CN115043761B - Process for producing triethanolamine alkyl sulfate - Google Patents
Process for producing triethanolamine alkyl sulfate Download PDFInfo
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- CN115043761B CN115043761B CN202210797818.5A CN202210797818A CN115043761B CN 115043761 B CN115043761 B CN 115043761B CN 202210797818 A CN202210797818 A CN 202210797818A CN 115043761 B CN115043761 B CN 115043761B
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- triethanolamine
- kathon
- alkyl sulfate
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- -1 triethanolamine alkyl sulfate Chemical class 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims description 27
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000000463 material Substances 0.000 claims abstract description 76
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 150000008051 alkyl sulfates Chemical class 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- UOFRJXGVFHUJER-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;hydrate Chemical compound [OH-].OCC[NH+](CCO)CCO UOFRJXGVFHUJER-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960004418 trolamine Drugs 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 38
- 229940080117 triethanolamine sulfate Drugs 0.000 claims description 24
- 125000000129 anionic group Chemical group 0.000 claims description 20
- 150000002191 fatty alcohols Chemical class 0.000 claims description 17
- 238000005670 sulfation reaction Methods 0.000 claims description 16
- 239000011368 organic material Substances 0.000 claims description 13
- 230000019635 sulfation Effects 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 abstract description 15
- 230000002335 preservative effect Effects 0.000 abstract description 7
- 239000003755 preservative agent Substances 0.000 abstract description 5
- 150000008052 alkyl sulfonates Chemical class 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 21
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 18
- 239000000523 sample Substances 0.000 description 17
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 16
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 16
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 16
- 239000003085 diluting agent Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 9
- 239000013543 active substance Substances 0.000 description 8
- 235000015141 kefir Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000012086 standard solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RZRILSWMGXWSJY-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;sulfuric acid Chemical compound OS(O)(=O)=O.OCCN(CCO)CCO RZRILSWMGXWSJY-UHFFFAOYSA-N 0.000 description 6
- JPENACUQEHMSRR-UHFFFAOYSA-N 2-methyl-1,2-oxazol-3-one Chemical compound CN1OC=CC1=O JPENACUQEHMSRR-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 230000001180 sulfating effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical class O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 description 1
- 125000006538 C11 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 125000000373 fatty alcohol group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/12—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by hydroxy groups
-
- 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
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C305/00—Esters of sulfuric acids
- C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
- C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
- C07C305/06—Hydrogenosulfates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/02—Alkyl sulfonates or sulfuric acid ester salts derived from monohydric alcohols
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention aims to solve the defect that the preservative has insufficient duration of preservative effect in aqueous triethanolamine alkyl sulfate, and the production method of the surfactant product by adopting the triethanolamine alkyl sulfate comprises the following steps: (1) obtaining an alkyl sulfonate; (2) Neutralizing alkyl sulfate with triethanolamine water solution to obtain alkyl sulfate triethanolamine salt intermediate material I; (3) Mixing the triethanolamine alkyl sulfate intermediate material I with the Kathon and the Kathon auxiliary agent; the Kathon auxiliary agent comprises the technical scheme of hydrogen peroxide, so that the technical problem is well solved, and the Kathon auxiliary agent can be used for producing triethanolamine alkyl sulfate surfactant products.
Description
Background
Triethanolamine alkyl sulfate salt is SO via fatty alcohol 3 Continuously sulfating and neutralizing with triethanolamine. In the detergent and care industry, triethanolamine alkyl sulfate can be widely applied to various shampoos and bath products, and is an excellent basic active ingredient. It is particularly suitable for use in high quality concentrated shampoos with relatively low viscosity. Because of its very good dissolution characteristics, the cloud point of the product can be effectively reduced, thereby improving the quality of the formulation.
Aqueous triethanolamine alkyl sulfate liquid or paste products are susceptible to bacterial microorganism growth and even seriously spoil the product during storage and transportation, especially in summer hot weather, and in order to overcome the problem of bacterial microorganism growth, an antibacterial biocide or preservative is generally required.
Kathon (also known as kathon) is a well-known antimicrobial biocide and is widely used as a preservative in various fields. The active ingredients of the Kathon are isothiazolinone derivatives, and the active ingredients are 5-chloro-2-methyl-4-isothiazolin-3-one (CIT) and 2-methyl-4-isothiazolin-3-one (MIT). However, the preservation effect of Kathon in aqueous triethanolamine alkyl sulfate is not durable enough.
Disclosure of Invention
One of the technical problems to be solved by the invention is the defect of insufficient duration of the preservative effect of the preservative in the aqueous triethanolamine alkyl sulfate salt, and the invention provides a novel production method of the triethanolamine alkyl sulfate salt product.
In order to solve one of the technical problems, the technical scheme of the invention is as follows:
a process for producing a triethanolamine alkyl sulfate surfactant product comprising:
(1) Obtaining alkyl sulfonate;
(2) Neutralizing alkyl sulfate with triethanolamine water solution to obtain alkyl sulfate triethanolamine salt intermediate material I;
(3) Mixing the triethanolamine alkyl sulfate intermediate material I with the Kathon and the Kathon auxiliary agent;
the Kathon auxiliary agent comprises hydrogen peroxide.
We find that when the Kathon is used for the antibacterial and putrefactive application of the alkyl triethanolamine sulfate intermediate material, the Kathon is very unstable, and when hydrogen peroxide is used as the Kathon auxiliary agent and the Kathon is used for the alkyl triethanolamine sulfate intermediate material together, the stability of the Kathon is greatly improved. We have found that when Kathon is used for the antibacterial and putrefactive inhibition of alkyl sodium sulfate intermediate materials, the Kathon is not so unstable, and we consider that an unknown side reaction may occur during the process of neutralizing alkyl sulfate with triethanolamine aqueous solution, which affects the stability of Kathon, and the use of Kathon auxiliary reduces or even eliminates the side effect of the unknown side reaction on the stability of Kathon.
In the above technical scheme, the source and the obtaining mode of the alkyl sulfate are not particularly limited as long as the step of neutralizing the alkyl sulfate with the triethanolamine aqueous solution is adopted. For example, but not limited to, the alkyl sulfate is prepared from fatty alcohol as organic raw material by SO 3 And (3) performing a sulfation process.
As the organic raw material of fatty alcohol, SO is used 3 Process for sulfating alkyl sulfateNon-limiting examples of process conditions, the SO 3 In a form diluted with a gaseous diluent.
As the organic raw material of fatty alcohol, SO is used 3 The process conditions under which the sulfation process is carried out result in alkyl sulfates are, by way of non-limiting example, air or nitrogen as the gaseous diluent.
As the organic raw material of fatty alcohol, SO is used 3 Non-limiting examples of process conditions for carrying out the sulfation process to obtain alkyl sulfate esters, by weight, SO 3 Occupying SO 3 And 0.1 to 10% by weight of the total weight of the gaseous diluent, further non-limiting examples of SO 3 Occupying SO 3 And 0.5%, 1%, 1.5%, 2.0%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% of the total weight of the gaseous diluent, etc.
As the organic raw material of fatty alcohol, SO is used 3 Non-limiting examples of process conditions for carrying out the sulfation process to obtain alkyl sulfates, SO 3 The molar ratio of the organic material to the organic material is 1.02-1.03.
As the organic raw material of fatty alcohol, SO is used 3 The process conditions under which the sulfation is carried out result in alkyl sulfates are, by way of non-limiting example, 35 to 45 ℃.
In the above embodiments, the alkyl group is preferably a C8-C18 alkyl group, such as, but not limited to, a C9 alkyl group, a C10 alkyl group, a C11 alkyl group, a C12 alkyl group, a C13 alkyl group, a C14 alkyl group, a C15 alkyl group, a C16 alkyl group, a C17 alkyl group, or the like. Only by way of comparison, examples and comparative examples are all C12-14 alkyl.
In the above technical scheme, the pH of the intermediate material I in the step (2) is preferably 6.0 to 8.0. Such as, but not limited to, pH 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, etc., more preferably pH 6.0-7.5.
In the above technical scheme, the neutralization temperature in the step (2) is preferably 55-65 ℃. Such as, but not limited to, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, and the like.
In the above embodiments, the triethanolamine concentration in the triethanolamine solution of step (2) is preferably 10 to 23% by weight, such as, but not limited to, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23% and the like.
In the above technical solution, the temperature of the mixing in the step (3) is not particularly limited, and a person skilled in the art can reasonably select and do not need to do creative work. For example, the temperature of the mixing in step (3) may be 10 to 45℃such as, but not limited to, 15℃20℃25℃30℃35℃40℃and the like.
In the above technical solution, the mixing time in the step (3) is preferably at least 30 minutes. Such as, but not limited to, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, and the like.
In the above technical scheme, the mixing mode of the triethanolamine alkyl sulfate salt intermediate material I and the kefir and kefir auxiliary agent in the step (3) is not particularly limited, for example, the following three modes can be adopted to realize the mixing in the step (3):
mode 3.1
Comprising the following steps:
step 3.1.1, mixing the triethanolamine alkyl sulfate intermediate material I with Kathon to obtain an intermediate material II;
and 3.1.2, mixing the intermediate material II with a Kathon auxiliary agent.
Mode 3.2
Mixing the triethanolamine alkyl sulfate intermediate material I with the Kathon auxiliary agent and Kathon simultaneously (for example, mixing the Kathon auxiliary agent and Kathon simultaneously with the triethanolamine alkyl sulfate intermediate material I);
mode 3.3
Comprising the following steps:
step 3.3.1, mixing the triethanolamine alkyl sulfate intermediate material I with a Kathon auxiliary agent to obtain an intermediate material II;
step 3.3.2, mixing the intermediate material II with Kathon.
We found that mode 3.3 is significantly better than mode 3.2 in improving kefir stability, and mode 3.2 is also significantly better than mode 3.1.
In the above embodiments, the temperature of the mixing of step 3.1.1 and step 3.1.2 may independently be 10 to 45℃such as, but not limited to, 15℃20℃25℃30℃35℃40℃and the like.
In the above technical solution, the mixing time in step 3.1.1 is preferably at least 30 minutes. Such as, but not limited to, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, and the like.
In the above technical solution, the mixing time of step 3.1.2 is not limited, and the longer the mixing time, the more fully the mixing, for example, the mixing time of step 3.1.2 is 30 minutes or more, for example, but not limited to, 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, and the like.
In the above embodiments, the temperature of the mixing of step 3.3.1 and step 3.3.2 may independently be 10 to 45℃such as, but not limited to, 15℃20℃25℃30℃35℃40℃and the like.
In the above technical solution, the mixing time in the step 3.3.1 is preferably at least 30 minutes. Such as, but not limited to, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, and the like.
In the above technical solution, the mixing time of step 3.3.2 is not limited, and the longer the mixing time, the more sufficient the mixing, for example, the mixing time of step 3.3.2 is 30 minutes or more, for example, but not limited to, 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, and the like.
However, we find that when the amount of hydrogen peroxide is higher than a certain value, the chromaticity of the product is obviously increased, the Kathon stability is comprehensively improved and the chromaticity of the product is not obviously affected, preferably, the amount of hydrogen peroxide is H 2 O 2 0 to 100ppm, such as, but not limited to, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm, 15ppm, 16ppm, 17ppm, 18ppm, 19ppm, 20ppm, 21ppm, 22ppm, 23ppm, 24ppm, 25ppm, 26ppm, 27ppm, 28ppm, 29ppm, 35ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, etc., more preferably 10 to 100ppm, based on the weight of triethanolamine salt of alkyl sulfate intermediate material I.
As known, commercial Kathon products are usually provided in the form of a solution, and the active ingredients are 5-chloro-2-methyl-4-isothiazolin-3-one (abbreviated as CIT) and 2-methyl-4-isothiazolin-3-one (abbreviated as MIT), wherein the molar ratio of CIT to MIT can be 2.5-4. The content of the active substances in the Kathon commodity (based on the total weight percentage of CIT and MIT) has different specifications (such as 1.5%, 2.5%, 14% and the like by way of non-limiting example) and can be used in the present invention, and can achieve comparable technical effects. Only by way of comparison, 1.5% solution was used for Kathon in the present embodiment. In the invention, the consumption of Kathon is calculated by the total amount of CIT and MIT.
It is clear to the person skilled in the art that when the composition is used for bacteriostasis and putrefaction inhibition of the triethanolamine alkyl sulfate intermediate material I, the amount of Kathon is not particularly limited, and the composition can be reasonably selected according to the factors such as the time length of storage and transportation required by the product, the storage season and the like, and the creative labor is not required.
By way of non-limiting example only, the amount of Kathon may be greater than 0ppm and less than 500ppm based on the weight of the fatty alcohol triethanolamine sulfate salt intermediate material I, and more specifically, by way of example, the point value of the non-limiting amount may be 2ppm, 4ppm, 6ppm, 8ppm, 10ppm, 12ppm, 14ppm, 16ppm, 18ppm, 20ppm, 25ppm, 30ppm, 35ppm, 40ppm, 45ppm, 50ppm, 55ppm, 60ppm, 65ppm, 70ppm, 75ppm, 80ppm, 85ppm, 90ppm, 95ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm, and the like.
In the technical scheme, when the hydrogen peroxide is not used as the kathon auxiliary agent in the step (3) and EDTA or salt thereof is used for replacing the hydrogen peroxide, if the effect on stabilizing the kathon is a little, the effect is not obvious, but when the hydrogen peroxide is used as the kathon auxiliary agent in the step (3) and EDTA or salt thereof is also used as the kathon auxiliary agent, the stabilizing effect of the hydrogen peroxide on the kathon is obviously enhanced by the EDTA or salt thereof.
By way of non-limiting example, when the Kathon aid includes hydrogen peroxide and EDTA or salts thereof, the EDTA or salts thereof are each present in an amount of greater than 0% and less than 2% by weight of triethanolamine alkyl sulfate salt intermediate material I, such as, but not limited to, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, and the like, based on ethylenediamine tetraacetic acid.
In the above technical scheme, when the kathon auxiliary agent in step (3) uses both hydrogen peroxide and EDTA or its salt, the mode of mixing in step 3.3.1 may be:
mode 3.3.1.1
Step 3.3.1.1.1, mixing the triethanolamine alkyl sulfate intermediate material I with hydrogen peroxide to obtain an intermediate material Ia;
step 3.3.1.1.2, mixing intermediate Ia with EDTA or a salt thereof to intermediate II.
Mode 3.3.1.2
Mixing the triethanolamine alkyl sulfate intermediate material I with hydrogen peroxide and EDTA (or salts thereof) at the same time (for example, mixing the hydrogen peroxide and the EDTA (or salts thereof) with the triethanolamine alkyl sulfate intermediate material I) at the same time to obtain a material II.
Mode 3.3.1.3
Step 3.3.1.3.1, mixing the triethanolamine alkyl sulfate intermediate material I with EDTA or salts thereof to obtain an intermediate material Ib;
step 3.3.1.3.2, mixing the intermediate material Ib with hydrogen peroxide to obtain an intermediate material II.
We found that pattern 3.3.1.3 was significantly better than patterns 3.3.1.2 and 3.3.1.1 in improving kefir stability, whereas pattern 3.3.1.2 was comparable to pattern 3.3.1.1.
In the above embodiments, the temperature of the mixture of step 3.3.1.1.1 and step 3.3.1.1.2 may independently be 10 to 45 ℃, such as, but not limited to, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ and the like of the mixture of step 3.3.1.1.1 and step 3.3.1.1.2.
In the above embodiments, the mixing time of step 3.3.1.1.1 and step 3.3.1.1.2 is preferably at least 30 minutes independently. For example, but not limited to, step 3.3.1.1.1 and step 3.3.1.1.2 are independently 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, and the like.
In the above embodiments, the temperature of the mixture of step 3.3.1.3.1 and step 3.3.1.3.2 may independently be 10 to 45 ℃, such as, but not limited to, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ and the like of the mixture of step 3.3.1.3.1 and step 3.3.1.3.2.
In the above embodiments, the mixing time of step 3.3.1.3.1 and step 3.3.1.3.2 is preferably at least 30 minutes independently. For example, but not limited to, step 3.3.1.3.1 and step 3.3.1.3.2 are independently 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, and the like.
In the above embodiments, the anionic active content of triethanolamine alkyl sulfate salt in the product is preferably 30-43% by weight, such as, but not limited to, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43% and the like.
The second technical problem to be solved by the invention is to provide an alkyl triethanolamine sulfate surfactant product.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
a triethanolamine alkyl sulfate salt surfactant product obtained by the production method according to any one of the technical problems.
The third technical problem to be solved by the invention is the application of the triethanolamine alkyl sulfate surfactant product as a storage and transportation form of the triethanolamine alkyl sulfate surfactant.
In order to solve the third technical problem, the technical scheme of the invention is as follows:
use of a triethanolamine alkyl sulfate surfactant product as described in the second technical solution or a product obtained by the production process according to any one of the technical solutions described in the second technical solution as a storage form of a triethanolamine alkyl sulfate surfactant.
Method for measuring content of anionic active matters in surfactant material
In the present invention, the content of anionic active substances in all materials containing triethanolamine alkyl sulfate and materials or sodium alkyl sulfate salts is determined according to the standard (GB/T5173-2018 direct two-phase titration method for determining the anionic active substance content of the surfactant detergent).
Method for measuring pH
In the present invention, the pH of the product is measured according to standard (GB/T6368-2008 method for measuring the pH of aqueous surfactant solution).
Kathon stability evaluation method
(1) Determination of Kathon content in New products
(2) 150g of the new product is placed in a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the bottle mouth is placed in a constant temperature box with the temperature of 40+/-0.5 ℃ and is stored for 168 hours, and then the content of Kathon in a sample after constant temperature treatment is measured.
(3) Calculation of Kathon loss Rate
Kefir loss rate= ((original addition of kefir in product-amount of kefir in product stored at constant temperature for 168 hours)/original addition of kefir in product) ×100%.
Determination of Kathon content:
the method is suitable for measuring the Kathon content in the surfactant.
1. Principle of
After the sample is treated, the sample is separated by high performance liquid chromatography, detected by an ultraviolet detector and quantified by an external standard method.
2. Reagent(s)
Methanol: liquid chromatography grade
Kathon standard: 1.5% Kathon solution from Ronga Hasi containing 0.35% of 2-methyl-4-isoxazolin-3-one (MIT) and 1.15% of 5-chloro-2-methyl-isoxazolin-3-one (CIT).
3. Mobile phase solution
Solution a: filtered methanol, solution B: filtered distilled water
350mL of solution A is measured and placed in a 1000mL volumetric flask, diluted to the scale with solution B, shaken well, poured into a clean plastic bottle, and placed in an ultrasonic cleaner for degassing for 30min.
4. Instrument for measuring and controlling the intensity of light
Liquid chromatograph: with ultraviolet detectors
5. Step (a)
5.1. Instrument parameter setting
Chromatographic column: c18 column
A detector: ultraviolet (272 nm)
Mobile phase: 35% methanol solution
Flow rate: 1.0ml/min
Column temperature: 40 DEG C
Run time: 10min
5.2 preparation of Kathon standard solution
5.2.1 Kathon stock solution (30 ppm Kathon active)
Weighing 0.18-0.22 g (accurate to +/-0.0002 g) of Kathon standard substance to a 100ml volumetric flask, and diluting with distilled water to scale to obtain Kathon stock solution.
5.2.2 Kathon standard solution
Remove 8.0ml of Kathon stock solution to a 25ml volumetric flask and dilute to scale with distilled water. The solution contained about 10ppm of kathon active.
5.3 preparation of samples
10g of the sample to be analyzed is weighed and diluted twice with water
The aqueous layer of 5ml was filtered off with a 0.45um microfiltration membrane into 10ml vials labeled "S", and S-1, S-2 if more than one sample was to be detected.
5.4 detection
An appropriate amount of 10ppm of Kathon standard solution was aspirated with a sample injection needle and injected into the chromatograph, and as a reference sample, peak areas of 2-methyl-4-isoxazolin-3-one (MIT) and 5-chloro-2-methyl-isoxazolin-3-one (CIT) were recorded.
The filtered samples were injected into a chromatograph for analysis and peak areas of 2-methyl-4-isoxazolin-3-one (MIT) and 5-chloro-2-methyl-isoxazolin-3-one (CIT) were recorded.
5.5 calculation of
5.5.1 calculation of 2-methyl-4-isoxazolin-3-one (MIT) and 10ppm Kathon standard solution
Content (ppm) of 5-chloro-2-methyl-isoxazolin-3-one (CIT)
MIT content M in standard solution T (ppm)：
M T =32×standard weight×0.35
Content C of CIT in Standard solution T (ppm)：
C T =32×standard weight×1.15
In the formula, "standard weight" is the weight actually weighed in the section "5.2.1" mentioned above.
5.5.2 calculating the Content (CIT) ppm of 2-methyl-4-isoxazolin-3-one (MIT) and 5-chloro-2-methyl-isoxazolin-3-one and the total content of kathon actives in the samples
MIT content M in sample S (ppm)：
M S = (sample peak area/standard liquid peak area) ×m T CIT content C in dilution of X sample S (ppm)：
Cs= (sample peak area/standard solution peak area) ×c T X dilution of sample total kathon active content (ppm) in sample:
total content of kathon active in sample = content M of MIT in sample S Content Cs of CIT in + sample.
5.6 washing of chromatographic column
After all sample analyses were completed, the column was rinsed with mobile phase.
The present invention will be described in detail with reference to the following embodiments.
Detailed Description
1. Method 1 for obtaining fatty alcohol triethanolamine sulfate intermediate material I in specific embodiment
Step 1, obtaining organic materials
The fatty alcohol is directly used as organic material for the sulfation in the following step 2, and the fatty alcohol is C12-14 fatty alcohol.
Step 2 sulfation in sulfonation reactor
The organic material and the sulfur trioxide dry air mixture with the sulfur trioxide content of 4% are introduced from the top of the sulfonation reactor, the feeding speed of the organic material is 1130 kg/hour, the feeding mole ratio of the sulfur trioxide to the organic material is 1.03, and the sulfation reaction temperature is 45 ℃. After the end of the sulfation reaction, a sulfation product in the form of a sulfate is obtained, which is then followed by:
step 3, neutralization of sulfate
The sulfate type sulfating product is neutralized by triethanolamine water solution with the weight concentration of 20 percent, the neutralization temperature is 55-65 ℃, the alkyl triethanolamine sulfate is obtained, then water and a pH regulator are added for adjustment, and the mixture is stirred uniformly, so that the alkyl triethanolamine sulfate intermediate material I with the weight content of anion active substances of 40.39 percent and the pH value of 7.03 is obtained.
2. Method for obtaining diluent of fatty alcohol triethanolamine sulfate intermediate material I in specific embodiment
And (3) adding water into the triethanolamine alkyl sulfate intermediate material I to adjust the content of active substances, and uniformly stirring to obtain a diluted material of the triethanolamine alkyl sulfate intermediate material I, wherein the content of anionic active substances is 29.87%, and the pH value is 7.02.
3. Method for obtaining sodium alkyl sulfate diluent in specific embodiment
The method for obtaining sodium alkyl sulfate diluent in comparative example 3 is as follows:
step 1, obtaining organic materials
The C12-14 fatty alcohol is directly used as organic material for the sulfation described in the following step 2.
Step 2 sulfation in sulfonation reactor
The organic material and the sulfur trioxide dry air mixture with the sulfur trioxide content of 4% are introduced from the top of the sulfonation reactor, the feeding speed of the organic material is 1740 kg/hour, the feeding mole ratio of the sulfur trioxide to the organic material is 1.03, and the sulfation reaction temperature is 40 ℃. After the end of the sulfation reaction, a sulfation product in the form of a sulfate is obtained, which is then followed by:
step 3, neutralization of sulfate
The sulfated product in the form of the sulfate ester was neutralized with 32% by weight sodium hydroxide aqueous solution at a neutralization temperature of 60℃to give a sodium alkyl sulfate salt of pH 8.56 having an anionic active weight content of 70.89%.
Step 4, preparation of 30% content water system sodium alkyl sulfate salt
And (3) diluting and adjusting the sodium alkyl sulfate material with the weight content of the anionic active substance of 70.89%, and finally obtaining the fatty alcohol sodium sulfate diluent with the weight content of the anionic active substance of 29.67% and the pH value of 7.04.
4. Kathon solution used in specific embodiments
The Kathon solutions used in examples and comparative examples were identified as having a weight concentration of 1.5%, and as measured before use, contained 2-methyl-4-isoxazolin-3-one at a weight concentration of 0.35%, 5-chloro-2-methyl-isoxazolin-3-one at a weight concentration of 1.16%, and contained 1.51% of the total active matter content of the Kathon solution. The detection was carried out according to the standard (GB/T29666-2013 cosmetic preservative methyl chloroisothiazolinone and a mixture of methyl isothiazolinone and magnesium chloride and magnesium nitrate).
[ example 1 ]
Adding Kathon and hydrogen peroxide into the fatty alcohol triethanolamine sulfate intermediate material I together, wherein the steps are as follows:
10.0Kg of fatty alcohol triethanolamine sulfate intermediate material I (the weight content of anionic active matters in the intermediate material I is 40.39%, the pH value is 7.03) is taken, and 1.45g of hydrogen peroxide with the weight concentration of 27.5% (namely H) is added 2 O 2 40ppm by weight of intermediate I) and 6.662g of a 1.51% strength by weight Kathon solution (10 ppm by weight of intermediate I) were stirred at 40℃for 300 minutes to give the product.
150g of the product is put into a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the flask is put into a constant temperature box with the temperature of 40+/-0.5 ℃ and is stored for 168 hours, and the sampling content of Kathon is 9.33ppm.
Kesong loss rate= ((10-9.33)/10) ×100% =6.7%.
For comparison, the experimental results are presented in Table 1.
[ example 2 ]
Firstly adding hydrogen peroxide into the fatty alcohol sulfuric acid triethanolamine salt intermediate material I, and then adding Kathon, wherein the specific steps are as follows:
10.0Kg of fatty alcohol triethanolamine sulfate intermediate material I (the weight content of anionic active matters in the intermediate material I is 40.39%, the pH value is 7.03) is taken, and 1.45g of hydrogen peroxide with the weight concentration of 27.5% (namely H) is added 2 O 2 40ppm by weight of intermediate I), stirring at 40℃for 60 minutes; then, 6.662g (the amount of which is 10ppm based on the weight of the intermediate I) of a Kathon solution having a weight concentration of 1.51% was added thereto, and the mixture was stirred at 40℃for 300 minutes to obtain a product.
150g of the product is put into a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the bottle mouth is put into a constant temperature box with the temperature of 40+/-0.5 ℃ and is stored for 168 hours, and the sampling content of Kathon is 9.79ppm.
Kesong loss rate= ((10-9.79)/10) ×100% =2.1%.
For comparison, the experimental results are presented in Table 1.
[ example 3 ]
Firstly, adding Kathon into a fatty alcohol sulfuric acid triethanolamine salt intermediate material I, and then adding hydrogen peroxide, wherein the specific steps are as follows:
10.0Kg of fatty alcohol triethanolamine sulfate intermediate material I (the weight content of anionic active matters in the intermediate material I is 40.39 percent, the pH value is 7.03) is taken, 6.662g of kathon solution with the weight concentration of 1.51 percent (the dosage is 10ppm of the weight of the intermediate material I) is added, and the mixture is stirred at 40 ℃ for 60 minutes; then adding 1.45g (H) of hydrogen peroxide with the weight concentration of 27.5 percent 2 O 2 40ppm by weight of intermediate material I), and stirring at 40℃for 300 minutes to obtain the product.
150g of the product is put into a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the flask is put into a constant temperature box with the temperature of 40+/-0.5 ℃ and is stored for 168 hours, and the sampling content of Kathon is 7.35ppm.
Kesong loss rate= ((10-7.35)/10) ×100% =26.5%.
For comparison, the experimental results are presented in Table 1.
[ example 4 ]
Adding Kathon, hydrogen peroxide and EDTA-4Na into the fatty alcohol triethanolamine sulfate intermediate material I together, wherein the steps are as follows:
10.0Kg of fatty alcohol triethanolamine sulfate intermediate material I (the weight content of anionic active matters in the intermediate material I is 40.39%, the pH value is 7.03) is taken, and 1.45g of hydrogen peroxide with the weight concentration of 27.5% (namely H) is added 2 O 2 40ppm by weight of intermediate I), 6.662g of a 1.51% strength by weight Kathon solution (the amount corresponding to 10ppm by weight of intermediate I) and 10g of EDTA-4Na (calculated as EDTA) were stirred at 40℃for 300 minutes to obtain the product.
150g of the product is put into a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the flask is put into a constant temperature box with the temperature of 40+/-0.5 ℃ and is stored for 168 hours, and the sampling content of Kathon is 9.45ppm.
Kesong loss rate= ((10-9.45)/10) ×100% =5.5%.
For comparison, the experimental results are presented in Table 1.
[ example 5 ]
Firstly, adding hydrogen peroxide and EDTA-4Na into an intermediate material I of fatty alcohol triethanolamine sulfate, and then adding Kathon, wherein the specific steps are as follows:
10.0Kg of fatty alcohol triethanolamine sulfate intermediate material I (the weight content of anionic active matters in the intermediate material I is 40.39%, the pH value is 7.03) is taken, and 1.45g of hydrogen peroxide with the weight concentration of 27.5% (namely H) is added 2 O 2 40ppm by weight of intermediate I) and 10g of EDTA-4Na (calculated as EDTA) (0.1% by weight of intermediate I), stirring at 40℃for 60 minutes; then, 6.662g (the amount of which is 10ppm based on the weight of the intermediate I) of a Kathon solution having a weight concentration of 1.51% was added thereto, and the mixture was stirred at 40℃for 300 minutes to obtain a product.
150g of the product is put into a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the bottle mouth is put into a constant temperature box with the temperature of 40+/-0.5 ℃ and is stored for 168 hours, and the sampling content of Kathon is 9.86ppm.
Kesong loss rate= ((10-9.86)/10) ×100% = 1.4%.
For comparison, the experimental results are presented in Table 1.
[ example 6 ]
Firstly, adding hydrogen peroxide, EDTA-4Na and Kathon into a fatty alcohol triethanolamine sulfate intermediate material I, wherein the specific steps are as follows:
10.0Kg of fatty alcohol triethanolamine sulfate intermediate material I (the weight content of anionic active matters in the intermediate material I is 40.39%, the pH value is 7.03) is taken, and 1.45g of hydrogen peroxide with the weight concentration of 27.5% (namely H) is added 2 O 2 40ppm by weight of intermediate I), stirring at 40℃for 60 minutes; then, 10g (equivalent to 0.1% by weight of intermediate I) of EDTA-4Na (calculated as EDTA) was added, and stirred at 40℃for 60 minutes; finally, 6.662g (the dosage is 10ppm of the weight of the intermediate material I) of Kathon solution with the weight concentration of 1.51 percent is added, and the mixture is stirred for 300 minutes at the temperature of 40 ℃ to obtain the product.
150g of the product is put into a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the flask is put into a constant temperature box with the temperature of 40+/-0.5 ℃ and stored for 168 hours, and the sampling content of Kathon is 9.84ppm.
Kesong loss rate= ((10-9.84)/10) ×100% = 1.6%.
For comparison, the experimental results are presented in Table 1.
[ example 7 ]
Firstly, EDTA-4Na is added into fatty alcohol triethanolamine sulfate intermediate material I, then hydrogen peroxide is added, and finally Kathon is added, specifically:
10.0Kg of fatty alcohol triethanolamine sulfate intermediate I (the weight content of anionic active matters in the intermediate I is 40.39 percent, the pH value is 7.03) is taken, 10g of EDTA-4Na (calculated by EDTA) is added (equivalent to 0.1 percent of the weight of the intermediate I), and the mixture is stirred at 40 ℃ for 60 minutes; then, 1.45g of hydrogen peroxide (namely H) with the weight concentration of 27.5 percent is added 2 O 2 40ppm by weight of intermediate I), stirring at 40℃for 60 minutes; finally, 6.662g (the dosage is 10ppm of the weight of the intermediate material I) of Kathon solution with the weight concentration of 1.51 percent is added, and the mixture is stirred for 300 minutes at the temperature of 40 ℃ to obtain the product.
150g of the product is put into a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the flask is put into a constant temperature box with the temperature of 40+/-0.5 ℃ and is stored for 168 hours, and the sampling content of Kathon is 9.94ppm.
Kesong loss rate= ((10-9.94)/10) ×100% =0.6%.
For comparison, the experimental results are presented in Table 1.
[ example 8 ]
The Kathon and EDTA-4a are added into the fatty alcohol triethanolamine sulfate intermediate material I together, and the specific steps are as follows:
10.0Kg of fatty alcohol triethanolamine sulfate intermediate I (the weight content of anionic active matters in the intermediate I is 40.39 percent, the pH value is 7.03), 6.662g of Kathon solution with the weight concentration of 1.51 percent (which is equivalent to 10ppm of the weight of the intermediate I) and 10g of EDTA-4Na (which is calculated by EDTA) are taken, and the mixture is stirred at 40 ℃ for 300 minutes to obtain the product.
150g of the product is put into a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the flask is put into a constant temperature box with the temperature of 40+/-0.5 ℃ for 168 hours, and the content of the Kathon is measured by sampling to be 2.91ppm.
Kesong loss rate= ((10-2.91)/10) ×100% =70.9%.
For comparison, the experimental results are presented in Table 1.
[ comparative example 1 ]
10.0Kg of fatty alcohol triethanolamine sulfate intermediate material I (the weight content of anionic active matters in the intermediate material I is 40.39 percent, the pH value is 7.03) is taken, 6.662g of Kathon solution with the weight concentration of 1.51 percent (which is equivalent to 10ppm of the weight of the intermediate material I) is added, and the mixture is stirred at 40 ℃ for 300 minutes to obtain the product.
150g of the product is put into a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the flask is put into a constant temperature box with the temperature of 40+/-0.5 ℃ and is stored for 168 hours, and then sampling is carried out to measure the Kathon content to be 2.68ppm.
Kesong loss rate= ((10-2.68)/10) ×100% =73.2%.
For comparison, the experimental results are presented in Table 1.
[ comparative example 2 ]
10.0Kg (the content of anionic active matters is 29.87 percent, the pH value is 7.02) of diluted material of the triethanolamine alkyl sulfate salt intermediate material I is taken, 6.662g (equivalent to 10ppm of the weight of the intermediate material I) of Kathon solution with the weight concentration of 1.51 percent is added, and the mixture is stirred at 40 ℃ for 300 minutes to obtain the product.
150g of the product is put into a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the flask is put into a constant temperature box with the temperature of 40+/-0.5 ℃ and is stored for 168 hours, and then sampling is carried out to measure the Kathon content to be 3.19ppm.
Kesong loss rate= ((10-3.19)/10) ×100% =68.1%.
For comparison, the experimental results are presented in Table 1.
[ comparative example 3 ]
10.0Kg of fatty alcohol sodium sulfate diluent (the weight content of anionic active matters in the fatty alcohol sodium sulfate diluent is 29.67 percent, the pH value is 7.04), 6.662g of kathon solution with the weight concentration of 1.51 percent (which is equivalent to 10ppm of the weight of the fatty alcohol sodium sulfate diluent) is added, and the mixture is stirred for 300 minutes at 40 ℃ to obtain the product.
150g of the product is put into a 250ml glass triangular flask, the bottle mouth is plugged by a rubber plug, the flask is put into a constant temperature box with the temperature of 40+/-0.5 ℃ and is stored for 168 hours, and then the sample is taken to measure the Kathon content to be 9.71ppm.
Kesong loss rate= ((10-9.81)/10) ×100% =1.9%.
For comparison, the experimental results are presented in Table 1.
As is evident from comparison of comparative examples 1 and 2, there is no significant unstable Kathon content in the production of sodium alkyl sulfate.
TABLE 1
* : the fatty alcohol sodium sulfate diluent is adopted to replace the fatty alcohol triethanolamine sulfate intermediate material I.
Claims (10)
1. A process for producing a triethanolamine alkyl sulfate surfactant product comprising:
(1) Obtaining alkyl sulfate;
(2) Neutralizing alkyl sulfate with triethanolamine water solution to obtain alkyl sulfate triethanolamine salt intermediate material I;
(3) Mixing the triethanolamine alkyl sulfate intermediate material I with Kathon and hydrogen peroxide;
hydrogen peroxide is used in an amount of H 2 O 2 1-100 ppm of the weight of the triethanolamine alkyl sulfate salt intermediate material I;
the weight of the Kathon accounting for the weight of the fatty alcohol triethanolamine sulfate intermediate material I is more than 0ppm and less than 500 ppm;
the anionic active matter weight content of the triethanolamine alkyl sulfate salt in the product is 30-43%.
2. The process according to claim 1, wherein the alkyl sulfate is an organic material comprising fatty alcohol and SO 3 And (3) carrying out sulfation.
3. The method according to claim 1, wherein the alkyl group is a C8-C18 alkyl group.
4. The production method according to claim 1, wherein the intermediate material I in step (2) has a pH of 6.0 to 8.0.
5. The process according to claim 1, wherein the neutralization temperature in step (2) is 55 to 65 ℃.
6. The production method according to claim 1, wherein the triethanolamine in the triethanolamine aqueous solution in the step (2) is 10 to 23% by weight.
7. The production method according to claim 1, wherein the temperature of the mixing in the step (3) is 10-45 ℃.
8. The process according to claim 1 or 7, wherein the mixing in step (3) takes at least 30 minutes.
9. The triethanolamine alkyl sulfate salt surfactant product obtained by the production method according to any one of claims 1 to 8.
10. Use of a triethanolamine alkyl sulfate surfactant product according to claim 9 as a storage form of triethanolamine alkyl sulfate surfactant.
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| CN117586154A (en) | 2024-02-23 |
| CN115043761A (en) | 2022-09-13 |
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