CN101979426A - Olefin Addition Synthesis Method of Fatty Alcohol (Alkylphenol) Polyoxyethylene Ether Sulfonate - Google Patents

Abstract

The invention discloses a method for synthesizing fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate. Fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate is a new type of surfactant for tertiary oil recovery that can be used in three high (high temperature, high salinity, high calcium and magnesium ion) reservoirs with excellent performance. The present invention uses the olefin addition method, using fatty alcohol (alkylphenol) polyoxyethylene ether and chloropropene as raw materials, and synthesizes fatty alcohol (alkylphenol) polyoxyethylene ether through allylation and sulfonation two-step reaction Sulfonate products. The method has simple synthesis steps, cheap and easy-to-obtain raw materials, high product yield, easy control of the reaction, and can realize industrial production.

Description

Olefin Addition Synthesis Method of Fatty Alcohol (Alkylphenol) Polyoxyethylene Ether Sulfonate

technical field

The invention discloses a method for synthesizing fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate, belonging to the technical field of chemical oil displacement agents.

Background technique

At present, EOR is the main oil displacement method used in most oilfields in my country, and surfactant flooding is an important oil displacement method in EOR. The types of oil displacement surfactants researched and developed at home and abroad mainly include cationic surfactants, anionic surfactants, nonionic surfactants, nonionic-anionic composite surfactants and polymer surfactants. Sulfonate anionic surfactants are the most widely used surfactants in heavy oil emulsification, three-recovery oil flooding and foam flooding formulations. They have high interfacial activity and good temperature resistance. The disadvantage is that they are resistant to high mineralization Poor performance; polyoxyethylene ether nonionic surfactants have strong salt resistance and good resistance to multivalent cations, but they are not resistant to high temperatures and have a large adsorption loss in the formation; nonionic-anionic surfactants The agent has two hydrophilic groups with different properties on one molecule, which can combine the advantages of non-ionic and anionic surfactants to form a temperature-resistant and salt-resistant surfactant with excellent performance, and avoid non-ionic surfactants. The chromatographic separation caused by the combination of solvent and anionic surfactant. Fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate is one of the more researched nonionic-anionic surfactants.

At present, there are many reports on the synthesis method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate, and the most discussed ones are Strecker reaction synthesis method, sulfoalkylation reaction synthesis method, sulfate ester salt conversion method, olefin addition method, etc. Into the law and so on.

Strecker reaction synthesis method (Hodgson P K G. Alkylethoxyethanesulphonates: two techniques for improving synthetic conversions [J]. JAOCS, 1990, 67 (11): 730-734) will alcohol (phenol) ether in the amine compound (such as pyridine) Under catalysis, use thionyl chloride or sulfuryl chloride for chlorination to generate chlorinated alcohol (phenol) ether, and then react with sulfite to obtain alcohol (phenol) ether sulfonate. Alkyl/alkylphenol polyoxyethylene ether sulfonate was first synthesized by Bruson (Bruson.Aryloxypolyalkylene ether sulphonates[P].US: 2115192, 1938-04-26), using sodium sulfite as sulfonating agent and water as solvent , Carrying out the substitution reaction in an autoclave, the reaction is difficult to control, and the conversion rate can only reach 70%. On this basis, Stewart (Stewart, Nevin J.Preparation of surfactants [P]. US: 4764307, 1988-08-16) has been improved, replaced sodium sulfite with potassium sulfite and ammonium sulfite as sulfonating agent, in A diluent is added before or during the reaction, and the product after the reaction is treated with isopropanol and dichloromethane, and the total conversion rate is increased to 90%. This method needs to use thionyl chloride or sulfuryl chloride as a halogenating agent, which has high cost, and has certain toxicity and corrosiveness. At the same time, acid gas sulfur dioxide and hydrogen chloride are generated in the reaction process, which pollutes the environment, so it is difficult to carry out industrial production. The document CN101279937A generally adopts the Strecker method, which is difficult to expand production as mentioned above.

Sulfoalkylation synthesis methods include chloro(bromo)sodium ethanesulfonate method, sodium isethionate method, propane sultone method, etc. (Fang Yun. Sulfoethylation reaction in surfactant synthesis[J] . Daily Chemical Industry, 1992(3): 23-28; Fang Yun. Sulfopropylation reaction [J]. Daily Chemical Industry, 1992(6): 26-32). Chloro(bromo)sodium ethanesulfonate method is harsher to reaction condition requirement, and reaction requires to carry out under anhydrous condition, and sodium isethionate method reaction is difficult to control, and foam can be produced in the reaction process, and product yield is not high, Reach 70～80%, and although propane sultone method product yield is higher, can reach 80～90%, but because 1,3-propane sultone industry source is not wide, explosive, price is high, especially has Potential carcinogenicity limits its application, making it difficult to carry out industrial production.

Sulphate salt conversion method (Wang Yefei, Zhao Fulin. Research on the synthesis of fatty alcohol polyoxyethylene ether sulfonate sodium by AES [J]. Fine Petrochemical Industry, 1996 (5): 22-24) uses sodium sulfite and sodium bisulfite The mixed sulfonating agent converts polyoxyethylene ether sulfate into sulfonate under high temperature and high pressure conditions, and the conversion rate is not high, only reaching 60%. The document CN101255127A uses a similar method, the catalyst adopts the chloride of zinc, manganese, copper, iron, titanium, zirconium or vanadium, and the synthesized product is a mixture of sulfonate and sulfate ester salt, wherein the content of sulfonate is up to 89% . This method uses polyoxyethylene ether sulfate as raw material, and the cost is relatively high, and the sources of raw materials are also limited.

The olefin addition method was first adopted by Yeakey (Yeakey E L. Ether sulfonate: DE2748722[P].1978-09-07). The reaction is carried out in two steps, using alkylphenol polyoxyethylene ether and chloropropene in the presence of sodium hydroxide Under the action, allyl ether is generated, and then radical addition reaction is carried out with sodium bisulfite to obtain the product sulfonate, and the yields of the intermediate allyl ether and the final product sulfonate are relatively low. Chen et al. (Chen S H, Schmitt D, Williams L.Method of preparing porpane sulfonates: US4267123[P].1981-05-12) first sodiumized nonylphenol polyoxyethylene ether with metal sodium in toluene solvent, Then reflux reaction with allyl chloride to obtain the intermediate, then use the mixture of sodium bisulfite and sodium sulfite (2:1) as sulfonating agent, water-soluble alcohol as solvent, and add a certain amount of product for sulfonation reaction, the obtained sulfonate Salt yield reaches 80-90%. The reaction conditions are harsh, the allylation step requires strict anhydrous, and the reaction process is cumbersome, which is also unfavorable for industrial production.

Contents of the invention

The purpose of this invention is to provide a kind of method of synthetic fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate, and this method can be suitable for industrialized production. The method has the characteristics of cheap and easy-to-obtain raw materials, simple process flow, easy control of reaction, and easy production. Include the following steps:

a) Put fatty alcohol (alkylphenol) polyoxyethylene ether, propylene chloride, alkali metal hydroxide aqueous solution, and catalyst A in the reaction kettle according to the proportion, stir and react for several hours to obtain an intermediate product, take it out after cooling, and adjust the pH When the value is about 7, wash with heated distilled water for several times, shake vigorously and then separate into layers, discard the water layer, and distill the organic layer under reduced pressure to obtain an intermediate product;

Alkali metal hydroxide is sodium hydroxide, potassium hydroxide;

Catalyst A selects quaternary ammonium salts or polyethylene glycol phase transfer catalyst, and its consumption is 1～5% of the amount of substance of reactant;

The molar ratio of fatty alcohol (alkylphenol) polyoxyethylene ether to propylene chloride is 1: 1.0 to 2.0, and the molar ratio to alkali metal hydroxide is 1: 1.0 to 2.0, and the aqueous alkali metal hydroxide solution has a content of 30-50 wt%, the reaction temperature is 90°C-160°C, and the reaction time is 2h-8h.

b) The intermediate product synthesized in step a) and solvent, sodium sulfite, sodium bisulfite, catalyst B and pre-generated sulfonate product are placed in a reactor in a certain amount, stirred and reacted for several hours, and a certain amount is added after cooling The organic solvent is carried out desalination, leaves standstill, the inorganic salt of filtering off precipitation, concentrating under reduced pressure obtains finished product fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate;

Catalyst B selects NaNO for use _{The aqueous} solution, its consumption is 1～5wt% of reactant gross mass;

The consumption of the pre-generated sulfonate product in the reaction mixture is: the ratio of the substance amount with the intermediate product must be greater than 1: 10;

The sulfonating agent is selected from an aqueous solution of sodium sulfite and sodium bisulfite (1:2), and its consumption is 1 to 2 times the stoichiometric amount;

Solvent selects ethanol/water solution for use, and its ratio is 1: 1 to 3: 1, and consumption is about 40～60wt% of all reactants;

Stirring reaction time 4h ~ 12h;

Selection of organic solvents for desalting: methanol, ethanol, isopropanol, dichloromethane, chloroform.

In the above-mentioned technical scheme, it is best to select PGE-600 as the catalyst in the step a), and the consumption is 3 to 5% of the amount of the reactant, and the molar ratio of fatty alcohol (alkylphenol) polyoxyethylene ether and chloropropene The preferred range is 1:1.5-2.0, the molar ratio with the alkali metal hydroxide is preferably 1:1.1-1.5, and the content of the aqueous alkali metal hydroxide solution is 50 wt%. The preferred range of reaction temperature is 100°C-120°C, and the preferred range of stirring reaction time is 3h-5h. b) In the step, the catalyst B is selected from an aqueous solution of NaNO ₃ , and its dosage is 3-5 wt% of the total mass of the reactants. For the reaction mixture to have pre-formed sulfonate product, the ratio of the amount of substance to the intermediate product must be greater than 1:8. The sulfonating agent is an aqueous solution of sodium sulfite and sodium bisulfite (1:2), and its dosage is twice the stoichiometric amount. The solvent is ethanol/water solution, the preferred ratio is 2:1, and the consumption is about 50wt% of the total reactants. The preferred range of reaction temperature is 120°C-140°C, and the preferred range of stirring reaction time is 6h-8h.

The synthesized fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate can be characterized by infrared analysis spectrum. See accompanying drawings 1 and 2 (taking octylphenol polyoxyethylene ether sulfonate as an example). Accompanying drawing 1 is the infrared spectrum of the intermediate allyl ether synthesized by OP-10 and allyl chloride. The characteristic peak of the double bond "-C=C-" appears at 1641.45cm ^-1 , and 3112.10cm ^-1 is the "=CH" stretching vibration frequency, indicating that the double bond of chloropropene has been added to OP-10. Accompanying drawing 2 is the infrared spectrum of the product after intermediate allyl ether is sulfonated. The characteristic peak of its sulfonic acid group "-SO ₃ " appeared at 1047.78cm ^-1 . The strong peak at 1111.85cm ^-1 is the characteristic absorption of polyoxyethylene chain. Indicates that the sulfonic acid group has been added to the allyl ether.

Detailed ways

【Example 1】

Synthesis of sodium octylphenol polyoxyethylene ether sulfonate.

Add 0.1mol octylphenol polyoxyethylene ether (OP-10), 0.15mol propylene chloride, 6g sodium hydroxide aqueous solution (50wt%), 0.005mol phase transfer catalyst PGE-600 to the autoclave at one time, and adjust the temperature to 110 ℃, the rotation speed is 700-800 rpm, the reaction pressure is about 0.2-0.3MPa, and the reaction time is 4h. Wash the brown liquid intermediate allyl ether obtained above two or three times with hot distilled water, adjust the pH value to about 7 with an appropriate amount of dilute hydrochloric acid, and then separate into layers at rest, and the lower layer is an oil layer. The lower layer was removed and purified with a rotary evaporator. The yield of the intermediate allyl ether calculated by measuring the hydroxyl value of the product is 94.2%.

Add 0.1mol of the above-mentioned intermediate allyl ether, 120ml of ethanol water (2:1), 12.6g of sodium sulfite and 20.8g of sodium bisulfite aqueous solution (33wt%), 3g of sodium nitrate and 0.02mol of sulfonic acid to the autoclave at one time. Salt product, adjust the temperature to 120°C, the rotation speed is 700-800 rpm, the reaction pressure is about 0.1-0.2MPa, and the reaction time is 8h. After the reaction was completed, the reaction mixture was extracted with isopropanol, filtered with suction, extracted with dichloromethane, filtered with suction, and the filtrate was purified with a rotary evaporator to obtain a light yellow viscous liquid product. The product was determined by two-phase titration and the calculated yield was 90.7%.

[Example 2]

Synthesis of Sodium Laureth Sulfonate.

Add 0.1mol polyoxyethylene lauryl ether, 0.15mol propylene chloride, 6g aqueous sodium hydroxide solution (50wt%), and 0.005mol phase transfer catalyst PGE-600 to the autoclave at one time, adjust the temperature to 120°C, and rotate at a speed of 700~ 800 rev/min, the reaction pressure is about 0.2-0.3MPa, and the reaction time is 4h. Wash the brown liquid intermediate allyl ether obtained above two or three times with hot distilled water, adjust the pH value to about 7 with an appropriate amount of dilute hydrochloric acid, and separate layers at rest, with the upper layer being an oil layer. Take the upper layer and purify it with a rotary evaporator. The yield of the intermediate allyl ether calculated by the bromination method was 92.6%.

Add 0.1mol of the above-mentioned intermediate allyl ether, 120ml of ethanol water (2:1), 12.6g of sodium sulfite and 20.8g of sodium bisulfite aqueous solution (33wt%), 3g of sodium nitrate and 0.02mol of sulfonic acid to the autoclave at one time. Salt product, adjust the temperature to 140°C, the rotation speed is 700-800 rpm, the reaction pressure is about 0.1-0.2MPa, and the reaction time is 8h. After the reaction was completed, the reaction mixture was extracted with isopropanol, filtered with suction, extracted with dichloromethane, filtered with suction, and the filtrate was purified with a rotary evaporator to obtain a light yellow viscous liquid product. The product was determined by two-phase titration and the calculated yield was 88.5%.

