WO2015101355A1 - 磺酸盐型生物质表面活性剂及其合成方法 - Google Patents
磺酸盐型生物质表面活性剂及其合成方法 Download PDFInfo
- Publication number
- WO2015101355A1 WO2015101355A1 PCT/CN2015/070174 CN2015070174W WO2015101355A1 WO 2015101355 A1 WO2015101355 A1 WO 2015101355A1 CN 2015070174 W CN2015070174 W CN 2015070174W WO 2015101355 A1 WO2015101355 A1 WO 2015101355A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fatty acid
- methyl ester
- acid methyl
- sulfonate
- type biomass
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
- C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
Definitions
- the invention belongs to the field of organic compound synthesis, and in particular to a sulfonate type biomass surfactant which is mainly based on fatty acid methyl ester in waste oil of kitchen waste and a synthetic method thereof, and is applied to petroleum exploitation.
- the fatty acid methyl ester prepared from the waste oil of the kitchen is widely used as a diesel fuel because of its advantages of good storage stability, low boiling point, easy fractionation, and low corrosivity.
- the most important use is as an intermediate material for the production of surfactants. Based on this, a series of non-toxic and harmless products have been developed.
- the degradable "bio-based surfactant” is an ideal substitute for petrochemical diesel-based surfactants with excellent environmental characteristics.
- the fatty acid methyl ester sulfonate belongs to the sulfonate anionic surfactant, and its temperature and salt resistance effects are good, and the sulfonate surfactant is widely used in the tertiary oil recovery process
- CN101759612A discloses a hard Methyl fatty acid is used as a raw material to prepare a fatty acid methyl ester sulfonate surfactant by sulfonation with SO 3 gas in a multi-tube membrane reaction vessel, but the reactor requires high reactivity and SO 3 sulfonation during the synthesis process.
- the agent has a certain toxicity.
- CN101774936A discloses a process for preparing an alkanolamide based on a fatty acid ester, which has simple preparation process, low energy consumption, good foam stability of alkanolamide, emulsification, wetting and the like, but belongs to
- the non-ionic surfactant has a general temperature resistance property, limits the range of its use, and has many side reactions in the synthesis process, and the yield is low, and the purification of the reaction product is difficult. Therefore, considering the advantages and disadvantages of the alkanolamide synthesis reaction and the wide application of the sulfonate surfactant, based on the fatty acid methyl ester, the development of mild reaction conditions, simple preparation process, good temperature and salt resistance can be used.
- the synthesis process of novel sulfonate surfactants for tertiary oil recovery is of great significance and has broad application prospects and practical value.
- the present invention provides a sulfonate-type biomass surfactant based on a fatty acid methyl ester and a method for synthesizing the same, which uses a fatty acid methyl ester prepared in a kitchen waste oil as a raw material. Synthetic bioactive surfactant, a new green surfactant.
- the present invention adopts the following scheme:
- R is an alkane group of C 11 to C 17 .
- the synthesis method of the fatty acid methyl ester-based sulfonate type biomass surfactant is as follows:
- the application of the fatty acid methyl ester-based sulfonate-type biomass surfactant is applied to the field of petroleum exploitation.
- the present invention has the following beneficial effects:
- the sulfonate-type biomass surfactant synthesized by the present invention has good surface activity, and the surface tension of the surfactant solution having a mass fraction of 0.3% at 25 ° C is about 25 mN/m.
- the sulfonate surfactant synthesized by the invention has good interfacial activity, and the surfactant solution and the land beam with a mass fraction of 0.3% at 50 ° C and 7 ⁇ 10 4 mg/L salinity.
- the interfacial tension of crude oil can reach 2.35 ⁇ 10 -3 mN/m, which can effectively improve oil washing efficiency and improve oil recovery in tertiary oil recovery.
- the surfactant synthesized by the invention is a biomass surfactant, non-toxic, harmless, degradable, less damage to the environment and formation, can replace the traditional petrochemical diesel-based surfactant, and realize the urban kitchen The goal of comprehensive utilization of waste resources.
- the surfactant synthesized by the invention has low cost and meets the resource comprehensive utilization of urban kitchen waste, and has profound significance and good application prospect.
