CN116589385A - Preparation method of low dioxane ethoxylated alkyl sodium sulfate - Google Patents
Preparation method of low dioxane ethoxylated alkyl sodium sulfate Download PDFInfo
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- CN116589385A CN116589385A CN202310516447.3A CN202310516447A CN116589385A CN 116589385 A CN116589385 A CN 116589385A CN 202310516447 A CN202310516447 A CN 202310516447A CN 116589385 A CN116589385 A CN 116589385A
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- polyoxyethylene ether
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- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 49
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 49
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 11
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 266
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 139
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 139
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 110
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 98
- -1 ethoxylated sodium alkyl sulfate Chemical class 0.000 claims abstract description 84
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 65
- 239000012535 impurity Substances 0.000 claims abstract description 62
- 239000002994 raw material Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 239000000047 product Substances 0.000 claims abstract description 52
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 239000011552 falling film Substances 0.000 claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 238000007670 refining Methods 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 141
- 238000003860 storage Methods 0.000 claims description 74
- 239000012495 reaction gas Substances 0.000 claims description 54
- 239000002253 acid Substances 0.000 claims description 20
- 239000002699 waste material Substances 0.000 claims description 20
- 239000007844 bleaching agent Substances 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 17
- 238000007086 side reaction Methods 0.000 abstract description 11
- 238000005086 pumping Methods 0.000 description 65
- 238000007789 sealing Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 18
- 238000005070 sampling Methods 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a preparation method of low dioxane ethoxylated alkyl sodium sulfate, which comprises the following steps: s1, filtering and purifying fatty alcohol polyoxyethylene ether to remove impurities in raw materials; s2, burning sulfur, catalyzing and purifying the obtained sulfur dioxide gas, cooling, and finally introducing pure air for mixing to obtain sulfur trioxide mixed gas; s3, carrying out sulfonation reaction on mixed gas of fatty alcohol-polyoxyethylene ether and sulfur trioxide in a multitube falling film type sulfonation reactor; s4, adding sodium hydroxide solution, pure water and a reaction auxiliary agent into a neutralization reactor for neutralization reaction, and refining the reaction product after the reaction to obtain a finished product; the whole preparation process is carried out under vacuum. The method has simple process steps, can effectively reduce the occurrence of side reactions, and greatly reduces the dioxane content in the ethoxylated sodium alkyl sulfate product.
Description
Technical Field
The application relates to the technical field of surfactant synthesis, in particular to a preparation method of low dioxane ethoxylated alkyl sodium sulfate.
Background
The ethoxylated alkyl sodium sulfate belongs to an anionic surfactant and is a multifunctional high-efficiency fine chemical raw material. The ethoxylated alkyl sodium sulfate is a very good cleaning agent and is widely applied to the industries of daily chemical industry, textile industry, petroleum industry, leather industry, printing and dyeing industry and the like. The ethoxylated alkyl sodium sulfate has excellent biodegradability and low-temperature performance, and has high active matter content and no influence of water hardness. In particular, the detergent composition is suitable for various powdery washing products, and is more suitable for various detergents, such as washing pastes (detergents), detergents, dry washes, cleaning agents, removers, shampoos (lotions), various shower gels and the like with various types and various purposes.
At present, the preparation of ethoxylated alkyl sodium sulfate mainly takes fatty alcohol polyoxyethylene ether as a raw material, sulfur trioxide as a sulfonating agent, and the fatty alcohol polyoxyethylene ether is prepared by sulfonation in a falling film type sulfonation reactor; and then neutralizing and saponifying the product by sodium hydroxide to prepare the finished product. Because of the side reactions which are difficult to avoid in the preparation process, the ethoxylated alkyl sodium sulfate prepared by the prior art can be mixed with partial dioxane.
Dioxane, also known as dioxane, can be absorbed into the body by inhalation, ingestion and percutaneous absorption, and has anesthetic and stimulating effects and accumulation effects in the body. Dioxane is irritating to the skin, eyes and respiratory system, and may cause damage to the liver, kidneys and nervous system, and acute poisoning may lead to death, which has been listed as a carcinogen in the united states.
