CN1884460A - Method for non-catalytic lanolin hydrolyzed preparation of lanolin acid and lanolin alcohol using in near critical water medium - Google Patents
Method for non-catalytic lanolin hydrolyzed preparation of lanolin acid and lanolin alcohol using in near critical water medium Download PDFInfo
- Publication number
- CN1884460A CN1884460A CN 200610050876 CN200610050876A CN1884460A CN 1884460 A CN1884460 A CN 1884460A CN 200610050876 CN200610050876 CN 200610050876 CN 200610050876 A CN200610050876 A CN 200610050876A CN 1884460 A CN1884460 A CN 1884460A
- Authority
- CN
- China
- Prior art keywords
- lanolin
- acid
- warming
- wool wax
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 235000019388 lanolin Nutrition 0.000 title claims abstract description 84
- 239000004166 Lanolin Substances 0.000 title claims abstract description 83
- 239000002253 acid Substances 0.000 title claims abstract description 65
- 229940039717 lanolin Drugs 0.000 title claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title description 2
- 230000003197 catalytic effect Effects 0.000 title 1
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 238000010792 warming Methods 0.000 claims description 61
- 239000012071 phase Substances 0.000 claims description 41
- 238000000926 separation method Methods 0.000 claims description 41
- 238000000605 extraction Methods 0.000 claims description 32
- 230000007062 hydrolysis Effects 0.000 claims description 24
- 238000006460 hydrolysis reaction Methods 0.000 claims description 24
- 229920006395 saturated elastomer Polymers 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 21
- 239000001110 calcium chloride Substances 0.000 claims description 21
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 21
- 239000000413 hydrolysate Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 20
- 229910052791 calcium Inorganic materials 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 20
- 239000012141 concentrate Substances 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000008025 crystallization Effects 0.000 claims description 20
- 239000007790 solid phase Substances 0.000 claims description 20
- 230000003068 static effect Effects 0.000 claims description 20
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000012736 aqueous medium Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000638 solvent extraction Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 3
- 239000003054 catalyst Substances 0.000 abstract 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 230000008719 thickening Effects 0.000 abstract 1
- 238000007127 saponification reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 6
- 238000003808 methanol extraction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000003513 alkali Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 235000012000 cholesterol Nutrition 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 239000005446 dissolved organic matter Substances 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 150000003431 steroids Chemical class 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229930182558 Sterol Natural products 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003432 sterols Chemical class 0.000 description 2
- 235000003702 sterols Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 235000002722 Dioscorea batatas Nutrition 0.000 description 1
- 235000006536 Dioscorea esculenta Nutrition 0.000 description 1
- 240000001811 Dioscorea oppositifolia Species 0.000 description 1
- 235000003416 Dioscorea oppositifolia Nutrition 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229940088623 biologically active substance Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007957 coemulsifier Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000003248 secreting effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003270 steroid hormone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003648 triterpenes Chemical class 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
Landscapes
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses the method of preparing adeps lanae acid and lanolin alcohol. The method comprises the following steps: 1 adding deionized water and adeps lanae, the ratio of them being 1:1-6:1, stirring, heating, opening the air outlet valve for 2-5min; 2 heating to 200-350Deg.C, hydrolyzing for 1-8 hour; 3 cooling, separating, adding calcii chloridum fat solution, stirring for 10-60min, heating to 70-80Deg.C, separating oil and water; 4 extracting with organic solvent, acidifying, getting adeps lanae acid product, thickening, crystallizing, and getting product. The invention has the advantages of non catalyst, solving pollution problem, simple technology and high productivity.
Description
Technical field
The present invention relates to the method that lanolin non-catalysis hydrolyzation in a kind of near critical aqueous medium prepares lanoceric acid and Wool wax alcohol.
Background technology
Lanolin is the oiliness secretory product of lamb skin adipose gland, attached to wool surface.Produce the organic waste water that contains lanolin in a large number in woollen mill's waste water from washing wool, lanolin is because saponification becomes the suspension emulsified state with emulsifying effect, and is highly muddy, if directly discharging is not only wasted resource but also can be produced severe contamination to environment.Therefore from waste water from washing wool, reclaim lanolin and develop related products and can reduce pollution greatly, have good economic worth again environment.
