CN110698364B - Method for synthesizing mono/dialkyl sodium benzenesulfonate - Google Patents
Method for synthesizing mono/dialkyl sodium benzenesulfonate Download PDFInfo
- Publication number
- CN110698364B CN110698364B CN201911049063.5A CN201911049063A CN110698364B CN 110698364 B CN110698364 B CN 110698364B CN 201911049063 A CN201911049063 A CN 201911049063A CN 110698364 B CN110698364 B CN 110698364B
- Authority
- CN
- China
- Prior art keywords
- benzene
- sodium
- ionic liquid
- alkylbenzene
- olefin
- 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.)
- Active
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
- C07C2/70—Catalytic processes with acids
-
- 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
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
Abstract
The invention discloses a method for synthesizing mono/dialkyl benzene sulfonate, which uses ionic liquid to catalyze medium-chain alpha-olefin to synthesize alkylbenzene and sulfonate thereof and researches the surface performance of the alkylbenzene and the sulfonate. The invention firstly takes alpha-olefin and benzene as raw materials to carry out alkylation reaction in acidic ionic liquid, aiming at synthesizing various surfactant intermediates, and the obtained intermediates are taken as raw materials to carry out sulfonation by using chlorosulfonic acid and neutralization by using sodium hydroxide, thus finally obtaining various sodium alkyl benzene sulfonate surfactants. The surfactant obtained by the invention can obviously reduce the surface tension of water, and the emulsifying property and the wettability of the surfactant are obviously superior to those of sodium dodecyl benzene sulfonate.
Description
Technical Field
The invention relates to a method for synthesizing mono/dialkyl sodium benzenesulfonate, belonging to the field of synthesis and application of surfactants.
Background
The Fischer-Tropsch synthesis (FTS) is one of the most effective ways for utilizing coal resources by converting coal synthesis gas into clean liquid fuel. As is well known, alpha-olefins (C)5 - C11) The content in the FTS product is higher. However, these α -olefins are generally used as liquid fuels having low added values. Therefore, it is essential and valuable to improve the high value-added utilization of α -olefins by various means.
Linear alkyl benzene sulfonates are an important surfactant and are widely used in industrial and consumer products. It is well known that their synthesis is generally via long chain olefins (C)10-C14) In HF and H2SO4And the benzene is alkylated over an acidic catalyst. However, these catalysts also pose serious environmental problems, and the post-treatment, separation and recovery of these catalysts is a cumbersome work. In recent years, acidic ionic liquids have been considered to be greener catalysts and solvents. Characteristics of ionic liquids include their negligible vapor pressure, potential for recycling, compatibility with various organic compounds and organometallic catalysts, and the ability to be easily separated from the reaction product. Many research results have been obtained by using ionic liquid as a catalyst and carrying out alkylation reaction on benzene to improve the conversion rate and selectivity of a target product.
The structure-activity relationship of mono-substituted long-chain alkyl benzene sulfonate has been widely studied, but the research mainly focuses on alkyl benzene sulfonate with different chain lengths and different substituent positions. In the disubstituted and polysubstituted alkylbenzene sulfonates, the majority of long chain alkyl groups and short chain alkyl groups are attached to the benzene ring. The research finds that the long-chain alkyl benzene sulfonate can obviously reduce the surface tension of water, and the critical micelle concentration is lower. A long-chain alkylbenzene having a chain length of (C)10 - C14) The alpha-olefin is mainly from paraffin in petroleum production processDehydrogenation technology. However, depletion of crude oil reserves and rising crude oil prices, new sources of alpha olefin feedstocks are urgently needed.
Disclosure of Invention
The invention aims to provide a method for synthesizing mono/dialkyl sodium benzenesulfonate, which utilizes ionic liquid to catalyze and prepare the mono/dialkyl sodium benzenesulfonate and aims to utilize C in Fischer-Tropsch synthesis6、C8Medium and long chain olefins. The ionic liquid catalyst is mild and efficient, is easy to separate from the product, and overcomes the defects of environmental pollution, strong toxicity and strong corrosivity of the traditional alkylation catalyst.
The invention takes benzene and medium-long chain alpha-olefin as raw materials, ionic liquid as a catalyst to synthesize alkylbenzene, and the alkylbenzene is subjected to sulfonation and neutralization reaction to obtain a final product of mono/dialkyl sodium benzenesulfonate.
