CN105505368A - Supercritical carbon dioxide flooding soluble profile control foaming agent and preparation method thereof - Google Patents
Supercritical carbon dioxide flooding soluble profile control foaming agent and preparation method thereof Download PDFInfo
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- CN105505368A CN105505368A CN201410489420.0A CN201410489420A CN105505368A CN 105505368 A CN105505368 A CN 105505368A CN 201410489420 A CN201410489420 A CN 201410489420A CN 105505368 A CN105505368 A CN 105505368A
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- whipping agent
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Abstract
The present invention relates to an oil extraction efficiency improving chemical additive for oil fields, and a preparation method thereof, particularly to a profile control foaming agent soluble in supercritical carbon dioxide, and a preparation method thereof, wherein the structure of the surfactant is characterized in that carbon dioxide-philic branched epoxy alkyl, an ester group and a carboxylate characteristic group are introduced into the hydrophobic chain, such that the surfactant has characteristics of good carbon dioxide affinity and good hydrophilicity. According to the present invention, the alkyl alcohol is adopted as the starting agent to initiate the epoxy alkane polymerization, and the carboxylation reaction is performed to prepare the final product; and the surfactant has advantages of mature and easy-operating synthetic route, and high solubility in supercritical carbon dioxide.
Description
Technical field
The present invention relates to oil field and improve chemical assistant of oil-production efficiency and preparation method thereof, be specifically related to a kind of profile control whipping agent solvable at supercritical co and preparation method thereof.
Background technology
CO
2technology of reservoir sweep, due to the displacement of reservoir oil principle of its uniqueness, embodies huge application potential, and worldwide progressively develops into a kind of main tertiary oil recovery means in the tertiary oil recovery engineering of the oil reservoirs such as high temperature and high salt, hyposmosis and viscous crude.Domestic, carbon dioxide flooding carries out ASP flooding test at large oilfield such as grand celebration, triumph, Central Plains, Jilin, and obtains good oil displacement efficiency.But due to CO
2viscosity and density less, compared to water drive, more easily there is viscous fingering and gravity segregation phenomenon, inject for a long time, has channeling passage can be formed and cause serious has channeling, thus cause the swept volume of gas to decline, have a strong impact on gas injection development effect.
Research shows that aerated fluid has and meets water and stablize, meet oily froth breaking, and shut-off capacity is the characteristic such as increase along with the increase of rate of permeation, utilizes aerated fluid can by CO
2mobility reduces by more than 50%.Effectively can adjust contradiction in the interlayer of inhomogeneous formation and layer in porous medium, simultaneously because the density of gas phase in foam is relatively low, effectively can improve the development degree of top oil reservoir, reduce the impact of onlap phenomenon.Domestic CO
2drive indoor and also there is the report utilizing foam to improve Flooding Efficiency at scene, if Daqing oil field is for CO
2gas input well virtue 188-138 gas well gas is altered serious situation and is carried out profile control, adopts liquid CO
222m3, foaming agent 20m
3, the mode in 24 cycles of alter least-squares processes, and after completing, injection pressure rises to some extent.Zhongyuan Oil Field is for high temperature, high salt, and especially the oil reservoir present situation of high contents of calcium and magnesium, carries out the CO being adapted to Zhongyuan Oil Field high temperature and high salt oil deposit
2anti-gas channeling foam system is studied.Adopt the CY-1 pore forming material of experiment screening, reach 20 × 10 for Zhongyuan Oil Field formation temperature 82.5 DEG C, salinity
4the CO of ppm
2drive block, carry out deep profile controlling+foam system and carry out envelope and alter.Inject gel particle adjusting driving agnet+cross-linking copolymer transfer drive system 2550m altogether
3, the special foam 300m of carbonic acid gas
3, envelope is altered and is achieved good effect.CY-1 carbon dioxide foaming agent is also for the CO in northeast branch office of China Petrochemical Industry waist Ying Tai oil field
2drive foam envelope to alter, this block prime stratum temperature, at 97.8 DEG C, the average 16190mg/L of local water total mineralization, has been filled with this foaming agent solution of thousands of side at present, has achieved certain effect.Chinese patent CN101089117A discloses a kind of acid resistant foamed plugging agent, and foam solution is made up of Sodium dodecylbenzene sulfonate, modification guanidine glue and water.
