CN1148254C - Preparation method of alkylbenzenesulfonate - Google Patents
Preparation method of alkylbenzenesulfonate Download PDFInfo
- Publication number
- CN1148254C CN1148254C CNB011366532A CN01136653A CN1148254C CN 1148254 C CN1148254 C CN 1148254C CN B011366532 A CNB011366532 A CN B011366532A CN 01136653 A CN01136653 A CN 01136653A CN 1148254 C CN1148254 C CN 1148254C
- Authority
- CN
- China
- Prior art keywords
- alkyl benzene
- alkylbenzenesulfonate
- temperature
- preparation
- hour
- 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.)
- Expired - Lifetime
Links
Images
Abstract
The present invention relates to a method for preparing alkylbenzenesulfonate. Heavy alkyl benzene ranging from C10 to C23 is selected as raw materials and is sulfonated according to that the molar ratio of SO3 to the heavy alkyl benzene is 1.0 to 1.5 at the temperature of 30 to 50 DEG C, and the concentration of the SO3 is 3 to 5 % of the volume; intermediate products of alkyl benzene sulfonic acid are obtained for ageing 0.5 to 1 hour at the same temperature; alkyl benzene sulfonate is obtained by neutralizing the alkyl benzene sulfonic acid of which the pH value is from 7 to 9 by alkali liquid of which the volume ratio is 20% to 40% at the temperature of 30 to 80 DEG C; the alkyl benzene sulfonate is put in an extraction kettle, C3 to C5 10 to 20 % of low carbon alcohol is added according to the weight ratio, the extraction temperature is from 30 to 40 DEG C, and the extraction time is from 0.5 to 1 hour; extraction liquid is put in a distillating kettle for distillation at the temperature of 100 degrees to obtain final products of alkyl benzene sulfonate. The preparation method has the advantages of convenience, practicality and low manufacturing cost, and is an ideal surface active agent in asp flooding.
Description
Technical field
The present invention relates to a kind of oil field (displacement of reservoir oil) and use surfactant, relate in particular to a kind of preparation method of alkylbenzenesulfonate.
Background technology
The application surface activating agent recovers the oil to study in the theory and practice so far and has all obtained very big development in petroleum technology.At present, following several injection systems have been formed basically.(1) active water drive; (2) micellar solution flooding; (3) the low interfacial tension system is recovered the oil; (4) ternary composite driving.Wherein ternary composite driving (alkali+polymer+surfactant) still can obtain higher oil displacement efficiency under the situation of low surfactant consumption significantly, and therefore, it becomes the new technology in economic and technical raising recovery ratio that can both be successful.
After the oil field enters high water-cut stage, remaining oil with discontinuous oil clot by trap in the reservoir rocks hole, two main power that act on the oil droplet are adhesive tape power and capillary force.As use suitable surfactant system, reduce the interfacial tension between profit, just reduced the resistance that the oil droplet distortion is brought when using residual oil to move, thus oil displacement efficiency improved.
Yet, employed surfactant generally is an alkylbenzenesulfonate in ternary composite driving at present, but this production cost of products is too high, thereby price is more expensive, especially in the large usage quantity in oil field, not only increased the cost of investment of chemical agent in the ternary composite driving, and it can not form excellent compatibility with the oil field in use.
Summary of the invention
Purpose of the present invention is to provide a kind of preparation method of alkylbenzenesulfonate, and this preparation method is simple and practical, and cost of manufacture is cheap, is surfactant desirable in the ternary composite driving.
For achieving the above object, preparation method of the present invention comprises the steps:
Select C
10-C
23Between heavy alkyl benzene be raw material;
Press SO down at 30-50 ℃
3With the heavy alkyl benzene mol ratio be that the ratio of 1.0-1.5 is with heavy alkyl benzene sulfonation, SO
3Concentration be volume ratio 3-5%; Under same temperature, wore out 0.5-1 hour, obtain the intermediate product alkyl benzene sulphonate;
Under 30-80 ℃, with in the alkali lye of volume ratio 20%-40% and alkyl benzene sulphonate to pH value be 7-9, obtain alkylbenzenesulfonate;
Alkylbenzenesulfonate is put into extraction kettle, add C by weight
3-C
5Low-carbon alcohols 10-20%, extraction temperature 30-40 ℃, extracted time 0.5-1 hour, extract is put into distillation still, in the distillation down of 100 degree, obtain the final product alkylbenzenesulfonate.
Among the above-mentioned preparation method, described alkali lye is NaOH or potassium hydroxide, C
3-C
5Low-carbon alcohols is isopropyl alcohol, butanols or amylalcohol.
Description of drawings
Fig. 1 is an alkylbenzenesulfonate preparation technology schematic flow sheet of the present invention.
The specific embodiment
Below provide embodiment, and in conjunction with the accompanying drawings the present invention is described in detail.
Embodiment 1:
According to the technological process of Fig. 1, C
10-C
23Heavy alkyl benzene and concentration be 5% sulfur trioxide (SO
3) to squeeze into treating capacity together in molar ratio=1: 1.5 ratio be that sulfonation temperature is 30 ℃ in 1 ton/hour the film sulfonator to gas, sulfonating reaction is instantaneous successive reaction; Product is behind gas-liquid separator, liquid partly enters aging still and wears out half an hour down in sulfonation temperature, in squeezing into afterwards and still, to in and still in add 20% sodium hydroxide solution by volume, under 80 ℃, carry out neutralization reaction, stir after 2 hours, adjust the pH value to 7-9, obtain sodium alkyl benzene sulfonate with NaOH.But exist heterocomplexs such as the indenes tetralin that contains by raw material itself, hexichol alkane in this product, the stability when these heterocomplexs can influence alkylbenzenesulfonate as surfactant.For removing these heterocomplexs, stability when improving alkylbenzenesulfonate as surfactant, sodium alkyl benzene sulfonate after will neutralizing is again put into extraction kettle, adds 20% isopropyl alcohol by weight, under 40 ℃, extracted 0.5 hour, extract is put into distillation still, and in the distillation down of 100 degree, the isopropanol recovering of volatilization is to the extractant storage tank, to wait to continue use, remaining composition is the higher sodium alkyl benzene sulfonate of stability.
Embodiment 2:
Heavy alkyl benzene and concentration are 3% sulfur trioxide (SO
3) to squeeze into treating capacity together in molar ratio=1: 1 ratio be that sulfonation temperature is 50 ℃ in 1 ton/hour the film sulfonator to gas, aging 1 hour; In and add 40% sodium hydroxide solution by volume in the still, under 30 ℃, carry out neutralization reaction, stirs after 2 hours, to 7-9, add 10% butanols with NaOH adjustment pH value in the extraction kettle by weight, under 30 ℃, extracted 1 hour.All the other operating conditions and step are with embodiment 1.
Embodiment 3:
Heavy alkyl benzene and concentration are 4% sulfur trioxide (SO
3) to squeeze into treating capacity together in molar ratio=1: 1.2 ratio be that sulfonation temperature is 40 ℃ in 1 ton/hour the film sulfonator to gas, aging 45 minutes; In and still in add 30% potassium hydroxide solution by volume, under 60 ℃, carry out neutralization reaction, stir after 1.5 hours, adjust the pH value to 7-9 with potassium hydroxide, obtain alkyl benzene sulphonate potassium, add 15% amylalcohol in the extraction kettle by weight, under 35 ℃, extracted 45 minutes, and obtained the higher alkyl benzene sulphonate potassium of stability.All the other operating conditions and step are with embodiment 1.
Interfacial tension performance evaluation:
The present invention has carried out interfacial tension performance evaluation to the alkylbenzenesulfonate of being developed.Interfacial tension is measured and is adopted the rotation of U.S. Texas-500 type to drip interfacial tensimeter.Interfacial tension is measured and oil displacement experiment carries out under 45 ℃ without exception, and experiment used oil, water are Daqing oil field four factories degassing dewatered oil and inject sewage.
The result shows, the surfactant concentration of broad (0.05-0.3wt%, effectively) and the interior alkylbenzenesulfonate compound system of alkali concn (0.6-1.2wt%) scope all can form ultralow interfacial tension and reach 10 with crude oil
-3The mN/m order of magnitude or lower, as shown in Figures 2 and 3.
The interfacial tension estimation of stability:
Because under the highly basic condition, the chemical stability of activating agent system is determining the interfacial tension stability of this system, for this reason, we determine and each link such as composite is all eliminated the chemically unstable factor from the processing of raw material, process for sulfonation parameter in the development process of alkylbenzenesulfonate as far as possible, thereby have developed the comparatively desirable little trial product of interfacial tension stability.Evaluation result such as Fig. 4.
Indoor natural core oil displacement experiment research:
(polymer=1200ppm) oil displacement experiment is studied for activating agent=0.2wt%, NaOH=1.0wt%, and it the results are shown in Table 1 to have carried out the alkylbenzenesulfonate three-component compound system on the natural core of the grand celebration of φ 2.5cm * 10cm.The result shows that alkylbenzenesulfonate compound system oil displacement efficiency has improved about 20% (OOIP) than water drive.
Table 1 alkylbenzenesulfonate three-component compound system oil displacement experiment result
Sequence number | Permeability | Contain saturation degree % | Waterflood recovery efficiency factor % (OOIP) | Chemical flooding recovery ratio % (OOIP) | Overall recovery factor % (OOIP) |
1 | 872 | 73.95 | 40.41 | 21.23 | 61.64 |
2 | 867 | 76.59 | 43.92 | 22.84 | 66.76 |
In conjunction with the foregoing description and effect assessment data, can sum up the beneficial effect that the present invention reaches:
With the method for heavy alkyl benzene synthesis of alkyl benzene sulfonate, simple, practical, repeatability is good, be easy to realize large-scale production, low production cost;
With the alkylbenzenesulfonate of the inventive method preparation, emulsification and demulsification performance are good, and during itself and other additive compound, interfacial tension is lower than 10
-3MN/m, adsorbance<1mg/g sand, and have excellent compatibility, meet the index request of tertiary oil recovery oil displacement agent;
The three-component compound system that alkylbenzenesulfonate of the present invention forms improves more than 20% in the recovery ratio average specific water drive on the core, and it is applied in the tertiary oil recovery as composite dose, and effect is obvious.
Claims (3)
1, a kind of preparation method of alkylbenzenesulfonate comprises the steps:
Select C
10-C
23Between heavy alkyl benzene be raw material;
Press SO down at 30-50 ℃
3With the heavy alkyl benzene mol ratio be that the ratio of 1.0-1.5 is with heavy alkyl benzene sulfonation, SO
3Concentration be volume ratio 3-5%; Under same temperature, wore out 0.5-1 hour, obtain the intermediate product alkyl benzene sulphonate;
Under 30-80 ℃, with in the alkali lye of volume ratio 20%-40% and alkyl benzene sulphonate to pH value be 7-9, obtain alkylbenzenesulfonate;
Alkylbenzenesulfonate is put into extraction kettle, add C by weight
3-C
5Low-carbon alcohols 10-20%, extraction temperature 30-40 ℃, extracted time 0.5-1 hour, extract is put into distillation still, in the distillation down of 100 degree, obtain the final product alkylbenzenesulfonate.
2, the preparation method of alkylbenzenesulfonate according to claim 1 is characterized in that, described alkali lye is NaOH or potassium hydroxide.
