CN113582885B - Production method of sodium alkyl sulfonate - Google Patents
Production method of sodium alkyl sulfonate Download PDFInfo
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- CN113582885B CN113582885B CN202111003891.2A CN202111003891A CN113582885B CN 113582885 B CN113582885 B CN 113582885B CN 202111003891 A CN202111003891 A CN 202111003891A CN 113582885 B CN113582885 B CN 113582885B
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- C07—ORGANIC CHEMISTRY
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- 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
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- 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
- C07C303/22—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 from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- C07—ORGANIC CHEMISTRY
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
Abstract
The invention discloses a production method of sodium alkyl sulfonate, which comprises the following steps: (1) Mixing alkenyl sulfonic acid and hydrogen to form a mixed raw material, heating the mixed raw material to a first set temperature, and then entering a hydrogenation reactor for hydrogenation reaction to generate a reaction mixture; (2) Carrying out gas-liquid separation on the reaction mixture, removing hydrogen in the reaction mixture to form an alkyl sulfonic acid crude product, and returning the removed hydrogen to the mixed raw material for recycling; (3) Reacting the crude product of alkyl sulfonic acid with sodium hydroxide to generate a crude product of sodium alkyl sulfonate; (4) And separating the crude sodium alkyl sulfonate to obtain sodium alkyl sulfonate. In the present application, the hydrogenation of the alkenylsulfonic acid proceeds, and the sultone proceeds to ring-opening reaction, and finally converted into sodium alkylsulfonate. The conversion rate of the raw materials can reach more than 96%, the product does not need to be refined for the second time, the raw materials do not need to be recycled, the production process route is shortened, and the product cost is reduced.
Description
Technical Field
The invention relates to a method for producing sodium alkyl sulfonate.
Background
The main production method is that alkane sulfoxidation method is adopted, the raw material of the method adopts normal alkane, and under the action of ultraviolet light, the normal alkane reacts with sulfur dioxide (sulfonating agent), oxygen and water to generate alkyl sulfonic acid and by-product sulfuric acid, and the alkyl sulfonic acid is neutralized by NaOH to generate sodium alkyl sulfonate. And secondly, sodium alkyl sulfonate can also be prepared by adopting the methods of chlorosulfonylation reaction of alkane, addition sulfonation of alkene, oxidation of mercaptan and other sulfur-containing compounds, reaction of halogenated hydrocarbon and sodium sulfite, and the like.
However, in the alkane sulfoxidation process, about 95% of alkane needs to be recycled, the energy consumption is high, a large amount of byproduct sulfuric acid is difficult to treat, the requirement on equipment materials is high, and the investment cost is high. The remaining methods
The same yield of sodium alkyl sulfonate produced by adopting an olefin addition sulfonation method is low, and the operation is complex; the process of oxidizing mercaptan and other sulfur-containing compounds to generate alkyl sulfonic acid and neutralizing the alkyl sulfonic acid with sodium hydroxide to produce sodium alkyl sulfonate is complex, and the byproducts are more; the raw materials of the method for generating the sodium alkyl sulfonate by adopting the reaction of the halohydrocarbon and the sodium sulfite are usually bromoalkane or iodoalkane, and the method has the advantages of low atom utilization rate, high production cost and a large amount of byproducts, and is not beneficial to industrial production; the chlorosulfonylation reaction of alkane has the same quantity of byproducts, is not easy to separate and affects the quality of products.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for producing sodium alkyl sulfonate, comprising the following steps:
(1) Mixing alkenyl sulfonic acid and hydrogen to form a mixed raw material, heating the mixed raw material to a first set temperature, and then entering a hydrogenation reactor for hydrogenation reaction to generate a reaction mixture;
(2) Carrying out gas-liquid separation on the reaction mixture, removing hydrogen in the reaction mixture to form an alkyl sulfonic acid crude product, and mixing the removed hydrogen with alkenyl sulfonic acid to form a mixed raw material for recycling;
(3) Reacting the crude product of alkyl sulfonic acid with sodium hydroxide to generate a crude product of sodium alkyl sulfonate;
(4) And separating the crude sodium alkyl sulfonate to obtain sodium alkyl sulfonate.
