Alkylphenol-polyethenoxy one polyoxypropylene alcohol ether is used for emulsified viscous oil and falls glutinous research lJ1_ oilfield chemistry, 2003,20 (1): 7 one l0. king's generation tigers, Tian Zhongqiang, Du Yongxin, etc. having investigated alkylphenol-polyethenoxy one oxypropylene block polyethers to emulsified viscous oil, glutinous effect is fallen, especially to high-salinity thick oil oil reservoir, discovery R carbon number is that the adduct number of 9, EO accounts for 50% ~ 95% of EO and PO adduct number, when HLB value is greater than 13, reducing viscosity by emulsification effect is optimum.But APEO (alkylphenol polyoxyethylene) has similar female hormone effect, the chemical substance of the normal hormone secretion of energy harmful to human, i.e. said " female effect " and distortion.After all states in Europe have specified on January in 2005 17, completely forbid the product (comprising containing alkylphenol, alkyl ethoxylate alkylphenol ether) used containing APEO.In mid-June, 2006, USEPA (EPA) advocates a proposal and urges chemical manufacturers and stain remover producer inactive nonyl phenol ethoxy compound (NPEs) in stain remover voluntarily.
The thick oil properties of Shengli Oil Field is in table 8:
Table 8 Shengli Oil Field viscous crude character
For implementing reducing viscosity by emulsifying to viscous crude, being beneficial to pipe defeated, usually adding viscosity-depression agent.
Should the viscosity-depression agent that adopts of use-case 3 be Nonyl pheno (10) ether (Reagent Company's buying) and m-xylene base Stearyl alcohol polyoxypropylene (5) polyoxyethylene (25) ether (synthetic method is with embodiment 1) type viscosity-depression agent, determine respectively the w/o type oil in water emulsion of water ratio 50% kinetic viscosity and after adding 600mgL difference viscosity-depression agent the water ratio that formed be the kinetic viscosity of the O/W type oil in water emulsion of 50%.After adding viscosity-depression agent, water ratio be the viscosity degradation of the w/O type oil in water emulsion of 50% clearly, the viscosity break ratio of two kinds of viscosity-depression agents is all more than 96%, this shows that arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer is as emulsifying pour depressor, alkylphenol polyoxyethylene can be substituted completely, the oil in water emulsion of w/o type can be made to be transformed into the oil in water emulsion of O/W type, to significantly reduce thick oil viscosity.
Claims (9)
1. an arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer, is characterized in that having formula I structure:
Wherein, m+n is 0-30 positive integer;
P is 1-5000 positive integer;
Q is 0 or 1-5000 positive integer;
R is phenyl, tolyl, m-xylene base, p-Xylol base, o-Xylol base, ethylbenzene, n-propyl phenyl, isopropyl phenyl, n-butylphenyl, isobutyl phenenyl, tert-butyl-phenyl, naphthyl, methyl naphthyl, dimethyl naphthyl, ethyl naphthyl, propyl group naphthyl, butyl naphthyl, xenyl, the one in phenylol.
2. arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer according to claim 1, is characterized in that: described m+n is 15, p is 5,6 ... 49,50 positive integers, q is 5,6 ... 49,50 positive integers, R is m-xylene.
3. the preparation method of a kind of arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer as claimed in claim 1, is characterized in that: comprise the following steps:
(1). preparation arylalkyl carboxylic acids methyl esters
1. Friedel-Crafts alkylation: the alkylated reaction that alkene-carboxylic acid and aromatic hydrocarbon carry out under an acidic catalyst effect, obtains arylalkyl carboxylic acids;
Esterification: arylalkyl carboxylic acids and methyl alcohol carry out dehydration condensation and obtains arylalkyl carboxylic acids's methyl esters under solid acid catalyst effect;
2. or by alkene-carboxylic acid's methyl esters and aromatic hydrocarbon under an acidic catalyst effect, arylalkyl carboxylic acids's methyl esters is obtained by reacting;
(2). prepare arylalkyl alcohol
Reduction reaction: the arylalkyl carboxylic acids's methyl ester hydrogenation 1. or 2. obtained by method is reduced into arylalkyl alcohol;
(3). prepare arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer
Ring-opening reaction: the arylalkyl alcohol obtained by method (2) and propylene oxide carry out ring-opening reaction under catalyst action, obtains arylalkyl alcohol polyethenoxy ether;
Ethoxylation: arylalkyl alcohol polyethenoxy ether carries out ethoxylation with oxyethane again under catalyst action, obtains arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer.
4. preparation method according to claim 3, is characterized in that: described step 1. in alkene-carboxylic acid be one or more in undecylenic acid, oleic acid, erucic acid.
5. preparation method according to claim 3, is characterized in that: described step 2. in alkene-carboxylic acid's methyl esters be one or more in methyl undecylenate, Witconol 2301, methyl erucate.
6. preparation method according to claim 3, is characterized in that: described step 1. or 2. in an acidic catalyst be any one or a few in sulfuric acid, hydrofluoric acid, methylsulphonic acid, trifluoromethanesulfonic acid, the trifluoromethanesulfonic acid root of metal salts of trifluoromethane sulphonic acid or load, heteropolyacid, solid super-strong acid, acid zeolite, perfluorinated resin, ionic liquid.
7. preparation method according to claim 3, is characterized in that: described (2) reduction reaction is the liquid-phase hydrogenatin technique under the effect of Cu-Cr/Cu-Zn/Cu-Si mixed catalyst.
8. preparation method according to claim 3, is characterized in that: described step ring-opening reaction or ethoxylation an acidic catalyst are selected from BF
3, SbCI
5, SnCI
4, solid acid, heteropolyacid, one in carried molecular sieve catalyst; Or the one be selected from potassium hydroxide, sodium hydroxide, sodium methylate, sodium ethylate, Mg/AI composite oxides, the oxide compound of barium and the mixture of oxyhydroxide, aluminum alkoxide sulfonate, rare metal alcoxyl vitriol, alkaline earth metal oxide and phosphoric acid.
9. the application of arylalkyl alcohol polyoxyethylene polyoxypropylene segmented copolymer as claimed in claim 1 in residual oil emulsification, reducing thick oil viscosity, heavy oil pour point depression, tertiary oil recovery, nanoemulsions preparation, daily-use chemical industry.
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