The invention provides a method for synthesizing mono/dialkyl sodium benzenesulfonate, which comprises the following steps:
(1) taking alpha-olefin and benzene as raw materials, carrying out alkylation reaction in acidic ionic liquid, and controlling the yield of mono/dialkyl benzene by controlling the benzene-olefin ratio; synthesizing monoalkylbenzene, controlling the benzene-olefin ratio to be 8: 1-14: 1, synthesizing dialkyl benzene, and controlling the benzene-olefin ratio to be 1: 2-1: 8;
(2) carrying out sulfonation reaction on mono/dialkyl benzene and chlorosulfonic acid to obtain sulfonic acid;
(3) neutralizing the purified mono/dialkyl benzene with sodium hydroxide to obtain the final product of the mono/dialkyl benzene sodium sulfonate.
In the synthesis step, the acidic ionic liquid used is triethylamine hydrochloride-aluminum chloride (Et)3NHCl-AlCl3) (ii) a The alpha-olefin used is any one of hexene and octene.
In the synthesis step, the sulfonation temperature is controlled to be 5-15 ℃, and the mass ratio of the mono/dialkyl benzene to the chlorosulfonic acid is 1: 1.05-1: 1.1.
In the synthesis step, the mass percent of the sodium hydroxide is 10-30%, and the pH value after neutralization is 7-8.
The invention provides the mono/dialkyl sodium benzenesulfonate prepared by the method;
the general formula of the monoalkyl benzene sodium sulfonate obtained by the synthesis method is as follows:
Cn-MSABS ；
the general formula of the sodium dialkyl benzene sulfonate obtained by the synthesis method is as follows:
Cn-DSABS
wherein n =6 or 8.
The invention has the beneficial effects that:
(1) the invention improves the high value-added utilization of alpha-olefin, the reaction product is easy to separate from the catalyst, the experimental operation is simple, and the requirement on equipment is lower.
(2) The yield of the mono/dialkyl benzene can be controlled by controlling the benzene-olefin ratio, and the mono/dialkyl sodium benzenesulfonate with higher purity can be finally obtained; compared with single-chain alkyl benzene sulfonate, the double-chain alkyl benzene sulfonate has better performance of reducing water surface tension due to the increase of the number of hydrophobic chains on a benzene ring.
(3) The sodium dialkylbenzenesulfonate obtained in the present invention has a reduced surface tension of water, and in addition, has better emulsifying and wetting properties, as compared with commercial sodium dodecylbenzenesulfonate.
Drawings
Fig. 1 is a surface tension chart of the sodium alkylbenzenesulfonate surfactant synthesized in example 1 to example 10.
Fig. 2 shows the emulsifying properties of the sodium alkylbenzenesulfonate surfactants synthesized in examples 1 to 10.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
in the synthesis of sodium monoalkyl benzenesulfonate in this embodiment, the synthesis steps include the following aspects:
a fixed amount of triethylamine hydrochloride (1.8 mmol), n-decane (5.34 g) and anhydrous aluminum chloride (3.6 mmol) were charged in a 100 mL three-necked flask equipped with a reflux condenser, and stirred at 60 ℃ for 1 h under an argon atmosphere. After the stirring is stopped, the mixture is separated into layers, the upper layer is n-decane and the lower layer is [ Et ]3NH+][Al2Cl7 -]The ionic liquid catalyst is composed. According to the benzene: the mol ratio of 1-hexene is 14:1, benzene is added into the ionic liquid, and the required 1-hexene is slowly dropped under the stirring at 60 ℃. After the alkylation reaction is finished, the mixture is cooled to room temperature and then layered, wherein the upper layer is a n-decane and alkylbenzene products and unreacted substances, and the lower layer is an ionic liquid catalyst. And (4) taking the upper-layer liquid product, washing with water, and then distilling under reduced pressure to obtain the monohexylbenzene.
The analysis result of the product by a gas chromatograph shows that: the 1-hexene conversion was 100% and the monohexylbenzene selectivity was 94%.
The sulfonation of alkylbenzene was carried out in a 100 mL flask equipped with a magnetic stir bar using chlorosulfonic acid as the sulfonating agent. The molar ratio of alkylbenzene to chlorosulfonic acid was fixed at 1: 1.05. After reacting for 2 h, neutralizing the reaction product with 20% (w/w) sodium hydroxide solution to pH = 7, extracting and purifying with ethanol and petroleum ether respectively, and drying to obtain sodium monohexylbenzenesulfonate (C)6-MSABS). The active content was 94% by two-phase titration.