In the method, alkenyl sulfonic acid is used as a raw material, alkyl sulfonic acid is generated through hydrogenation reaction, and then sodium alkyl sulfonate is generated after neutralization with sodium hydroxide. Compared with the methods such as alkane sulfoxidation, olefin addition sulfonation and sulfur-containing compound oxidation, the method has the advantages of simple process flow, high conversion rate, no by-products such as sulfuric acid and the like. A certain amount of sultone is generated in the process of producing the alkenyl sulfonic acid, and the sultone has weak hydrophilicity compared with sodium alkenyl sulfonate and does not have surface activity; although some sultone is hydrolyzed and neutralized into sodium alkenyl sulfonate or sodium hydroxyalkylsulfonate during the neutralization of alkenyl sulfonic acid, the sultone is completely hydrolyzed, and the hydrolysis temperature is high, and the product color is deepened due to an excessively high temperature, so that the hydrolysis temperature of sultone is difficult to grasp.
In the present application, the hydrogenation of the alkenylsulfonic acid proceeds, and the sultone proceeds to ring-opening reaction, and finally converted into sodium alkylsulfonate. In the method, the conversion rate of the raw materials can reach more than 96%, related product requirements can be completely met, secondary refining is not needed, the raw materials are not needed to be recycled, the production process route is shortened, and corresponding process equipment and related operation cost are reduced. In addition, by-products such as sulfuric acid, hydrochloric acid and the like are not generated in the method, so that the raw material utilization rate is improved, meanwhile, by-product separation equipment is omitted, the by-product treatment cost is saved, and the method is friendly to the environment.
Preferably, in step (1), the alkenyl sulfonic acid is an alkenyl sulfonic acid having 12 to 22 carbon atoms. The alkenylsulfonic acids used in this application contain 5-40wt% sultone.
When the above-mentioned alkenyl sulfonic acid having a carbon number is used, an alkyl sulfonic acid having a corresponding carbon number can be obtained when the hydrogenation reaction is performed. Sodium c 12 alkyl sulfonate is commonly used in the chemical and light textile industries as an emulsifier, flotation agent, and saturation agent; sodium alkyl sulfonate of 13 to 14 carbon atoms has very good wetting power, sodium alkyl sulfonate of 15 to 17 carbon atoms can obtain the best detergency and foamability, and sodium alkyl sulfonate of 13 to 17 carbon atoms is an excellent detergent raw material; the sodium alkyl sulfonate with carbon number of 18 to 22 is an excellent oil displacement agent for oil fields, and is very suitable for crude oil taking paraffin base as a main body in China. Therefore, sodium alkyl sulfonate having 12 to 22 carbon atoms is most widely used in China and has the greatest market demand.
As the alkenyl sulfonic acid is directly sulfonated and generated by alpha-olefin and sulfur trioxide, the method has mild reaction conditions and low sulfonation temperature, and is generally 40-50 ℃; the conversion rate is higher and is more than 84%, and the highest conversion rate can even reach more than 96%; while fewer byproducts are produced. Therefore, the conversion rate of the alkenyl sulfonic acid serving as the raw material for producing the sodium alkyl sulfonate is higher than that of other sodium alkyl sulfonate production methods, the byproducts are fewer, and the raw material utilization rate is higher even if the raw material is calculated based on alpha-olefin.
Further, in order to make the reaction smoothly proceed, in the hydrogenation reactor, the reaction temperature is 40-200 deg.C, the pressure is 2.0-6.0MPa, and the mass space velocity of alkenyl sulfonic acid is 0.1-1h -1 Hydrogen oil volume ratio 200-1000:1.
under the reaction conditions, the hydrogenation saturation of alkenyl can be successfully completed, the ring opening of sultone can be ensured, alkane sulfonic acid is generated, and few byproducts are generated. When the reaction temperature is too high, the hydrogenation activity of the catalyst is increased, so that the hydrodeoxygenation and desulfurization amount of the alkenyl sulfonic acid is increased, the generated byproduct alkane is increased, meanwhile, the raw material is cracked at high temperature, a large amount of byproducts are generated, and the separation equipment is required to be additionally arranged, so that the investment cost is increased; when the reaction temperature is too low, the hydrogenation saturation of alkenyl is incomplete, and sultone cannot be opened, so that the product quality is poor.
