Background technology
At present in the articles for washing; It is to be main tensio-active agent with MES that a kind of articles for washing is arranged, and all disclosing with MES like Chinese patent document CN1037191C, Chinese patent document CN100543120C, Chinese patent document CN101445768A, Chinese patent document CN101671605A etc. is the articles for washing of main tensio-active agent.CN1037191C is that paste detergent is used for decontamination, and CN100543120C is a laundry liquid for washing machine, and CN101445768A is that liquid washing agent is used to wash industry, and CN101671605A also is a kind of liquid washing agent that is used for fabric.These documents are all not mentioned to be can be used in the perfumed soap, though also there is the hand washing of proposition not hinder hand, has the advantages of good skin consistency,, contain the carcinogenic substance Methylsulfate in the existing research expression MES, human body there is certain harm.Therefore, this type of articles for washing not only is not suitable for washing by hand, in the perfumed soap that MES can not add as tensio-active agent directly with human body contacts.
Chinese patent document CN101003771A is a kind of " laundry powdered soap with no phosphor and benzene " that the applicant applies for; Its tensio-active agent is a fatty-acid ethyl ester sulphonate, also comprises soap base, fatty diglycollic amide, AEO, sodium sulfate and water glass etc.This laundry powdered soap only is applicable to washing clothes etc., is not suitable for the shower and the beauty treatment of human body.
Traditional perfumed soap is basal component with the soap base.Soap base (soap) is meant and contains that moisture is about 18% to 38%, the pure matter molten soap of fatty hydrochlorate about 60% to 80%, and claim clean soap (good soap) again, it is work piece of making perfumed soap or soap, and soap wherein belongs to AS.The raw material of soap base is grease and alkali lye, and the method for grease being processed soap base has two kinds, and a kind of is fat saponification method (abbreviation saponification method), and another kind is a neutralisation.
Saponification method is divided into cauldron saponification method and continuous saponification method again.The cauldron saponification method is the reaction that grease and alkali lye are taken place mainly to generate under heating state for soap (sodium soap, lipid acid potassium or lipid acid ammonium) and glycerine; When greasy transformation efficiency (also claiming saponification degree) reaches 95% to 98%; Free alkali was less than 0.5% o'clock; Saponification reaction is accomplished, and the material after the saponification is called soap glue.In soap glue, add ionogen (using sodium-chlor usually) after the saponification reaction and saltout, separate out (being called grained soap) and make soap become solid, thereby separate with water, glycerine, impurity; After saltouing, form soap base (clean soap), grain soap (containing the more soap of ionogen), soap stock (massfraction is lower than 40% soap lye, wherein contains more impurity) and waste liquid (mainly being G & W) etc. are mutually.Then resulting grained soap being carried out alkali analyses; Just grained soap is added water boil, add excessive sodium hydrate alkali lye again and handle, make a small amount of grease that is present in the grained soap that is left after the saponification reaction first time fully saponified; Standing demix again, upper materials is the soap base work in-process.Again the soap base work in-process are put in order, also promptly adjusted soap in the soap base, power and water is separated the ratio between the matter three, and soap base is fully separated with soap stock; During arrangement, replenish salt solution, alkali lye or water as required, make final soap base reach certain standard; The massfraction of its each composition (also being mass percent) is: soap 60% to 63%, and glycerine is about 0.2%, unsaponifiables about 0.5%; Sodium-chlor 0.3% to 0.7%, free alkali 0.1% to 0.3%, moisture about 35%.