Therefore, how to reduce the dioxane content in the ethoxylated alkyl sodium sulfate product is a technical problem which needs to be solved urgently at present.
Disclosure of Invention
In order to solve at least one technical problem, a preparation process is developed, wherein the preparation process is simple in process steps, can effectively reduce side reactions, and greatly reduces the dioxane content in an ethoxylated alkyl sodium sulfate product.
The application provides a preparation method of low dioxane ethoxylated alkyl sodium sulfate, which comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether: filtering and purifying the fatty alcohol-polyoxyethylene ether to remove impurities in the raw materials, thereby obtaining pretreated fatty alcohol-polyoxyethylene ether;
s2, preparing sulfur trioxide reaction gas: burning sulfur to generate sulfur dioxide gas, catalyzing and purifying the sulfur dioxide gas obtained by burning, filtering out impurities, cooling, and finally introducing pure air to mix to obtain sulfur trioxide mixed gas; the pure air adopts air with dew point controlled between minus 60 ℃ and minus 90 ℃;
s3, sulfonation reaction: carrying out sulfonation reaction on the pretreated fatty alcohol polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 in a multitube falling film type sulfonation reactor, and purifying a reaction product to remove redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
S4, neutralization: adding sodium hydroxide solution, pure water and a reaction auxiliary agent into the sulfonation reaction product prepared in the step S3 in a neutralization reactor to perform neutralization reaction, and refining the reaction product after the reaction to prepare low-dioxane ethoxylated alkyl sodium sulfate;
the whole preparation process is carried out under vacuum.
By adopting the technical scheme, the raw materials are pretreated, the water content of the fatty alcohol-polyoxyethylene ether raw materials is effectively reduced through filtration and purification, meanwhile, the sulfur trioxide mixed gas is prepared through a specific process, the water content in the sulfur trioxide mixed gas is effectively reduced, the generation of sulfuric acid in the reaction process is greatly reduced, and the occurrence rate of side reactions is effectively reduced; meanwhile, the pretreatment of raw materials and the purification treatment of sulfonated products effectively reduce the content of impurities and other byproducts, ensure the occurrence rate of side reactions in the whole preparation process and further reduce the generation amount of dioxane; the whole process is carried out under the vacuum condition, so that the reaction efficiency can be effectively improved, the gas-liquid two-phase reaction can be accelerated, meanwhile, the situation that moisture in the environment is mixed into a reaction system due to the water absorption of reaction raw materials and intermediate products can be effectively avoided, the occurrence rate of side reactions is further ensured to be at an extremely low level, and the generation amount of dioxane is further reduced.
Optionally, in the step S1, the pretreatment further includes controlling the temperature of the pretreated fatty alcohol-polyoxyethylene ether to be 20-40 ℃.
Optionally, in the step S2, the cooling is performed by cooling the sulfur trioxide gas to 230-270 ℃.
Optionally, in the step S2, the temperature of the purified air is controlled to be 4-8 ℃.
Optionally, in the step S2, the concentration of the prepared sulfur trioxide mixed gas is controlled to be 3-7%, and the temperature is controlled to be 40-60 ℃.
Optionally, in the step S3, the feeding ratio of the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 to the sulfur trioxide mixed gas prepared in the step S2 is 1 according to the molar ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide: 0.90 to 1.10.
Optionally, in the step S3, the reaction temperature of the sulfonation reaction is controlled to be 30-50 ℃ and the time is controlled to be 10-30S.
Optionally, in the step S4, the reaction temperature of the neutralization reaction is controlled to be 20-40 ℃ and the reaction time is controlled to be 1-3 h.
Optionally, in the step S4, the reaction auxiliary agent includes a bleaching agent and a pH adjuster.