Traditional blowing agents is water-soluble, needing with aqueous phase is that carrier is sent to underground, for the foam profile control of carbon dioxide flooding, may not overlap due to carbon dioxide flows passage at the bottom of ground and aqueous phase flow passage, cause adjusting stifled less effective, therefore, develop, in carbonic acid gas, there is certain deliquescent whipping agent, bring tensio-active agent into object that underground realizes profile control shutoff by supercritical co as solvent, there is realistic meaning.
Tensio-active agent can improve the consistency of two immiscible materials usually, and this character is determined by its ad hoc structure.General surfactant molecule is jointly made up of when the group of high hydrophilic (oleophobic) the group of nonpolar oleophylic (hydrophobic) and polar phase, and two ends, two portions office, forms unsymmetrical structure.
For carbonic acid gas, if form emulsion or the foam of carbonic acid gas and water or organic solvent, then require that tensio-active agent one end is dissolved in carbonic acid gas, the water-soluble or organic solvent of the other end, only in this way could reduce polar organic solvent or the interfacial tension between water and carbonic acid gas.Therefore in the Application Areas of supercritical co, as to metal ion or medical separation extraction, oil field with in carbon-dioxide flooding process, all the solvability of Surfactant in carbonic acid gas proposes certain requirement.Therefore develop and study and there is the carbon functional tensio-active agent of close titanium dioxide become focus.But supercritical co has more weak Van der Waals force and lower specific inductivity, the solubleness of most of tensio-active agent in supercritical co is limited, particularly ionic surface active agent.
Nineteen ninety Consani and Smith 50 DEG C, under 10-50MPa condition, determine the facile ion of the commercial appearance of kind more than 130 and the solubleness of nonionogenic tenside in supercritical co.Result shows, all these tensio-active agents all insoluble or be slightly soluble in supercritical co (Liu Juncheng, prune help, Han Buxing. daily chemical industry, 2002,32 (1): 31-34).
But Ritter and Paulaitis result of study shows, under proper condition, some tensio-active agent can form molecule aggregates (LeeCT, RyooJW, SmithPG in supercritical co, eta1.JAmChemSoc, 2003,125:3181-3189).
Chinese patent CN102224186A discloses a kind of composition for oil recovery, and its main ingredient is CO
2have the nonionogenic tenside alkyl polyoxyalkyl ether of certain affinity, this tensio-active agent can promote that carbonic acid gas and water form stable foam.
A kind of oil soluble surfactant for carbon dioxide flooding disclosed in Chinese patent CN102337874A is tri-n-butyl citrate, n-octyl, this kind of tensio-active agent slight soluble in carbonic acid gas, but cannot be soluble in the aqueous phase.
Other tensio-active agents solvable in carbonic acid gas are mainly fluorochemical surfactant, organosilicone surfactants, as the people such as Desimone have synthesized a kind of fluorinated polymer tensio-active agent of close carbonic acid gas.
But make a general survey of these whipping agent agent, all there is certain deficiency, as the shortcomings such as solvability is lower in expensive or carbonic acid gas.
Summary of the invention
What an object of the present invention there are provided a kind of novel texture dissolves in CO
2profile control whipping agent.
Two of object of the present invention there are provided and thisly dissolves in CO
2the preparation method of profile control whipping agent.
Of the present inventionly dissolve in CO
2whipping agent, there is following structural formula:
Wherein, R is selected from branched-chain alkyl, cycloalkyl and the alkaryl with 4-16 carbon atom, preferably from the branched-chain alkyl with 8-12 carbon atom.
R
1, R
2, R
3, R
4independently be selected from H separately, there is branched-chain alkyl, the straight chained alkyl of 1-4 carbon atom, and be H during four differences.Be preferably R
1, R
2, R
3for H, R
4be selected from methyl, ethyl, propyl group, sec.-propyl.
X is the integer of 2-10, preferred 4-8.Y is the integer of 0-5, preferred 1-3.