The continuous saponification ratio juris is basic similar with the cauldron saponification method; Use morely in the world and be alpha-acetol's Laval continuous saponification method (claiming centrifugal purification continuous saponification method again); The used device of this method is totally-enclosed, full-automatic system, is constituted jointly by the device of saponification, washing and three workshop sections of arrangement.In the saponification section, because charging is to have the great amount of fat hydrochlorate to exist in continuously feeding and the saponification column all the time, as far as initiate material; Saponification reaction is 80% beginning from saponification degree all the time, also is that grease and alkali lye one get into saponification column, can disperse equably; Accelerated the speed of saponification reaction greatly; When reacted saponification liquor left cat head, saponification degree can reach 99.5%, and free alkali is merely about 0.2%.Because saponification column is a totally-enclosed system, saponification temperature can be brought up to 125 ℃, is 62% soap base thereby not only can produce fatty hydrochlorate, can also produce fatty hydrochlorate 72% to the soap base more than 73%.At washing section, generally carry out 2 to 4 washings, be example with 2 washings; Saponification liquor gets in the first step washing mixing tank, mixes for the brinish washings with the staple from second stage whizzer, and makes soap in the saponification liquor become solid and quilt is separated out; Glycerine then is present in the washings, and the material after the washing is sent into and carried out solid-liquid separation in the first step whizzer, the solid after telling waste liquid and saltouing; Waste liquid is used to reclaim glycerine, and the solid after saltouing then gets into second mixing tank, gets into the soap stock that also has salt solution and sent here by the arrangement section of second mixing tank simultaneously; Send into after mixing and carry out solid-liquid separation in the whizzer of the second stage; Tell after further saltouing solid and as the liquid of washings, washings is delivered to first step washing mixing tank, the solid after saltouing is sent into the arrangement tower.Solid after saltouing with after ionogen mixes, forms soap base and soap stock two mutually in the arrangement tower, material system entering third stage whizzer separates then, and the gained soap base is imported moulding Workshop Production washing soap or perfumed soap, and soap stock is sent washing section back to.
It is simpler than fat saponification method that neutralisation prepares soap base, and it is to be lipid acid and glycerine with fat hydrolysis earlier, and then with alkali lipid acid is neutralized into soap; In lipid acid is carried out and the time because the existence of no glycerine need not saltoutd; Alkali such as analyses at operation, borrows the pressure in the tower, and the soap base after the neutralization directly sprays in the moisture eliminator of normal pressure or decompression; If in the time add 50% high alkali liquid, can obtain the soap massfraction and be 78% to 80% soap base, can directly be used to make perfumed soap after the cooling.
For traditional perfumed soap, wherein except containing soap base (activeconstituents is a soap), also added such as additives such as filler, greasiness agent, sterilant, spices, oxidation inhibitor, sequestrants, to improve the performance of perfumed soap.Added filler is in order to improve the transparency of perfumed soap, to cover the additive that color added of raw material.Filler commonly used has: white titanium pigment and white dyes; The main effect of white titanium pigment wherein is the white that increases perfumed soap, reduces transparency, and general add-on is 0.025% to 0.20%; White dyes can absorb the UV-light in the daylight; Complementary with gold-tinted, have whitening effect, add-on is no more than 0.20% usually.Customary fillers also has dyestuff and pigment, to reach the purpose of adjustment perfumed soap color.Greasiness agent commonly used can be used separately by Triple Pressed Stearic Acid, cocinic acid, phosphatide, yolk, paraffin etc., also can mix use, and add-on is generally 1.0% to 5.0%.Because the alkali content of the soap base in the perfumed soap is higher, and skin is had degreasing property, pungency is bigger, add the greasiness agent help in the alkalescence of perfumed soap, reduce spinoff, wash back greasiness agent and stay skin surface and make skin moisturizing smooth.Sterilant commonly used has thiuram, SPC-D, and add-on is 0.5% to 1.0%, and the herbal medicine that also can select sterilization to dispel smelly replaces sterilant.Essence commonly used has: floral type, fruit flavour type, scent type, sandalwood type etc., and add-on is 10.% to 2.5%, essence both can have been covered the smell of soap base raw material, can make perfumed soap distribute pure and fresh pleasant fragrance again.Oxidation inhibitor commonly used has bubble flower alkali (consumption is 10.% to 1.5%), 2, and the 6-di-t-butyl is to sylvan (consumption is 0.05% to 0.1%); Oxidation inhibitor can stop the unsaturated fatty acids that contains in the perfumed soap raw material by oxidations such as oxygen, light, mikrobes, produces phenomenon such as become sour.Sequestrant commonly used is EDTA, and general addition is 0.1% to 0.2%, can stop the trace metal of bringing in the perfumed soap soap base, to avoid like the autocatalytically oxidation to soap body such as copper, iron.