- the synthesis method of the invention has mild reaction conditions, simple preparation process and reasonable process, and is suitable for large-scale production.
- the sulfonate-type biomass surfactant of the present invention is used in the chemical flooding system of petroleum exploitation, and can form an ultra-low interfacial tension of 10 -3 mN/m with underground crude oil to achieve the best drive. Oil effect. Under the condition of 50 °C and 7 ⁇ 10 4 mg/L salinity, it can form ultra-low interfacial tension with the crude oil on the order of 10 -3 mN/m, thus achieving the effect of washing oil and improving oil recovery by about 11.9%. , achieved a better oil displacement effect.
- FIG. 1 is a schematic view showing a synthesis apparatus of a sulfonate type biomass surfactant based on a fatty acid methyl ester.
- Example 2 is an infrared spectrum diagram of a surfactant of N-lauroylamide-N,N-diethoxypropylsulfonate in Example 1.
- Example 3 is a nuclear magnetic resonance spectrum of a surfactant of N-lauroylamide-N,N-diethoxypropylsulfonate in Example 1.
- a fatty acid methyl ester-based sulfonate-type biomass surfactant having a molecular formula of:
- R is an alkane group of C 11 to C 17 .
- the synthesis method specifically includes the following steps:
- the three-necked flask 2 is a glass container commonly used for the synthesis of organic substances, and generally has the appearance of a round neck and a narrow neck. It has three ports, one side is installed with the water separator 3 and the condensing tube 4, the evaporated steam is condensed into a liquid and then returned to the reaction system to avoid the reaction liquid being evaporated; the middle mouth is sealed with a rubber stopper to prevent the solution. Spill or reduce the evaporation of the solution; install the thermometer 5 on the other side and record the reaction temperature. After the reaction material is added, the magnetic rotor 6 is added thereto, and it is placed in a collecting thermostatic magnetic stirrer 1 during the reaction, and the reaction can be achieved while stirring.
- the propane lactone is dissolved in tetrahydrofuran, and then the fatty acid alkanolamide is added thereto according to the molar ratio of the alkanolamide to the propane lactone of 1.02:2 to 1.05:2, and the solution is fully dissolved and then charged with a magnetic force.
- the total reactant mass (sum of the mass of the fatty acid alkanolamide and propane sultone) was 1.0% added to the three-necked flask.
- the surface tension measurement conditions are: the measurement temperature is 25 ° C, the mass fraction is 0.3%; the interfacial tension measurement conditions are: the measurement temperature is 50 ° C, the salinity is 7 ⁇ 10 4 mg / L, the crude oil is the Luliang crude oil, The mass score is 0.3%.
- the product obtained in this example had a surface tension of 25.82 mN/m and an interfacial tension of 2.65 x 10 -3 mN/m.
- a simulated flooding experiment was performed on a core having a length of 10 cm, a diameter of 2.5 cm, and a permeability of 0.4 ⁇ m 2 .
- the surfactant prepared in this example (N,N-di(1-ethoxy-)3) was firstly injected with water from the Luliang oilfield to 98% of water and transferred to 0.3PV (core pore volume) concentration of 0.3%.
- - sulfonate propyl lauryl amide sulfonate surfactant water driven to 100% water, can increase oil recovery by about 11.9% on the basis of water flooding.
- the product obtained in this example had a surface tension of 26.12 mN/m and an interfacial tension of 2.83 x 10 -3 mN/m.
- the product obtained in this example had a surface tension of 25.21 mN/m and an interfacial tension of 2.73 x 10 -3 mN/m.
- the product obtained in this example had a surface tension of 25.45 mN/m and an interfacial tension of 2.62 x 10 -3 mN/m.