3, the preparation method of alkylbenzenesulfonate according to claim 1 is characterized in that, described C
3-C
5Low-carbon alcohols is isopropyl alcohol, butanols or amylalcohol.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB011366532A CN1148254C (en) | 2001-10-25 | 2001-10-25 | Preparation method of alkylbenzenesulfonate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB011366532A CN1148254C (en) | 2001-10-25 | 2001-10-25 | Preparation method of alkylbenzenesulfonate |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1413762A CN1413762A (en) | 2003-04-30 |
CN1148254C true CN1148254C (en) | 2004-05-05 |
Family
ID=4673810
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB011366532A Expired - Lifetime CN1148254C (en) | 2001-10-25 | 2001-10-25 | Preparation method of alkylbenzenesulfonate |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1148254C (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100386402C (en) * | 2004-12-01 | 2008-05-07 | 中国石油天然气股份有限公司 | Alkyl benzene sulfonate composition and preparing method |
CN107298971B (en) * | 2016-04-14 | 2020-01-17 | 中国石油化工股份有限公司 | High-temperature-resistant heavy alkylbenzene sulfonate system and preparation method thereof |
CN109627195A (en) * | 2018-05-18 | 2019-04-16 | 南京科技职业学院 | A method of heavy alkylbenzene sulfonate is prepared using microreactor |
CN117049985A (en) * | 2023-08-11 | 2023-11-14 | 安徽金桐精细化学有限公司 | High-carbon sodium alkylbenzenesulfonate and preparation method and application thereof |
-
2001
- 2001-10-25 CN CNB011366532A patent/CN1148254C/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CN1413762A (en) | 2003-04-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101185866A (en) | Gemini anionic surface active agent and preparation method thereof | |
CN110791273B (en) | Gas well foam scrubbing agent composition, preparation method and application thereof | |
CN106140007A (en) | A kind of oil field sulfomethylated lignin acidic group beet alkali surface activator and preparation method thereof | |
CN1148254C (en) | Preparation method of alkylbenzenesulfonate | |
CN107501135B (en) | Preparation and application of sulfonate anionic surfactant containing double long-chain alkyl | |
CN112266776B (en) | Surfactant for oil displacement and preparation method thereof | |
US4494604A (en) | Extraction of acidic materials from organic liquids and use thereof in enhanced oil recovery | |
CN112707865A (en) | Zwitterionic surfactant and preparation method thereof | |
CN1120038C (en) | Alkyl benzene sulfonate surfactant, its preparation method and application in tertiary oil recovery | |
CN111087347B (en) | Alkyl imidazoline sulfonate zwitterionic surfactant, composition, preparation method and application thereof | |
CN111073621A (en) | Double-long-chain anionic-non-composite surfactant for oil displacement and preparation method thereof | |
CN112694443B (en) | Alkyl imidazoline polyether sulfonate surfactant and preparation method thereof | |
CN114315661B (en) | Aralkyl alcohol polyoxypropylene ether sulfate and preparation and application thereof | |
US4442043A (en) | Oil recovery method utilizing a dicyclopentadiene derived ethoxysulfonate | |
CN112251209B (en) | Surfactant for efficiently improving recovery efficiency and preparation method thereof | |
CN113583648B (en) | Fatty amine polyoxyethylene ether surfactant for improving recovery ratio and preparation method thereof | |
CN114479810B (en) | Surfactant composition, preparation method and application thereof | |
CN104673265A (en) | Research of binary compounding system capable of generating ultralow interfacial tension | |
CN1128006C (en) | Petroleum sulfonate surfactant for oil field, its preparation process and use in tertiary oil recovery | |
CN117467423B (en) | High-temperature-resistant foam oil displacement agent | |
SU931115A3 (en) | Method for flooding oil-bearing formation | |
CN112457836B (en) | Sulfonated crude phenol Bola type surfactant and synthesis method and application thereof | |
CN112251210B (en) | Preparation method of surfactant for universality improvement of crude oil recovery rate | |
CN1123620C (en) | Three-element built-up composition containing lignosulfonate surfactant and its application in tertiary petroleum recovery | |
CN113930227B (en) | Composition containing anionic-nonionic and cationic-nonionic surfactants, preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
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 | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20210304 Address after: 100007 Oil Mansion, 9 North Avenue, Dongcheng District, Beijing, Dongzhimen Patentee after: PetroChina Co.,Ltd. Patentee after: Daqing Oilfield Co.,Ltd. Address before: 163453, Daqing, Heilongjiang Province Lake Road District Daqing Oil Field Co Patentee before: Daqing Oilfield Co.,Ltd. |
|
CX01 | Expiry of patent term | ||
CX01 | Expiry of patent term |
Granted publication date: 20040505 |