The content standard of soap that is used to make neat soap or the soap flakes of perfumed soap is about 80%; Contain moisture 10.5% to 12.5%; Because the soap base water cut is higher; Therefore need the content of drying and dehydrating to required soap, the various raw materials that will make perfumed soap then mix according to prescription, be used as again homogenization installation refining plodder extruding, disperse and shearing and/or as the grinding of the roll grinding machine of homogenization installation; Make the crystal formation major part of perfumed soap change the β phase into, and obtain hard, the fizzy application performance of quality.Soap flakes or the neat soap that will pass through homogenizing processed the bar shaped soap of certain sectional area through vacuum plodder, also is soap bar is taken out the bubble that degass in vacuum plodder after, to be extruded moulding.Last soap bar gets in the dicer, by blade soap bar is cut into bulk continuously, and the soap blank after will cutting again is pressed into the shape of regulation in die, and extrudes decorative pattern or brand mark.
For increasing perfumed soap hardness, also add small amounts of silicate or talcum powder in traditional perfumed soap as filler, life-time service can cause water drain to stop up and soil compaction.Because fatty acid calcium and fatty acid magnesium are water insoluble, so when in running into water, containing certain calcium and mg ion, the use perfumed soap can form calcium soap and magnesium soap is deposited on health, the washbowl, is difficult for removing.In addition, though perfumed soap after adding the greasiness agent, help in the alkalescence of perfumed soap, can not eliminate alkalescence, skin still can not use perfumed soap to the alkali allergy sufferers.
Related per-cent is if no special indicating is mass percent in the above-mentioned description to background technology.
Embodiment
(perfumed soap of embodiment 1, fatty acid ethyl ester sulfonate)
The raw material of the perfumed soap of present embodiment comprises:
(1) soap base 77g, fatty acids sodium 80wt% wherein, moisture 18wt%, the pH value of soap base is 10;
(2) the mixture 10g of fatty acid ethyl ester sulfonate;
(3) the carbon atom number is 18 fatty diglycollic amide 5g in the carbochain;
(4) USP Kosher 6g;
(5) spices 0.9g, what present embodiment adopted is face powder;
(6) essence 0.9g, this essence can adopt various essence such as nerolux perfume compound, lemon flavour, rose compound, jasmine flower essence, vanilla according to client's needs, and what present embodiment adopted is nerolux perfume compound;
(7) sanitas 0.1g, what present embodiment adopted is triumphant loose 515 (Shanghai light industry Research Institute);
(8) sterilant 0.1g, what present embodiment adopted is Hua Ke-98 (activeconstituents is an isothiazolones).
The mixture of above-mentioned fatty acid ethyl ester sulfonate makes through the method for the mixture of the powdery fatty acids ethyl ester sodium sulfonate of the embodiment 8 described preparations of Chinese invention patent document CN100469430C; In this mixture, fatty-acid ethyl ester sulphonate 93 weight parts, fatty acid sulfonate 3 weight parts; Vitriol 2 weight parts; Fatty-acid ethyl ester 1 weight part, sulfovinate 1 weight part, water 5 weight parts.The pH value of the mixture of this fatty acid ethyl ester sulfonate is 4.5.
The main raw material of the mixture of above-mentioned fatty acid ethyl ester sulfonate is that the carbon atom number of the carbochain of iodine number >=1 is 12 to 18 saturated straight chain fatty-acid ethyl ester and sulphur trioxide; Operate according to the preparation process of mixture of the fatty acid ethyl ester sulfonate among the Chinese invention patent document CN100469430C by these two kinds of main raw materials, that is wear out, extract, can obtain with the alkali metal cpd reaction again the mixture of above-mentioned fatty acid ethyl ester sulfonate by hydrogen peroxide bleaching, through organic extractant through sulfonation reaction, through ethanol.The carbon atom number of the carbochain of described iodine number >=1 is that (for example be preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate or Stearic ethyl stearate, content is >=99wt%) is obtained by commercially available for 12 to 18 saturated straight chain fatty-acid ethyl ester.
Method by the perfumed soap of the fatty acid ethyl ester sulfonate of the feedstock production present embodiment of above-mentioned perfumed soap is following: under indoor environment temperature; According to said ratio each raw materials mix stirring is obtained mixture; Grind through three-roll grinder then, again abrasive material is extruded the plodder extrusion molding through vacuum, become soap bar as homogenization installation; Again soap bar is printed cutting block forming, the opening for feed that the scrap stock that downcut carry back vacuum to extrude plodder is reused.Through after the assay was approved, packing is dispatched from the factory through the perfumed soap that is printed as type.
The pH value of gained perfumed soap is 7.The main ingredient of this perfumed soap is: sodium soap 61.6g, fatty-acid ethyl ester sodium sulfonate 8.86g, fatty diglycollic amide 5g, USP Kosher 6g, water 14.34g, spices 0.9g, essence 0.9g, sanitas 0.1g, sterilant 0.1g.The gross weight of every perfumed soap is 100g, and the weight of main ingredient wherein is 96.9g.
(embodiment 2)
The rest part of present embodiment is identical with embodiment 1, and difference is:
The main raw material of mixture of the fatty acid ethyl ester sulfonate in the raw material of preparation perfumed soap is that iodine number is that the carbon atom number of 0.1 carbochain is 12 to 18 saturated straight chain fatty-acid ethyl ester and sulphur trioxide; Operate according to the preparation process of mixture of the fatty acid ethyl ester sulfonate among the Chinese invention patent document CN100469430C by these two kinds of main raw materials, that is wear out, extract, can obtain with the alkali metal cpd reaction again the mixture of above-mentioned fatty acid ethyl ester sulfonate by hydrogen peroxide bleaching, through organic extractant through sulfonation reaction, through ethanol.Described iodine number is that the carbon atom number of 0.1 carbochain be 12 to 18 saturated straight chain fatty-acid ethyl ester by the carbon atom number of the carbochain of commercially available iodine number >=1 is that 12 to 18 saturated straight chain fatty-acid ethyl ester (for example is preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate or Stearic ethyl stearate; Content is >=99wt%) through behind the following catalytic hydrogenation reaction, makes through following distillation decoloration again.
With the carbon atom number of the carbochain of commercially available iodine number >=1 is that 12 to 18 saturated straight chain fatty-acid ethyl ester is (hereinafter to be referred as fatty-acid ethyl ester; Be preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate, Stearic ethyl stearate or both, three or four mixture between them) and hydrogen input well heater in; With after the heater heats to 170 ℃; The materials pump pumps into the fatty acid methyl ester of liquid state in the fixed-bed type hydrofining reactor that hydrogenation catalyst is housed together with hydrogen, flows through hydrogenation catalyst from top to bottom.The bulk density of said hydrogenation catalyst is every cubic centimetre 0.96 gram, and the reaction bed aspect ratio is 10.Reaction conditions is: pressure 3.0~6.0Mpa, hydrogen-oil ratio are 300~500, and the weight space velocity of fatty-acid ethyl ester is 0.3 h
-1Hydrogen flows through hydrogenation catalyst in company with the fatty-acid ethyl ester of liquid state, thus make carbon-carbon double bond or the carbon carbon triple bond of the unsaturated molecule in the fatty-acid ethyl ester material under the katalysis of hydrogenation catalyst with hydrogen generation addition reaction and saturated.
After flowing out the fixed-bed type hydrofining reactor through the fatty-acid ethyl ester of hydrogenation reaction, isolate hydrogen through HP separator and light pressure separator successively earlier, be admitted to the distillation tower distillation decoloration again, obtain water white iodine number and be 0.1 fatty-acid ethyl ester.
Above-mentioned hydrogenation catalyst comprises carrier S iO
2-Al
2O
3, active ingredient and auxiliary agent.
Said active ingredient comprises Mo, Ti, Zr and Ni, and each active ingredient is respectively in the per-cent that oxide compound accounts for the hydrogenation catalyst gross weight:
MoO
3 10wt%,
TiO
2 10wt%,
ZrO
2 10wt%,
NiO 20wt%。
Said auxiliary agent is a rare earth lanthanum salt, accounts for the 3wt% of hydrogenation catalyst gross weight in oxide compound.
Described hydrogenization catalyst preparation method is: with SiO
2-Al
2O
3Carrier is earlier with the aqueous solution dipping of the molybdenum salt, titanium salt, zirconates and the nickel salt that contain solubility, and then with the lanthanum salt brine solution dipping that contains solubility, follows dry 12h under 140 ℃ temperature, obtains at 550 ℃ roasting temperature 4h again.
(embodiment 3)
The preparation method of present embodiment is identical with embodiment 1, and difference is:
Raw material:
Soap base 78g, fatty acids sodium 78wt% wherein, moisture 20wt%, the pH value of soap base is 9;
The mixture 9g of fatty acid ethyl ester sulfonate; The mixture of this fatty acid ethyl ester sulfonate can be through Chinese invention patent document CN100469430C the method for mixture of granular fatty acids ethyl ester sodium sulfonate of embodiment 7 described preparations make; Fatty-acid ethyl ester sulphonate 93 weight parts wherein, fatty acid sulfonate 3 weight parts, vitriol 2 weight parts; Fatty-acid ethyl ester 1 weight part; Sulfovinate 1 weight part, water 15 weight parts, the pH value of the mixture of this fatty acid ethyl ester sulfonate is 5;
Carbonatoms is 16 saturated straight chain fatty diglycollic amide 7g in the carbochain;
USP Kosher 4g;
Spices 1g, what present embodiment adopted is essential oil;
Essence 0.8g, what present embodiment adopted is lemon flavour;
Sanitas 0.1g, what present embodiment adopted is triumphant loose 515 (Shanghai light industry Research Institute);
Sterilant 0.1g, what present embodiment adopted is the general liter of Sha (active ingredient is an isothiazolinone).
The main raw material of the mixture of above-mentioned fatty acid ethyl ester sulfonate is that the carbon atom number is 12 to 18 saturated straight chain fatty-acid ethyl ester in the carbochain of iodine number >=1; With this saturated straight chain fatty-acid ethyl ester and sulphur trioxide is main raw material, can obtain the mixture of above-mentioned fatty acid ethyl ester sulfonate again according to the preparation process of mixture operation of the fatty acid ethyl ester sulfonate among the Chinese invention patent document CN100469430C.The carbon atom number is that (for example be preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate or Stearic ethyl stearate, content is >=99wt%) is obtained by commercially available for 12 to 18 saturated straight chain fatty-acid ethyl ester in the carbochain of this iodine number >=1.
The pH value of gained perfumed soap is 7.The main ingredient of this perfumed soap is: sodium soap 60.84g, fatty-acid ethyl ester sodium sulfonate 7.28g, fatty diglycollic amide 7g; USP Kosher 4g; Water 16.73g, spices 1g; Essence 0.8g; Sanitas 0.1g; Sterilant 0.1g.The gross weight of every perfumed soap is 100g, and the weight of main ingredient wherein is 97.85g.
(embodiment 4)
The rest part of present embodiment is identical with embodiment 3, and difference is:
The main raw material of mixture of the fatty acid ethyl ester sulfonate in the raw material of preparation perfumed soap is that iodine number is that the carbon atom number of 0.05 carbochain is 12 to 18 saturated straight chain fatty-acid ethyl ester and sulphur trioxide; Operate according to the preparation process of mixture of the fatty acid ethyl ester sulfonate among the Chinese invention patent document CN100469430C by these two kinds of main raw materials, that is wear out, extract, can obtain with the alkali metal cpd reaction again the mixture of above-mentioned fatty acid ethyl ester sulfonate by hydrogen peroxide bleaching, through organic extractant through sulfonation reaction, through ethanol.Described iodine number is that the carbon atom number of 0.05 carbochain be 12 to 18 saturated straight chain fatty-acid ethyl ester by the carbon atom number of the carbochain of commercially available iodine number >=1 is that 12 to 18 saturated straight chain fatty-acid ethyl ester (for example is preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate or Stearic ethyl stearate; Content is >=99wt%) through behind the following catalytic hydrogenation reaction, makes through following distillation decoloration again.
With the carbon atom number of the carbochain of commercially available iodine number >=1 is that 12 to 18 saturated straight chain fatty-acid ethyl ester is (hereinafter to be referred as fatty-acid ethyl ester; Be preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate, Stearic ethyl stearate or both, three or four mixture between them) and hydrogen input well heater in; With after the heater heats to 170 ℃; The materials pump pumps into the fatty acid methyl ester of liquid state in the fixed-bed type hydrofining reactor that hydrogenation catalyst is housed together with hydrogen, flows through hydrogenation catalyst from top to bottom.The bulk density of said hydrogenation catalyst is every cubic centimetre 0.96 gram, and the reaction bed aspect ratio is 10.Reaction conditions is: pressure 3.0~6.0Mpa, hydrogen-oil ratio are 300~500, and the weight space velocity of fatty-acid ethyl ester is 0.3 h
-1Hydrogen flows through hydrogenation catalyst in company with the fatty-acid ethyl ester of liquid state, thus make carbon-carbon double bond or the carbon carbon triple bond of the unsaturated molecule in the fatty-acid ethyl ester material under the katalysis of hydrogenation catalyst with hydrogen generation addition reaction and saturated.
After flowing out the fixed-bed type hydrofining reactor through the fatty-acid ethyl ester of hydrogenation reaction, isolate hydrogen through HP separator and light pressure separator successively earlier, be admitted to the distillation tower distillation decoloration again, obtain water white iodine number and be 0.1 fatty-acid ethyl ester.
Employed hydrogenation catalyst is identical with the hydrogenation catalyst that embodiment 2 is adopted in the above-mentioned catalytic hydrogenation reaction.
(embodiment 5)
The preparation method of present embodiment is identical with embodiment 1, and difference is:
Raw material:
Soap base 80g, fatty acids sodium 75wt% wherein, moisture 23wt%, the pH value of soap base is 8;
The mixture 8g of fatty acid ethyl ester sulfonate; The mixture of this fatty acid ethyl ester sulfonate can be through Chinese invention patent document CN100469430C the method for mixture of block fatty acids ethyl ester sodium sulfonate of embodiment 6 described preparations make; Fatty-acid ethyl ester sulphonate 93 weight parts wherein, fatty acid sulfonate 3 weight parts, vitriol 2 weight parts; Fatty-acid ethyl ester 1 weight part; Sulfovinate 1 weight part, water 17 weight parts, the pH value of the mixture of this fatty acid ethyl ester sulfonate is 5.5;
Carbonatoms is 16 saturated straight chain fatty diglycollic amide 3g in the carbochain;
USP Kosher 7g.
The main raw material of the mixture of above-mentioned fatty acid ethyl ester sulfonate is that the carbon atom number is 12 to 18 saturated straight chain fatty-acid ethyl ester in the carbochain of iodine number >=1; With this saturated straight chain fatty-acid ethyl ester and sulphur trioxide is main raw material, can obtain the mixture of above-mentioned fatty acid ethyl ester sulfonate again according to the preparation process of mixture operation of the fatty acid ethyl ester sulfonate among the Chinese invention patent document CN100469430C.The carbon atom number is that (for example be preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate or Stearic ethyl stearate, content is >=99wt%) is obtained by commercially available for 12 to 18 saturated straight chain fatty-acid ethyl ester in the carbochain of this iodine number >=1.
The pH value of gained perfumed soap is 6.5.The main ingredient of this perfumed soap is: sodium soap 60g, fatty-acid ethyl ester sodium sulfonate 6.36g, fatty diglycollic amide 3g, USP Kosher 7g, water 19.57g.The gross weight of every perfumed soap is 100g, and the weight of main ingredient wherein is 95.93g.