- the product obtained in this example had a surface tension of 26.03 mN/m and an interfacial tension of 2.92 x 10 -3 mN/m.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Lubricants (AREA)
Abstract
本发明属于有机化合物合成领域,具体地,涉及一种基于脂肪酸甲酯的磺酸盐型生物质表面活性剂及其合成方法。城市餐厨垃圾废弃油脂主要成分为脂肪酸甲酯,基于脂肪酸甲酯的磺酸盐型生物质表面活性剂由以下步骤制备:脂肪酸烷醇酰胺的制备,磺丙基化反应;所述的基于脂肪酸甲酯的磺酸盐型生物质表面活性剂,应用于石油开采领域。本发明合成的磺酸盐型生物质表面活性剂具有较好的表面活性、界面活性,无毒、无害、可降解,对环境和地层伤害均较小,可替代传统石化柴油基表面活性剂,同时实现了城市餐厨垃圾的资源化综合利用、提高附加值的目的,应用前景良好;另外该合成反应条件温和、制备工艺简单、工艺合理,适于规模化生产;该剂用于石油开采中化学驱油体系的洗油剂,提高洗油效果,从而提高原油采收率。
Description
本发明属于有机化合物合成领域,具体地,涉及一种基于餐厨垃圾废弃油脂中主要成分为脂肪酸甲酯的磺酸盐型生物质表面活性剂及其合成方法,并应用于石油开采。
我国城市餐厨垃圾中每年产生废弃油脂约400~600万吨,废弃油脂部分流入江河,白白浪费掉且污染水体;另外相当一部分被加工成“精炼油”回流餐桌,对我国食品安全构成严重威胁。而从餐厨废弃油脂中制备出的脂肪酸甲酯,由于其具有储存稳定性好、沸点低、分馏容易、腐蚀性小等优点而被广泛用做柴油机燃料。除此之外,随着人们对脂肪酸甲酯的深入研究,其用途也在不断扩大,最主要的用途是作为生产表面活性剂的中间体原料,以此为基础开发出系列无毒、无害、可降解的“生物基表面活性剂”是石化柴油基表面活性剂的理想替代品,具有优良的环保特性。
以脂肪酸甲酯为基础合成的表面活性剂产品种类很多,通过磺化中和生产脂肪酸甲酯磺酸盐(MES),与乙二醇胺热缩合反应生产烷醇酰胺等。脂肪酸甲酯磺酸盐属于磺酸盐阴离子型表面活性剂,其耐温抗盐效果均较好,且磺酸盐型表面活性剂在三次采油过程中应用较广泛,CN101759612A公开了一种以硬脂酸甲酯为原料,在多管膜反应容器上以SO3气体进行磺化制备脂肪酸甲酯磺酸盐表面活性剂的制备工艺,但是其合成过程中反应器要求较高且SO3磺化剂具有一定的毒性。CN101774936A公开了一种以脂肪酸酯为基础制备烷醇酰胺的工艺,尽管其制备工
艺简单、能耗低,且烷醇酰胺的泡沫稳定性好,具有乳化、润湿等功能,但因其属于非离子型表面活性剂,耐温性能一般,限制了其使用的范围,而且其合成过程中副反应较多,收率较低,反应产物提纯较困难。因此综合考虑烷醇酰胺合成反应的优缺点和磺酸盐型表面活性剂广泛应用,以脂肪酸甲酯为基础,开发出反应条件温和、制备工艺简单、耐温抗盐效果较好的可以用于三次采油的新型磺酸盐型表面活性剂的合成工艺具有重要的意义,并具有广泛的应用前景及实用价值。
发明内容
针对现有技术的不足,本发明提供一种基于脂肪酸甲酯的磺酸盐型生物质表面活性剂及其合成方法,该表面活性剂采用餐厨废弃油脂中制备出的脂肪酸甲酯为原料进而合成出生物质表面活性剂,属于新型绿色环保表面活性剂。
为实现上述目的,本发明采用下述方案:
基于脂肪酸甲酯的磺酸盐型生物质表面活性剂,其特征在于,分子通式为:
其中,R为C11~C17的烷烃基。
所述的基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的合成方法,合成路线如下:
具体包括以下步骤:
1)脂肪酸烷醇酰胺的制备
2)磺丙基化反应。
所述的基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的应用,应用于石油开采领域。
相对于现有技术,本发明具有如下的有益效果:
1、本发明合成的磺酸盐型生物质表面活性剂具有较好的表面活性,质量分数为0.3%的表面活性剂溶液在25℃下的表面张力为25mN/m左右。
2、本发明合成的磺酸盐型表面活性剂具有较好的界面活性,在50℃、7×104mg/L矿化度条件下,质量分数为0.3%的表面活性剂溶液与陆梁原油的界面张力可达到2.35×10-3mN/m,在三次采油中可以有效提高洗油效率,提高原油采收率。
3、本发明合成的表面活性剂为生物质表面活性剂,无毒、无害、可降解,对环境和地层伤害均较小,可替代传统石化柴油基表面活性剂,同时实现了城市餐厨垃圾的资源化综合利用的目标。