When the reaction pressure is too high, the hydrogenation degree is deepened, the deoxidization and desulfurization amount of the raw material is increased, the generated byproduct alkane is increased, meanwhile, the equipment pressure level is increased, and the investment cost is increased; when the reaction pressure is too low, the degree of hydrogenation is insufficient, resulting in a decrease in conversion.
When the mass space velocity is too high, the hydrogenation conversion rate is reduced, and the product quality is poor; when the mass airspeed is too low, the deoxidization and desulfurization amount of the raw material is increased, the generated byproduct alkane is increased, the treatment capacity is reduced, and the utilization rate of the catalyst and the equipment is low.
When the volume ratio of the hydrogen to the oil is too high, the hydrogenation degree is deepened, the deoxidization and desulfurization of the raw materials are increased, the generated byproducts of alkane are increased, the type selection of a circulating compressor is large, and the equipment investment is increased; when the volume ratio of hydrogen to oil is too low, the hydrogenation conversion rate is reduced, and the reaction heat release cannot be taken out, so that the temperature of the reactor is increased sharply, raw materials are cracked, a large amount of byproducts are generated, and even safety accidents are caused.
Specifically, the hydrogenation reactor is a fixed bed reactor, and a hydrogenation catalyst is filled in the hydrogenation reactor, wherein the hydrogenation catalyst is a silicon oxide carrier loaded nickel, palladium or platinum. Preferably, when the hydrogenation catalyst is a silica carrier supported nickel, the content of nickel in the hydrogenation catalyst is 10-40wt%, and when the hydrogenation catalyst is a silica carrier supported palladium or platinum, the content of palladium or platinum in the hydrogenation catalyst is 0.1-1wt%.
The catalyst can complete catalysis by adopting a silicon oxide carrier to load single metal. The existing hydrogenation catalyst generally adopts an alumina-supported composite metal catalyst to improve the hydrogenation effect. Experiments show that the raw material alkenyl sulfonic acid has stronger acidity, can generate aluminum sulfonate with aluminum oxide at high temperature, so that the catalyst is lost, and the catalytic performance is rapidly reduced; meanwhile, the composite metal hydrogenation effect is strong, besides alkenyl hydrogenation saturation, hydrodeoxygenation and desulfurization can be further enhanced, a large amount of alkane is produced, and the selectivity of the alkyl sulfonic acid is difficult to control. In the application, experiments show that the catalyst is preferably selected, a silicon oxide carrier is adopted to load a nickel, palladium or platinum single-metal catalyst, the alkenyl hydrogenation saturation effect is good, the hydrodeoxygenation desulfurization rate is lower than 0.5%, the selectivity of the alkyl sulfonic acid is high, the carrier silicon oxide does not react with the sulfonic acid, the catalyst performance is stable, and meanwhile, the cost is lower than that of the composite metal catalyst. The separated sulfur is formed into hydrogen sulfide and enters hydrogen gas, so that the sulfur can be removed easily.
Specifically, in the step (3), the molar ratio of the total amount of sulfonic acid in the crude product of the alkyl sulfonic acid to sodium hydroxide is 1:1, the neutralization temperature is 30-60 ℃, and when the pH value of the reaction solution reaches 8-9, the reaction is stopped; the sodium hydroxide is added in the form of sodium hydroxide aqueous solution, and the mass concentration of the sodium hydroxide aqueous solution is 10-50%.