Claims (14)

1. a method for synthesizing fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate, comprises following reaction steps: a) Put fatty alcohol (alkylphenol) polyoxyethylene ether, propylene chloride, alkali metal hydroxide aqueous solution, and catalyst A in the reaction kettle according to the ratio, and react for several hours to obtain an intermediate product, take it out after cooling, and adjust the pH value is about 7, heated distilled water and washed several times, after vigorous shaking, static layering, discarding the water layer, and distilling the organic layer under reduced pressure to obtain an intermediate product; Alkali metal hydroxide is sodium hydroxide, potassium hydroxide; Catalyst A selects quaternary ammonium salts or polyethylene glycol phase transfer catalysts, quaternary ammonium salts catalysts such as benzyltriethylammonium chloride, cetyltrimethylammonium bromide, dodecyltrimethylammonium Ammonium bromide, tetrabutylammonium bromide, polyethylene glycol catalysts such as PEG-200, PEG-400, PEG-600, PEG-1000, the amount of which is 1 to 5% of the amount of the reactant substance; The molar ratio of fatty alcohol (alkylphenol) polyoxyethylene ether to propylene chloride is 1: 1.0 to 2.0, and the molar ratio to alkali metal hydroxide is 1: 1.0 to 2.0, and the aqueous alkali metal hydroxide solution has a content of 30-50 wt%, the reaction temperature is 90°C-160°C, and the reaction time is 2h-8h. b) The intermediate product synthesized in step a) and solvent, sodium sulfite, sodium bisulfite, catalyst B and pre-generated sulfonate product are placed in a reactor in a certain amount, stirred and reacted for several hours, and a certain amount is added after cooling The organic solvent is carried out desalination, leaves standstill, the inorganic salt of filtering off precipitation, concentrating under reduced pressure obtains finished product fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate; Catalyst B selects the aqueous solution of _NaNO3 for use, and its _NaNO3 consumption is 1～5wt% of all reactants; The consumption of the pre-generated sulfonate product in the reaction mixture is: the ratio of the substance amount with the intermediate product must be greater than 1: 10; The sulfonating agent is selected from an aqueous solution of sodium sulfite and sodium bisulfite (1:2), and its consumption is 1 to 2 times the stoichiometric amount; Solvent selects ethanol/water solution for use, and its ratio is 1: 1 to 3: 1, and consumption is about 40～60wt% of all reactants; Stirring reaction time 4h ~ 12h; Selection of organic solvents for desalting: methanol, ethanol, isopropanol, dichloromethane, chloroform. 2. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1, is characterized in that in a) step, catalyzer selects PEG-600 as the best, and consumption is the amount of reactant substance 3-5% of the total. 3. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1 is characterized in that the mole of fatty alcohol (alkylphenol) polyoxyethylene ether and chloropropene in a) step The ratio is 1:1.5～2.0. 4. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1 is characterized in that in a) step fatty alcohol (alkylphenol) polyoxyethylene ether and alkali metal hydroxide The molar ratio of the compound is 1:1.1-1.5, and the content of the alkali metal hydroxide aqueous solution is 50 wt%. 5. The synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1, characterized in that the reaction temperature in the a) step is 100°C to 120°C. 6. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1, is characterized in that the reaction time in a) step is 3h～5h. 7. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1 is characterized in that the intermediate product yield can reach 94.2% in a) step. 8. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1 is characterized in that in b) step, catalyst B selects NaNO for use _The aqueous solution, its NaNO _Consumption is the total reactant 3 to 5 wt% of the mass. 9. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1 is characterized in that there will be pre-generated sulfonate product in the reaction mixture in b) step, and it and intermediate The ratio of the amount of substance of the body product is greater than 1:8. 10. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1 is characterized in that b) in the step, sulfonating agent selects the mixture of sodium sulfite and sodium bisulfite (1: 2) Aqueous solution, the dosage is 2 times the stoichiometric amount. 11. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1 is characterized in that in b) step, solvent selects ethanol/water solution for use, and its ratio is 2: 1, and consumption is about 50 wt% of all reactants. 12. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1, is characterized in that the reaction time in b) step is 6h～8h; 13. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1, is characterized in that in the b) step, desalting organic solvent is selected ethanol or Virahol as the best. 14. the synthetic method of fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate according to claim 1 is characterized in that the final product yield can reach 90.7% in b) step.

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