The derivative product that is developed by lanolin has had tens kinds, wherein most of products with lanoceric acid and Wool wax alcohol by means such as acetylize, epoxy alkylization, esterification in addition modification form.Therefore be a vital step by set out preparation lanoceric acid and Wool wax alcohol of lanolin to the development and use of lanolin.
Lanoceric acid not only can be directly as tensio-active agent, and can be used as the additive of the cosmetics of super quality.The emulsifying capacity of lanoceric acid, emulsifying stability and water-retentivity are all very strong, and skin is also had the effect of well moistening, and can promote the infiltration of water vapour to skin fat; Metallic soap and the soap analog derivative made by lanoceric acid are a kind of good oleophilic emulsifier and metal antirusting agent.
Contain a large amount of sterols materials in the Wool wax alcohol, as cholesterol, triterpene alcohol etc., can be used as nutrition agent and biologically active substance joins in the cosmetics of super quality, also can in the W/O cosmetic formulations, be used as emulsifying agent, co-emulsifier and reverse emulsive stablizer, skin is had good affinity and wettability.Wherein cholesterol is not only the important source material of liquid crystal industry; or the important intermediate of medicine industry; can be used for synthesis of vitamin d 3, artificial Calculus Bovis etc.; cholesterol can make nearly all steroid hormone medicine as a kind of natural steroid resource of steroid drugs by chemistry or microbial conversion process.The raw materials for production of China's steroid drugs still rely on resource so far and are on the brink of exhausted Chinese yam, so the sterol development of resources is extremely urgent.
At present, the method for hydrolysis of lanolin mainly contains the alkaline saponification method and changes esterification process.Saponification method mainly contains the alkali aqueous solution saponification method, alkali aqueous solution adds auxiliary agent saponification method and alkali alcoholic solution saponification method etc.; Changeing esterification process is that reactions such as lanolin and methyl alcohol are generated lanoceric acid methyl esters and Wool wax alcohol.At present domestic still based on alkali saponification method, there are problems such as lanoceric acid soap and Wool wax alcohol separation difficulty, complex process and process instability, quality product be relatively poor in this method.
(Near Critical Water NCW) typically refers to the compressed liquid water of temperature between 200～350 ℃ to near-critical water.Water has following three key properties in this zone:
1) depresses at saturated vapo(u)r, the ionization constant of NCW has a maximum value to be about 10-11 (mol/kg) 2 near 275 ℃, its value is 1000 times of normal temperature and pressure water, and ionization constant increases with the increase of pressure, [H3O+] among the NCW and [OH-] are near weak acid or weak base, therefore the function that self has acid catalysis and base catalysis can make some acid-base catalyzed reaction needn't add acid base catalysator, thereby avoid the neutralization of soda acid, the operations such as processing of salt;
2) depress at saturated vapo(u)r, the specific inductivity of 20 ℃ of water is 80.1, and has only 23.5 275 ℃ the time.Although the specific inductivity of NCW is still bigger, solubilized even ionized salts, but it is enough little with dissolved organic matter, the density that adds NCW is big, and (275 ℃ of saturated vapo(u)rs density of depressing water is 0.76g/cm3, the specific inductivity of NCW, density and acetone are close), therefore NCW has extraordinary solubility property, has the characteristic of energy while dissolved organic matter and inorganics.This can carry out the building-up reactions in many NCW media in homogeneous phase, thereby eliminates resistance to mass transfer, improves speed of response, and the reaction back only needs simple cooling just can realize separating of hydrolysate and water simultaneously, and water can be recycled;
3) physicochemical property such as the specific inductivity of near-critical water, ion-product constant, density, viscosity, spread coefficient, solubleness are adjustable continuously in the scope of broad with temperature, pressure, the rerum natura that is near-critical water has controllability, therefore as reaction medium, near-critical water has different solvent properties and reactivity worth at different states.
The present invention is applied to near-critical water on the non-catalysis hydrolyzation of lanolin as reaction medium, utilize the characteristic of near-critical water to realize no catalysis, efficient, the green hydrolysis of lanolin, and then utilize lanoceric acid to separate with the difference on the Wool wax alcohol rerum natura.
Summary of the invention
The purpose of this invention is to provide a kind of green, the lanolin non-catalysis hydrolyzation prepares the method for lanoceric acid and Wool wax alcohol in the near critical aqueous medium efficiently.
The step of method is as follows:
1) add deionized water and lanolin in autoclave, deionized water and lanolin mass ratio are 1: 1～6: 1, open stirring, are warming up to boiling under the normal pressure, open vent valve 2～5min;
2) continue to be warming up to 200～350 ℃ of hydrolysis 1～8h;
3) hydrolysate cooling back solid-liquid separation adds the calcium chloride saturated aqueous solution in the solid phase, stirs 10～60min, is warming up to 70～80 ℃, static back oily water separation;
4) oil reservoir is used organic solvent extraction after washing, and extracting phase is a lanoceric acid calcium, after acidifying the lanoceric acid product, extraction phase through concentrate, must the Wool wax alcohol product after the crystallization.
The purpose that " is warming up to 100 ℃, opened vent valve 2～5 minutes " in the step 1) of the present invention is to utilize water vapour to take away the interior oxygen of still, to reduce the generation of side reaction, improves the yield of product.The consumption of calcium chloride saturated aqueous solution is advisable with 1.1～1.3 times of theoretical consumption in the step 4).
The present invention need not add any catalyzer in reaction process, self acid-base catalysis characteristic of utilizing near-critical water makes lanolin hydrolysis in near-critical water generate lanoceric acid and Wool wax alcohol with characteristic that can dissolved organic matter, solved the pollution problem of existing method serious environmental, reaction process is simple, product yield is higher, and has realized the greenization of production process.
Description of drawings
Accompanying drawing is the process flow diagram that the lanolin non-catalysis hydrolyzation prepares lanoceric acid and Wool wax alcohol in the near critical aqueous medium.
Embodiment
Embodiment 1
In 500mL intermittent type autoclave, add 200g deionized water and 200g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 2min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 200 ℃ of hydrolysis 8h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 60min, is warming up to 70 ℃, static back oily water separation; Oil reservoir is used methanol extraction after washing, extracting phase is a lanoceric acid calcium, behind sulfuric acid acidation lanoceric acid 60.2g, extraction phase through concentrate, must Wool wax alcohol 50.7g after the crystallization.
Embodiment 2
In 500mL intermittent type autoclave, add 260g deionized water and 130g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 3min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 240 ℃ of hydrolysis 6h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 50min, is warming up to 72 ℃, static back oily water separation; Oil reservoir is used alcohol extraction after washing, extracting phase is a lanoceric acid calcium, behind hcl acidifying lanoceric acid 43.1g, extraction phase through concentrate, must Wool wax alcohol 35.6g after the crystallization.
Embodiment 3
In 500mL intermittent type autoclave, add 300g deionized water and 100g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 4min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 260 ℃ of hydrolysis 4h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 40min, is warming up to 74 ℃, static back oily water separation; With Virahol extraction, extracting phase is a lanoceric acid calcium to oil reservoir after washing, behind sulfuric acid acidation lanoceric acid 35.0g, extraction phase through concentrate, must Wool wax alcohol 29.1g after the crystallization.
Embodiment 4
In 500mL intermittent type autoclave, add 300g deionized water and 75g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 5min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 280 ℃ of hydrolysis 3h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 30min, is warming up to 76 ℃, static back oily water separation; Oil reservoir is used methanol extraction after washing, extracting phase is a lanoceric acid calcium, behind hcl acidifying lanoceric acid 31.6g, extraction phase through concentrate, must Wool wax alcohol 26.5g after the crystallization.
Embodiment 5
In 500mL intermittent type autoclave, add 300g deionized water and 60g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 2min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 300 ℃ of hydrolysis 2h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 20min, is warming up to 78 ℃, static back oily water separation; Oil reservoir is used alcohol extraction after washing, extracting phase is a lanoceric acid calcium, behind sulfuric acid acidation lanoceric acid 25.5g, extraction phase through concentrate, must Wool wax alcohol 21.3g after the crystallization.
Embodiment 6
In 500mL intermittent type autoclave, add 300g deionized water and 50g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 3min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 350 ℃ of hydrolysis 1h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 10min, is warming up to 80 ℃, static back oily water separation; With Virahol extraction, extracting phase is a lanoceric acid calcium to oil reservoir after washing, behind hcl acidifying lanoceric acid 20.5g, extraction phase through concentrate, must Wool wax alcohol 15.8g after the crystallization.
Embodiment 7
In 500mL intermittent type autoclave, add 260g deionized water and 130g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 4min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 290 ℃ of hydrolysis 2h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 10min, is warming up to 80 ℃, static back oily water separation; Oil reservoir is used methanol extraction after washing, extracting phase is a lanoceric acid calcium, behind sulfuric acid acidation lanoceric acid 49.4g, extraction phase through concentrate, must Wool wax alcohol 40.1g after the crystallization.
Embodiment 8
In 500mL intermittent type autoclave, add 260g deionized water and 130g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 5min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 280 ℃ of hydrolysis 2.5h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 20min, is warming up to 78 ℃, static back oily water separation; Oil reservoir is used alcohol extraction after washing, extracting phase is a lanoceric acid calcium, behind hcl acidifying lanoceric acid 50.1g, extraction phase through concentrate, must Wool wax alcohol 42.6g after the crystallization.
Embodiment 9
In 500mL intermittent type autoclave, add 300g deionized water and 100g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 2min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 270 ℃ of hydrolysis 3h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 30min, is warming up to 76 ℃, static back oily water separation; With Virahol extraction, extracting phase is a lanoceric acid calcium to oil reservoir after washing, behind sulfuric acid acidation lanoceric acid 36.2g, extraction phase through concentrate, must Wool wax alcohol 30.5g after the crystallization.
Embodiment 10
In 500mL intermittent type autoclave, add 300g deionized water and 100g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 3min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 260 ℃ of hydrolysis 4h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 40min, is warming up to 74 ℃, static back oily water separation; Oil reservoir is used methanol extraction after washing, extracting phase is a lanoceric acid calcium, behind hcl acidifying lanoceric acid 35.1g, extraction phase through concentrate, must Wool wax alcohol 29.8g after the crystallization.
Embodiment 11
In 500mL intermittent type autoclave, add 300g deionized water and 75g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 4min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 250 ℃ of hydrolysis 5h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 50min, is warming up to 72 ℃, static back oily water separation; Oil reservoir is used alcohol extraction after washing, extracting phase is a lanoceric acid calcium, behind sulfuric acid acidation lanoceric acid 30.5g, extraction phase through concentrate, must Wool wax alcohol 25.4g after the crystallization.
Embodiment 12
In 500mL intermittent type autoclave, add 300g deionized water and 75g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 5min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 240 ℃ of hydrolysis 6h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 60min, is warming up to 70 ℃, static back oily water separation; With Virahol extraction, extracting phase is a lanoceric acid calcium to oil reservoir after washing, behind hcl acidifying lanoceric acid 29.8g, extraction phase through concentrate, must Wool wax alcohol 24.7g after the crystallization.
Embodiment 13
In 500mL intermittent type autoclave, add 260g deionized water and 130g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 2min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 235 ℃ of hydrolysis 8h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 20min, is warming up to 70 ℃, static back oily water separation; Oil reservoir is used methanol extraction after washing, extracting phase is a lanoceric acid calcium, behind sulfuric acid acidation lanoceric acid 41.6g, extraction phase through concentrate, must Wool wax alcohol 33.9g after the crystallization.
Embodiment 14
In 500mL intermittent type autoclave, add 260g deionized water and 130g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 3min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 245 ℃ of hydrolysis 7h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 30min, is warming up to 72 ℃, static back oily water separation; Oil reservoir is used alcohol extraction after washing, extracting phase is a lanoceric acid calcium, behind hcl acidifying lanoceric acid 43.7g, extraction phase through concentrate, must Wool wax alcohol 35.1g after the crystallization.
Embodiment 15
In 500mL intermittent type autoclave, add 300g deionized water and 100g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 4min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 255 ℃ of hydrolysis 6h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 40min, is warming up to 74 ℃, static back oily water separation; With Virahol extraction, extracting phase is a lanoceric acid calcium to oil reservoir after washing, behind sulfuric acid acidation lanoceric acid 34.8g, extraction phase through concentrate, must Wool wax alcohol 28.5g after the crystallization.
Embodiment 16
In 500mL intermittent type autoclave, add 300g deionized water and 100g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 5min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 265 ℃ of hydrolysis 5h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 20min, is warming up to 76 ℃, static back oily water separation; Oil reservoir is used methanol extraction after washing, extracting phase is a lanoceric acid calcium, behind hcl acidifying lanoceric acid 36.1g, extraction phase through concentrate, must Wool wax alcohol 30.2g after the crystallization.
Embodiment 17
In 500mL intermittent type autoclave, add 300g deionized water and 75g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 3min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 275 ℃ of hydrolysis 4h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 30min, is warming up to 78 ℃, static back oily water separation; Oil reservoir is used alcohol extraction after washing, extracting phase is a lanoceric acid calcium, behind sulfuric acid acidation lanoceric acid 32.0g, extraction phase through concentrate, must Wool wax alcohol 27.1g after the crystallization.
Embodiment 18
In 500mL intermittent type autoclave, add 300g deionized water and 75g lanolin, open stirring, be warming up to boiling under the normal pressure, open vent valve 4min, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 285 ℃ of hydrolysis 3h; Hydrolysate cooling back solid-liquid separation, water recycles, and adds the calcium chloride saturated aqueous solution in the solid phase, stirs 40min, is warming up to 80 ℃, static back oily water separation; With Virahol extraction, extracting phase is a lanoceric acid calcium to oil reservoir after washing, behind hcl acidifying lanoceric acid 31.5g, extraction phase through concentrate, must Wool wax alcohol 26.9g after the crystallization.
Claims (5)
1. the lanolin non-catalysis hydrolyzation prepares the method for lanoceric acid and Wool wax alcohol in the near critical aqueous medium, it is characterized in that the step of method is as follows:
1) add deionized water and lanolin in autoclave, deionized water and lanolin mass ratio are 1: 1～6: 1, open stirring, are warming up to boiling under the normal pressure, open vent valve 2～5min;
2) continue to be warming up to 200～350 ℃ of hydrolysis 1～8h;
3) hydrolysate cooling back solid-liquid separation adds the calcium chloride saturated aqueous solution in the solid phase, stirs 10～60min, is warming up to 70～80 ℃, static back oily water separation;
4) oil reservoir is used organic solvent extraction after washing, and extracting phase is a lanoceric acid calcium, after acidifying the lanoceric acid product, extraction phase through concentrate, must the Wool wax alcohol product after the crystallization.
2. the lanolin non-catalysis hydrolyzation prepares the method for lanoceric acid and Wool wax alcohol in a kind of near critical aqueous medium according to claim 1, it is characterized in that described deionized water and lanolin mass ratio are 2: 1～4: 1.
3. the lanolin non-catalysis hydrolyzation prepares the method for lanoceric acid and Wool wax alcohol in a kind of near critical aqueous medium according to claim 1, it is characterized in that described hydrolysis temperature is 240～290 ℃.
4. the lanolin non-catalysis hydrolyzation prepares the method for lanoceric acid and Wool wax alcohol in a kind of near critical aqueous medium according to claim 1, it is characterized in that the organic solvent described in the step 4) is methyl alcohol, ethanol or Virahol.
5. the lanolin non-catalysis hydrolyzation prepares the method for lanoceric acid and Wool wax alcohol in a kind of near critical aqueous medium according to claim 1, it is characterized in that the acid that the acidization described in the step 4) adopts is sulfuric acid or hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100508762A CN100398633C (en) | 2006-05-19 | 2006-05-19 | Method for non-catalytic lanolin hydrolyzed preparation of lanolin acid and lanolin alcohol using in near critical water medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100508762A CN100398633C (en) | 2006-05-19 | 2006-05-19 | Method for non-catalytic lanolin hydrolyzed preparation of lanolin acid and lanolin alcohol using in near critical water medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1884460A true CN1884460A (en) | 2006-12-27 |
| CN100398633C CN100398633C (en) | 2008-07-02 |
Family
ID=37582767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100508762A Expired - Fee Related CN100398633C (en) | 2006-05-19 | 2006-05-19 | Method for non-catalytic lanolin hydrolyzed preparation of lanolin acid and lanolin alcohol using in near critical water medium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100398633C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127178A (en) * | 2010-11-30 | 2011-07-20 | 浙江大学 | Method for preparing vinyl methyl ether/vinyl alcohol copolymer through hydrolysis of poly(vinyl methyl ether) in nearcritical water |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3815755A1 (en) * | 1988-05-09 | 1989-11-23 | Henkel Kgaa | METHOD FOR CATALYTIC HYDRATING LANOLIN |
| CN1256412C (en) * | 2003-11-27 | 2006-05-17 | 陈天晓 | Method for low-pressure continuous hydrolysis preparation of fatty acid |
| CN1304545C (en) * | 2005-05-16 | 2007-03-14 | 浙江大学 | Method for preparing fatty acid through continuous hydrolyzing grease without catalysis in near critical aqueous medium |
-
2006
- 2006-05-19 CN CNB2006100508762A patent/CN100398633C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127178A (en) * | 2010-11-30 | 2011-07-20 | 浙江大学 | Method for preparing vinyl methyl ether/vinyl alcohol copolymer through hydrolysis of poly(vinyl methyl ether) in nearcritical water |
| CN102127178B (en) * | 2010-11-30 | 2012-05-30 | 浙江大学 | Method for preparing vinyl methyl ether/vinyl alcohol copolymer through hydrolysis of poly(vinyl methyl ether) in nearcritical water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100398633C (en) | 2008-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101067091B (en) | Solid catalysis process of preparing biodiesel oil continuously with high acid value material | |
| AU2010261615B2 (en) | Process for production of sugars and alcohols from a cellulosic material | |
| US7667060B2 (en) | Method of producing biodiesel | |
| CN102659590B (en) | Alcoholysis recovery method of waster polylactic acid in ionic liquid environment | |
| CN109721471B (en) | Method for purifying glycerin from by-product of biodiesel production | |
| CN103189518B (en) | Method of preparing alkyl butyrate from fermented liquid using microorganisms | |
| CN1304545C (en) | Method for preparing fatty acid through continuous hydrolyzing grease without catalysis in near critical aqueous medium | |
| CN105132189B (en) | A kind of fine separation method of C18 series and C20~C22 series fatty acid methyl esters | |
| CN113072444A (en) | Method for separating and extracting R-3-hydroxy methyl butyrate | |
| CN1844319A (en) | Process for preparing bio- diesel oil by conversion of subcritical - supercritical fluid | |
| CN101289630A (en) | Method for preparing biodiesel from chinaberry seed oil | |
| CN1884460A (en) | Method for non-catalytic lanolin hydrolyzed preparation of lanolin acid and lanolin alcohol using in near critical water medium | |
| CN101074389A (en) | Production of biological diesel oil | |
| CN113717796B (en) | Method for converting fatty acid by ultrasonic-assisted nigre pressurized hydrolysis in one step | |
| CN101045878A (en) | Two-step solid acid and solid alkali catalyzing process for producing biodiesel oil | |
| CN103588639B (en) | A kind of alcoholysis recovery method of useless poly 3-hydroxy butyrate material | |
| CN1911881A (en) | Method of separating wool acid and lanonol from wool grease | |
| CN101812700A (en) | Bipolar membrane electrolysis method for ester-type hydrolysis | |
| CN111018665A (en) | Method for recycling trichloropropane in epichlorohydrin heavy component | |
| CN100586914C (en) | Method for preparing Alpha-terpineol by turpentine catalysis-free hydration in near criticality aqueous medium | |
| CN110038547B (en) | Preparation method of tin-loaded aluminum oxide nanosheet | |
| CN1834080A (en) | Process of preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalytic of cinnamaldehyde in near critical water | |
| CN105037085A (en) | Method for efficiently preparing policosanol from Chinese wax by two-stage process | |
| JP2008266418A (en) | Method for producing fatty acid alkyl ester and/or glycerin | |
| CN1323086C (en) | Method for synthesizing fatty ester of maltose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080702 Termination date: 20110519 |