To ensure complete neutralization of the alkyl sulfonic acid, the molar ratio of total sulfonic acid to sodium hydroxide in this application is 1:1. in addition, in the neutralization process of the alkyl sulfonic acid and the sodium hydroxide, the concentration of the sodium hydroxide aqueous solution is particularly important, the concentration of the sodium hydroxide aqueous solution is too high, the heat release amount is large, the temperature rise is difficult to control, and the product has poor fluidity, so that the neutralization is uneven and incomplete; the concentration is too low, the dewatering amount of the subsequent work is increased, the energy consumption is increased, and the operation cost is high. In the application, the mass concentration of the sodium hydroxide aqueous solution is 10-50%, so that the neutralization reaction can be smoothly completed, the generation of excessive water quantity can be effectively avoided, and the subsequent water discharge is reduced.
The neutralization temperature is also an important condition in the neutralization process, the neutralization temperature is too low, the fluidity of the product is poor, the neutralization efficiency is low, and the neutralization time is long; the temperature is too high, the neutralization speed is increased, the heat release is aggravated, the temperature rise is difficult to control, the pressure of the reaction tank is increased, and the safety accident is easy to cause. In the application, the neutralization temperature is 30-60 ℃, so that sulfonic acid can be effectively completely neutralized. When the pH of the reaction solution reached 8 to 9, the neutralization reaction was completed, and the reaction was terminated.
Further, as the alkenyl sulfonic acid is adopted for hydrogenation to prepare the alkyl sulfonic acid, byproducts such as sulfuric acid, hydrochloric acid and the like are avoided, and a deacidification step is not required; meanwhile, the hydrocarbon byproducts are extremely low and not more than 0.5 weight percent, the extraction and deoiling steps are omitted, and in the step (4), the sodium alkyl sulfonate crude product is evaporated and dehydrated when the sodium alkyl sulfonate crude product is separated, so that the sodium alkyl sulfonate is obtained.
Further, the alkenyl sulfonic acid hydrogenation is an exothermic reaction, and in step (1), the inlet temperature of the mixed raw material in the hydrogenation reactor is 20-180 ℃ in order to control the reactor temperature.
Further, in order to ensure the separation effect and reduce the liquid phase component carried in the hydrogen, the temperature during the gas-liquid separation in the step (2) is 20-50 ℃. In order to reduce the influence of trace hydrogen sulfide carried by hydrogen on equipment, a hydrogen purification tank is preferably arranged, alkaline metal oxides such as zinc oxide and the like are filled in the tank, separated hydrogen is purified, hydrogen sulfide is adsorbed, and hydrogen stripped from a reaction mixture is preferably purified by the hydrogen purification tank and then mixed with alkenyl sulfonic acid after passing through a circulating compressor together with new hydrogen which is supplemented.
In order to fully recycle the reaction heat and reduce the energy consumption of the system, the mixed raw materials sequentially pass through a refrigerant channel of a feeding heat exchanger and a heating furnace and then enter a hydrogenation reactor for hydrogenation reaction; the reaction mixture sequentially passes through a heating medium channel and a cooler of the feeding heat exchanger and then enters a gas-liquid separator to carry out gas-liquid separation.
Drawings
Fig. 1 is a schematic flow chart of the present invention.
Detailed Description
In the present application, the ring opening rate of sultone contained in alkenyl sulfonic acid is analyzed and detected according to the chromatographic analysis sultone method provided in "determination of sultone in alpha-alkenyl sulfonate and influence of its content on product quality" published by Liu Yanfang, bao Zhong, gu Xiuying et al. The saturation rate of alkenyl sulfonic acid is analyzed by adopting a method for analyzing unsaturated bonds by potassium permanganate according to the method provided in the process study of synthesizing alpha-alkenyl sulfonate by wax cracking alpha-olefin in the published master paper of fish Kunshi. And detecting the content of hydrogen sulfide in the hydrogen after the gas-liquid separator by adopting a hydrogen sulfide detection tube, and calculating the desulfurization rate of the alkenyl sulfonic acid.