4、本发明合成的表面活性剂成本低,且满足城市餐厨垃圾的资源化综合利用,意义深远,具有良好的应用前景。
5、本发明的合成方法,反应条件温和、制备工艺简单、工艺合理,适于规模化生产。
6、本发明的磺酸盐型生物质表面活性剂用于石油开采中的化学驱的驱油体系,能与地下原油形成10-3mN/m数量级的超低界面张力,达到最佳的驱油效果。在50℃、7×104mg/L矿化度的油藏条件下能与原油形成10-3mN/m数量级的超低界面张力,从而达到洗油的效果,提高采收率11.9%左右,取得了较好的驱油效果。
图1为基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的合成装置示意图。
图中:1、集热式恒温磁力搅拌器,2、三口烧瓶,3、分水器,4、冷凝管,5、温度计,6、磁力转子。
图2为实施例一中N-月桂酰胺-N,N-二乙氧基丙基磺酸钠表面活性剂的红外光谱图。
图3为实施例一中N-月桂酰胺-N,N-二乙氧基丙基磺酸钠表面活性剂的核磁共振谱图。
基于脂肪酸甲酯的磺酸盐型生物质表面活性剂,其分子通式为:
其中,R为C11~C17的烷烃基。
上述基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的合成方法,其合成路线是:
该合成方法,具体包括以下步骤:
1)脂肪酸烷醇酰胺的制备
将脂肪酸甲酯与二乙醇胺按摩尔比为1:1.05~1:1.15混合于装有磁力转子6、冷凝管4、温度计5的三口烧瓶2中,向三口烧瓶中加入占总反应物(脂肪酸甲酯和二乙醇胺的质量之和)质量0.6%~0.8%的催化剂氢氧化钠,然后将烧瓶置于油浴中加热至110℃~130℃搅拌反应4h~6h,最后旋蒸干燥冷却后得到脂肪酸烷醇酰胺。
三口烧瓶2是有机物质合成反应常用的玻璃容器,其通常具有圆肚细颈的外观,
它有三个口,一个边口安装分水器3和冷凝管4,将蒸发出来的蒸汽冷凝成液体再回流到反应体系中,避免反应液体被蒸干;中间的口用橡皮塞密封,防止溶液溅出或减少溶液的蒸发;另一边口安装温度计5,记录反应温度。加入反应物料后向其中加入磁力转子6,反应过程中将其置于集热式恒温磁力搅拌器1中,可以实现边搅拌边反应。
上述脂肪酸甲酯的结构式为CnH2n+1COOCH3,n=11~17。
2)磺丙基化反应
先将丙磺酸内酯溶于四氢呋喃中,然后按照烷醇酰胺与丙磺酸内酯为1.02:2~1.05:2的摩尔比向其中加入脂肪酸烷醇酰胺,充分溶解后装入连有磁力转子、冷凝管、温度计的三口烧瓶中(三口烧瓶同步骤1中的三口烧瓶),向三口烧瓶中加入占总反应物质量(脂肪酸烷醇酰胺和丙磺酸内酯的质量之和)1.0%~1.5%的催化剂氢氧化钠,加热至回流温度(66℃,四氢呋喃的沸点温度),搅拌反应12~16h后,旋蒸干燥冷却后得到N,N-二(1-乙氧基-)3-磺酸基丙基脂肪酰胺表面活性剂。
下面实施例中,表面张力测定条件为:测定温度25℃、质量分数为0.3%;界面张力测定条件为:测定温度50℃、矿化度7×104mg/L、原油为陆梁原油、质量分数为0.3%。
实施例一
将21.43g月桂酸甲酯(C11H23COOCH3,0.1摩尔)与11.04g二乙醇胺(0.105摩尔)混合于装有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入0.20g氢氧化钠(占总反应物的质量百分比为0.62%),将烧瓶置于油浴中加热至110℃,搅拌反应5h后,旋蒸干燥冷却后得到24.21g月桂酸烷醇酰胺,收率为84.24%。
将12.20g丙磺酸内酯(0.1摩尔)溶于一定体积的四氢呋喃中,然后向其中加入月桂酸烷醇酰胺14.66g(0.051摩尔),充分溶解后装入连有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入0.27g氢氧化钠(占总反应物的质量百分比为1.00%),加热至回流温度,搅拌反应16h后,旋蒸干燥冷却后得到14.42g N,N-二(1-
乙氧基-)3-磺酸基丙基月桂酰胺磺酸盐表面活性剂,收率为54.25%。
本实施例得到的产物表面张力为25.82mN/m,界面张力为2.65×10-3mN/m。
本实施例得到的产物红外谱图如附图2所示,由谱图解析可知:3399.71cm-1处为磺酸基的O-H的吸收峰;2924.94cm-1、2853.89cm-1处为—CH3、—CH2的伸缩振动峰;1620.61cm-1处为羰基的伸缩振动吸收峰;1462.70cm-1、1417.42cm-1处为—CH3、—CH2的弯曲振动吸收峰;1347.15cm-1处为酰胺—CON的特征吸收峰;1167.72cm-1处为醚键C—O—C的吸收峰;1192.61cm-1、1041.09cm-1处为SO3的特征吸收峰。