Optionally, in the step S4, the pH value of the refined product is controlled to be 7-11, and the storage temperature of the refined product is controlled to be 30-40 ℃.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the method, the raw materials are pretreated, the water content of the fatty alcohol-polyoxyethylene ether raw materials is effectively reduced through filtration and purification, meanwhile, the sulfur trioxide mixed gas is prepared through a specific process, the water content in the sulfur trioxide mixed gas is also effectively reduced, the generation of sulfuric acid in the reaction process is greatly reduced, the occurrence rate of side reactions is effectively reduced, and the generation amount of dioxane is reduced.
2. According to the application, through purification treatment in the process and the adoption of the whole-process vacuum preparation condition, the reaction efficiency can be greatly improved, and the generation amount of dioxane can be further reduced.
3. The active matter content of the ethoxylated alkyl sodium sulfate prepared by the application exceeds 70%, the sodium sulfate content is lower than 0.5%, the free oil content is lower than 2%, and the product performance is very excellent.
4. In the ethoxylated alkyl sodium sulfate prepared by the method, the content of dioxane can be reduced to below 10ppm, the safety of a product can be greatly ensured, and the subsequent treatment of removing dioxane is not needed.
Detailed Description
The present application will be described in further detail with reference to examples.
The application relates to a preparation method of low dioxane ethoxylated alkyl sodium sulfate, which comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether: filtering and purifying the fatty alcohol-polyoxyethylene ether to remove impurities in the raw materials, thereby obtaining pretreated fatty alcohol-polyoxyethylene ether;
s2, preparing sulfur trioxide reaction gas: burning sulfur to generate sulfur dioxide gas, catalyzing and purifying the sulfur dioxide gas obtained by burning, filtering out impurities, cooling, and finally introducing pure air to mix to obtain sulfur trioxide mixed gas; the pure air adopts air with dew point controlled between minus 60 ℃ and minus 90 ℃;
s3, sulfonation reaction: carrying out sulfonation reaction on the pretreated fatty alcohol polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 in a multitube falling film type sulfonation reactor, and purifying a reaction product to remove redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
s4, neutralization: adding sodium hydroxide solution, pure water and a reaction auxiliary agent into the sulfonation reaction product prepared in the step S3 in a neutralization reactor to perform neutralization reaction, and refining the reaction product after the reaction to prepare low-dioxane ethoxylated alkyl sodium sulfate;
The whole preparation process is carried out under vacuum.
Before the application, the preparation process of ethoxylated alkyl sodium sulfate widely industrialized in the field mainly takes fatty alcohol polyoxyethylene ether as a raw material, takes sulfur trioxide as a sulfonating agent, and carries out sulfonation preparation through a falling film type sulfonation reactor; and then neutralizing and saponifying the product by sodium hydroxide to prepare the finished product. The dioxane content of the existing ethoxylated sodium alkyl sulfate products is generally more than 20ppm through detection of the existing ethoxylated sodium alkyl sulfate products.
The ethoxylated alkyl sodium sulfate is an important raw material for washing cream (agent), dry cleaning agent, shampoo (dew), various bath lotions and the like at present, has extremely wide application and extremely large annual usage. The ethoxylated sodium alkyl sulfate products contain relatively large amounts of dioxane and clearly pose a significant threat to human health.
Although, in the current cosmetic specifications in China, the content of dioxane is not specified in the raw materials or the products. However, considering the toxic nature of the product, it is necessary to reduce the content of the product. The prior art can not effectively solve the technical problem of too high dioxane content in the product.
The inventor of the application has conducted intensive studies on the existing preparation process of ethoxylated alkyl sodium sulfate products, and has found that, as the fatty alcohol-polyoxyethylene ether raw material is easy to absorb water, the existing water can undergo side reaction with sulfur trioxide to produce sulfuric acid, and under the action of sulfuric acid, side reaction can occur that ethylene oxide groups in the raw material are cracked to generate dioxane, so that the existing ethoxylated alkyl sodium sulfate products can contain dioxane. The applicant has further improved the existing preparation process, designed the preparation process of the application, through controlling raw materials, reaction process, have reduced the incidence of side reaction effectively, and then has reduced the content of dioxane in the product by a wide margin.
The following are examples of the application.
The raw materials and equipment information of each component of the embodiment of the application are as follows:
the reaction raw materials and intermediate products required by the reaction are all stored by adopting a sealed storage tank, the preparation of sulfur trioxide reaction gas adopts a fully sealed reactor, a neutralization reactor adopts a fully sealed reactor, and a finished product storage tank adopts a sealed storage tank; the storage tanks are connected with the reactor through sealing pipelines, and pumping is adopted for material conveying;
Fatty alcohol polyoxyethylene ether: purity over 95%, purchased from light and medium daily chemical technology limited company;
sulfur: liquid sulfur, purchased from south Beijing refinery, inc.
Example 1
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating the fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in the raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing the pretreated fatty alcohol-polyoxyethylene ether at normal temperature for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to below 400 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of 15%; the pure air adopts normal temperature air with dew point controlled at-90 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be more than 90 ℃;
s3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:2, so that the mixed gas is subjected to sulfonation reaction in a multitube falling film type sulfonation reactor for 1min, and treating the reaction product by a purifier to remove redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
S4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 40% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 4 hours, sampling and detecting the pH value of the reaction product, wherein the pH value is 11; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at normal temperature.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 2
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing at 40 ℃ for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 280 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of 8%; the pure air adopts normal temperature air with dew point controlled at-80 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 74 ℃;
S3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1.2, so that the mixed gas is subjected to sulfonation reaction in a multi-tube falling film type sulfonation reactor for 45 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
s4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding a little excessive amount of 35% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 3h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 9.5; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 45 ℃.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 3
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing at 40 ℃ for later use;
S2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 270 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of 7%; the dew point of the pure air is controlled at-70 ℃ and the temperature is controlled at 10 ℃; the temperature of the obtained sulfur trioxide mixed gas is 68 ℃;
s3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1.2, so that the mixed gas is subjected to sulfonation reaction in a multi-tube falling film type sulfonation reactor for 45 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
s4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 2.5h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 8.5; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 45 ℃.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 4
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing at 40 ℃ for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 250 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 6%; the dew point of the pure air is controlled at-60 ℃ and the temperature is 8 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 60 ℃;
s3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1.1, so that the mixed gas is subjected to sulfonation reaction in a multi-tube falling film type sulfonation reactor for 45 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
S4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 2.5h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 8.5; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 45 ℃.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 5
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing at 36 ℃ for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 250 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 4%; the dew point of the pure air is controlled at-65 ℃ and the temperature of the pure air is 8 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 54 ℃;
S3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1.1, so that the mixed gas is subjected to sulfonation reaction in a multi-tube falling film type sulfonation reactor for 40 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
s4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 2.5h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 8; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 40 ℃.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 6
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing the fatty alcohol-polyoxyethylene ether at 32 ℃ for later use;
S2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 230 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of 3%; the pure air adopts air with dew point controlled at-75 ℃ and temperature controlled at 4 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 40 ℃;
s3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1.05, so that the mixed gas is subjected to sulfonation reaction in a multi-tube falling film type sulfonation reactor for 40 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
s4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 2.5h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 8; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 40 ℃.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 7
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing the fatty alcohol-polyoxyethylene ether at 32 ℃ for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 240 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 5%; the dew point of the pure air is controlled at-85 ℃ and the temperature of the pure air is controlled at 6 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 48 ℃;
s3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1.05, so that the mixed gas is subjected to sulfonation reaction in a multi-tube falling film type sulfonation reactor for 35 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
S4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 2.5h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 8; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 40 ℃.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 8
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing the fatty alcohol-polyoxyethylene ether at 32 ℃ for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 240 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 5%; the dew point of the pure air is controlled at-70 ℃ and the temperature is controlled at 6 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 48 ℃;
S3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1, so that the mixed gas is subjected to sulfonation reaction in a multitube falling film type sulfonation reactor for 30 seconds, and treating the reaction product by a purifier to remove redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
s4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 2h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 8.5; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 35 ℃.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 9
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing the fatty alcohol-polyoxyethylene ether at 32 ℃ for later use;
S2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 240 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 5%; the dew point of the pure air is controlled at-80 ℃ and the temperature of the pure air is 6 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 48 ℃;
s3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1, so that the mixed gas is subjected to sulfonation reaction in a multitube falling film type sulfonation reactor, controlling the reaction temperature at 50 ℃ and the reaction time at 25 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
s4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 2h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 8.5; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 35 ℃.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 10
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing the fatty alcohol-polyoxyethylene ether at 32 ℃ for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 240 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 5%; the dew point of the pure air is controlled at-80 ℃ and the temperature of the pure air is 6 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 48 ℃;
s3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1, so that the mixed gas is subjected to sulfonation reaction in a multitube falling film type sulfonation reactor, controlling the reaction temperature to be about 45 ℃, reacting for 20 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
S4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 2h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 8.5; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 35 ℃.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 11
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing the fatty alcohol-polyoxyethylene ether at 24 ℃ for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 260 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 6%; the dew point of the pure air is controlled at-70 ℃ and the temperature is controlled at 5 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 50 ℃;
S3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1, so that the mixed gas is subjected to sulfonation reaction in a multitube falling film type sulfonation reactor, controlling the reaction temperature to be about 40 ℃, reacting for 20 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
s4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 2h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 8.5; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 30 ℃.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 12
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
S1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing the fatty alcohol-polyoxyethylene ether at 24 ℃ for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 260 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 6%; the pure air adopts air with dew point controlled at-90 ℃ and temperature controlled at 5 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 50 ℃;
s3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:0.95, so that the mixed gas is subjected to sulfonation reaction in a multi-tube falling film type sulfonation reactor, controlling the reaction temperature to be about 35 ℃, controlling the reaction time to be 15 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
S4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 1.5h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 7.5; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 30 ℃.
In the whole reaction process, the whole reaction device system is ensured to be in a vacuum state.
Example 13
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol polyoxyethylene ether, pumping the pretreated fatty alcohol polyoxyethylene ether into a sealed storage tank, and sealing and storing at 20 ℃ for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 220 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 6%; the dew point of the pure air is controlled at-60 ℃ and the temperature is controlled at 5 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 38 ℃;
S3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:0.95, so that the mixed gas is subjected to sulfonation reaction in a multi-tube falling film type sulfonation reactor, controlling the reaction temperature to be about 26 ℃, reacting for 18 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
s4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for 1h, sampling and detecting the pH value of the reaction product, wherein the pH value is 7; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at the normal temperature of 24 ℃.
Example 14
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing the fatty alcohol-polyoxyethylene ether at 30 ℃ for later use;
S2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 230 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 3%; the pure air adopts air with dew point controlled at-60 ℃ and temperature controlled at 4 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled at 40 ℃;
s3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:0.90, so that the mixed gas is subjected to sulfonation reaction in a multi-tube falling film type sulfonation reactor, controlling the reaction temperature to be about 30 ℃, reacting for 10 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to obtain a sulfonation reaction product;
s4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at 20 ℃ for 1h, sampling and detecting the pH value of the reaction product, wherein the pH value is 7; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 30 ℃.
Example 15
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing the fatty alcohol-polyoxyethylene ether at 30 ℃ for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 260 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 5%; the pure air adopts air with dew point controlled at-60 ℃ and temperature controlled at 4 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 50 ℃;
s3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1.0, so that the mixed gas is subjected to sulfonation reaction in a multi-tube falling film type sulfonation reactor, controlling the reaction temperature to be about 40 ℃, reacting for 20 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
S4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at 30 ℃ for 2h, sampling and detecting the pH value of the reaction product, wherein the pH value is 8; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 40 ℃.
Example 16
The preparation of the ethoxylated alkyl sodium sulfate of this example comprises the following steps:
s1, pretreatment of fatty alcohol polyoxyethylene ether raw materials: treating fatty alcohol-polyoxyethylene ether by a filter and a purifier to remove impurities in raw materials to obtain pretreated fatty alcohol-polyoxyethylene ether, pumping the pretreated fatty alcohol-polyoxyethylene ether into a sealed storage tank, and sealing and storing at 40 ℃ for later use;
s2, preparing sulfur trioxide reaction gas: in a sealed reactor, burning liquid sulfur to generate sulfur dioxide gas, passing the sulfur dioxide gas obtained by burning through a catalytic bed and a purifier, catalyzing and removing impurities, cooling to 270 ℃, and pumping into a reaction gas storage tank; introducing pure air into a reaction gas storage tank for mixing to obtain sulfur trioxide mixed gas with the concentration of about 6%; the pure air adopts air with dew point controlled at-80 ℃ and temperature controlled at 5 ℃; the temperature of the obtained sulfur trioxide mixed gas is controlled to be about 50 ℃;
S3, sulfonation reaction: feeding the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:0.95, so that the mixed gas is subjected to sulfonation reaction in a multi-tube falling film type sulfonation reactor, controlling the reaction temperature to be about 40 ℃, reacting for 30 seconds, treating the reaction product by a purifier, and removing redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
s4, neutralization: pumping the sulfonation reaction product obtained in the step S3 into a neutralization reactor, adding a little excessive 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at 40 ℃ for 3h, sampling and detecting the pH value of the reaction product, wherein the pH value is 7; and then refining and purifying the reaction product to obtain low dioxane ethoxylated sodium alkyl sulfate, pumping the refined ethoxylated sodium alkyl sulfate into a sealed storage tank, and preserving the temperature at 30 ℃.
Comparative example
The present application takes prior art processes as comparative examples.
The prior art process adopted by the comparative example comprises the following specific steps:
s1, preparing fatty alcohol polyoxyethylene ether raw materials: analytical grade fatty alcohol polyoxyethylene ether with purity of more than 99.9% is selected as a raw material, and the raw material is stored in a sealing way.
S2, preparing sulfur trioxide reaction gas: the canned sulfur trioxide gas produced by Sigma-Aldrich was purchased, and the product with a purity of 99.5% or more was selected and stored in a sealed state.
S3, sulfonation reaction: feeding fatty alcohol-polyoxyethylene ether and sulfur trioxide reaction gas into a multitube falling film type sulfonation reactor according to the mol ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide of 1:1.2, and carrying out sulfonation reaction, and reacting at normal temperature until the reaction is complete; and (3) treating the reaction product by a purifier to remove redundant sulfur trioxide gas, waste acid and impurities, thereby preparing a sulfonation reaction product.
S4, neutralization: pouring the sulfonation reaction product into a neutralization reactor, adding a small excess of 32% sodium hydroxide solution, pure water, bleaching agent and pH regulator, carrying out neutralization reaction, reacting at normal temperature for more than 3h, sampling and detecting the pH value of the reaction product, wherein the pH value is about 8.5; and then refining and purifying the reaction product to obtain pure ethoxylated sodium alkyl sulfate, and storing in a normal temperature tank.
The ethoxylated sodium alkyl sulfate products prepared in examples 1 to 16 of the present application and the ethoxylated sodium alkyl sulfate product prepared in comparative example were respectively subjected to quality detection by sampling in a product tank after 15 days of storage, and the active matter content, sodium sulfate, free oil content and dioxane content thereof were detected. The results obtained are shown in Table 1 below.