Preparation of the catalyst:
1. placing the formed silicon oxide carrier into a rotary evaporator, vacuumizing for 1 hour at the temperature of 50-80 ℃, and discharging air in pores of the silicon oxide carrier to facilitate impregnation of active metals;
2. dissolving one soluble salt of active metal nickel, platinum or palladium into water to prepare an active metal aqueous solution;
3. adding the active metal aqueous solution into a rotary evaporator, and carrying out rotary impregnation for 30 minutes at normal temperature;
4. after the impregnation is finished, drying at the temperature of 80-100 ℃ under negative pressure;
5. drying and roasting at 500-600 deg.c for 4-6 hr to obtain hydrogenation catalyst containing active metal.
Wherein the nickel salt can be selected from nickel dichloride hexahydrate, nickel nitrate hexahydrate or nickel sulfate and hydrate thereof, the palladium salt can be selected from palladium chloride and palladium tetra-ammine dichloride, and the platinum salt can be selected from platinum tetra-ammine dichloride or chloroplatinic acid. In the examples below, nickel nitrate hexahydrate, palladium chloride and chloroplatinic acid were each used to prepare the corresponding hydrogenation catalyst.
In the examples below, the alkenyl sulfonic acids used were all produced by Toming club evolutionary Co.Ltd.
The sultone ring opening rate in each of the following examples is the conversion rate of sultone in the raw material, the olefin saturation rate is the conversion rate of alkenyl sulfonic acid in the raw material, and the total raw material conversion rate is the sum of the two parts folded according to the corresponding proportion.
Example 1
Referring to fig. 1, the production method of the 1# alkyl sodium sulfonate is carried out according to the following steps:
(1) Mixing alkenyl sulfonic acid 110 and hydrogen 130 to form a mixed raw material, sequentially passing through a refrigerant channel of a feeding heat exchanger 12 and a heating furnace 11, enabling the temperature to reach 160 ℃, then entering a hydrogenation reactor 10, and carrying out hydrogenation reaction at 180 ℃ and under the pressure of 5.0MPa to generate a reaction mixture. Wherein alkenyl sulfonic acid 110 is a carbon 14 alkenyl sulfonic acid. In the hydrogenation reactor, the mass space velocity of the alkenyl sulfonic acid is 0.8h -1 Hydrogen oil volume ratio 1000:1. the hydrogenation reactor is a fixed bed reactor, and the hydrogenation catalyst is 10wt% nickel loaded on a silicon oxide carrier.
(2) After passing through the heat medium passage of the feed heat exchanger 12 and the cooler 13 in this order, the temperature of the reaction mixture was lowered to 30 c, and then it was introduced into the gas-liquid separator 20 to perform gas-liquid separation. Unreacted hydrogen in the reaction mixture is discharged from the top of the gas-liquid separator 20, purified by the hydrogen purification tank 24, returned together with the replenished new hydrogen by the recycle compressor 25 and mixed with the alkenyl sulfonic acid to form a mixed raw material for recycling. The hydrogen purging tank 24 is filled with zinc oxide as a hydrogen purging agent. The reaction mixture after removal of hydrogen formed crude alkylsulfonic acid.
(3) The crude product of the alkyl sulfonic acid is discharged from the bottom of the gas-liquid separator 20, and after the temperature is reduced to 30 ℃ by the first heat exchanger 27, the crude product of the alkyl sulfonic acid enters the neutralization tank 30 to carry out neutralization reaction with a 50wt% concentration sodium hydroxide aqueous solution 140, the neutralization reaction temperature is controlled to be 30-35 ℃, and the molar ratio of the total amount of the sulfonic acid in the crude product of the alkyl sulfonic acid to the sodium hydroxide is 1:1, generating a crude product of sodium alkyl sulfonate, and stopping the reaction when the pH value reaches 9.
(4) And heating the crude sodium alkyl sulfonate to 120 ℃ by a second heat exchanger 34, then entering a dehydration tower 50, evaporating and dehydrating, discharging water from the top 51 of the dehydration tower, and discharging dehydrated materials from the bottom of the dehydration tower 50 to obtain the sodium 1# alkyl sulfonate 170. The sodium 1# alkyl sulfonate is sodium C14 alkyl sulfonate.