在长度为10cm,直径为2.5cm,渗透率为0.4μm2的岩心上模拟驱油实验。先用陆梁油田注入水驱至含水98%,转注0.3PV(岩心孔隙体积)浓度为0.3%的本实施例所制备的表面活性剂(N,N-二(1-乙氧基-)3-磺酸基丙基月桂酰胺磺酸盐表面活性剂),水驱至含水100%,可以在水驱的基础上提高原油采收率11.9%左右。
实施例二
将21.43g月桂酸甲酯(C11H23COOCH3,0.1摩尔)与11.56g二乙醇胺(0.11摩尔)混合于装有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入0.231g氢氧化钠(占总反应物的质量百分比为0.70%),将烧瓶置于油浴中加热至120℃,搅拌反应5h后,旋蒸干燥冷却后得到24.55g月桂酸烷醇酰胺,收率为85.41%。
将12.20g丙磺酸内酯(0.1摩尔)溶于一定体积的四氢呋喃中,然后向其中加入月桂酸烷醇酰胺15.09g(0.0525摩尔),充分溶解后装入连有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入0.33g氢氧化钠(占总反应物的质量百分比为1.21%),加热至回流温度,搅拌反应12h后,旋蒸干燥冷却后得到13.45g N,N-二(1-乙氧基-)3-磺酸基丙基月桂酰胺磺酸盐表面活性剂,收率为50.62%。
本实施例得到的产物表面张力为26.12mN/m,界面张力为2.83×10-3mN/m。
实施例三
将24.23g豆蔻酸甲酯(C13H27COOCH3,0.1摩尔)与12.09g二乙醇胺(0.115摩尔)
混合于装有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入0.22g氢氧化钠(占总反应物的质量百分比为0.61%),将烧瓶置于油浴中加热至130℃,搅拌反应6h后,旋蒸干燥冷却后得到24.75豆蔻酸烷醇酰胺,收率为78.45%。
将12.20g丙磺酸内酯(0.1摩尔)溶于一定体积的四氢呋喃中,然后向其中加入豆蔻酸烷醇酰胺16.40g(0.052摩尔),充分溶解后装入连有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入0.42g氢氧化钠(占总反应物的质量百分比为1.47%),加热至回流温度,搅拌反应14h后,旋蒸干燥冷却后得到16.82g N,N-二(1-乙氧基-)3-磺酸基丙基豆蔻酰胺磺酸盐表面活性剂,收率为60.12%。
本实施例得到的产物表面张力为25.21mN/m,界面张力为2.73×10-3mN/m。
实施例四
将27.03g棕榈酸甲酯(C15H31COOCH3,0.1摩尔)与11.04g二乙醇胺(0.105摩尔)混合于装有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入0.30g氢氧化钠(占总反应物的质量百分比为0.78%),将烧瓶置于油浴中加热至110℃,搅拌反应5h后,旋蒸干燥冷却后得到26.91g棕榈酸烷醇酰胺,收率为80.71%。
将12.20g丙磺酸内酯(0.1摩尔)溶于一定体积的四氢呋喃中,然后向其中加入棕榈酸烷醇酰胺17.52g(0.051摩尔),充分溶解后装入连有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入0.39g氢氧化钠(占总反应物的质量百分比为1.31%),加热至回流温度,搅拌反应16h后,旋蒸干燥冷却后得到17.27g N,N-二(1-乙氧基-)3-磺酸基丙基棕榈酰胺磺酸盐表面活性剂,收率为58.80%。
本实施例得到的产物表面张力为25.45mN/m,界面张力为2.62×10-3mN/m。
实施例五
将29.83g硬脂酸甲酯(C17H35COOCH3,0.1摩尔)与11.04g二乙醇胺(0.105摩尔)混合于装有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入0.32g氢氧化钠(占总反应物的质量百分比为0.78%),将烧瓶置于油浴中加热至120℃,搅拌反应4h后,旋蒸干燥冷却后得到30.67g硬脂酸烷醇酰胺,收率为82.58%。
将12.20g丙磺酸内酯(0.1摩尔)溶于一定体积的四氢呋喃中,然后向其中加入硬脂酸烷醇酰胺19.13g(0.0515摩尔),充分溶解后装入连有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入0.44g氢氧化钠(占总反应物的质量百分比为1.40%),加热至回流温度,搅拌反应15h后,旋蒸干燥冷却后得到17.27gN,N-二(1-乙氧基-)3-磺酸基丙基硬脂酰胺磺酸盐表面活性剂,收率为56.12%。