TABLE 1 product Performance test Table
| Active/% | Sulfate/% | Free oil/% | Dioxane/ppm | |
| Example 1 | 70.2 | Within 0.45 | 1.90 | 9 |
| Example 2 | 70.4 | Within 0.45 | 1.86 | 7 |
| Example 3 | 70.5 | Within 0.45 | 1.88 | 7 |
| Example 4 | 70.8 | Within 0.45 | 1.84 | 6 |
| Example 5 | 70.9 | Within 0.45 | 1.82 | 6 |
| Example 6 | 71.8 | Within 0.45 | 1.77 | 4 |
| Example 7 | 72.1 | Within 0.45 | 1.75 | 4 |
| Example 8 | 72.1 | Within 0.45 | 1.76 | 4 |
| Example 9 | 72.4 | Within 0.45 | 1.74 | 3 |
| Example 10 | 72.3 | Within 0.45 | 1.73 | 3 |
| Example 11 | 72.7 | Within 0.45 | 1.69 | 2 |
| Example 12 | 72.8 | Within 0.45 | 1.71 | 3 |
| Example 13 | 70.8 | Within 0.45 | 1.84 | 5 |
| Example 14 | 72.6 | Within 0.45 | 1.72 | 2 |
| Example 15 | 73.6 | Within 0.45 | 1.64 | 1 |
| Example 16 | 73.2 | Within 0.45 | 1.73 | 2 |
| Comparative example | 69.8 | 0.66 | 2.26 | 34 |
The detection method comprises the following steps:
the content of active substances and sodium sulfate are detected according to GB/T13530-2008 "test method for ethoxylated alkyl sodium sulfate";
detecting the content of the free oil by adopting a high performance liquid chromatography;
the dioxane content is detected according to the method specified by the detection method of dioxane in cosmetics in the national food and drug administration document No. 2010.
As can be seen from the data in table 1, the comparative example uses the ethoxylated sodium alkyl sulfate product prepared by the current prior art, and the raw materials are very strictly controlled in purity on the basis of the current process, but are not subjected to special sealing control and overall process vacuum control; thus, although the raw materials are extremely high in purity and extremely low in impurity and moisture content, the dioxane content of the prepared product still reaches 34ppm; the quality of the product can meet the requirements of the current national standard in terms of active matter content and free oil content. The ethoxylated alkyl sodium sulfate products prepared in the embodiments 1 to 16 adopt impurity removal and water removal treatment, and the whole process adopts vacuum control, so that the influence of environmental factors is effectively avoided, and the dioxane content of the prepared ethoxylated alkyl sodium sulfate products can be controlled below 10ppm and is far lower than that of the products prepared by the prior process; meanwhile, the quality of the product is superior to that of the product prepared by the prior art in terms of active matter content and free oil content.
As can be seen from the data in Table 1, the ethoxylated sodium alkyl sulfate products prepared in examples 1 to 5 of the present application, whether they are of a product quality or a dioxane content, have a relatively significant difference from examples 6 to 16; the ethoxylated sodium alkyl sulfate products prepared in examples 6 to 8, whether they are of good quality or have a dioxane content, also differ from examples 9 to 12 and 14 to 16. Therefore, the temperature control of the mixed gas of the fatty alcohol-polyoxyethylene ether raw material and the sulfur trioxide has obvious influence on the sulfonation reaction temperature, and the influence of the temperature can influence the occurrence rate of side reaction, so that the quality of the prepared product is slightly lower. Therefore, the temperature of the mixed gas of the fatty alcohol-polyoxyethylene ether raw material and the sulfur trioxide, the reaction temperature and the reaction time of the sulfonation reaction are strictly controlled, so that the content of dioxane in the product can be further effectively reduced, and the quality of the product is effectively improved.
It can also be seen from the data in Table 1 that the sodium ethoxylated alkyl sulfate product of example 13 of the present application, whether it is of product quality or dioxane content, is significantly different from the sodium ethoxylated alkyl sulfate products of the remaining examples of examples 9-16. It can be seen that in addition to the above-mentioned influencing factors, the storage temperature of the ethoxylated sodium alkyl sulfate product has a certain influence on the stability and quality of the product, and the ethoxylated sodium alkyl sulfate product can be kept relatively stable by adopting the storage temperature which is relatively slightly higher than the normal temperature and the sealed storage condition.
The above embodiments are not intended to limit the scope of the present application, so: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.
Claims (10)
1. A process for preparing a low dioxane ethoxylated sodium alkyl sulfate comprising the steps of:
s1, pretreatment of fatty alcohol polyoxyethylene ether: filtering and purifying the fatty alcohol-polyoxyethylene ether to remove impurities in the raw materials, thereby obtaining pretreated fatty alcohol-polyoxyethylene ether;
s2, preparing sulfur trioxide reaction gas: burning sulfur to generate sulfur dioxide gas, catalyzing and purifying the sulfur dioxide gas obtained by burning, filtering out impurities, cooling, and finally introducing pure air to mix to obtain sulfur trioxide mixed gas; the pure air adopts air with dew point controlled between minus 60 ℃ and minus 90 ℃;
s3, sulfonation reaction: carrying out sulfonation reaction on the pretreated fatty alcohol polyoxyethylene ether prepared in the step S1 and the sulfur trioxide mixed gas prepared in the step S2 in a multitube falling film type sulfonation reactor, and purifying a reaction product to remove redundant sulfur trioxide gas, waste acid and impurities to prepare a sulfonation reaction product;
S4, neutralization: adding sodium hydroxide solution, pure water and a reaction auxiliary agent into the sulfonation reaction product prepared in the step S3 in a neutralization reactor to perform neutralization reaction, and refining the reaction product after the reaction to prepare low-dioxane ethoxylated alkyl sodium sulfate;
the whole preparation process is carried out under vacuum.
2. The method for preparing low dioxane ethoxylated alkyl sodium sulfate according to claim 1, wherein the pretreatment in step S1 further comprises controlling the temperature of the pretreated fatty alcohol-polyoxyethylene ether at 20-40 ℃.
3. The method for preparing low dioxane ethoxylated sodium alkyl sulfate according to claim 1, wherein in the step S2, the cooling is performed by cooling sulfur trioxide gas to 230-270 ℃.
4. The method for preparing low dioxane ethoxylated sodium alkyl sulfate according to claim 1, wherein the temperature of the purified air is controlled between 4 and 8 ℃ in the step S2.
5. The method for preparing low dioxane ethoxylated sodium alkyl sulfate according to claim 1, wherein in the step S2, the concentration of the prepared sulfur trioxide mixed gas is controlled to be 3-7%, and the temperature is controlled to be 40-60 ℃.
6. The method for preparing low dioxane ethoxylated alkyl sodium sulfate according to claim 1, wherein in the step S3, the feeding ratio of the pretreated fatty alcohol-polyoxyethylene ether prepared in the step S1 to the sulfur trioxide mixed gas prepared in the step S2 is 1 according to the molar ratio of the fatty alcohol-polyoxyethylene ether to the sulfur trioxide: 0.90 to 1.10.
7. The method for preparing low dioxane ethoxylated alkyl sodium sulfate according to claim 1, wherein in the step S3, the reaction temperature of the sulfonation reaction is controlled to be 30-50 ℃ and the time is controlled to be 10-30S.
8. The method for preparing low dioxane ethoxylated alkyl sodium sulfate according to claim 1, wherein in the step S4, the reaction temperature of the neutralization reaction is controlled to be 20-40 ℃ and the reaction time is controlled to be 1-3 h.
9. The method for preparing low dioxane ethoxylated sodium alkyl sulfate according to claim 1, wherein in the step S4, the reaction auxiliary agent comprises a bleaching agent and a pH adjuster.
10. The method for preparing low dioxane ethoxylated alkyl sodium sulfate according to claim 1, wherein in the step S4, the pH value of the refined product is controlled to 7-11, and the storage temperature of the refined product is controlled to 30-40 ℃.
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| CN111100284A (en) * | 2019-12-27 | 2020-05-05 | 赞宇科技集团股份有限公司 | Production process and device of high-quality fatty alcohol-polyoxyethylene ether sulfate |
| CN211734231U (en) * | 2019-12-27 | 2020-10-23 | 嘉兴赞宇科技有限公司 | Production system of high-quality fatty alcohol polyoxyethylene ether sulfate |
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