(embodiment 6)
The rest part of present embodiment is identical with embodiment 5, and difference is:
The main raw material of mixture of the fatty acid ethyl ester sulfonate in the raw material of preparation perfumed soap is that iodine number is that the carbon atom number of 0.01 carbochain is 12 to 18 saturated straight chain fatty-acid ethyl ester and sulphur trioxide; Operate according to the preparation process of mixture of the fatty acid ethyl ester sulfonate among the Chinese invention patent document CN100469430C by these two kinds of main raw materials, that is wear out, extract, can obtain with the alkali metal cpd reaction again the mixture of above-mentioned fatty acid ethyl ester sulfonate by hydrogen peroxide bleaching, through organic extractant through sulfonation reaction, through ethanol.Described iodine number is that the carbon atom number of 0.01 carbochain be 12 to 18 saturated straight chain fatty-acid ethyl ester by the carbon atom number of the carbochain of commercially available iodine number >=1 is that 12 to 18 saturated straight chain fatty-acid ethyl ester (for example is preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate or Stearic ethyl stearate; Content is >=99wt%) through behind the following catalytic hydrogenation reaction, makes through following distillation decoloration again.
With the carbon atom number of the carbochain of commercially available iodine number >=1 is that 12 to 18 saturated straight chain fatty-acid ethyl ester is (hereinafter to be referred as fatty-acid ethyl ester; Be preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate, Stearic ethyl stearate or both, three or four mixture between them) and hydrogen input well heater in; With after the heater heats to 170 ℃; The materials pump pumps into the fatty acid methyl ester of liquid state in the fixed-bed type hydrofining reactor that hydrogenation catalyst is housed together with hydrogen, flows through hydrogenation catalyst from top to bottom.The bulk density of said hydrogenation catalyst is every cubic centimetre 0.96 gram, and the reaction bed aspect ratio is 10.Reaction conditions is: pressure 3.0~6.0Mpa, hydrogen-oil ratio are 300~500, and the weight space velocity of fatty-acid ethyl ester is 0.3 h
-1Hydrogen flows through hydrogenation catalyst in company with the fatty-acid ethyl ester of liquid state, thus make carbon-carbon double bond or the carbon carbon triple bond of the unsaturated molecule in the fatty-acid ethyl ester material under the katalysis of hydrogenation catalyst with hydrogen generation addition reaction and saturated.
After flowing out the fixed-bed type hydrofining reactor through the fatty-acid ethyl ester of hydrogenation reaction, isolate hydrogen through HP separator and light pressure separator successively earlier, be admitted to the distillation tower distillation decoloration again, obtain water white iodine number and be 0.1 fatty-acid ethyl ester.
Employed hydrogenation catalyst is identical with the hydrogenation catalyst that embodiment 2 is adopted in the above-mentioned catalytic hydrogenation reaction.
(embodiment 7)
The preparation method of present embodiment is identical with embodiment 1, and difference is:
Raw material:
Soap base 73g, fatty acids sodium 80wt% wherein, moisture 18wt%, the pH value of soap base is 10;
The mixture 12g of fatty acid ethyl ester sulfonate; The mixture of this fatty acid ethyl ester sulfonate can be through Chinese invention patent document CN100469430C the method for mixture of strip fatty acids ethyl ester sodium sulfonate of embodiment 5 described preparations make; Fatty-acid ethyl ester sulphonate 93 weight parts wherein, fatty acid sulfonate 3 weight parts, vitriol 2 weight parts; Fatty-acid ethyl ester 1 weight part; Sulfovinate 1 weight part, water 12 weight parts, the pH value of the mixture of this fatty acid ethyl ester sulfonate is 5;
The carbon atom number is 16 saturated straight chain fatty diglycollic amide 7g in the carbochain;
USP Kosher 8g.
The main raw material of the mixture of above-mentioned fatty acid ethyl ester sulfonate is that the carbon atom number is 12 to 18 saturated straight chain fatty-acid ethyl ester in the carbochain of iodine number >=1; With this saturated straight chain fatty-acid ethyl ester and sulphur trioxide is main raw material, can obtain the mixture of above-mentioned fatty acid ethyl ester sulfonate again according to the preparation process of mixture operation of the fatty acid ethyl ester sulfonate among the Chinese invention patent document CN100469430C.The carbon atom number is that (for example be preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate or Stearic ethyl stearate, content is >=99wt%) is obtained by commercially available for 12 to 18 saturated straight chain fatty-acid ethyl ester in the carbochain of this iodine number >=1.
The pH value of gained perfumed soap is 7.5.The main ingredient of this perfumed soap is: sodium soap 58.4g, fatty-acid ethyl ester sodium sulfonate 9.96g, fatty diglycollic amide 7g, USP Kosher 8g, water 14.42g.The gross weight of every perfumed soap is 100g, and the weight of main ingredient wherein is 97.78g.
(embodiment 8)
The main raw material of mixture of the fatty acid ethyl ester sulfonate in the raw material of preparation perfumed soap is that iodine number is that the carbon atom number of 0.08 carbochain is 12 to 18 saturated straight chain fatty-acid ethyl ester and sulphur trioxide; Operate according to the preparation process of mixture of the fatty acid ethyl ester sulfonate among the Chinese invention patent document CN100469430C by these two kinds of main raw materials, that is wear out, extract, can obtain with the alkali metal cpd reaction again the mixture of above-mentioned fatty acid ethyl ester sulfonate by hydrogen peroxide bleaching, through organic extractant through sulfonation reaction, through ethanol.Described iodine number is that the carbon atom number of 0.08 carbochain be 12 to 18 saturated straight chain fatty-acid ethyl ester by the carbon atom number of the carbochain of commercially available iodine number >=1 is that 12 to 18 saturated straight chain fatty-acid ethyl ester (for example is preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate or Stearic ethyl stearate; Content is >=99wt%) through behind the following catalytic hydrogenation reaction, makes through following distillation decoloration again.
With the carbon atom number of the carbochain of commercially available iodine number >=1 is that 12 to 18 saturated straight chain fatty-acid ethyl ester is (hereinafter to be referred as fatty-acid ethyl ester; Be preferably Laurate ethyl, myristic acid ethyl ester, ethyl palmitate, Stearic ethyl stearate or both, three or four mixture between them) and hydrogen input well heater in; With after the heater heats to 170 ℃; The materials pump pumps into the fatty acid methyl ester of liquid state in the fixed-bed type hydrofining reactor that hydrogenation catalyst is housed together with hydrogen, flows through hydrogenation catalyst from top to bottom.The bulk density of said hydrogenation catalyst is every cubic centimetre 0.96 gram, and the reaction bed aspect ratio is 10.Reaction conditions is: pressure 3.0~6.0Mpa, hydrogen-oil ratio are 300~500, and the weight space velocity of fatty-acid ethyl ester is 0.3 h
-1Hydrogen flows through hydrogenation catalyst in company with the fatty-acid ethyl ester of liquid state, thus make carbon-carbon double bond or the carbon carbon triple bond of the unsaturated molecule in the fatty-acid ethyl ester material under the katalysis of hydrogenation catalyst with hydrogen generation addition reaction and saturated.
After flowing out the fixed-bed type hydrofining reactor through the fatty-acid ethyl ester of hydrogenation reaction, isolate hydrogen through HP separator and light pressure separator successively earlier, be admitted to the distillation tower distillation decoloration again, obtain water white iodine number and be 0.1 fatty-acid ethyl ester.
Employed hydrogenation catalyst is identical with the hydrogenation catalyst that embodiment 2 is adopted in the above-mentioned catalytic hydrogenation reaction.
In the above embodiments 2,4,6,8; The iodine number of resulting water white fatty-acid ethyl ester can be set before carrying out shortening; When the iodine number of target setting product, can realize the iodine number of title product according to the setting of the size of the size of the weight space velocity of the size of the iodine number of raw material, material, hydrogen-oil ratio and the system pressure in the fixed-bed type hydrofining reactor.