本实施例得到的产物表面张力为26.03mN/m,界面张力为2.92×10-3mN/m。
Claims (10)
- 根据权利要求2所述的基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的合成方法,其特征在于,该合成方法具体包括以下步骤:1)脂肪酸烷醇酰胺的制备;2)磺丙基化反应。
- 根据权利要求3所述的基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的合成方法,其特征在于,脂肪酸烷醇酰胺的制备的具体方法如下:将脂肪酸甲酯与二乙醇胺按摩尔比为1:1.05~1:1.15混合于装有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入占总反应物质量0.6%~0.8%的催化剂氢氧化钠,然后将烧瓶置于油浴中加热至110℃~130℃搅拌反应4h~6h,最后旋蒸干燥冷却后得到脂肪酸烷醇酰胺,上述总反应物为脂肪酸甲酯和二乙醇胺之和。
- 根据权利要求3-4中任一所述的基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的合成方法,其特征在于,磺丙基化反应的具体方法如下:先将丙磺酸内酯溶于 四氢呋喃中,然后按照烷醇酰胺与丙磺酸内酯为1.02:2~1.05:2的摩尔比向其中加入脂肪酸烷醇酰胺,充分溶解后装入连有磁力转子、冷凝管、温度计的三口烧瓶中,向三口烧瓶中加入占总反应物质量1.0%~1.5%的催化剂氢氧化钠,加热至回流温度,搅拌反应12~16h后,旋蒸干燥冷却后得到N,N-二(1-乙氧基-)3-磺酸基丙基脂肪酰胺表面活性剂;总反应物为脂肪酸烷醇酰胺和丙磺酸内酯之和。
- 根据权利要求3-5中任一所述的基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的合成方法,其特征在于,回流温度为66℃,即四氢呋喃的沸点温度。
- 根据权利要求3-6中任一所述的基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的合成方法,其特征在于,所述的脂肪酸甲酯的结构式为CnH2n+1COOCH3,n=11~17。
- 根据权利要求3-7中任一所述的基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的合成方法,其特征在于,三口烧瓶有圆肚细颈的外观,具有三个口,一个边口安装分水器和冷凝管,将蒸发出来的蒸汽冷凝成液体再回流到反应体系中,避免反应液体被蒸干;中间的口用橡皮塞密封,防止溶液溅出或减少溶液的蒸发;另一边口安装温度计,记录反应温度。加入反应物料后向其中加入磁力转子,反应过程中将其置于集热式恒温磁力搅拌器中,可以实现边搅拌边反应。
- 根据权利要求3-8中任一所述的基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的合成方法,其特征在于,脂肪酸甲酯为月桂酸甲酯、豆蔻酸甲酯、棕榈酸甲酯或者硬脂酸甲酯。
- 权利要求1所述的基于脂肪酸甲酯的磺酸盐型生物质表面活性剂的应用,其特征在于,应用于石油开采领域。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410004834 | 2014-01-06 | ||
CN201410004834.X | 2014-01-06 | ||
CN201410040399.6A CN103805155B (zh) | 2014-01-06 | 2014-01-27 | 磺酸盐型生物质表面活性剂及其合成方法 |
CN201410040399.6 | 2014-01-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015101355A1 true WO2015101355A1 (zh) | 2015-07-09 |
Family
ID=50702557
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2015/070174 WO2015101355A1 (zh) | 2014-01-06 | 2015-01-06 | 磺酸盐型生物质表面活性剂及其合成方法 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN103805155B (zh) |