Example 2
In the synthesis of sodium dialkylbenzenesulfonate in this embodiment, the synthesis steps include the following aspects:
a fixed amount of triethylamine hydrochloride (1.8 mmol), n-decane (5.34 g) and anhydrous aluminum chloride (3.6 mmol) were charged in a 100 mL three-necked flask equipped with a reflux condenser, and stirred at 60 ℃ for 1 h under an argon atmosphere. After the stirring is stopped, the mixture is separated into layers, the upper layer is n-decane and the lower layer is [ Et ]3NH+][Al2Cl7 -]The ionic liquid catalyst is composed. According to the benzene: the mol ratio of 1-hexene is 1:6 respectively, benzene is added into the ionic liquidTo the mixture, the desired 1-hexene was then slowly added dropwise with stirring at 60 ℃. After the alkylation reaction is finished, the mixture is cooled to room temperature and then layered, wherein the upper layer is the n-decane and alkylbenzene products and unreacted substances, and the lower layer is the ionic liquid catalyst. And (4) taking the upper-layer liquid product, washing with water, and then distilling under reduced pressure to obtain the dihexyl benzene.
The analysis result of the product by a gas chromatograph shows that: benzene conversion was 100% and dihexylbenzene selectivity was 52%.
The sulfonation of alkylbenzene was carried out in a 100 mL flask equipped with a magnetic stir bar, using chlorosulfonic acid as the sulfonating agent. The molar ratio of alkylbenzene to chlorosulfonic acid was fixed at 1: 1.1. After reacting for 2 h, neutralizing the reaction product with 10% (w/w) sodium hydroxide solution to pH = 7, extracting and purifying with ethanol and petroleum ether respectively, and drying to obtain sodium dihexylbenzenesulfonate (C)6-DSABS). The active content was determined to be 95% by two-phase titration.
Example 3
In the synthesis of sodium monoalkyl benzenesulfonate in this embodiment, the synthesis steps include the following aspects:
fixed amounts of triethylamine hydrochloride (1.5 mmol), n-decane (5.34 g) and anhydrous aluminium chloride (3.9mmol) were added to a 100 mL three-necked flask equipped with a reflux condenser and stirred at 60 ℃ for 1 h under an argon atmosphere. After the stirring is stopped, the mixture is separated into layers, the upper layer is n-decane and the lower layer is [ Et ]3NH+][Al2Cl7 -]The ionic liquid catalyst is composed. According to the benzene: the mol ratio of 1-octene is 12:1, benzene is added into ionic liquid, and the required 1-octene is slowly dropped after stirring at 60 ℃. After the alkylation reaction is finished, the mixture is cooled to room temperature and then layered, wherein the upper layer is the n-decane and alkylbenzene products and unreacted substances, and the lower layer is the ionic liquid catalyst. And (4) taking the upper-layer liquid product, washing with water, and then distilling under reduced pressure to obtain the mono-octyl benzene.
The analysis result of the product by a gas chromatograph shows that: the 1-octene conversion was 100% and the mono-octylbenzene selectivity was 93%.
The sulfonation of alkylbenzene was carried out in a 100 mL flask equipped with a magnetic stir bar using chlorosulfonic acid as the sulfonating agent.The molar ratio of alkylbenzene to chlorosulfonic acid was fixed at 1: 1.05. After reacting for 2 h, neutralizing the reaction product with 30% (w/w) sodium hydroxide solution to pH = 7, extracting and purifying with ethanol and petroleum ether respectively, and drying to obtain sodium monooctylphenylsulfonate (C)8-MSABS). The active content was determined to be 96% by two-phase titration.
Example 4
In the synthesis of sodium dialkylbenzenesulfonate in this embodiment, the synthesis steps include the following aspects:
a fixed amount of triethylamine hydrochloride (1.8 mmol), n-decane (5.34 g) and anhydrous aluminum chloride (3.6 mmol) were charged in a 100 mL three-necked flask equipped with a reflux condenser, and stirred at 60 ℃ for 1 h under an argon atmosphere. After the stirring is stopped, the mixture is separated into layers, the upper layer is n-decane and the lower layer is [ Et ]3NH+][Al2Cl7 -]The ionic liquid catalyst is composed. According to the benzene: the mol ratio of 1-octene is 1:4, benzene is added into ionic liquid, and the required 1-octene is slowly dropped after stirring at 60 ℃. After the alkylation reaction is finished, the mixture is cooled to room temperature and then layered, wherein the upper layer is a n-decane and alkylbenzene products and unreacted substances, and the lower layer is an ionic liquid catalyst. And (4) taking the upper-layer liquid product, washing with water, and then distilling under reduced pressure to obtain the dioctyl benzene.
The analysis result of the product by a gas chromatograph shows that: the benzene conversion was 100% and the selectivity to dioctylbenzene was 56%.
The sulfonation of alkylbenzene was carried out in a 100 mL flask equipped with a magnetic stir bar using chlorosulfonic acid as the sulfonating agent. The molar ratio of alkylbenzene to chlorosulfonic acid was fixed at 1: 1.1. After reacting for 2 h, neutralizing the reaction product with 20% (w/w) sodium hydroxide solution to pH = 7, extracting and purifying with ethanol and petroleum ether respectively, and drying to obtain sodium dioctylbenzenesulfonate (C)8-DSABS). The active content was 94% by two-phase titration.
Example 5
In the synthesis of sodium dialkylbenzenesulfonate in this embodiment, the synthesis steps include the following aspects:
a fixed amount of triethylamine hydrochloride (1.5 mmol) and n-decane (5.3 mmol)4 g) And anhydrous aluminum chloride (3.9mmol) were charged into a 100 mL three-necked flask equipped with a reflux condenser, and stirred at 60 ℃ for 1 h under an argon atmosphere. After the stirring is stopped, the mixture is separated into layers, the upper layer is n-decane and the lower layer is [ Et ]3NH+][Al2Cl7 -]The ionic liquid catalyst is composed. According to the benzene: adding benzene into the ionic liquid at a molar ratio of 1 to 2 respectively, stirring at 60 ℃, and then slowly dropwise adding the required 1-hexene. After the alkylation reaction is finished, the mixture is cooled to room temperature and then layered, wherein the upper layer is a n-decane and alkylbenzene products and unreacted substances, and the lower layer is an ionic liquid catalyst. And (4) taking the upper-layer liquid product, washing with water, and then distilling under reduced pressure to obtain the dihexyl benzene.
The analysis result of the product by a gas chromatograph shows that: benzene conversion was 95% and dihexylbenzene selectivity was 42%.
The sulfonation of alkylbenzene was carried out in a 100 ml flask equipped with a magnetic stir bar, using chlorosulfonic acid as the sulfonating agent. The molar ratio of alkylbenzene to chlorosulfonic acid was fixed at 1: 1.05. After reacting for 2 h, neutralizing the reaction product with 30% (w/w) sodium hydroxide solution to pH = 7, extracting and purifying with ethanol and petroleum ether respectively, and drying to obtain sodium dihexylbenzenesulfonate (C)6-DSABS). The active content was determined by two-phase titration to be 96%.
Example 6
In the synthesis of sodium dialkylbenzenesulfonate in this embodiment, the synthesis steps include the following aspects:
fixed amounts of triethylamine hydrochloride (1.5 mmol), n-decane (5.34 g) and anhydrous aluminium chloride (3.9mmol) were added to a 100 mL three-necked flask equipped with a reflux condenser and stirred at 60 ℃ for 1 h under an argon atmosphere. After the stirring is stopped, the mixture is separated into layers, the upper layer is n-decane and the lower layer is [ Et ]3NH+][Al2Cl7 -]The ionic liquid catalyst is composed. According to the weight percentage of benzene: the mol ratio of 1-octene is 1:2, benzene is added into ionic liquid, and then required 1-octene is slowly dropped under the stirring at 60 ℃. After the alkylation reaction is finished, the mixture is cooled to room temperature and then layered, the upper layer is the n-decane and alkylbenzene products and unreacted substances, and the lower layer is ionic liquidA bulk catalyst. And (4) taking the upper-layer liquid product, washing with water, and then distilling under reduced pressure to obtain the dioctyl benzene.
The analysis result of the product by a gas chromatograph shows that: the benzene conversion was 97% and the selectivity to dioctylbenzene was 56%.
The sulfonation reaction of alkylbenzene was carried out in a 100 mL flask equipped with a magnetic stir bar using chlorosulfonic acid as a sulfonating agent. The molar ratio of alkylbenzene to chlorosulfonic acid was fixed at 1: 1.1. After reacting for 2 h, neutralizing the reaction product with 20% (w/w) sodium hydroxide solution to pH = 7, extracting and purifying with ethanol and petroleum ether respectively, and drying to obtain sodium dioctylbenzenesulfonate (C)8-DSABS). The active content was determined to be 96% by two-phase titration.
Example 7
In the synthesis of sodium dialkylbenzenesulfonate in this embodiment, the synthesis steps include the following aspects:
a fixed amount of triethylamine hydrochloride (1.8 mmol), n-decane (5.34 g) and anhydrous aluminum chloride (3.6 mmol) were charged in a 100 mL three-necked flask equipped with a reflux condenser, and stirred at 60 ℃ for 1 h under an argon atmosphere. After the stirring is stopped, the mixture is separated into layers, the upper layer is n-decane and the lower layer is [ Et ]3NH+][Al2Cl7 -]The ionic liquid catalyst is composed. According to the benzene: the mol ratio of 1-hexene is 1:8, benzene is added into the ionic liquid, and the required 1-hexene is slowly dripped into the ionic liquid under stirring at 60 ℃. After the alkylation reaction is finished, the mixture is cooled to room temperature and then layered, wherein the upper layer is a n-decane and alkylbenzene products and unreacted substances, and the lower layer is an ionic liquid catalyst. And (4) taking the upper-layer liquid product, washing with water, and then distilling under reduced pressure to obtain the dihexyl benzene.
The analysis result of the product by a gas chromatograph shows that: benzene conversion was 100% and dihexylbenzene selectivity was 52%.
The sulfonation of alkylbenzene was carried out in a 100 mL flask equipped with a magnetic stir bar using chlorosulfonic acid as the sulfonating agent. The molar ratio of alkylbenzene to chlorosulfonic acid was fixed at 1: 1.1. After reacting for 2 h, neutralizing the reaction product with 10% (w/w) sodium hydroxide solution to pH = 7, extracting and purifying with ethanol and petroleum ether respectively, and drying to obtain sodium dihexylbenzenesulfonate (C)6-DSABS). The active content was determined to be 94% by two-phase titration.
Example 8
In the synthesis of sodium dialkylbenzenesulfonate in this embodiment, the synthesis steps include the following aspects:
a fixed amount of triethylamine hydrochloride (1.5 mmol), n-decane (5.34 g) and anhydrous aluminum chloride (3.9mmol) were charged in a 100 mL three-necked flask equipped with a reflux condenser, and stirred at 60 ℃ for 1 h under an argon atmosphere. After the stirring is stopped, the mixture is separated into layers, the upper layer is n-decane and the lower layer is [ Et ]3NH+][Al2Cl7 -]The ionic liquid catalyst is composed. According to the benzene: the mol ratio of 1-octene is 1:6, benzene is added into ionic liquid, and then required 1-octene is slowly dropped under stirring at 60 ℃. After the alkylation reaction is finished, the mixture is cooled to room temperature and then layered, wherein the upper layer is a n-decane and alkylbenzene products and unreacted substances, and the lower layer is an ionic liquid catalyst. And (4) taking the upper-layer liquid product, washing with water, and then distilling under reduced pressure to obtain the dioctyl benzene.
The analysis result of the product by a gas chromatograph shows that: the benzene conversion was 100% and the selectivity to dioctylbenzene was 65%.
The sulfonation of alkylbenzene was carried out in a 100 mL flask equipped with a magnetic stir bar, using chlorosulfonic acid as the sulfonating agent. The molar ratio of alkylbenzene to chlorosulfonic acid was fixed at 1: 1.05. After reacting for 2 h, neutralizing the reaction product with 30% (w/w) sodium hydroxide solution to pH = 7, extracting and purifying with ethanol and petroleum ether respectively, and drying to obtain sodium dioctylbenzenesulfonate (C)8-DSABS). The active content was determined to be 98% by two-phase titration.
Example 9
In the synthesis of sodium dialkylbenzenesulfonate in this embodiment, the synthesis steps include the following aspects:
a fixed amount of triethylamine hydrochloride (1.8 mmol), n-decane (5.34 g) and anhydrous aluminum chloride (3.6 mmol) were charged in a 100 mL three-necked flask equipped with a reflux condenser, and stirred at 60 ℃ for 1 h under an argon atmosphere. After the stirring is stopped, the mixture is separated into layers, the upper layer is n-decane and the lower layer is [ Et ]3NH+][Al2Cl7 -]The ionic liquid catalyst is composed. According to the benzene: the mol ratio of 1-hexene is 1:4, benzene is added into the ionic liquid, and the required 1-hexene is slowly dropped under the stirring at 60 ℃. After the alkylation reaction is finished, the mixture is cooled to room temperature and then layered, wherein the upper layer is a n-decane and alkylbenzene products and unreacted substances, and the lower layer is an ionic liquid catalyst. And (4) taking the upper-layer liquid product, washing with water, and then distilling under reduced pressure to obtain the dihexyl benzene.
The analysis result of the product by a gas chromatograph shows that: benzene conversion was 100% and dihexylbenzene selectivity was 52%.