The preparation method of carbon dioxide soluble zwitterionics of the present invention comprises the following steps:
(1) synthesis of alkyl polyoxyalkyl ether
A certain amount of Organic Alcohol initiator and catalyzer KOH is added, with N in autoclave
2air 3 times in displacement still, then, heating kettle temperature, to 50-80 DEG C, vacuumizes after dewatering and adds calculated amount epoxy alkane, be heated to 120-160 DEG C carry out ring-opening polymerization 2-5h after, continuing to add reacting ethylene oxide 1-3h, obtaining product to terminating out still discharging.Reaction equation is as follows:
(2) synthesis of alkyl polyoxyalkyl ether carboxylic acid sodium
Add alkyl polyoxyalkyl ether, sodium hydroxide, sodium chloroacetate successively in a kettle.; the mol ratio of alkyl polyoxyalkyl ether and sodium hydroxide, sodium chloroacetate is 1:1.0-4.0:1.0-4.0; be heated to 60-95 DEG C under nitrogen protection, product of lowering the temperature to obtain after reaction 3h.Reaction equation is as follows:
In above-mentioned steps, the mol ratio of alkyl polyoxyalkyl ether and sodium chloroacetate is preferably 1:1.1, to promote completing and avoiding excess chlorine sodium acetate to exist and increase last handling process of esterification as far as possible.By dissolution experiment in supercritical co (40 DEG C, 20MPa), determine that such surfactant dissolves amount is 0.1-0.6wt%.
The invention has the advantages that, adopt specific Molecular Structure Design, the groups such as the branched paraffin of close carbonic acid gas, side chain epoxy alkane, carboxylate radical are introduced in tensio-active agent, significantly increase its solvability in carbonic acid gas, compared to the molten tensio-active agent of fluorine-containing, silicone based carbonic acid gas, carbochain tensio-active agent preparation method disclosed by the invention is simple, easy to operate, and product price is cheap.
Embodiment
Below by embodiment, the present invention is further illustrated, and its object is only better to understand the present invention and unrestricted the scope of protection of the invention.
The synthesis of embodiment 1 alkyl polyoxyalkyl ether
20.0g isooctyl alcohol and catalyzer 1.0gKOH is added, with N in autoclave
2air 3 times in displacement still, then, heating kettle temperature to 80 DEG C, vacuumizes after dewatering and adds 53.4g propylene oxide, be heated to 160 DEG C carry out ring-opening polymerization 3h after, continue to add oxyethane 13.5g and react 2h, drive still after terminating and lower the temperature, discharging obtains product.
The synthesis of embodiment 2 alkyl polyoxyalkyl ether carboxylic acid sodium
Product 56.6g(0.10mol in embodiment 1 is added) in three-necked bottle; sodium hydroxide 4.0g(0.1mol); sodium chloroacetate 11.6g(0.1mol) load onto thermometer, reflux condensing tube and motor machine agitator; nitrogen protection is led at the reflux condensation mode mouth of pipe; start and stir and be heated to 90 DEG C; after reaction 3h, lower the temperature and obtain product.
Solvability test in embodiment 3-8 tensio-active agent carbonic acid gas
Respectively product 0.15 in Example 2,0.25,0.35,0.45,0.55,0.65g, be added in the autoclave of band glass vision panel successively, pass into carbonic acid gas to 15MPa, after being heated to 40 DEG C, fine setting pressure to 20.0MPa, by reactor volume computing now supercritical co be 95.3g.Start mechanical stirring, observe the dissolving situation of solid state surface promoting agent, the results are shown in Table 1.
Solvability test in table 1 tensio-active agent carbonic acid gas
| Embodiment | Surfactant qualities | Surfactant concentration (wt%) | Dissolving situation |
| 3 | 0.15 | 0.157 | Dissolve complete, clear |
| 4 | 0.25 | 0.262 | Dissolve complete, clear |
| 5 | 0.35 | 0.367 | Dissolve complete, clear |
| 6 | 0.45 | 0.472 | Dissolve complete, clear |
| 7 | 0.55 | 0.577 | Dissolve complete, clear |
| 8 | 0.65 | 0.682 | Solution is muddy, occur insolubles |
Embodiment 9: the performance evaluation of whipping agent
Get 10.0g embodiment 2 sample, add 990.0g distilled water and be mixed with foaming agent solution.100mL solution is poured in the high-temperature high-pressure air flow method foam device of band form, sealing post-heating passes into carbon dioxide to design temperature (foam device internal pressure controls at 5Mpa by temperature after 100 DEG C) in solution, make generation foam 500mL, record lather volume becomes the time of 250mL, the stability (transformation period) of characterization of foam, data list in table 2.