WO (1) | WO2015101355A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114315572A (zh) * | 2022-01-12 | 2022-04-12 | 西南石油大学 | 一种阴离子超支化含油钻屑清洗剂及其制备方法 |
CN115028785A (zh) * | 2022-06-16 | 2022-09-09 | 陕西科技大学 | 一种耐温耐盐型驱油用表面活性剂及其制备方法 |
CN115368915A (zh) * | 2021-07-22 | 2022-11-22 | 山东大学 | 一种季铵盐羧酸钠磺酸型表面活性剂及其制备方法与应用 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104817479A (zh) * | 2015-04-09 | 2015-08-05 | 武斐 | 一种驱油用生物质表面活性剂的制备技术优化方法 |
CN112300770B (zh) * | 2020-09-25 | 2022-04-22 | 西南石油大学 | 一种耐温耐盐泡排剂的制备方法 |
CN114181718B (zh) * | 2021-12-09 | 2023-06-20 | 中石化石油工程技术服务有限公司 | 一种Bola型表面活性剂和一种纳米乳液及应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3262951A (en) * | 1960-11-25 | 1966-07-26 | Katz Jacob | High molecular weight fatty acid amido amine surfactant and preparation thereof |
JPH01182400A (ja) * | 1988-01-14 | 1989-07-20 | Kao Corp | 液体洗浄剤組成物 |
CN1061243A (zh) * | 1990-09-28 | 1992-05-20 | 普罗格特-甘布尔公司 | 包含多羟基脂肪酸酰胺和烷基苯磺酸盐的洗涤剂组合物 |
CN102464598A (zh) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | 脂肪酸酰胺聚氧乙烯醚苯磺酸盐及其制备方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101935521B (zh) * | 2010-07-19 | 2013-01-02 | 江南大学 | 一种无碱驱油用醇酰胺类非离子型表面活性剂的应用 |
ES2554952T3 (es) * | 2011-09-13 | 2015-12-28 | Lubrizol Advanced Materials, Inc. | Microgeles sensibles a tensioactivos |
CN103508914B (zh) * | 2012-06-27 | 2015-06-17 | 中国石油化工股份有限公司 | 疏水性可聚合单体和驱油剂组合物及其制备方法 |
-
2014
- 2014-01-27 CN CN201410040399.6A patent/CN103805155B/zh active Active
-
2015
- 2015-01-06 WO PCT/CN2015/070174 patent/WO2015101355A1/zh active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3262951A (en) * | 1960-11-25 | 1966-07-26 | Katz Jacob | High molecular weight fatty acid amido amine surfactant and preparation thereof |
JPH01182400A (ja) * | 1988-01-14 | 1989-07-20 | Kao Corp | 液体洗浄剤組成物 |
CN1061243A (zh) * | 1990-09-28 | 1992-05-20 | 普罗格特-甘布尔公司 | 包含多羟基脂肪酸酰胺和烷基苯磺酸盐的洗涤剂组合物 |
CN102464598A (zh) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | 脂肪酸酰胺聚氧乙烯醚苯磺酸盐及其制备方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115368915A (zh) * | 2021-07-22 | 2022-11-22 | 山东大学 | 一种季铵盐羧酸钠磺酸型表面活性剂及其制备方法与应用 |
CN115368915B (zh) * | 2021-07-22 | 2024-05-24 | 山东大学 | 一种季铵盐羧酸钠磺酸型表面活性剂及其制备方法与应用 |
CN114315572A (zh) * | 2022-01-12 | 2022-04-12 | 西南石油大学 | 一种阴离子超支化含油钻屑清洗剂及其制备方法 |
CN115028785A (zh) * | 2022-06-16 | 2022-09-09 | 陕西科技大学 | 一种耐温耐盐型驱油用表面活性剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN103805155A (zh) | 2014-05-21 |
CN103805155B (zh) | 2016-05-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2015101355A1 (zh) | 磺酸盐型生物质表面活性剂及其合成方法 | |
CN104232045B (zh) | 复合型表面活性剂组合物、制备方法及应用 | |
CN101745343B (zh) | 具有居贝特结构的烷基聚氧乙烯醚表面活性剂及其制备方法和用途 | |
CN101502772B (zh) | 松香基磺酸盐型双子表面活性剂及制备方法 | |
CN103113868B (zh) | 一种无碱化学复合驱油用组合物及在三次采油中的应用 | |
CN105670590B (zh) | 一种适用于高温高矿化度油藏的三元复合体系、表面活性剂及其制备方法 | |
CN106047369A (zh) | 苯并菲己烷氧基桥连十二烷氧基苯基卟啉二元化合物盘状液晶材料的合成方法 | |
CN102304069B (zh) | 一种驱油用饱和腰果酚磺酸盐表面活性剂的合成方法 | |
CN102154000B (zh) | 过渡金属磺酸盐络合物稠油水热催化降粘剂及其制备方法 | |
CN103540303B (zh) | 复合型表面活性剂组合物及其制备方法 | |
CN102516064A (zh) | 一种非离子-阴离子复合型表面活性剂的制备方法及其应用 | |
CN103396306A (zh) | 一种腰果酚Gemini聚氧乙烯醚羧酸盐及其制备方法 | |
CN102516958B (zh) | 一种用于油品的高温油基泡沫剂及其制备方法 | |
CN104529756B (zh) | 芳基烷基醇聚氧乙烯醚羧酸盐及其制备与应用 | |
CN102863948A (zh) | 一种驱油用羟磺基甜菜碱两性表面活性剂及其制备方法 | |
CN102464974A (zh) | 可大幅度提高原油采收率的组合物及其制备方法 | |
CN104817479A (zh) | 一种驱油用生物质表面活性剂的制备技术优化方法 | |
CN109679678A (zh) | 从模拟汽油中萃取碱性/非碱性氮的低共熔溶剂及方法 | |
CN102503863A (zh) | 一种双烷基醚双磺酸盐表面活性剂及其制备方法 | |
CN104927823B (zh) | 双阴离子表面活性剂驱油剂及其制备方法和应用 | |
CN101935522A (zh) | 一种长链烷基酰基苯磺酸钠盐的制备及其在提高石油采收率中的应用 | |
CN107384357B (zh) | 聚氧乙烯-苯磺酸盐型复合双子表面活性剂及其制备方法 | |
CN103173197A (zh) | 一种双子表面活性剂及其制备方法和在三次采油中的应用 | |
CN104910024A (zh) | 一种驱油用表面活性剂 | |
CN105566174A (zh) | 一种长链叔胺常压无水季铵化合成甜菜碱的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15733114 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15733114 Country of ref document: EP Kind code of ref document: A1 |