The sulfonation of alkylbenzene was carried out in a 100 mL flask equipped with a magnetic stir bar using chlorosulfonic acid as the sulfonating agent. The molar ratio of alkylbenzene to chlorosulfonic acid was fixed at 1: 1.1. After reacting for 2 h, neutralizing the reaction product with 30% (w/w) sodium hydroxide solution to pH = 7, extracting and purifying with ethanol and petroleum ether respectively, and drying to obtain sodium dihexylbenzenesulfonate (C)6-DSABS). The active content was determined to be 95% by two-phase titration.
Example 10
In the synthesis of sodium dialkylbenzenesulfonate in this embodiment, the synthesis steps include the following aspects:
a fixed amount of triethylamine hydrochloride (1.8 mmol), n-decane (5.34 g) and anhydrous aluminum chloride (3.6 mmol) were charged in a 100 mL three-necked flask equipped with a reflux condenser, and stirred at 60 ℃ for 1 h under an argon atmosphere. After stopping stirring, the mixture was partitioned into an upper layer of n-decane and a lower layer of [ Et ]3NH+][Al2Cl7 -]The ionic liquid catalyst is composed. According to the benzene: adding benzene into the ionic liquid at a molar ratio of 1:8, stirring at 60 ℃, and then slowly dropwise adding the required 1-octene. After the alkylation reaction is finished, the mixture is cooled to room temperature and then layered, wherein the upper layer is a n-decane and alkylbenzene products and unreacted substances, and the lower layer is an ionic liquid catalyst. And (4) taking the upper layer liquid product, washing with water, and then distilling under reduced pressure to obtain the dioctyl benzene.
The analysis result of the product by a gas chromatograph shows that: the benzene conversion was 100% and the selectivity to dioctylbenzene was 65%.
The sulfonation of alkylbenzene was carried out in a 100 mL flask equipped with a magnetic stir bar using chlorosulfonic acid as the sulfonating agent. The molar ratio of alkylbenzene to chlorosulfonic acid was fixed at 1: 1.05. After reacting for 2 h, neutralizing the reaction product with 10% (w/w) sodium hydroxide solution to pH = 7, extracting and purifying with ethanol and petroleum ether respectively, and drying to obtain sodium dioctylbenzenesulfonate (C)8-DSABS). The active content was determined to be 97% by two-phase titration.
The surface tension of the product obtained in the above example was measured using the Kruss K100 tensiometer chip hanging method, and fig. 1 is a surface tension chart of the sodium alkylbenzenesulfonate surfactant synthesized in example 1 to example 10.
Table 1 shows the surface activity parameters of the sodium alkylbenzenesulfonate surfactants synthesized in examples 1 to 10. The parameter calculation method comprises the following steps:
TABLE 1
As can be seen from fig. 1 and table 1, the surface tension decreased with increasing concentration, and the surface tension value stabilized after the CMC was exceeded. However, C6MSABS and C8MSABS does not show CMC points, probably due to too short hydrophobic chains, at which concentration the aggregates at the air-water interface cannot form micelles. Comparison of SDBS, C6-DSABS and C8DSABS found that the hydrophobic effect increased with increasing alkyl chain length, which allowed the alkyl chain to migrate easily to the air-water surface, with a significant decrease in surface tension and critical micelle concentration.
Fig. 2 shows the emulsifying properties of the sodium alkylbenzenesulfonate surfactants synthesized in examples 1 to 10, and the specific test procedures are as follows: the emulsifying properties were determined by the water separation time method. Liquid paraffin (40 mL) was used as the oil phase, which contained 1.0 g L−1Sodium alkyl benzene sulfonateAn aqueous solution of surfactant (40 mL) was poured into 100 mL of the oil phase. The stoppered cylinder was inverted 5 times and then allowed to stand for 1 minute. The experiment was performed 5 times and the separation time of 10 mL of water was recorded to characterize the emulsifying power.
FIG. 2 shows the water split versus time, qualitatively evaluating the emulsification performance in terms of the time required to separate a 10 mL aqueous phase; the longer the separation time, the higher the emulsifying power. The results show that C is comparable to other sodium alkyl benzene sulfonates8The emulsifying capacity of the DSABS on the liquid paraffin is enhanced. C6The emulsifying capacity of DSABS is slightly better than that of SDBS. The stability of the emulsion is related to the interfacial properties of the adsorption film. In general, the longer the hydrophobic chain, the greater the interfacial expansion modulus, the greater the adsorption of the surfactant at the interface, the stronger the interfacial film formed and, therefore, the more stable the emulsion formed.
Table 2 shows the wetting properties of the sodium alkylbenzenesulfonate surfactants synthesized in examples 1 to 10, and standard reference HG/T2575-94 was determined.