The detection of the sodium 1# alkyl sulfonate shows that the sultone ring opening rate is 100%, the olefin saturation rate is 96.7% and the desulfurization rate is 0.5%.
The carbon 14 alkenyl sulfonic acid used in this example contained 12wt% of sultone, and the total conversion of the raw material was 97.1%.
Example 2
The production method of the No. 2 sodium alkyl sulfonate comprises the following steps:
(1) Mixing alkenyl sulfonic acid 110 and hydrogen 130 to form a mixed raw material, sequentially passing through a refrigerant channel of a feeding heat exchanger 12 and a heating furnace 11, enabling the temperature to reach 100 ℃, then entering a hydrogenation reactor 10, and carrying out hydrogenation reaction at 120 ℃ under the pressure of 2.0MPa to generate a reaction mixture. Wherein alkenyl sulfonic acid 110 is a carbon 16 alkenyl sulfonic acid. In the hydrogenation reactor, the mass space velocity of the alkenyl sulfonic acid is 0.5h -1 Hydrogen oil volume ratio 800:1. the hydrogenation reactor is a fixed bed reactor, and the hydrogenation catalyst is 30wt% nickel loaded on a silicon oxide carrier.
(2) After passing through the heat medium passage of the feed heat exchanger 12 and the cooler 13 in this order, the temperature of the reaction mixture was lowered to 40 c, and then it was introduced into the gas-liquid separator 20 to perform gas-liquid separation. Unreacted hydrogen in the reaction mixture is discharged from the top of the gas-liquid separator 20, purified by the hydrogen purification tank 24, returned together with the replenished new hydrogen by the recycle compressor 25 and mixed with the alkenyl sulfonic acid to form a mixed raw material for recycling. The hydrogen purging tank 24 is filled with zinc oxide as a hydrogen purging agent. The reaction mixture after removal of hydrogen formed crude alkylsulfonic acid.
(3) The crude product of the alkyl sulfonic acid is discharged from the bottom of the gas-liquid separator 20, and after the temperature is reduced to 40 ℃ by a first heat exchanger, the crude product of the alkyl sulfonic acid enters a neutralization tank 30 to be subjected to neutralization reaction with 40wt% sodium hydroxide aqueous solution, the neutralization reaction temperature is controlled to be 40-45 ℃, and the molar ratio of the total amount of the sulfonic acid in the crude product of the alkyl sulfonic acid to the sodium hydroxide is 1:1, generating a crude product of sodium alkyl sulfonate, and stopping the reaction when the pH value reaches 8.7.
(4) And heating the sodium alkyl sulfonate crude product to 120 ℃ through a second heat exchanger, then entering the dehydration tower 50, evaporating and dehydrating, and discharging the dehydrated material from the bottom of the dehydration tower 50 to obtain sodium 2 alkyl sulfonate, wherein the sodium 2 alkyl sulfonate is sodium C16 alkyl sulfonate.
The detection of the sodium 2# alkyl sulfonate shows that the sultone ring opening rate is 100%, the olefin saturation rate is 96.2% and the desulfurization rate is 0.1%.
The carbon 16 alkenyl sulfonic acid used in this example contained 19 weight percent sultone and had a total feed conversion of 96.9%.
Example 3
The production method of the 3# alkyl sodium sulfonate comprises the following steps:
(1) Mixing alkenyl sulfonic acid 110 and hydrogen 130 to form a mixed raw material, sequentially passing through a refrigerant channel of a feeding heat exchanger 12 and a heating furnace 11, enabling the temperature to reach 80 ℃, then entering a hydrogenation reactor 10, and carrying out hydrogenation reaction at 100 ℃ and under the pressure of 4.0MPa to generate a reaction mixture. Wherein alkenyl sulfonic acid 110 is a carbon 16 alkenyl sulfonic acid. In the hydrogenation reactor, the mass space velocity of the alkenyl sulfonic acid is 0.4h -1 Hydrogen oil volume ratio 500:1. the hydrogenation reactor is a fixed bed reactor, and the hydrogenation catalyst is platinum with the weight percent of 0.5 percent of the silicon oxide carrier.
(2) After passing through the heat medium passage of the feed heat exchanger 12 and the cooler 13 in this order, the temperature of the reaction mixture was lowered to 50 c, and then it was introduced into the gas-liquid separator 20 to perform gas-liquid separation. Unreacted hydrogen in the reaction mixture is discharged from the top of the gas-liquid separator 20, purified by the hydrogen purification tank 24, returned together with the replenished new hydrogen by the recycle compressor 25 and mixed with the alkenyl sulfonic acid to form a mixed raw material for recycling. The hydrogen purging tank 24 is filled with zinc oxide as a hydrogen purging agent. The reaction mixture after removal of hydrogen formed crude alkylsulfonic acid.
(3) The crude product of the alkyl sulfonic acid is discharged from the bottom of the gas-liquid separator 20, and after the temperature is reduced to 50 ℃ by a first heat exchanger, the crude product of the alkyl sulfonic acid enters a neutralization tank 30 to carry out neutralization reaction with 30wt% concentration sodium hydroxide aqueous solution, the neutralization reaction temperature is controlled to be 48-52 ℃, and the molar ratio of the total amount of the sulfonic acid in the crude product of the alkyl sulfonic acid to the sodium hydroxide is 1:1, generating a crude product of sodium alkyl sulfonate, and stopping the reaction when the pH value reaches 8.4.
(4) And heating the crude sodium alkyl sulfonate to 120 ℃ by a second heat exchanger, then entering the dehydration tower 50, evaporating and dehydrating, and discharging the dehydrated material from the bottom of the dehydration tower 50 to obtain sodium 3# alkyl sulfonate, wherein the sodium 3# alkyl sulfonate is sodium C16 alkyl sulfonate.
The detection of the 3# sodium alkyl sulfonate shows that the sultone ring opening rate is 100%, the olefin saturation rate is 95.5% and the desulfurization rate is 0.2%.
The carbon 16 alkenyl sulfonic acid used in this example contained 16wt% sultone and the total feed conversion was 96.2%.
Example 4
The production method of the sodium 4# alkyl sulfonate comprises the following steps:
(1) Mixing alkenyl sulfonic acid 110 and hydrogen 130 to form a mixed raw material, sequentially passing through a refrigerant channel of a feeding heat exchanger 12 and a heating furnace 11, enabling the temperature to reach 130 ℃, then entering a hydrogenation reactor 10, and carrying out hydrogenation reaction at 150 ℃ and under the pressure of 3.0MPa to generate a reaction mixture. Wherein alkenyl sulfonic acid 110 is a carbon 14 alkenyl sulfonic acid. In the hydrogenation reactor, the mass space velocity of the alkenyl sulfonic acid is 0.2h -1 Hydrogen oil volume ratio 600:1. the hydrogenation reactor is a fixed bed reactor, and the hydrogenation catalyst is a silicon oxide carrier loaded with 0.8wt% of palladium.
(2) After passing through the heat medium passage of the feed heat exchanger 12 and the cooler 13 in this order, the temperature of the reaction mixture was lowered to 30 c, and then it was introduced into the gas-liquid separator 20 to perform gas-liquid separation. Unreacted hydrogen in the reaction mixture is discharged from the top of the gas-liquid separator 20, purified by the hydrogen purification tank 24, returned together with the replenished new hydrogen by the recycle compressor 25 and mixed with the alkenyl sulfonic acid to form a mixed raw material for recycling. The hydrogen purging tank 24 is filled with zinc oxide as a hydrogen purging agent. The reaction mixture after removal of hydrogen formed crude alkylsulfonic acid.
(3) The crude product of the alkyl sulfonic acid is discharged from the bottom of the gas-liquid separator 20, and after the temperature is reduced to 60 ℃ by a first heat exchanger, the crude product of the alkyl sulfonic acid enters a neutralization tank 30 to be subjected to neutralization reaction with a sodium hydroxide aqueous solution with the concentration of 20wt%, the neutralization reaction temperature is controlled to be 55-60 ℃, and the molar ratio of the total amount of the sulfonic acid in the crude product of the alkyl sulfonic acid to the sodium hydroxide is 1:1, generating a crude product of sodium alkyl sulfonate, and stopping the reaction when the pH value reaches 8.1.
(4) And heating the crude sodium alkyl sulfonate to 120 ℃ by a second heat exchanger, then entering the dehydration tower 50, evaporating and dehydrating, and discharging the dehydrated material from the bottom of the dehydration tower 50 to obtain sodium 4 alkyl sulfonate, wherein the sodium 4 alkyl sulfonate is sodium alkyl sulfonate with carbon 14.
The detection is carried out on the sodium 4# alkyl sulfonate, the ring opening rate of sultone is 100%, the olefin saturation rate is 95.9%, and the desulfurization rate is 0.3%.
The carbon 14 alkenyl sulfonic acid used in this example contained 14wt% of sultone and the total conversion of the raw material was 96.5%.
Claims (6)
1. A method for producing sodium alkyl sulfonate, which is characterized by comprising the following steps:
(1) Mixing alkenyl sulfonic acid and hydrogen to form a mixed raw material, heating the mixed raw material to a first set temperature, and then entering a hydrogenation reactor for hydrogenation reaction to generate a reaction mixture; the alkenyl sulfonic acid is C12-22 alkenyl sulfonic acid;
(2) Carrying out gas-liquid separation on the reaction mixture, removing hydrogen in the reaction mixture to form an alkyl sulfonic acid crude product, and mixing the removed hydrogen with alkenyl sulfonic acid to form a mixed raw material for recycling;
(3) Reacting the crude product of alkyl sulfonic acid with sodium hydroxide to generate a crude product of sodium alkyl sulfonate;
(4) Separating the crude sodium alkyl sulfonate to obtain sodium alkyl sulfonate;
in a hydrogenation reactor, the reaction temperature is 40-200 ℃, the pressure is 2.0-6.0MPa, and the mass airspeed of the alkenyl sulfonic acid is 0.1-1h -1 Hydrogen oil volume ratio 200-1000:1, a step of;
the hydrogenation reactor is a fixed bed reactor, a hydrogenation catalyst is filled in the hydrogenation reactor, and the hydrogenation catalyst is silicon oxide carrier loaded nickel, palladium or platinum; when the hydrogenation catalyst is nickel supported by a silica carrier, the content of nickel in the hydrogenation catalyst is 10-40wt%, and when the hydrogenation catalyst is palladium or platinum supported by a silica carrier, the content of palladium or platinum in the hydrogenation catalyst is 0.1-1wt%.
2. The method according to claim 1, wherein,
in the step (3), the molar ratio of the total amount of sulfonic acid in the crude product of the alkyl sulfonic acid to sodium hydroxide is 1:1, the neutralization temperature is 30-60 ℃, and when the pH value of the reaction solution reaches 8-9, the reaction is stopped;
the sodium hydroxide is added in the form of sodium hydroxide aqueous solution, and the mass concentration of the sodium hydroxide aqueous solution is 10-50%.
3. The method according to claim 1, wherein in the step (4), the crude sodium alkylsulfonate is evaporated and dehydrated to obtain sodium alkylsulfonate when the crude sodium alkylsulfonate is separated.
4. The method according to claim 1, wherein,
in the step (1), the inlet temperature of the mixed raw material in the hydrogenation reactor is 20-180 ℃.
5. The method according to claim 1, wherein,
in the step (2), the temperature during gas-liquid separation is 20-50 ℃.
6. The production method according to claim 1, wherein the mixed raw materials sequentially pass through a refrigerant channel of a feeding heat exchanger and a heating furnace and then enter a hydrogenation reactor for hydrogenation reaction; the reaction mixture sequentially passes through a heating medium channel and a cooler of the feeding heat exchanger and then enters a gas-liquid separator to carry out gas-liquid separation.
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