CN1067448A - Produce peaceful etc. the method for thiaminogen, periodontal simultaneously by the hair oil extracted from rice husks - Google Patents
Produce peaceful etc. the method for thiaminogen, periodontal simultaneously by the hair oil extracted from rice husks Download PDFInfo
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Abstract
The invention provides a kind of new rational hair oil extracted from rice husks comprehensive utilization method, be characterized in that with the hair oil extracted from rice husks be raw material, take to come unstuck, an alkali refining, when obtaining the alkali refining Rice pollard oil, improved thiaminogen, the peaceful capture rate of periodontal; Utilize the method for vacuum distilling, fully reclaimed lipid acid, and in technological process, progressively improve thiaminogen and the peaceful concentration rate of periodontal; Abolishment methyl alcohol changes ethanol into or Virahol is to extract solvent, has not only helped environment protection but also improved thiaminogen, the peaceful yield of periodontal, and both can reach the clean crude oil of 18-20 kilogram/ton.Formed the peaceful produced in series method of alkali refining Rice pollard oil, mixed fatty acid, thiaminogen and periodontal.
Description
The present invention relates to produce the method for series product, more specifically to the new technology of the comprehensive utilization of hair oil extracted from rice husks by vegetables oil.
Thiaminogen and periodontal rather all are emerging pharmaceutical prod, the research of thiaminogen starts from the fifties, produced by Japan at first, (seeing the clear 40-17600 of Japan's special permission communique for details, clear and 49-15922 and clear 55-41677) the thiaminogen production technique of Japan at present has two kinds:
(1) Rice pollard oil is directly isolated the thiaminogen crude product through the soap stock that alkali refining or secondary alkali refining obtain with methyl alcohol, through refining finished product.
(2) make fatty acid methyl ester from rice bran oil soapstock, distillation concentrates then, and adopting methyl alcohol is the separated from solvent thiaminogen, again through refining finished product.
Above-mentioned production technique does not all relate to the peaceful production of periodontal.
China is in the research success in 1971 and the thiaminogen of going into operation, and the at present domestic soap stock that all adopts hair oil extracted from rice husks secondary alkali refining directly adds methyl alcohol and separates, get the thiaminogen crude product, get finished product after refinement treatment such as washing, in clean crude oil thiaminogen content 2%, the highest yield of ton crude oil is 5.8 kilograms.
Periodontal rather is to be master's unsaponifiables goods from sterol, is produced by France at first, extracts from Semen Maydis oil.The domestic peaceful production technique of periodontal is raw materials for production with the secondary alkali refining soap stock of Rice pollard oil generally at present, make soap glue through the saponification of methyl alcohol alkali lye, then with sherwood oil extract repeatedly the peaceful crude product of periodontal, get finished product again with refining methanol, clean crude oil per ton is the highest to get peaceful about 11 kilograms of periodontal, but the thiaminogen that can not get both simultaneously.
The problem that existing technology exists mainly is: its finished product yield of (1) existing thiaminogen production technique only reaches about 28% of theoretical content, still has a large amount of thiaminogen improper because of art breading, fails more effectively to capture extraction.(2) directly add methyl alcohol by soap stock and separate thiaminogen,, need to drop into a large amount of methyl alcohol (soap stock amount four times), cause the production operation amount big, forms a large amount of soap methanol solvates, the loss of increase thiaminogen, unsaponifiables because of the soap stock amount is big.Because methyl alcohol is lower boiling noxious solvent, toxicity MAC is 200ppm, very hinders the environmental health of productive labor simultaneously.(3) contain the lipid acid of nearly half in the soap stock, with going into the methyl alcohol raffinate, fail to obtain reasonable use at last.(4) the peaceful production of thiaminogen and periodontal is raw material with the secondary alkali refining soap stock of Rice pollard oil all, generally can only get a major product (be clean crude oil per ton obtain 5.8 kilograms of thiaminogen or for 10-11 kilogram periodontal peaceful).So fail to reach the purpose of reasonable utilization.Though also utilize thiaminogen depleted leftover bits and pieces residue to produce the peaceful product of periodontal, the yield of two kinds of products is all lower, and production technique shortage continuity, fail to form rational produced in series method.
The purpose of this invention is to provide a kind of new rational production technique, when improving thiaminogen and the peaceful product yield of periodontal, make it to form rational alkali refining Rice pollard oil, high-quality mixed fatty acid and thiaminogen, the peaceful produced in series method of periodontal.
Principal feature of the present invention is to be that raw material is taked to come unstuck, an alkali refining with the hair oil extracted from rice husks, obtains alkali refining Rice pollard oil and an alkali refining soap stock; Soap stock is fully reclaimed lipid acid and distillation enriched material through additional saponification, acidifying, vacuum distilling; And in technological process, progressively improving thiaminogen and the peaceful concentration rate of periodontal in the distillation enriched material, abolishment methyl alcohol changes ethanol into or Virahol is the extraction solvent, obtains thiaminogen and unsaponifiables enriched material by the distillation enriched material through pure alkaline solution extraction; After the ethanol alkaline solution handle the unsaponifiables enriched material and extract to such an extent that periodontal is peaceful repeatedly with sherwood oil.
Raw material of the present invention is that concentration that clean hair oil extracted from rice husks that filter to remove the chaff bits (acid number below 20, thiaminogen content 2.0%) adds oily heavy 0.2-0.5% is 85% phosphoric acid, comes unstuck according to a conventional method.The temperature of coming unstuck is 60-85 ℃, is the best with 60-70 ℃.
Adding is based on the NaOH of the 130-200% of the theoretical alkali number of acid number in the degummed oil of gained, and with the ordinary method alkali refining, whole temperature is no more than 64 ℃.Soap stock is removed in centrifugation, and the amount that captures thiaminogen in the soap stock should be no less than 80% of theoretical amount.Alkali refining Rice pollard oil yield contains the thiaminogen amount and need be lower than 0.5% more than 70% in the alkali refining oil, acid value is less than 0.5mgKOH/g oil.
Soap stock adds 10-14 ° of Be'NaOH solution, at 80-90 ℃ of additional saponification 2-3 hour, treats that saponification finishes, and adds an amount of HCl or rare H
2SO
4100-105 ℃ of acidifying one hour, add then and be washed to neutrality, acidifying oil, its neutralization value is about 165mgKOH/g oil, contains thiaminogen greater than 6.5%.
Acidifying oil is after the dehydration degassing, entering the scraper plate film distillator distills concentrated, residual voltage is controlled at below the 0.1mmHg, (the most suitable) with 0.1-0.01mmHg, be heated to 200-240 ℃ (the most suitable) with 200-210 ℃, distill out the 60-80% mixed fatty acid of total amount, must not have thiaminogen to detect in the mixed fatty acid, the distillation enriched material contains thiaminogen should be greater than 17%.
Ethanol or the Virahol of the 75%-95% that adding 4-7 doubly measures in the above-mentioned distillation enriched material, 1-2 gram KOH or NaOH, 40-70 ℃ of reaction 1-2 hour, and it is the most suitable with 60-70% that alcoholic solution progressively is diluted to 50-80%(), leave standstill at 40-70 ℃ and to separate out the 55-70% of unsaponifiables enriched material amount for distillation enriched material total amount, with this as extracting the peaceful raw material of periodontal.And the mother liquor that is dissolved with thiaminogen is neutralized to pH=6.7-7.0 in 40-70 ℃ of adding hydrochloric acid or other weak acid (routine citric acid, acetic acid, tartrate, phosphoric acid-hydrogen sodium etc.), the thiaminogen of separating out is in 40-70 ℃ of filtration, get white thiaminogen crude product, again after ethanol or Virahol are refining, receive thiaminogen 60-80 ℃ of drying under vacuum, obtain meeting the thiaminogen finished product of national medicine inspection standard, amount to clean crude oil yield per ton more than 8kg.
Above-mentioned unsaponifiables enriched material add the 50-95% concentration that 3-6 doubly measures ethanolic soln (with 4-5 doubly, the ethanol of 75-80% is the most suitable), the KOH of the 5-10% of solvent or NaOH, reflux 4-8 hour, make soap glue, the sherwood oil of doubly measuring with 5-10 is in 40-50 ℃ of extraction three times, and combining extraction liquid adds the aqueous ethanol repetitive scrubbing and is neutral to pH, reclaim sherwood oil, get the peaceful crude product of periodontal.Again the ethanol of doubly measuring through 20-30 refining the peaceful finished product of periodontal, quality meets national medicine inspection standard.Amounting to clean hair oil extracted from rice husks yield per ton is the 10-11 kilogram.(using methyl alcohol can obtain equal effect herein) for extracting solvent.
Thus, adopting this technology, is raw material with the hair oil extracted from rice husks, has formed the alkali refining Rice pollard oil, and the linking up of the peaceful four kinds of products of mixed fatty acid, thiaminogen and periodontal, comparatively reasonably the produced in series method has further improved a hair oil extracted from rice husks comprehensive utilization value.
The advantage of the inventive method mainly is:
(1) be raw material with the hair oil extracted from rice husks, the secondary alkali refining of existing technology changed into come unstuck, an alkali refining, can avoid in the existing technology about 15% thiaminogen and about 20% unsaponifiables to run off like this, thereby improve thiaminogen capture rate about 15% and the peaceful capture rate of periodontal about 20% with the soap stock of going into the slubbing alkali refining.
(2) utilize boiling point difference under lipid acid and thiaminogen, the sterol ester equal vacuum, adopt scraper plate film vacuum distilling method, isolate high-quality lipid acid, improved thiaminogen and the peaceful concentration rate of periodontal in the raw materials for production simultaneously, compressed production operation amount and solvent consumption.
(3) with the distillation enriched material as the raw materials for production of thiaminogen and adopt ethanol or Virahol as extracting solvent.Because it is higher than methyl alcohol to thiaminogen solubleness, can improve the thiaminogen extraction efficiency.And ethanol, Virahol is medium-boiling solvent, and vapor pressure solvent all is lower than methyl alcohol, and volatility is low, and the gas escape amount is few, can reduce solvent and consume.The toxicity of ethanol and Virahol all is lower than methyl alcohol (alcohol toxicity MAC is 1000ppm, and Virahol toxicity MAC is 400ppm), helps improving the productive labor environment.
(4) because integrated artistic is reasonable, when extracting thiaminogen, enrichment unsaponifiables, it is peaceful to produce periodontal as raw material, can get 10-11 kilogram/ton crude oil only.Add the thiaminogen recovery rate greater than 8 kilograms of/ton clean crude oils, both altogether 18-20 kilogram/ton crude oil only.
The thiaminogen extraction effect of novel process of the present invention and existing technology relatively sees table 1 for details.
Table 1
Current technology and technology of the present invention
The thiaminogen retention rate relatively
| The operation title | Current technology | Technology of the present invention | ||
| Each operation retention rate % | Total retention rate % | Each operation retention rate % | Total retention rate % | |
| Come unstuck | 96.09 | 96.09 | ||
| An alkali refining | 80.99 | 80.99 | 88.59 | 85.13 |
| The secondary alkali refining | 85.63 | 69.35 | ||
| Vacuum concentration | 89.28 | 76.00 | ||
| Solvent extraction | 40-45 | 29.47 | 56.17 | 42.69 |
| Total yield % | 29.47 | 42.69 | ||
| The clean crude oil of thiaminogen kilogram/ton | 5.894 | 8.538 | ||
The comparison of technology of the present invention and existing technology products obtained therefrom sees table 2 for details.
Table 2
Clean hair oil extracted from rice husks per ton can get product relatively
(1) existing domestic most of factories are raw materials for production with hair oil extracted from rice husks secondary alkali refining soap stock in the existing technology, produce single thiaminogen product, and clean hair oil extracted from rice husks per ton gets 5.8 kilograms of thiaminogen; There only have indivedual factories to utilize it to produce residue system periodontal again to be peaceful, and it is peaceful that its highest yield is that clean mao of oil extracted from rice husks per ton gets 4.8 kilograms of periodontals.(2) be raw materials for production with hair oil extracted from rice husks secondary alkali refining soap stock, only extract the clean crude oil of the peaceful 9-11 kilogram of periodontal/ton.
Embodiment 1
Take by weighing the clean hair of 1500 grams oil extracted from rice husks (acid number
[1]13.80, thiaminogen content
[2]1.84%), keep oily temperature 60-70 ℃, 85% phosphatase 24 .5 gram is added in the oil, stirred 15 minutes, precipitate is removed through the whizzer separation in the oil, gets degummed oil 1448 grams, and (acid number 13.80, thiaminogen content 1.84%), the degummed oil yield is 96.53%.
With this degummed oil 1448 grams heating while stirring, be warming up to 30 ℃ and add 24 ° of Be'NaOH alkali lye, 130 grams, continue to heat and stirred one hour, be warming up to 64 ℃, stop to stir and heating, the oil soap is through centrifugation, get alkali refining oil 1158 grams, (oily two-story valley dimension cellulose content 0.3%, acid number 0.42,) obtain soap stock 580 grams simultaneously, contain acidifying oil 50%.
Soap stock calculates by saponification value and adds alkali number, replenishes to add 14 ° of Be'NaOH alkali lye, and in 80-90 ℃, saponification three hours adds rare H then
2SO
4To pH=3,100-105 ℃ of acidifying one hour, put waste acid water, add the clear water of 2 times of oil masses, intensification 100-105 ℃, wash three times, make washing lotion be neutral.Get acidifying oil 275 grams, its neutralization value is a 167mgKOH/g oil, thiaminogen content 8.18%.Acidifying oil dewaters under 150 ℃, 30mmHg, enters vacuum scraper plate thin film distillation device then, (its heat transfer area: 0.6 meter
2Device diameters φ 300mm, equipment virtual height L=600mm, scraper plate rotating speed: 100 rev/mins, power of agitator: 0.8 kilowatt, evaporator room vacuum tightness: 0.05-0.1mmHg, heating medium: thermal oil, Heating temperature: 240 ℃), under 210 ℃, 0.1mmHg, distill concentrated, obtain mixed fatty acid 178 grams, distillation enriched material 95 grams include thiaminogen 22.49%.
Get above-mentioned distillation enriched material 20 grams, add 95% ethanol 100ml, the NaOH2 gram mixes, and is warming up to 65 ℃, reacted 80 minutes, and progressively add dilution determining alcohol to 70%, and left standstill two hours, separate out the unsaponifiables enriched material in the solution, unsaponifiables enriched material 13 grams are told in filtration, mother liquor under agitation adds dilute hydrochloric acid and phosphoric acid-hydrogen is received to pH=7.0 in 50 ℃, and mother liquor is separated out thiaminogen, filter thiaminogen crude product 6.4 grams, adding 20 times of aqueous ethanols refluxes refining, filter, at 80 ℃, 30mmHg is oven dry down, gets white powdery finished product thiaminogen 2.56 grams, purity 99.5%, yield are amounted to 8.65 kilograms of clean crude oils per ton.
In above-mentioned unsaponifiables enriched material 13 gram, add 4 times of 95% ethanolic solns of 10%NaOH, add water and fully stir, be heated to reflux temperature, react and be cooled to 45 ℃ then in 6 hours, add the sherwood oil of 10 times of amounts, stirred standing demix 20 minutes, tell the petroleum ether layer of extraction, the sherwood oil that in the soap lye of lower floor, adds 5 times of amounts, the re-extract secondary merges petroleum ether extraction liquid, add 60% ethanolic soln and wash, reclaim sherwood oil and promptly get peaceful crude product 4.1 grams of dark-brown periodontal to pH=7.The ethanol that adds 30 times again is refining, is warming up to reflux temperature, wait unsaponifiables to dissolve fully after, stop to stir, leave standstill and divide and get the upper strata refined soln, reclaim behind the ethanol peaceful finished product 3.25 grams of light yellow decorating film periodontal, total sterol content
[5]67.2%, yield is 25% of a unsaponifiables enriched material, and amounting to clean crude oil per ton is 11.38 kilograms, and quality meets the medicine inspection standard
[4]
Embodiment 2
Method similarly to Example 1 must be distilled enriched material 20 grams, include thiaminogen 17%, add 90% ethanol 100ml, KOH2.8 gram stirred 80 minutes in 60 ℃, and thin up determining alcohol to 70% progressively, left standstill two hours, divide and to remove unsaponifiables enriched material 12.25 grams, mother liquor stirs and adds dilute hydrochloric acid and citric acid to pH=6.7 in 50 ℃, white thick thiaminogen powder 4.8 restrains.Crude product refluxed refining 20 minutes with Diluted Alcohol, filter the thiaminogen powder, clean, dry under the vacuum with distilled water again, white thiaminogen finished product 1.95 grams, purity 98.0%, yield is 57.35% of distillation enriched material theoretical content.
85% ethanol and the 5 gram KOH that in above-mentioned unsaponifiables enriched material 12.25 grams, add 5 times of amounts, in 65 ℃ of reactions 6 hours, with petroleum ether extraction three times, merge petroleum ether extraction liquid then, add aqueous ethanol and wash to pH=7, get the peaceful crude product of dark-brown periodontal after reclaiming sherwood oil, 95% alcohol reflux with 30 times of amounts is refining, gets peaceful finished product 3.43 grams of periodontal behind the recovery ethanol, total sterol content 62%, quality meets the medicine inspection standard, and yield is 28% of a unsaponifiables enriched material.
Embodiment 3
Method similarly to Example 1 must be distilled enriched material 20 grams, adds 80% isopropyl acid and the KOH1.3 gram of 5 times of amounts, and in 70 ℃ of reactions 90 minutes, progressively thin up determining alcohol to 50% left standstill 1 hour, divides and removes unsaponifiables enriched material 13.5 grams.Mother liquor to pH=6.8, filters to such an extent that white thick thiaminogen 3.65 restrains in 50 ℃ of adding acetic acid, adds aqueous isopropanol and makes with extra care, and gets finished product thiaminogen 1.8 and restrains, and purity 95.45%, yield are 52.94% of distillation enriched material theoretical content.
75% of 5 times of amounts of adding ethanol and KOH4.2 gram in above-mentioned unsaponifiables enriched material 13.5 grams, refluxed 8 hours, add petroleum ether extraction then three times, get peaceful 4.35 grams of crude product periodontal after reclaiming sherwood oil, it is refining that pale brown look solid shape finished product periodontal peaceful 3.15 restrains to add ethanol, total sterol content 66.78%, yield is 23.33% of a unsaponifiables enriched material.
Embodiment 4
Clean mao oil extracted from rice husks 1500 grams (acid number 12.76, thiaminogen content 1.95%) add 2.50 ° of Be' alkali lye, 20 grams, stir 20 minutes at 70 °-75 ℃, and centrifugation removes the pin that removes photoresist, and get degummed oil 1435 grams, acid number 10.56, thiaminogen content 1.92%.
Degummed oil is pressed embodiment 1 method and is handled, and gets alkali refining oil 1152 grams (yield 80.1%), and wherein thiaminogen content 0.4%, and acid number 0.4 gets soap stock 568 grams.
Soap stock is pressed the method for embodiment 1 and is handled, and gets acidifying oil 284 grams.Acidifying oil is pressed the method for embodiment 1 and is handled, and obtains mixed fatty acid 187 grams, and distillation enriched material 96 grams include thiaminogen 21.45%.
Get above-mentioned distillation enriched material 20 grams, add 90% Virahol of 5 times of amounts, include the NaOH0.95 gram, heated and stirred is warming up to 60 ℃, reacted 80 minutes, and thin up determining alcohol to 50% progressively.Stop to stir, static one hour, tell unsaponifiables enriched material 13.8 grams.Mother liquor under agitation adds monosodium phosphate solution to pH=6.8 in 50 ℃, filter white thick thiaminogen 4.83 grams, it is refining to add 75% isopropyl acid, finished product thiaminogen 2.5 grams, content 96.2%, yield is 58.2% of distillation enriched material theoretical content.
75% ethanol and the NaOH5 gram that in above-mentioned unsaponifiables enriched material 13.8 grams, add 3 times of amounts, saponification refluxed 8 hours, then as the method for embodiment 1 with petroleum ether extraction three times, merging petroleum ether extraction liquid, add 40% washing with alcohol to pH=7, reclaim sherwood oil, get peaceful crude product 4.61 grams of dark-brown periodontal, refining with 30 times of amount alcohol refluxs again, get peaceful finished product 3.5 grams of periodontal, total sterol content 62.3% meets the drug standard, and yield is 26% of a unsaponifiables enriched material.
Embodiment 5
Must distill enriched material 20 grams with embodiment 4, add 85% ethanol 100ml, include the NaOH2 gram, heating while stirring, 65 ℃ were reacted 90 minutes, and thin up determining alcohol to 70%, left standstill two hours, filtering separation is removed the unsaponifiables enriched material of being separated out 12.6 grams then, and mother liquor adds alkene hydrochloric acid while stirring to pH=7.0 under 50 ℃, get thiaminogen crude product 5.9 grams, it is refining to add aqueous ethanol, filters and receives to such an extent that thiaminogen is dried under vacuum, gets finished product 2.49 grams, purity 98.3%, yield is 55.9% of distillation enriched material theoretical content.
85% of 3 times of amounts of adding ethanol in above-mentioned unsaponifiables enriched material 12.6 grams, include the NaOH3.5 gram, stirring and refluxing 8 hours, then as the method for embodiment 1, with petroleum ether extraction three times, reclaim sherwood oil and get peaceful crude product 4.32 grams of dark-brown periodontal, the ethanol that adds 30 times of amounts is refining, reclaim ethanol, get peaceful finished product 3.2 grams of yellow decorating film periodontal, total sterol content 66.3%, quality meets the medicine inspection standard, yield is 25.4% of a unsaponifiables enriched material, and amounting to clean crude oil yield per ton is 10.2 kilograms.
Embodiment 6
The oil extracted from rice husks 1500 of removal of impurities restrains, and (acid number 12.76, thiaminogen content 2.1%) adds clear water 45 grams, stirs 30 minutes at 75 °-80 ℃, and centrifugation removes the pin that removes photoresist, and gets degummed oil 1431 grams, acid number 12, thiaminogen content 2.0%.
Press the method for embodiment 1 and handle degummed oil, get alkali refining oil 1148 grams, wherein thiaminogen content 0.3%, and acid number 0.41 gets soap stock 567 grams simultaneously.
Soap stock is handled by the method for embodiment 1, gets acidifying oil 281 grams, and acidifying oil is handled by the method for embodiment 1 and obtained mixed fatty acid 171 grams, distills enriched material 107 grams, thiaminogen content 22.33%.
Get above-mentioned distillation enriched material 20 grams, 90% ethanol that adds 5 times of amounts, include the NaOH1.2 gram, heated and stirred, be warming up to 60 ℃ of reactions 70 minutes, and thin up determining alcohol to 60% progressively, stop to stir, left standstill two hours, tell unsaponifiables enriched material 12.9 grams, mother liquor adds citric acid solution while stirring until pH=6.9 under 50 ℃, filter to such an extent that white thiaminogen 5.7 restrains, and adds aqueous ethanol and makes with extra care, get finished product thiaminogen 2.4 grams, purity 96.3%, yield is 63% of distillation enriched material theoretical content, amounting to clean crude oil yield per ton is 8.27 kilograms.
90% ethanol that in 12.9 above-mentioned gram unsaponifiables enriched materials, adds 3 times of amounts, the NaOH4.8 gram, saponification refluxed 6 hours, then as the method for embodiment 1,, reclaim sherwood oil and get peaceful 4.3 grams of dark-brown crude product periodontal with petroleum ether extraction three times, refining that finished product periodontal peaceful 3.2 restrains with 30 times ethanol again, total sterol content 63.2%, yield is 24.8% of a unsaponifiables enriched material, amounting to clean crude oil yield per ton is 11.4 kilograms.
Embodiment 7
Get distillation enriched material (with embodiment 6) 20 grams, add 75% Virahol 100ml, include the KOH1 gram, heating while stirring in 50 ℃ of reactions 90 minutes, and adds water and makes determining alcohol be diluted to 50%, left standstill 2 hours, and removed by filter unsaponifiables enriched material 13.4 grams of separating out then.Mother liquor adds disodium-hydrogen solution while stirring to pH=6.8 under 50 ℃.Get thiaminogen crude product 5.9 grams, it is refining to add aqueous isopropanol, gets finished product thiaminogen 2.28 grams, and purity 96.2%, yield are 61.9% of distillation enriched material theoretical content.
80% ethanol that in above-mentioned unsaponifiables enriched material 13.4 grams, adds 4 times of amounts, the KOH4.5 gram, saponification refluxed 6 hours, all the other are with embodiment 1, with petroleum ether extraction three times, reclaim sherwood oil and get peaceful crude product 4.1 grams of dark-brown periodontal, refining with 30 times alcohol reflux again, get peaceful 3 grams of finished product periodontal, total sterol content 64.1%, yield is 22.3% of a unsaponifiables enriched material.
Embodiment 8
Take by weighing 1500 grams hair oil extracted from rice husks (acid number 13.9 grams, thiaminogen content 1.76%) only, be heated to 60-70 ℃, add 85% phosphatase 24 .5 gram, stirred 15 minutes, centrifugation removes the pin that removes photoresist, and gets degummed oil 1420 grams, acid number 14.8 grams, thiaminogen content 1.8%.Degummed oil adds 18 ° of Be'NaOH solution 170 according to a conventional method and restrains, and continues heated and stirred 1 hour, is warming up to 60 ℃, and oily soap gets alkali refining oil 1136 grams through centrifugation, oily two-story valley dimension cellulose content 0.4%, and acid value 0.45, and get soap stock 630 grams, contain acidifying oil 45%.
Soap stock adds 16 ° of Be'NaOH solution by saponification value, in 80-90 ℃ of saponification three hours, adds hydrochloric acid then to pH=3,100-105 ℃ of acidifying one hour, puts waste acid water, adds clear water and is washed till neutrality repeatedly.Acidifying oil 278 grams, thiaminogen content 7.56%, neutralization value 168, dehydration enters vacuum distillation plant and distills concentratedly under 240 ℃/0.1mmHg then, obtains mixed fatty acid 193 grams, distillation enriched material 83 grams, thiaminogen content 23.5%.
Get above-mentioned distillation enriched material 20 grams, 95% ethanolic soln that adds 4 times of amounts, the NaOH1.5 gram mixes, be warming up to 60 ℃, reacted 90 minutes, and thin up determining alcohol to 75% progressively, insulation was left standstill two hours, separate out unsaponifiables enriched material 12.2 grams, mother liquor under agitation adds tartrate to pH=6.7 in 50 ℃, separates out thiaminogen crude product 6.5 grams, adds clear water and is washed till neutrality, adding acidic ethanol then refluxes refining, be washed till neutrality with distilled water, filter, in the following 80 ℃ of oven dry of vacuum, get white powdery finished product thiaminogen 2.6 grams, yield is 54.16% of distillation enriched material theoretical content, and purity 98.5%, quality meet the medicine inspection standard
[3]
In above-mentioned 12.2 gram unsaponifiables enriched materials, add 70% ethanol of 4 times of amounts, the NaOH4 gram, temperature rising reflux 8 hours is made peaceful 3.4 grams of periodontal by embodiment 1 method, total sterol content 60.8%, yield is 27.86% of a unsaponifiables enriched material.
Embodiment 9
Take by weighing 1500 and restrain the clean hair oil extracted from rice husks (acid number 17, thiaminogen content 1.7%) that removes by filter the chaff bits, add clear water 4.5%, come unstuck at 70-85 ℃, centrifugation removes the pin that removes photoresist, and gets degummed oil 1455 grams (acid number 16.2, thiaminogen content 1.7%).In this degummed oil, add 18 ° of Be'NaOH solution, 188 grams, alkali refining according to a conventional method, temperature is 60 ℃ eventually, soap stock is removed in centrifugation, alkali refining oil 1620 grams (acid number 0.4, thiaminogen content 0.35%).
Soap stock replenishes saponification, acidifying by the method for embodiment 8, makes acidifying oil 433 grams, and neutralization value 168.0 gets mixed fatty acid 325 grams after distillation concentrates, and distillation enriched material 106 grams include thiaminogen 18.6%.
Get above-mentioned distillation enriched material 20 grams, add 90% ethanol and the KOH2 gram of 4 times of amounts, heat to 65 ℃ of reactions 100 minutes, progressively thin up to determining alcohol is 70%, and insulation was left standstill 2 hours, separated out unsaponifiables enriched material 11.5 grams.In mother liquor, add dilute hydrochloric acid and disodium-hydrogen to pH=7.0, separate out thick thiaminogen 4.8 grams, refining with Diluted Alcohol, with distilled water flush away ethanol, under vacuum, dry to such an extent that thiaminogen 1.93 restrains, purity 96.5%, yield is 51.88% of distillation enriched material content.
Gained unsaponifiables enriched material 11.5 grams get peaceful 2.8 grams of periodontal by embodiment 8 extracting method, total sterol content 60.6%, and yield is 24.35% of a unsaponifiables enriched material.
Annotate:
[1] acid number-77 year version Chinese Pharmacopoeia is two ones, 51 pages of appendix
[2] thiaminogen content-77 year version Chinese Pharmacopoeia
[3] thiaminogen medicine inspection standard-77 year version Chinese Pharmacopoeia
[4] the peaceful medicine inspection standard-88 of the periodontal year version Zhejiang Province drug standard
[5] total sterol content-88 year version Zhejiang Province drug standard are 134 pages
Claims (5)
1, a kind of is raw material with the hair oil extracted from rice husks, preparation Rice pollard oil, mixed fatty acid, thiaminogen and the peaceful produced in series method of periodontal, it is characterized in that the pulled wool oil extracted from rice husks through come unstuck, an alkali refining gets soap stock and rice finished product oil extracted from rice husks; Soap stock obtains distilling enriched material and finished product mixed fatty acid through additional saponification, acidifying, vacuum distilling; The distillation enriched material through pure alkaline solution extract unsaponifiables enriched material and contain the mother liquor of thiaminogen; The mother liquor that contains thiaminogen is through acidification, refining finished product thiaminogen, the unsaponifiables enriched material again through ethanol alkali lye handle and petroleum ether extraction to get the finished product periodontal peaceful.
2, the method for claim 1 is characterized in that described vacuum distilling is to adopt vacuum scraper plate thin film distillation method, and the distillation residual voltage is controlled at below the 0.1mmHg, and temperature is 200-240 ℃.
3, the method for claim 1, the Virahol or the alcoholic acid alkaline solution that it is characterized in that distilling enriched material and be the 75-95% that doubly measures with its 4-7 extract.
4, the method for claim 1 is characterized in that the unsaponifiables enriched material is to adopt the alcoholic acid alkaline solution of the 50%-95% concentration that 3-6 doubly measures to extract, and used alkali is KOH or NaOH.
5, method as claimed in claim 3 is characterized in that the concentration of employed pure alkaline solution progressively is diluted to 50-80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91103725 CN1067448A (en) | 1991-05-31 | 1991-05-31 | Produce peaceful etc. the method for thiaminogen, periodontal simultaneously by the hair oil extracted from rice husks |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91103725 CN1067448A (en) | 1991-05-31 | 1991-05-31 | Produce peaceful etc. the method for thiaminogen, periodontal simultaneously by the hair oil extracted from rice husks |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1067448A true CN1067448A (en) | 1992-12-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 91103725 Pending CN1067448A (en) | 1991-05-31 | 1991-05-31 | Produce peaceful etc. the method for thiaminogen, periodontal simultaneously by the hair oil extracted from rice husks |
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| Country | Link |
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| CN (1) | CN1067448A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999011142A1 (en) * | 1997-09-02 | 1999-03-11 | The Ricex Company | A process for obtaining micronutrient enriched rice bran oil |
| CN101805667A (en) * | 2010-04-02 | 2010-08-18 | 安徽省思润谷物油精炼有限公司 | Method for dry degumming and refining of edible rice bran oil |
| CN101456891B (en) * | 2008-12-26 | 2011-07-20 | 河南华泰粮油机械工程有限公司 | Method for extracting oryzanol from rice bran oil soapstock |
| CN106749480A (en) * | 2017-02-10 | 2017-05-31 | 山东三星玉米产业科技有限公司 | Oryzanol extracting method in Rice oil |
| CN111394173A (en) * | 2019-01-03 | 2020-07-10 | 宿迁雅来康生物科技有限公司 | Method for preparing oryzanol from rice oil |
| CN111440659A (en) * | 2020-01-08 | 2020-07-24 | 沈阳师范大学 | Deacidification method of rice bran oil |
-
1991
- 1991-05-31 CN CN 91103725 patent/CN1067448A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999011142A1 (en) * | 1997-09-02 | 1999-03-11 | The Ricex Company | A process for obtaining micronutrient enriched rice bran oil |
| CN101456891B (en) * | 2008-12-26 | 2011-07-20 | 河南华泰粮油机械工程有限公司 | Method for extracting oryzanol from rice bran oil soapstock |
| CN101805667A (en) * | 2010-04-02 | 2010-08-18 | 安徽省思润谷物油精炼有限公司 | Method for dry degumming and refining of edible rice bran oil |
| CN106749480A (en) * | 2017-02-10 | 2017-05-31 | 山东三星玉米产业科技有限公司 | Oryzanol extracting method in Rice oil |
| CN111394173A (en) * | 2019-01-03 | 2020-07-10 | 宿迁雅来康生物科技有限公司 | Method for preparing oryzanol from rice oil |
| CN111440659A (en) * | 2020-01-08 | 2020-07-24 | 沈阳师范大学 | Deacidification method of rice bran oil |
| CN111440659B (en) * | 2020-01-08 | 2023-11-21 | 沈阳师范大学 | Deacidification method of rice bran oil |
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