CN1834079A - Process of preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in near critical aqueous medium - Google Patents
Process of preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in near critical aqueous medium Download PDFInfo
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- CN1834079A CN1834079A CN 200610050396 CN200610050396A CN1834079A CN 1834079 A CN1834079 A CN 1834079A CN 200610050396 CN200610050396 CN 200610050396 CN 200610050396 A CN200610050396 A CN 200610050396A CN 1834079 A CN1834079 A CN 1834079A
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- 150000002191 fatty alcohols Chemical class 0.000 title claims abstract description 38
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 35
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000012736 aqueous medium Substances 0.000 title claims abstract description 10
- 239000004170 rice bran wax Substances 0.000 title claims description 47
- 235000019384 rice bran wax Nutrition 0.000 title claims description 47
- 230000003197 catalytic effect Effects 0.000 title claims description 9
- 230000008569 process Effects 0.000 title description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 239000007790 solid phase Substances 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical class [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims description 31
- 238000010792 warming Methods 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 18
- 238000000605 extraction Methods 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 239000001110 calcium chloride Substances 0.000 claims description 15
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 15
- 239000012141 concentrate Substances 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 15
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 15
- 239000000194 fatty acid Substances 0.000 claims description 15
- 229930195729 fatty acid Natural products 0.000 claims description 15
- 150000004665 fatty acids Chemical class 0.000 claims description 15
- 238000000638 solvent extraction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000413 hydrolysate Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 241000209094 Oryza Species 0.000 abstract 3
- 235000007164 Oryza sativa Nutrition 0.000 abstract 3
- 235000009566 rice Nutrition 0.000 abstract 3
- 235000021419 vinegar Nutrition 0.000 abstract 3
- 239000000052 vinegar Substances 0.000 abstract 3
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 235000013969 calcium salts of fatty acid Nutrition 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 238000002481 ethanol extraction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004164 Wax ester Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005815 base catalysis Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000005446 dissolved organic matter Substances 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 235000019386 wax ester Nutrition 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- IRHTZOCLLONTOC-UHFFFAOYSA-N hexacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCO IRHTZOCLLONTOC-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- 208000000112 Myalgia Diseases 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- -1 makeup Polymers 0.000 description 1
- 230000037323 metabolic rate Effects 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 230000003387 muscular Effects 0.000 description 1
- 230000010016 myocardial function Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229960001109 policosanol Drugs 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- 230000035488 systolic blood pressure Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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Abstract
This invention discloses a method to prepare high-grade fattly alcohols by noncatalytic hydrolysis of rice bran vinegar in near-critical aqueous media. The method includes following steps: a) deionized water and rice bran vinegar are added into a high-pressure reactor at a mass ratio of 1:1~6:1 and stirred, the temperature is raised to 100 deg. C and the vent valve is kept on for 2~5 minutes; b) the temperature is further raised to 200~300 deg. C at which hydrolysis is held for 0.5~8 hours; c) the hydrolyzed products are cooled and the aqueous phase is recycled after solid-liquid separation; d) the solid phase is extracted with organic solvent and unhydrolyzed rice bran vinegar as the leftover is returned to step a); e) saturated calcium chloride solution is added into the extract and calcium salts of fatty acid are obtained in solid phase, the liquid phase is concentrated, cooled and crystallized to obtain high-grade fatty alcohols and the concentrated solvent can be recycled and returned to step d). In this invention, no catalyst is necessary and therefore, the pollution problems in acid/alkali-catalytic hydrolysis can be solved and the procedure is simple, green and high-yield.
Description
Technical field
The present invention relates to the high fatty alcohol class, relate in particular to the method for preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in a kind of near critical aqueous medium.
Background technology
High fatty alcohol is the important source material of softening agent and tensio-active agent, is widely used in industries such as light textile, washing, rubber, makeup, plastics, papermaking, medicine, food, oil, synthon, process hides, ore dressing, machinery.Simultaneously, high fatty alcohol such as n-Hexacosanol, policosanol, triacontanol price quote etc. are the functional substance of important biologically active, have and 1. promote endurance, energy and muscle power; 2. shorten the muscular nerve reaction times, improve the reaction acuteness; 3. promote hormone function, alleviate myalgia; 4. improve myocardial function, reduce systolic blood pressure; 5. improve functions such as body basal metabolic rate(BMR).High fatty alcohol has the material of physiologically active as pure natural, has been subjected to countries in the world in recent years and has more and more paid close attention to, and demand is increasing year by year.
The source of high fatty alcohol mainly contains two approach: the one, and chemical synthesis comprises Ziegler process and oxo synthesis, the 2nd, from natural fats and oils, wax ester preparation.
Ziegler process is a raw material with ethene, hydrogen, aluminium, prepare the Z-type catalyst triethyl aluminum earlier, ethene oligomerisation under catalyst becomes trialkylaluminium, change into the aluminum alkyls oxide compound with atmospheric oxygen, then it is hydrolyzed into Fatty Alcohol(C12-C14 and C12-C18), this method technological process of production is long, technical sophistication, facility investment is big, the product cost height.Oxo synthesis is a raw material with the normal paraffin in the coal cut, obtain internal olefin through selective dehydrogenation, under catalyst action, carry out carbonylation and prepare Fatty Alcohol(C12-C14 and C12-C18), this method mature production technology with synthetic gas, but the straight chain rate that has the Fatty Alcohol(C12-C14 and C12-C18) product is not as the natural alcohol height, and pure product spectrum is narrow.
Can be divided into hydrolysis method and change esterification process from natural fats and oils, wax ester preparation high fatty alcohol.Hydrolysis method mainly contains saponification method, acid/alkali catalyzed hydrolysis and enzymatic hydrolysis etc.; Changeing esterification process is that reactions such as rice bran wax and methyl alcohol are generated fatty acid methyl ester and high fatty alcohol.Rise along with the back to nature trend, become important preparation method from natural fats and oils, wax ester preparation high fatty alcohol, wherein at present based on the highly basic saponification method, but there are the problems such as big, that product separation is difficult, technological process is unstable, quality product is relatively poor of polluting in this method.
Near-critical water typically refers to the compressed liquid water of temperature between 200～350 ℃.Water has following three key properties in this zone:
1) depress at saturated vapo(u)r, the ionization constant of near-critical water has a maximum value to be about 10 near 275 ℃
-11(mol/kg)
2, its value is 1000 times of normal temperature and pressure water, and ionization constant increases the [H in the near-critical water with the increase of pressure
3O
+] and [OH
-] near weak acid or weak base, self have the function of acid catalysis and base catalysis, therefore 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 near-critical water is still bigger, solubilized even ionized salts, enough little of dissolved organic matter, (275 ℃ of saturated vapo(u)rs density of depressing water is 0.76g/cm to add that the density of near-critical water is big
3, the specific inductivity of near-critical water, density and acetone are close), so near-critical water has extraordinary solubility property, has the characteristic of dissolved organic matter and inorganics simultaneously.This can carry out the building-up reactions in many near critical aqueous mediums in homogeneous phase, thereby eliminates resistance to mass transfer, improves speed of response, and the reaction back only needs simple cooling just can realize the wax water sepn 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 in the hydrolysis of rice bran wax as reaction medium, utilize no catalysis, efficient, the green hydrolysis of the characteristic realization rice bran wax of near-critical water.
Summary of the invention
The purpose of this invention is to provide rice bran wax in a kind of near critical aqueous medium and do not have the method that catalysis, green, effectively hydrolyzing prepare high fatty alcohol.
The step of method is as follows:
1) add deionized water and rice bran wax in autoclave, deionized water and rice bran wax mass ratio are 1: 1～6: 1, open stirring, are warming up to 100 ℃, open vent valve 2-5 minute;
2) continue to be warming up to 200～350 ℃ of hydrolysis 0.5～8h;
3) hydrolysate cooling, after solid-liquid separation, water recycles;
4) solid phase organic solvent extraction, extract remainder are that unhydrolysed rice bran wax returns step 1) again;
5) add the calcium chloride saturated aqueous solution in the extraction phase, again through solid-liquid separation, solid phase obtains fatty acid calcium, liquid phase through concentrate, must high fatty alcohol behind the crystallisation by cooling, concentrated recovered solvent can return step 4).
The purpose that " is warming up to 100 ℃, opened vent valve 2-5 minute " 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 present invention need not add any catalyzer in reaction process, self acid-base catalysis characteristic of utilizing near-critical water makes rice bran wax hydrolysis in near-critical water generate high fatty alcohol with characteristic that can dissolved organic matter, solved an acid-base catalysis hydrolysis pollution on the environment difficult problem, reaction process is simple, the product yield height, and realized the greenization of production process.
Description of drawings
Accompanying drawing is the process flow diagram of preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in the near critical aqueous medium.
Embodiment
Embodiment 1
In 500mL intermittent type autoclave, add 300g deionized water and 50g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 2 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 200 ℃ of hydrolysis 8h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase concentration expressed in percentage by volume is 90%, temperature is 70 ℃ hot ethanol extraction, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 2.6g after concentrating (concentrate the ethanol that reclaims and can return solvent extraction), crystallisation by cooling.
Embodiment 2
In 500mL intermittent type autoclave, add 300g deionized water and 60g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 3 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 220 ℃ of hydrolysis 7h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase acetone extract, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 6.1g after concentrating (concentrate the acetone that reclaims and can return solvent extraction), crystallisation by cooling.
Embodiment 3
In 500mL intermittent type autoclave, add 300g deionized water and 75g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 4 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 240 ℃ of hydrolysis 6h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase concentration expressed in percentage by volume is 92%, temperature is 65 ℃ hot ethanol extraction, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 13.9g after concentrating (concentrate the ethanol that reclaims and can return solvent extraction), crystallisation by cooling.
Embodiment 4
In 500mL intermittent type autoclave, add 300g deionized water and 75g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 5 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 250 ℃ of hydrolysis 6h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase acetone extract, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 15.8g after concentrating (concentrate the acetone that reclaims and can return solvent extraction), crystallisation by cooling.
Embodiment 5
In 500mL intermittent type autoclave, add 300g deionized water and 100g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 2 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 260 ℃ of hydrolysis 5h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase concentration expressed in percentage by volume is 94%, temperature is 65 ℃ hot ethanol extraction, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 21.2go after concentrating (concentrate the ethanol that reclaims and can return solvent extraction), crystallisation by cooling
Embodiment 6
In 500mL intermittent type autoclave, add 300g deionized water and 100g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 3 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 270 ℃ of hydrolysis 5h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase acetone extract, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 22.3g after concentrating (concentrate the acetone that reclaims and can return solvent extraction), crystallisation by cooling.
Embodiment 7
In 500mL intermittent type autoclave, add 300g deionized water and 100g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 4 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 280 ℃ of hydrolysis 4h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase concentration expressed in percentage by volume is 96%, temperature is 60 ℃ hot ethanol extraction, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 23.0g after concentrating (concentrate the ethanol that reclaims and can return solvent extraction), crystallisation by cooling.
Embodiment 8
In 500mL intermittent type autoclave, add 250g deionized water and 125g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 5 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 290 ℃ of hydrolysis 3h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase acetone extract, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 23.2g after concentrating (concentrate the acetone that reclaims and can return solvent extraction), crystallisation by cooling.
Embodiment 9
In 500mL intermittent type autoclave, add 250g deionized water and 125g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 3 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 310 ℃ of hydrolysis 2h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase concentration expressed in percentage by volume is 98%, temperature is 50 ℃ hot ethanol extraction, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 19.8g after concentrating (concentrate the ethanol that reclaims and can return solvent extraction), crystallisation by cooling.
Embodiment 10
In 500mL intermittent type autoclave, add 200g deionized water and 200g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 2 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 330 ℃ of hydrolysis 1h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase acetone extract, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 20.2g after concentrating (concentrate the acetone that reclaims and can return solvent extraction), crystallisation by cooling.
Embodiment 11
In 500mL intermittent type autoclave, add 200g deionized water and 200g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 3 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 350 ℃ of hydrolysis 0.5h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase concentration expressed in percentage by volume is 95%, temperature is 55 ℃ hot ethanol extraction, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 16.1g after concentrating (concentrate the ethanol that reclaims and can return solvent extraction), crystallisation by cooling.
Embodiment 12
In 500mL intermittent type autoclave, add 300g deionized water and 100g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 3 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 275 ℃ of hydrolysis 5h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase acetone extract, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 23.5g after concentrating (concentrate the acetone that reclaims and can return solvent extraction), crystallisation by cooling.
Embodiment 13
In 500mL intermittent type autoclave, add 250g deionized water and 125g rice bran wax, open stirring, be warming up to 100 ℃, opened vent valve 4 minutes, utilize water vapour to get rid of the interior air of still; Continue to be warming up to 285 ℃ of hydrolysis 4h; Cooling posthydrolysis product is through solid-liquid separation, water recycles, the solid phase concentration expressed in percentage by volume is 95%, temperature is 60 ℃ hot ethanol extraction, extract remainder be unhydrolysed rice bran wax again backwater separate step, add the calcium chloride saturated aqueous solution in the extraction phase, through solid-liquid separation, solid phase obtains fatty acid calcium again, and liquid phase gets high fatty alcohol 26.0g after concentrating (concentrate the ethanol that reclaims and can return solvent extraction), crystallisation by cooling.
Claims (5)
1. the method for preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in the near critical aqueous medium is characterized in that the step of method is as follows:
1) add deionized water and rice bran wax in autoclave, deionized water and rice bran wax mass ratio are 1: 1～6: 1, open stirring, are warming up to 100 ℃, open vent valve 2-5 minute;
2) continue to be warming up to 200～350 ℃ of hydrolysis 0.5～8h;
3) hydrolysate cooling, after solid-liquid separation, water recycles;
4) solid phase organic solvent extraction, extract remainder are that unhydrolysed rice bran wax returns step 1) again;
5) add the calcium chloride saturated aqueous solution in the extraction phase, again through solid-liquid separation, solid phase obtains fatty acid calcium, liquid phase through concentrate, must high fatty alcohol behind the crystallisation by cooling, concentrated recovered solvent can return step 4).
2. the method for preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in a kind of near critical aqueous medium according to claim 1, the mass ratio that it is characterized in that described deionized water and rice bran wax is 2: 1～4: 1.
3. the method for preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in a kind of near critical aqueous medium according to claim 1 is characterized in that described hydrolysis temperature is 240～290 ℃.
4. the method for preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in a kind of near critical aqueous medium according to claim 1 is characterized in that the organic solvent in the described step 4) is the ethanol or the pure acetone of concentration expressed in percentage by volume 90～98%.
5. according to the method for preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in claim 1 and the 4 described a kind of near critical aqueous mediums, it is characterized in that concentration expressed in percentage by volume 90～98% alcohol extraction temperature are 50～70 ℃ in the described step 4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100503966A CN100519495C (en) | 2006-04-18 | 2006-04-18 | Process of preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in near critical aqueous medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100503966A CN100519495C (en) | 2006-04-18 | 2006-04-18 | Process of preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in near critical aqueous medium |
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| Publication Number | Publication Date |
|---|---|
| CN1834079A true CN1834079A (en) | 2006-09-20 |
| CN100519495C CN100519495C (en) | 2009-07-29 |
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| CNB2006100503966A Expired - Fee Related CN100519495C (en) | 2006-04-18 | 2006-04-18 | Process of preparing high-grade fatty alcohol through non-catalytic hydrolysis of rice bran wax in near critical aqueous medium |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190873B (en) * | 2006-11-24 | 2010-09-29 | 樊献俄 | Method for preparing triacontanol |
| CN102060936A (en) * | 2011-01-05 | 2011-05-18 | 江苏大学 | Method for extracting rice bran polysaccharide from sub-critical water |
| CN103804135A (en) * | 2012-11-07 | 2014-05-21 | 中国林业科学研究院资源昆虫研究所 | Method used for preparing higher alkanols via sunflower wax normal pressure reduction |
-
2006
- 2006-04-18 CN CNB2006100503966A patent/CN100519495C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190873B (en) * | 2006-11-24 | 2010-09-29 | 樊献俄 | Method for preparing triacontanol |
| CN102060936A (en) * | 2011-01-05 | 2011-05-18 | 江苏大学 | Method for extracting rice bran polysaccharide from sub-critical water |
| CN102060936B (en) * | 2011-01-05 | 2012-08-15 | 江苏大学 | Method for extracting rice bran polysaccharide from sub-critical water |
| CN103804135A (en) * | 2012-11-07 | 2014-05-21 | 中国林业科学研究院资源昆虫研究所 | Method used for preparing higher alkanols via sunflower wax normal pressure reduction |
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| Publication number | Publication date |
|---|---|
| CN100519495C (en) | 2009-07-29 |
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