Table 2. whipping agent Evaluation results
| Numbering | Temperature | Pressure | Transformation period |
| 1 | 80℃ | Normal pressure | 25 min |
| 2 | 100℃ | 5 Mpa | 102 min |
| 3 | 110℃ | 5 Mpa | 80 min |
| 4 | 25℃ | Normal pressure | 150 min |
Claims (7)
1. supercritical co drives a solvable profile control whipping agent, it is characterized in that, the structural formula of this whipping agent is:
Wherein, R is selected from branched-chain alkyl, cycloalkyl and the alkaryl with 4-16 carbon atom; R
1, R
2, R
3, R
4independently be selected from H separately, there is branched-chain alkyl, the straight chained alkyl of 1-4 carbon atom, and be H during four differences; X is the integer of 2-10;
Y is the integer of 0-5.
2. whipping agent according to claim 1, is characterized in that, R is selected from the branched-chain alkyl with 8-12 carbon atom.
3. whipping agent according to claim 1, is characterized in that, R
1, R
2, R
3for H, R
4be selected from methyl, ethyl, propyl group, sec.-propyl.
4. whipping agent according to claim 1, is characterized in that, X is the integer of 4-8; Y is the integer of 1-3.
5. supercritical co drives a preparation method for solvable profile control whipping agent, and it is characterized in that, the method comprises the following steps:
(1) synthesis of alkyl polyoxyalkyl ether
Organic Alcohol initiator and catalyzer KOH is added, with N in autoclave
2displacement still in air, then, heating kettle temperature, to 50-80 DEG C, vacuumizes after dewatering and adds calculated amount epoxy alkane, be heated to 120-160 DEG C carry out ring-opening polymerization 2-5h after, continuing to add reacting ethylene oxide 1-3h, obtaining product to terminating out still discharging;
(2) synthesis of alkyl polyoxyalkyl ether carboxylic acid
Add alkyl polyoxyalkyl ether successively in a kettle., sodium hydroxide, sodium chloroacetate, the mol ratio of alkyl polyoxyalkyl ether and sodium hydroxide, sodium chloroacetate is 1:1.0-4.0:1.0-4.0, is heated to 60-95 DEG C under nitrogen protection, product of lowering the temperature to obtain after reaction 3h.
6. whipping agent according to claim 1, is characterized in that the mol ratio of alkyl polyoxyalkyl ether and sodium chloroacetate is 1:1.1.
7. whipping agent according to claim 1, is characterized in that, its solubleness in supercritical co is 0.1-0.6wt%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679616A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | The foaming water discharge agent and preparation method and application of pH value response |
| CN109844060A (en) * | 2016-10-18 | 2019-06-04 | 陶氏环球技术有限责任公司 | The non-ionic surfactant composition of oil recovery is improved by carbon dioxide drive |
| CN113621359A (en) * | 2021-10-11 | 2021-11-09 | 德仕能源科技集团股份有限公司 | Compound oil displacement agent for improving recovery ratio and preparation method and application thereof |
| CN113652219A (en) * | 2021-10-19 | 2021-11-16 | 山东德仕化工有限公司 | Carbon dioxide oil displacement method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109844060A (en) * | 2016-10-18 | 2019-06-04 | 陶氏环球技术有限责任公司 | The non-ionic surfactant composition of oil recovery is improved by carbon dioxide drive |
| CN109679616A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | The foaming water discharge agent and preparation method and application of pH value response |
| CN113621359A (en) * | 2021-10-11 | 2021-11-09 | 德仕能源科技集团股份有限公司 | Compound oil displacement agent for improving recovery ratio and preparation method and application thereof |
| CN113621359B (en) * | 2021-10-11 | 2022-01-11 | 德仕能源科技集团股份有限公司 | Composite oil displacement agent for improving carbon dioxide oil displacement recovery ratio and preparation method and application thereof |
| CN113652219A (en) * | 2021-10-19 | 2021-11-16 | 山东德仕化工有限公司 | Carbon dioxide oil displacement method |
| CN113652219B (en) * | 2021-10-19 | 2022-03-08 | 山东德仕化工有限公司 | Carbon dioxide oil displacement method |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |