CN102070496A - Preparation method of alpha-fatty acid methyl ester sulfonate - Google Patents
Preparation method of alpha-fatty acid methyl ester sulfonate Download PDFInfo
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- CN102070496A CN102070496A CN2010106044950A CN201010604495A CN102070496A CN 102070496 A CN102070496 A CN 102070496A CN 2010106044950 A CN2010106044950 A CN 2010106044950A CN 201010604495 A CN201010604495 A CN 201010604495A CN 102070496 A CN102070496 A CN 102070496A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000194 fatty acid Substances 0.000 title abstract 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 21
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 4
- 238000004061 bleaching Methods 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 10
- 238000005187 foaming Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 241000237502 Ostreidae Species 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 235000020636 oyster Nutrition 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 8
- 206010033546 Pallor Diseases 0.000 abstract 2
- 239000006071 cream Substances 0.000 abstract 2
- 238000005086 pumping Methods 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000011552 falling film Substances 0.000 abstract 1
- 229960002163 hydrogen peroxide Drugs 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 description 20
- 239000003921 oil Substances 0.000 description 16
- 238000006386 neutralization reaction Methods 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 159000000000 sodium salts Chemical class 0.000 description 8
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- -1 Laurate methyl (methyl dodecanoate) Chemical compound 0.000 description 4
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical class CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 206010020843 Hyperthermia Diseases 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000036031 hyperthermia Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZABKDTYOFYRFCI-UHFFFAOYSA-N 1-methoxy-1-oxotetradecane-2-sulfonic acid Chemical class CCCCCCCCCCCCC(S(O)(=O)=O)C(=O)OC ZABKDTYOFYRFCI-UHFFFAOYSA-N 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NSIKFNOYIGGILA-UHFFFAOYSA-N [Na].[Na].[K] Chemical class [Na].[Na].[K] NSIKFNOYIGGILA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- IKIGNQHSDISMLY-UHFFFAOYSA-N methyl octadecanoate;2-methyloctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC.CCCCCCCCCCCCCCCCC(C)C(O)=O IKIGNQHSDISMLY-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 239000005060 rubber Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- NPNCUQAIXIQSKQ-UHFFFAOYSA-M sodium;1-methoxy-1-oxotetradecane-2-sulfonate Chemical compound [Na+].CCCCCCCCCCCCC(S([O-])(=O)=O)C(=O)OC NPNCUQAIXIQSKQ-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of alpha-fatty acid methyl ester sulfonate, which comprises the three main steps of sulfonating, blanching and neutralizing, and specifically comprises the following steps: (a) carrying out a sulfonation reaction in a falling film microstructure reactor by using fatty acid methyl ester and sulfur trioxide as raw materials, thereby obtaining alpha-sulfo fatty acid methyl ester; (b) pumping the alpha-sulfo fatty acid methyl ester, oxydol and a methanol solution into the microstructure reactor, and blanching at 30-90 DEG C; and (c) pumping the blanched alpha-sulfo fatty acid methyl ester and an alkali solution into the microstructure reactor to react at 30-90 DEG C so as to obtain a cream white foamed substance, and drying the cream white foamed substance to obtain the powder product alpha-fatty acid methyl ester sulfonate. The method provided by the invention has the advantages of continuous and safe reaction process, light product color, high product quality and the like, and is easy to control the material proportion and reaction temperature.
Description
Technical field
The present invention is applied to the tensio-active agent field, relates to a kind of preparation method of α-Huang Jizhifangsuanjiazhiyan, is used for the alpha-sulfo fatty acid methyl ester that the fatty acid methyl ester sulfonation generates is carried out follow-up bleaching and neutralization preparation fatty acid methyl ester sulfonate.
Background technology
α-Huang Jizhifangsuanjiazhiyan is a kind of anion surfactant of excellent property, and its raw material source is from renewable resources, makes it have excellent biological compatibility and biodegradability and becomes the tensio-active agent raw material of environmental protection.The soil removability of alpha-sulfo fatty acid methyl ester sodium salt and resistance to hard water all are better than Sodium dodecylbenzene sulfonate (LAS) and aliphatic alcohol sulfate (AS), and along with the exhaustion day by day of petroleum resources, it is described as " third generation tensio-active agent " that can replace LAS and AS.In addition, α-Huang Jizhifangsuanjiazhiyan also can be applicable to the industrial circles such as production of plastic working, leather degreasing, silk printing and dyeing, mineral floating and makeup, coating, lubricating oil, rubber.
α-Huang Jizhifangsuanjiazhiyan generally is to generate alpha-sulfo fatty acid methyl ester by fatty acid methyl ester and SO 3 sulfonated reaction, again through bleaching, neutralization, dry making.Wherein bleaching process is the color and luster that reduces alpha-sulfo fatty acid methyl ester by the strong oxidation of hydrogen peroxide, makes the MES product that obtains reach composite required color and luster requirement; N-process is in order to synthesize corresponding salt in the alpha-sulfo fatty acid methyl ester.
Conventional alpha-sulfo fatty acid methyl ester bleaching and N-process segmentation in batch reactor are carried out, because bleaching and a large amount of heat releases of N-process meeting prevent that localized hyperthermia from making disodium salt content increase in the product so must reactant be mixed by the brute force stirring; In addition, thus reaction heat is difficult to discharge and causes the SYNTHETIC OPTICAL WHITNER hydrogen peroxide decomposition that product color is deepened easily.For this reason, the investigator by different technique means in the hope of addressing these problems.Chinese patent CN101074205A adopts rotor knifing shear mixer with alpha-sulfo fatty acid methyl ester and hydrogen peroxide mixed bleach in reactor, use cold wind or normal temperature peak to remove the heat that bleaching produces, add methyl alcohol again and carry out the resterification reaction, bleaching and resterification process need are more than 2 hours; Adopt the method for fractional neutralization also to use rotor knifing shear mixer with mixing of materials, and with cold wind or the normal temperature wind neutralization heat that leaves.This invention has used rotor knifing shear mixer to strengthen mixing of materials, and uses the method for wind heat radiation to obtain the more excellent product of quality, but has also increased the cost and the process cost of device simultaneously.Chinese patent CN101054354A also adds a small amount of modifying agent in bleaching process, though played certain bleaching effect, the adding of modifying agent has also increased productive expense, has increased impurity to product simultaneously, has influenced the quality of product.Alpha-sulfo fatty acid methyl ester elder generation adding methyl alcohol carries out resterification among the Chinese patent CN101759612A, the residence time 30～40min, sulfonic acid behind the resterification is isolated unreacted methanol under the vacuum condition through the interchanger heating in flash tank, bleach through neutralization back p-sulfonic acid sodium salt, the pH value is controlled at 6～6.5, and bleaching time is 6～8 hours.This technology is comparatively complicated, and long reaction time, and energy consumption is higher.The shortcoming of above processing step is: all carry out in the tank reactor at intermittence, can not form the continuous and automatic reaction; Increase heat abstractor or added modifying agent for reaching bleaching effect, all increased production cost; Reaction times, all more than 3 hours, energy consumption was very high.So, explore a good alpha-sulfo fatty acid methyl ester bleaching and a neutral operational path and have positive meaning.
In recent years, little reaction technology had the good control effect in the reaction of the explosion hazard of strong heat release.The mass transfer coefficient of micro-structured reactor can reach 10000m
2/ m
3More than, with respect to 300～600m of conventional tank reactor
2/ m
3The lifting of the order of magnitude has been arranged, reactant moment is mixed, accurately control reaction temperature; Micro-structured reactor can guarantee that reaction is continuous, safety, realizes the industrial production of automatization; In addition, little reaction process is not influenced by scale effect, and lab scale successfully gets final product industry and amplifies, and saves scientific research cost.Thus, the neutralization of alpha-sulfo fatty acid methyl ester is combined with little reaction technology be expected to save production cost, improve the quality of products.
Summary of the invention
The objective of the invention is to develop the preparation method of a continuous and automatic, easy to operate and safe, the reaction times is short, quality product is high a kind of α-Huang Jizhifangsuanjiazhiyan.
Technical scheme of the present invention is: in the popular response device, the danger that the existence of methyl alcohol is blasted easily in resterification and the bleaching process, and in micro passage reaction because conduct heat and mass transfer coefficient very high, under the situation of inlet amount and successive reaction, just can avoid the danger of exploding; In addition, the uniform mixing of material can shorten the reaction times greatly, reduce product color.In the N-process, alpha-sulfo fatty acid methyl ester I and equimolar sodium hydroxide solution (or potassium hydroxide) reaction generate principal product alpha-sulfo fatty acid methyl ester sodium salt II, because conventional mechanical stirring is difficult to make it to mix, this will cause localized hyperthermia and pH value too high, side reaction takes place makes principal product II further change into by product alpha-sulfo fatty acid methyl ester disodium salt III, influence the quality of product, to carry out in the alpha-sulfo fatty acid methyl ester and in micro passage reaction, can improve the mass transfer and the heat transfer efficiency of reaction, reduce the generation of by product III greatly.
Concrete technical scheme of the present invention is: a kind of method for preparing α-Huang Jizhifangsuanjiazhiyan in micro-structured reactor, its concrete steps are as follows: be that raw material carries out sulfonation reaction in the falling liquid film micro-structured reactor with fatty acid methyl ester and sulphur trioxide (a), concrete grammar is with reference to the Chinese patent CN101693678A by inventor's application; (b) alpha-sulfo fatty acid methyl ester, hydrogen peroxide and methanol solution are pumped in the microstructure mixing tank that the passage internal diameter is 0.5～5mm, after connect the microchannel reaction pipe that internal diameter is 0.5～6mm, temperature of reaction is bleached between 30～90 ℃; (c) alpha-sulfo fatty acid methyl ester, the alkaline solution after will bleaching is pumped in the microstructure mixing tank that the passage internal diameter is 50～3000 μ m, after connect the microchannel reaction pipe that internal diameter is 0.5～6mm, temperature of reaction is between 30～90 ℃, obtain the oyster white foaming material, the powdery product α-Huang Jizhifangsuanjiazhiyan that can obtain after the oven dry.
It is RC (HSO that wherein said alpha-sulfo fatty acid methyl ester is at least chemical formula
3) COOCH
3In a kind of, wherein R is C
4To C
20Alkyl, its purity is between 50%～90%.
Among the present invention, when the factor that influences alpha-sulfo fatty acid methyl ester bleaching and neutralization has the mass ratio of hydrogen peroxide and alpha-sulfo fatty acid methyl ester mass ratio, hydrogen peroxide and methyl alcohol, hydrogen peroxide concentration, bleaching the internal diameter of microstructure mixing tank, microchannel react pipe internal diameter, bleaching temperature and time, alkaline concentration, in and the time microstructure mixing tank internal diameter, neutral temperature and time.Through preferred reaction conditions, preferred hydrogen peroxide and usage quantity account for 5%～30% of alpha-sulfo fatty acid methyl ester quality, be preferably 5%～15% again; Preferred hydrogen peroxide: the mass ratio of methyl alcohol is 1: 2～2: 1; The mass concentration of preferred hydrogen peroxide is 20%～60%, is preferably 25%～50% again; The passage internal diameter of the microstructure mixing tank of preferred bleaching usefulness is 0.5～2mm; The internal diameter of preferred microchannel reaction pipe is 0.5～2mm; Preferred bleaching temperature is 50～80 ℃; The residence time of reactant in the microstructure mixing tank is 10～500ms in the preferred steps (b), is preferably 50～400ms; The residence time of reactant in microchannel reaction pipe is 5～20min, is preferably 5～15min again; The passage internal diameter of the microstructure mixing tank of preferred neutralization usefulness is for being 50～2000 μ m; Preferred neutral temperature is 40～80 ℃; The residence time of reactant in the microstructure mixing tank is 10～200ms in the preferred steps (c), is preferably 50～200ms; The residence time of reactant in microchannel reaction pipe is 5～20min, is preferably 5～15min again.Obtain pulverous alpha-sulfo fatty acid methyl ester sodium salt after the product oven dry that the present invention obtains, survey its free oil content, single sodium salt content and disodium salt content.Alkaline solution is a kind of in sodium hydroxide or the potassium hydroxide in the step (c); Its mass concentration is between 5%～50%; The add-on of alkaline solution makes the pH of reaction product between 6～8 for the flow velocity of control alkaline solution in the step (c).
Beneficial effect:
Provided by the inventionly utilize micro-structured reactor that alpha-sulfo fatty acid methyl ester is bleached and the method for preparing α-Huang Jizhifangsuanjiazhiyan that neutralizes has been simplified traditional technology, the reaction times, conventional shortened more than 3 hours greatly in 30 minutes; Reaction is continuous, and there is not explosion hazard in operational safety; Product α-Huang Jizhifangsuanjiazhiyan list sodium (potassium) the salts contg height that finally obtains, disodium (potassium) salts contg is low, and color and luster is conventional shallow.Generally speaking, the present invention has easy to operate and safe, reaction times weak point, serialization production, quality product advantages of higher.
Description of drawings
Figure 1 shows that α-Huang Jizhifangsuanjiazhiyan preparation technology schema;
Figure 2 shows that in the micro passage reaction alpha-sulfo fatty acid methyl ester bleaching and in and schema, 1 is water bath with thermostatic control, temperature is about 50 ℃, makes alpha-sulfo fatty acid methyl ester keep liquid; 2 is alpha-sulfo fatty acid methyl ester; 3 is hydrogen peroxide/methanol solution; 4,5,10 is the miniflow constant flow pump; 6,11 is the microstructure mixing tank; 7,12 are microchannel reaction pipe; 8 are water bath with thermostatic control, the control bleaching temperature; 9 is alkaline solution; 13 are water bath with thermostatic control, the control neutral temperature; 14 is sample collection; The thick line section is the heating pipeline, guarantees alpha-sulfo fatty acid methyl ester charging smoothness.
Embodiment
The raw material explanation:
The raw material alpha-sulfo fatty acid methyl ester that the present invention uses obtains (concrete grammar is by Chinese patent CN101693678A) by fatty acid methyl ester and sulphur trioxide reaction, Laurate methyl (methyl dodecanoate), myristic acid methyl esters (methyl tetradecanoate), Uniphat A60 (methyl palmitate), the methyl stearate (Methyl Stearate) that is provided by the safe chemical industry of Shanghai promise company limited is provided fatty acid methyl ester, iodine number approaches 0, and content is more than 99%; The hydrogenation plam oil that is provided by ancient cooking vessel chemistry company limited in the Jiangsu is made hydrogenation plam oil methyl esters through what transesterification reaction made, and iodine number is 0.4, and wherein containing lipid acid C chain is two kinds of fatty acid methyl esters of C16 and C18, and W (C16): W (C18)=72: 28.
Embodiment 1:
The flow of alpha-sulfo Laurate methyl is 2ml/min, the hydrogen peroxide consumption is 10% of an alpha-sulfo fatty acid methyl ester quality, hydrogen peroxide: methyl alcohol (wt%) is 1: 1 (wherein the mass concentration of hydrogen peroxide is 30%), T type threeway microstructure mixing tank is used in bleaching, the passage internal diameter is 2mm, the residence time is 400ms in the micro mixer, after to connect microchannel reaction bore be 2mm, bleaching temperature is 60 ℃, reaction time is 10min, use the sodium hydroxide solution of 20% massfraction, it is 7 that dominant discharge makes product pH value, and T type silica micro structure mixing tank is used in neutralization, the passage internal diameter is 100 μ m, the residence time is 50ms in the micro mixer, after to connect microchannel reaction bore be 2mm, neutral temperature is 50 ℃, reaction time is 5min, according to schema reaction shown in Figure 2, obtain white foaming shape product, obtain alpha-sulfo Laurate methyl sodium salt after the oven dry, be white powder, free oil content 5.2%, single sodium salt content are 82.4%, disodium salt content 0.6%.
Embodiment 2:
The flow of alpha-sulfo myristic acid methyl esters is 1.5ml/min, the hydrogen peroxide consumption is 15% of an alpha-sulfo fatty acid methyl ester quality, hydrogen peroxide: methyl alcohol (wt%) is 1: 1.5 (wherein the mass concentration of hydrogen peroxide is 50%), T type threeway microstructure mixing tank is used in bleaching, the passage internal diameter is 0.58mm, the residence time is 250ms in the micro mixer, after to connect microchannel reaction bore be 1mm, bleaching temperature is 65 ℃, reaction time is 15min, use the sodium hydroxide solution of 15% massfraction, it is 6.5 that dominant discharge makes product pH value, and intersection toe type silica micro structure mixing tank is used in neutralization, the passage internal diameter is 150 μ m, the residence time is 150ms in the micro mixer, after to connect microchannel reaction pipe 2 internal diameters be 1mm, neutral temperature is 45 ℃, reaction time is 10min, according to schema reaction shown in Figure 2, obtain white foaming shape product, obtain alpha-sulfo myristic acid methyl ester sodium salt after the oven dry, be pale yellow powder, free oil content 6%, single sodium salt content are 78.3%, disodium salt content 2.1%.
Embodiment 3:
The flow of alpha-sulfo Uniphat A60 is 2.5ml/min, the hydrogen peroxide consumption is 20% of an alpha-sulfo fatty acid methyl ester quality, hydrogen peroxide: methyl alcohol (wt%) is 1.5: 1 (wherein the mass concentration of hydrogen peroxide is 50%), T type threeway microstructure mixing tank is used in bleaching, the passage internal diameter is 0.58mm, the residence time is 180ms in the micro mixer, after to connect microchannel reaction bore be 2mm, bleaching temperature is 70 ℃, reaction time is 8min, use the potassium hydroxide solution of 30% massfraction, it is 8 that dominant discharge makes product pH value, and T type threeway microstructure mixing tank is used in neutralization, the passage internal diameter is 580 μ m, the residence time is 190ms in the micro mixer, after to connect microchannel reaction bore be 2mm, neutral temperature is 40 ℃, reaction time is 7min, according to schema reaction shown in Figure 2, obtain the product of white foaming shape, obtain alpha-sulfo Uniphat A60 sylvite after the oven dry, be white powder, free oil content 4.1%, monopotassium salt content are 83.3%, di-potassium content 0.6%.
Embodiment 4:
The flow of α-Huang Jiyingzhisuanjiazhi is 3ml/min, the hydrogen peroxide consumption is 25% of an alpha-sulfo fatty acid methyl ester quality, hydrogen peroxide: methyl alcohol (wt%) is 1: 1 (wherein the mass concentration of hydrogen peroxide is 25%), T type threeway microstructure mixing tank is used in bleaching, the passage internal diameter is 2mm, the residence time is 300ms in the micro mixer, after to connect microchannel reaction pipe 1 internal diameter be 2mm, bleaching temperature is 60 ℃, reaction time is 12min, use the potassium hydroxide solution of 20% massfraction, it is 7.5 that dominant discharge makes product pH value, and T type threeway microstructure mixing tank is used in neutralization, the passage internal diameter is 2000 μ m, the residence time is 350ms in the micro mixer, after to connect microchannel reaction pipe 2 internal diameters be 2mm, neutral temperature is 50 ℃, reaction time is 11min, according to schema reaction shown in Figure 2, obtain white foaming shape product, obtain α-Huang Jiyingzhisuanjiazhi sylvite after the oven dry, be pale yellow powder, free oil content 5.4%, monopotassium salt content are 82.8%, di-potassium content 1.2%.
Embodiment 5:
The flow of alpha-sulfo hydrogenation plam oil methyl esters is 3.5ml/min, the hydrogen peroxide consumption is 12% of an alpha-sulfo fatty acid methyl ester quality, hydrogen peroxide: methyl alcohol (wt%) is 1: 1 (wherein the mass concentration of hydrogen peroxide is 30%), T type threeway microstructure mixing tank is used in bleaching, the passage internal diameter is 2mm, the residence time is 280ms in the micro mixer, after to connect microchannel reaction pipe 1 internal diameter be 3mm, bleaching temperature is 65 ℃, reaction time is 7min, use the sodium hydroxide solution of 30% massfraction, it is 7 that dominant discharge makes product pH value, and T type threeway microstructure mixing tank is used in neutralization, the passage internal diameter is 580 μ m, the residence time is 120ms in the micro mixer, after to connect microchannel reaction bore be 0.5mm, neutral temperature is 55 ℃, reaction time is 12min, according to schema reaction shown in Figure 2, obtain white foaming shape product, obtain alpha-sulfo hydrogenation plam oil methyl ester sodium salt after the oven dry, be white powder, free oil content 6.1%, monopotassium salt content are 79.6%, di-potassium content 3.2%.
Embodiment 6:
The flow of alpha-sulfo hydrogenation plam oil methyl esters is 2ml/min, the hydrogen peroxide consumption is 9% of an alpha-sulfo fatty acid methyl ester quality, hydrogen peroxide: methyl alcohol (wt%) is 1: 1.2 (wherein the mass concentration of hydrogen peroxide is 40%), T type threeway microstructure mixing tank is used in bleaching, the passage internal diameter is 2mm, the residence time is 400ms in the micro mixer, after to connect microchannel reaction bore be 1mm, bleaching temperature is 60 ℃, reaction time is 10min, use the sodium hydroxide solution of 20% massfraction, it is 7.5 that dominant discharge makes product pH value, and intersection toe type silica micro structure mixing tank is used in neutralization, the passage internal diameter is 150 μ m, the residence time is 100ms in the micro mixer, after to connect microchannel reaction bore be 2mm, neutral temperature is 45 ℃, reaction time is 6min, according to schema reaction shown in Figure 1, obtain white foaming shape product, obtain alpha-sulfo hydrogenation plam oil methyl ester sodium salt after the oven dry, be white powder, free oil content 4.1%, single sodium salt content are 83.8%, disodium salt content 1.2%.
Embodiment 7:
The flow of alpha-sulfo hydrogenation plam oil methyl esters is 5ml/min, the hydrogen peroxide consumption is 8% of an alpha-sulfo fatty acid methyl ester quality, hydrogen peroxide: methyl alcohol (wt%) is 1.2: 1 (wherein the mass concentration of hydrogen peroxide is 30%), T type threeway microstructure mixing tank is used in bleaching, the passage internal diameter is 2mm, the residence time is 180ms in the micro mixer, after to connect microchannel reaction bore be 2mm, bleaching temperature is 65 ℃, reaction time is 13min, use the sodium hydroxide solution of 40% massfraction, dominant discharge product pH value is 7, and T type silica micro structure mixing tank is used in neutralization, the passage internal diameter is 100 μ m, the residence time is 18ms in the micro mixer, after to connect microchannel reaction bore be 2mm, neutral temperature is 50 ℃, reaction time is 11min, according to schema reaction shown in Figure 1, obtain white foaming shape product, obtain alpha-sulfo hydrogenation plam oil methyl ester sodium salt after the oven dry, be flaxen powder, free oil content 6.9%, single sodium salt content are 77.8%, disodium salt content 3.2%.
Claims (7)
1. the preparation method of a α-Huang Jizhifangsuanjiazhiyan, its concrete steps are as follows: be that raw material carries out sulfonation reaction and makes alpha-sulfo fatty acid methyl ester in the falling liquid film micro-structured reactor with fatty acid methyl ester and sulphur trioxide (a); (b) alpha-sulfo fatty acid methyl ester, hydrogen peroxide and methanol solution are pumped in the microstructure mixing tank that the passage internal diameter is 0.5～5mm, after connect the microchannel reaction pipe that internal diameter is 0.5～6mm, temperature of reaction is bleached between 30～90 ℃; (c) alpha-sulfo fatty acid methyl ester, the alkaline solution after will bleaching is pumped in the microstructure mixing tank that the passage internal diameter is 50～3000 μ m, after connect the microchannel reaction pipe that internal diameter is 0.5～6mm, temperature of reaction is between 30～90 ℃, obtain the oyster white foaming material, the powdery product α-Huang Jizhifangsuanjiazhiyan that can obtain after the oven dry.
2. the method for claim 1 is characterized in that it is a kind of among RC (HSO3) COOCH3 that described alpha-sulfo fatty acid methyl ester is at least chemical formula, and wherein R is the alkyl of C4 to C20.
3. the method for claim 1 is characterized in that the usage quantity of hydrogen peroxide in the step (b) accounts for 5%～30% of alpha-sulfo fatty acid methyl ester quality, and the mass ratio of hydrogen peroxide and methyl alcohol is between 1: 2～2: 1; The mass concentration of hydrogen peroxide is between 20%～60%.
4. the method for claim 1 is characterized in that temperature of reaction is between 50～80 ℃ in the step (b); The residence time of reactant in the microstructure mixing tank is between 10～500ms; Reactant reacts the residence time of pipe between 5～20min in the microchannel.
5. the method for claim 1 is characterized in that alkaline solution in the step (c) is a kind of in sodium hydroxide or the potassium hydroxide; Its mass concentration is between 5%～50%.
6. the method for claim 1 is characterized in that the flow velocity of control alkaline solution in the step (c) makes the pH of reaction product between 6～8.
7. the method for claim 1 is characterized in that temperature of reaction is between 40～80 ℃ in the step (c); The residence time of reactant in the microstructure mixing tank is between 10～200ms; Reactant reacts the residence time of pipe between 5～20min in the microchannel.
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| CN103467345A (en) * | 2013-09-18 | 2013-12-25 | 中国林业科学研究院林产化学工业研究所 | Lacquer-wax fatty acid methyl ester sulfonate and preparation method thereof |
| CN106744760A (en) * | 2016-05-03 | 2017-05-31 | 湖北大峪口化工有限责任公司 | The sedimentation agent and method of solids in rapid subsidence phosphoric acid by wet process |
| CN109574882A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | A kind of preparation method of p-methyl benzenesulfonic acid |
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| CN101508660A (en) * | 2009-03-31 | 2009-08-19 | 南京工业大学 | Method of preparing alpha-sulphonic acid fatty acid ester |
| CN101693678A (en) * | 2009-10-27 | 2010-04-14 | 南京工业大学 | Process for preparing alpha-sulfo fatty acid methyl ester sodium salt |
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| CN101508660A (en) * | 2009-03-31 | 2009-08-19 | 南京工业大学 | Method of preparing alpha-sulphonic acid fatty acid ester |
| CN101693678A (en) * | 2009-10-27 | 2010-04-14 | 南京工业大学 | Process for preparing alpha-sulfo fatty acid methyl ester sodium salt |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103467345A (en) * | 2013-09-18 | 2013-12-25 | 中国林业科学研究院林产化学工业研究所 | Lacquer-wax fatty acid methyl ester sulfonate and preparation method thereof |
| CN106744760A (en) * | 2016-05-03 | 2017-05-31 | 湖北大峪口化工有限责任公司 | The sedimentation agent and method of solids in rapid subsidence phosphoric acid by wet process |
| CN109574882A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | A kind of preparation method of p-methyl benzenesulfonic acid |
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