TABLE 2
The settling time of the circular canvas pieces in three aqueous solutions of sodium alkylbenzenesulfonate is shown in table 2. As can be seen from the table, the wettability of the three sodium alkyl benzene sulfonates increases with increasing surfactant concentration. When the concentration is 0.5 g L-1When the circular canvas is in C6The settling time in the aqueous DSABS and SDBS solutions increases rapidly at a concentration of 0.25 g L-1When the circular canvas is in C8The settling time in the DSABS aqueous solution increases rapidly. Because of C6-critical micelle concentration of DSABS and SDBS-0.5 g L-1And C is8-a critical micelle concentration of DSABS of-0.25 g L-1. The results show that the wettability of the fabric is excellent when the surfactant concentration is higher than the critical micelle concentration. At 1 g L-1At the concentration of (A), the wettability of three sodium alkylbenzenesulfonates was compared, and C was found8-DSABS is optimal, followed by C6DSABS, then SDBS.
Claims (2)
1. A method for synthesizing sodium dialkyl benzene sulfonate is characterized in that: benzene and medium-long chain alpha-olefin are used as raw materials, ionic liquid is used as a catalyst to synthesize alkylbenzene, and the alkylbenzene is subjected to sulfonation and neutralization reaction to obtain a final product, namely sodium dialkyl benzenesulfonate;
the medium-long chain alpha-olefin is hexene or octene;
the synthesis method of the sodium dialkyl benzene sulfonate comprises the following steps:
(1) taking alpha-olefin and benzene as raw materials, carrying out alkylation reaction in an acidic ionic liquid, and controlling the yield of dialkyl benzene by controlling the benzene-olefin ratio; the benzene-olefin ratio is controlled to be 1: 2-1: 8;
(2) carrying out sulfonation reaction on dialkyl benzene and chlorosulfonic acid under the condition of no need of a solvent to obtain dialkyl benzene sulfonic acid;
(3) neutralizing the dialkyl benzene sulfonic acid and sodium hydroxide, and extracting and purifying to obtain a final product, namely the dialkyl benzene sulfonic acid sodium salt;
the temperature of the alkylation reaction in the step (1) is 60 ℃;
the acidic ionic liquid in the step (1) is triethylamine hydrochloride-aluminum chloride;
in the step (2), the sulfonation temperature is controlled to be 5-15 ℃, and the mass ratio of the dialkyl benzene to the chlorosulfonic acid is 1: 1.05-1: 1.1.
2. The method for synthesizing sodium dialkylbenzenesulfonate according to claim 1, characterized in that: the mass percent of the sodium hydroxide is 10-30%, and the pH value after neutralization is 7-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911049063.5A CN110698364B (en) | 2019-10-31 | 2019-10-31 | Method for synthesizing mono/dialkyl sodium benzenesulfonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911049063.5A CN110698364B (en) | 2019-10-31 | 2019-10-31 | Method for synthesizing mono/dialkyl sodium benzenesulfonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110698364A CN110698364A (en) | 2020-01-17 |
| CN110698364B true CN110698364B (en) | 2022-06-21 |
Family
ID=69202986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911049063.5A Active CN110698364B (en) | 2019-10-31 | 2019-10-31 | Method for synthesizing mono/dialkyl sodium benzenesulfonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110698364B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225617A (en) * | 1996-07-22 | 1999-08-11 | 阿克佐诺贝尔公司 | Linear alkylbenzene formation using low temp. ionic liquid and long chain alkylating agent |
| CN101318917A (en) * | 2008-06-20 | 2008-12-10 | 辽宁天合精细化工股份有限公司 | Long chain (C18-C12) linear alkyl benzene sulfonate and method of preparing the same |
| CN109824467A (en) * | 2019-03-27 | 2019-05-31 | 太原理工大学 | It is a kind of to utilize the ionic liquid-catalyzed method and its application for preparing more alkylnaphthalenes |
-
2019
- 2019-10-31 CN CN201911049063.5A patent/CN110698364B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225617A (en) * | 1996-07-22 | 1999-08-11 | 阿克佐诺贝尔公司 | Linear alkylbenzene formation using low temp. ionic liquid and long chain alkylating agent |
| CN101318917A (en) * | 2008-06-20 | 2008-12-10 | 辽宁天合精细化工股份有限公司 | Long chain (C18-C12) linear alkyl benzene sulfonate and method of preparing the same |
| CN109824467A (en) * | 2019-03-27 | 2019-05-31 | 太原理工大学 | It is a kind of to utilize the ionic liquid-catalyzed method and its application for preparing more alkylnaphthalenes |
Non-Patent Citations (9)
| Title |
|---|
| "Et3NHCl-xAlCl3离子液体催化苯与1-十二烯烷基化反应";张海山;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20170715(第7期);第32-33页 * |
| "Studies of Synergism in Binary Alkylbenzene Sulfonate Mixtures for Producing Low Interfacial Tensions at Oil/Water Interface";Wang Li-cheng等;《Journal of Dispersion Science and Technology》;20140130;第35卷;Fig. 1，第308右栏-第309页左栏 * |
| "磺酸盐表面活性剂与疏水缔合聚合物作用的热力学";梁晓静等;《油田化学》;20130625;第30卷;第1.1部分，表3、5 * |
| "离子液体催化合成十六烷基苯的研究";齐晶等;《精细与专用化学品》;20090506;第17卷;第19-22页 * |
| C_(20～24)烷基二甲苯磺酸盐的合成与界面性能;陈明月等;《化学工程师》;20151125(第11期);第64-68页 * |
| Wang Li-cheng等."Studies of Synergism in Binary Alkylbenzene Sulfonate Mixtures for Producing Low Interfacial Tensions at Oil/Water Interface".《Journal of Dispersion Science and Technology》.2014,第35卷 * |
| 梁晓静等."磺酸盐表面活性剂与疏水缔合聚合物作用的热力学".《油田化学》.2013,第30卷 * |
| 氯铝酸离子液体催化苯与1-己烯的烷基化反应;陈慧等;《化学世界》;20030425(第04期);第171-173页 * |
| 系列长链烷基芳基磺酸盐的合成及性能研究;丁伟等;《青岛科技大学学报(自然科学版)》;20160815(第04期);摘要，第1部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110698364A (en) | 2020-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103025996B (en) | The method of recovering the oil from oil bearing bed | |
| AU2010245265B2 (en) | Sulfonated internal olefin surfactant for enhanced oil recovery | |
| US20050236300A1 (en) | Process for well fluids base oil via metathesis of alpha-olefins | |
| US9688621B2 (en) | Process for preparing an internal olefin sulfonate | |
| CN102924213B (en) | Method for producing isoalkanes from n-alkanes through catalysis | |
| US20030236175A1 (en) | Process for well fluids base oil via metathesis of alpha-olefins | |
| JP2017527651A (en) | Organoclay composition having a quaternary ammonium ion having one or more branched alkyl substituents | |
| CN104817419B (en) | A kind of method preparing alkylnaphthalene and its application | |
| CN110698364B (en) | Method for synthesizing mono/dialkyl sodium benzenesulfonate | |
| US9221750B2 (en) | Process for preparing an internal olefin sulfonate | |
| Kärkkäinen | Preparation and characterization of some ionic liquids and their use in the dimerization reaction of 2-methylpropene | |
| US20210070699A1 (en) | Amphiphilic Diphenyl Ether Compounds Derived from Alpha Olefins or Vinylidene Alpha Olefin Dimers | |
| CN110639426A (en) | Branched alkyl sulfonate surfactant and preparation process thereof | |
| US4925976A (en) | Olefin sulfonation method | |
| US11384052B2 (en) | Amphiphilic cyclohexylbenzene compounds derived from alpha olefins or vinylidene alpha olefin dimers | |
| RU2756954C1 (en) | Method for obtaining alkyl derivatives of arenes | |
| US11168053B2 (en) | Amphiphilic biphenyl compounds derived from alpha olefins or vinylidene alpha olefin dimers | |
| WO2019105844A1 (en) | New catalytic composition based on nickel and a phosphonium, and use thereof for the oligomerisation of olefins | |
| Kong et al. | Synthesis of alkylbenzene from medium-chain olefins catalyzed by an acidic ionic liquid and the surface properties of their sulfonate | |
| RU2001133270A (en) | METHOD FOR ISOLATING FUNCTIONALIZED ALPHA-OLEFINS FROM FUNCTIONALIZED NON-END OLEFINS | |
| CN115716791A (en) | Anionic sulfonate surfactant and preparation method and application thereof | |
| FR2589858A1 (en) | Process for selective alkylation of aromatic compounds | |
| WO2019105843A1 (en) | New catalytic composition based on nickel, a phosphorus compound and a sulfonic acid, and use thereof for the oligomerization of olefins | |
| JPH10273462A (en) | Medium oil for synthesizing dimethyl ether | |
| JPS597154A (en) | Preparation of alkanesulfonic acid salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |