CN104889141A - Comprehensive utilization method for soybean dregs - Google Patents
Comprehensive utilization method for soybean dregs Download PDFInfo
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- CN104889141A CN104889141A CN201510279929.7A CN201510279929A CN104889141A CN 104889141 A CN104889141 A CN 104889141A CN 201510279929 A CN201510279929 A CN 201510279929A CN 104889141 A CN104889141 A CN 104889141A
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- bean dregs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention provides a comprehensive utilization method for soybean dregs and particularly relates to a method, which is used for solving the problem of low soybean dreg comprehensive utilization efficiency in the prior art, for preparing biodiesel from soybean dregs to co-produce dietary fibers and phytosterols. The comprehensive utilization method comprises the following steps: firstly, removing redundant proteins from the soybean dregs through an enzyme treatment method; then, carrying out base-catalyzed hydrolysis and acidification solid-liquid separation, and carrying out washing and centrifugal drying on a solid state to obtain dietary fibers; by taking a great deal of free fatty acid and phytosterols rich in a liquid state as raw materials for biodiesel, adding a proper amount of alcohol to carry out esterification ester exchange reaction under the catalysis of solid acid catalysts such as macro-porous strongly acidic styrene type cation exchange resin, and distilling to obtain the biodiesel; and extracting the phytosterols from residual slag liquor through an ethyl acetate dissolution-crystallization method. According to the comprehensive utilization method, the extracted phytosterols, dietary fibers and biodiesel are good in purity and high in yield, so that the comprehensive utilization of the soybean dregs is realized and the utilization value of the soybean dregs is improved.
Description
Technical field
What the present invention relates to is a kind of method that bean dregs fully utilize, and is specifically related to one and utilizes bean dregs to prepare biodiesel, the method for coproduction dietary fiber, phytosterol.
Background technology
Bean dregs are accessory substances of the bean products such as production of bean curd, the skin of soya-bean milk, soya-bean milk, soybean protein, containing protein 19-23% in dry bean dregs, fat 8-16%, content of phytosterol 0.37% (200mg-500mg/100g), dietary fiber 50-57%, bean dregs are rich in so abundant dietary fiber, fat and sterol, and the utilization of bean dregs are only limitted to a kind of exploitation of composition, effectively can not make full use of the various compositions in bean dregs.The bean dregs steamed bun of patent 201210504597.4 invention, traditional Land use systems of bean dregs is that the composition of a lot of high nutrition can not absorb directly as forage feed animal, in Japan, Hong Kong all as offal treatment.Rough calculation often processes 1 ton of soybean can output 1.2 tons of wet bean dregs, and current domestic soy food product industry about produces 1,200 ten thousand tons of wet bean dregs every year.How to effectively utilize bean dregs so as seen and become the problem be badly in need of research and solved.
" the promoting that biological industry accelerates development some policies " of putting into effect in June, 2009 is clear and definite: to the non-grain alcohol fuel produced through approval, biodiesel, the important biomolecule energy products such as living beings thermoelectricity, country gives suitable support.China plans the year two thousand twenty, reach and produce biodiesel 2,000,000 tons of scales (Xiaoyu Yan.Bioethanol and Biodiesel as Alternative Transportation Fuels in China:Current Status per year, Future Potentials, and Life Cycle Analysis.Energy Source, Part A.2012,34:1067-1075).And China's biodiesel industry is subject to policy restriction in raw material supply, vegetable oil does not allow as production of biodiesel raw material, and the task of finding biodiesel raw material is extremely urgent.
The dietary fiber being described as " human body the 7th nutrient " has become the irreplaceable nutrient maintaining health, and dietary fiber has been widely deployed in food industry.Bean dregs are rich in abundant dietary fiber, draw materials conveniently, cheap, and bean dregs dietary fiber comprises a large amount of celluloses, occupies more than 50% of dietary fiber, and cellulosic is good, and bean dregs dietary fiber has been considered to the important safe sources of dietary fiber.But also there is the grease of 8-16% in bean dregs, the oxidation of grease can make bean dregs produce " beany flavor ", and traditional method is that lipase or alkaline process remove grease, although these class methods eliminate grease, wastes a large amount of energy simultaneously.This patent effectively this part energy of Appropriate application prepares biodiesel, in order to solve the limitation that biodiesel cannot be refined from vegetable oil.
The phytosterol being described as " key of life " can keep the stable of organism environment, regulate metabolism, human body can be suppressed the absorption of cholesterol, the heart disease, ulcer, Skin Squamous Cell Carcinoma, cervical carcinoma etc. of phytosterol to coronary atherosclerosis class has significantly prevention and curative effect simultaneously, in addition, the raw materials for production of phytosterol or important steroid drugs and vitamine D3.Phytosterol and derivative thereof have been widely deployed in all trades and professions as industries such as medical treatment, cosmetics, food, papermaking printings.In bean dregs, sterol is ignored by people always, and the present invention extracts the phytosterol of high added value while the fat, dietary fiber of effective exploitation bean dregs.
Summary of the invention
Drawing materials a limited difficult problem for overcoming biodiesel, is the comprehensive utilization effect improving bean dregs, and the invention provides the method for a kind of bean dregs comprehensive utilization, object is the preparing biodiesel from lipid effectively utilized in bean dregs, and coproduction dietary fiber, phytosterol.
Bean dregs method of comprehensive utilization of the present invention, comprises the following steps:
1) pretreatment: suppressed by wet bean dregs and dewater, pulverizes filter cake, and then use protease hydrolytic to remove protein in bean dregs, drying process obtains the dry bean dregs that water content is 5-12%;
2) dietary fiber is reclaimed
In dry bean dregs, add ethanol, aqueous slkali carries out basecatalyzed decomposition reaction, reacted rear adjustment pH=3-5, solid, liquid has been separated and is precipitated and mother liquor, drying precipitatedly obtain dietary fiber;
3) biodiesel is prepared
By step 2) in the mother liquor that obtains leave standstill and get oil phase, add water and rinse to neutral, then distillation removing superfluous water and ethanol; In the feed liquid after distillation, add ethanol, macroporous type strongly acidic styrene type cation exchange resin catalyst carries out esterification, in esterification, the mass ratio of feed liquid, ethanol and catalyst is: feed liquid: ethanol: catalyst=1:0.5-6:0.05-0.5; Reacted rear filtering recovering catalyst, liquid phase slowly heats up distillation, and when being warming up to 250 DEG C, distillation obtains biodiesel;
4) phytosterol is reclaimed
Add in remaining slag liquid in ethyl acetate, acetone, ethanol after distillation biodiesel one or more, decrease temperature crystalline after slag liquid dissolves, what crystallization went out is solid-stately phytosterol crude product, and mother liquor distillating recovering solvent reuses; The solvent added in residue slag liquid can be the one in ethyl acetate, acetone or alcohol, also can be that wherein multiple mixes with arbitrary proportion, preferred solvent has two kinds, for ethyl acetate, acetone and ethanol are the mixed mixed solvent of 4:1 with volume ratio.
In phytosterol crude product, add ethanol or re-crystallizing in ethyl acetate, insulation, centrifugation obtain fine work phytosterol, and mother liquor distillating recovering solvent reuses.
In the present invention, bean dregs remove unnecessary protein through pretreatment, by alkali catalyzed hydrolysis, acidifying Separation of Solid and Liquid, the solid-state washing centrifugal drying that passes through obtains dietary fiber, be rich in a large amount of free fatties and phytosterol in liquid state, use acetic acid ethyl dissolution method for crystallising extraction phytosterol wherein, remaining liq can be used as the raw material of biodiesel, add ethanol in proper amount at solid acid catalyst as under the catalysis of macroporous type strongly acidic styrene type cation exchange resin, preparation biodiesel.The method had both solved the Utilizing question of solid waste, can realize again production biodiesel coproduction dietary fiber, phytosterol, realize the comprehensive utilization of bean dregs, improved the value of bean dregs.
Preferably, step 1) in, bean dregs filter cake is crushed to 100-150 order; Proteolytic condition is: protease with suppress dewater after the bean dregs mass ratio of undried process be: 0.2-0.8:100, protease is neutral protein matter enzyme, and being hydrolyzed in temperature is 30 ~ 50 DEG C, and pH=6.5 ~ 7.5 time are carried out.
Preferably, step 2) carry out at 80 DEG C, described aqueous slkali is the NaOH solution of 5mol/L, dry bean dregs: ethanol: NaOH solution=1:1-3.5:0.2-0.55, and described ratio is mass ratio, and base catalyzed reactions carries out 3-5 hour; The acid of adjustment pH is the hydrochloric acid of mass fraction 37.5%; The preferred centrifugation of Separation of Solid and Liquid, after the precipitation obtained washes three times, centrifugal drying obtains dietary fiber, and the concrete operations condition of washing and drying is: centrifugal use filter cloth order number is 500 orders, and centrifugal speed is 5000rpm/min, the drying time is 30min/ pot, and baking temperature controls at 65 ~ 75 DEG C.
Preferably, step 3) carry out under the protection of nitrogen sealing liquid face, can free fatty be reduced oxidized.Reaction time of esterification preferably 9 hours, preferable reaction temperature is 84 DEG C, i.e. reflux state.The liquid that first the described slow distillation that heats up steams is water and ethanol; Continue to heat up, about 210 DEG C start to steam fatty-acid ethyl ester; Be warming up to 250 DEG C and no longer include distillate, stop distillation, distillate is biodiesel, distills remaining slag liquid and is rich in a large amount of phytosterols.
Preferably, step 4) crystallization solid-liquid ratio is 1:2.5 when preparing phytosterol crude product, curing temperature 10 DEG C, 16 hours curing times.Solvent preferred alcohol during recrystallization, can make that phytosterols crystals is needle-like, material is white, purity is high.
Compared with prior art, the invention has the beneficial effects as follows:
1) preparation method of the present invention is more simple, and extraction step is simple, and yield is high, and the phytosterol purity of extraction is higher than 96%, and it is 92% that insoluble diedairy fiber content all exceedes, and the purity of biodiesel is also 92.5%;
2) problem of raw material deficiency in preparation of biodiesel can be solved, solve biodiesel and vegetable oil can not be used to do the problem of raw material;
3) can be used in preparing biodiesel, dietary fiber and phytosterol, can realize the comprehensive utilization of bean dregs, improve the value of bean dregs, the utilization ratio of bean dregs is higher;
4) processing method of original bean dregs mostly is directly discarded, and method of the present invention can utilize discarded object to recycle, and solves the Utilizing question of solid waste, reduces the pressure of bean dregs to environment.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is further explained.
Wet bean dregs are carried out pretreatment according to following manner: suppressed by wet bean dregs and dewater, then filter cake to 120 order is shattered, re-using neutral protein matter enzyme in temperature is 45 DEG C, is hydrolyzed under pH=7, and protease is 0.5:100 with the mass ratio suppressing the bean dregs after dewatering, protein in removing bean dregs, dry at finally using insulating box 80 DEG C, obtaining water capacity is 6%, and fat content is 18.75%, insoluble diedairy fiber content is 36.2%, and content of phytosterol is the dry bean dregs of 0.5%.
Correlation formula calculates:
formula (1)
formula (2)
formula (3)
Embodiment 1
(dry bean dregs: ethanol: NaOH solution mass ratio=1:2:0.5, feed liquid: ethanol: catalyst quality ratio=1:3:0.35)
Get pretreated dry bean dregs 50g and put into there-necked flask, add 100g ethanol and be warming up to 80 DEG C of (reflux state) stirring and dissolving 30min, then in reaction system, the NaOH solution 25g of 5mol/L is dripped with funnel, be added dropwise to complete, react 3 hours under return stirring state, reaction completes, and starts in reaction system, drip hydrochloric acid (mass concentration is 37.5wt%) acidifying and regulates PH=3, stir 10min, repetition measurement PH.To feed liquid centrifugation, collecting precipitation and mother liquor, add water in precipitation and stir 30min, centrifugation again, collecting precipitation and mother liquor, so carry out 3 times, precipitation oven dry shatters and obtains insoluble diedairy fiber 15.5g, insoluble diedairy fiber content is 93.5%, and water capacity is 6%, and the yield of insoluble diedairy fiber is 80.1%.
The mother liquor collected leaves standstill and cuts water layer, collecting oil phase repeatedly washes until PH=7, be then heated to 80 DEG C, vacuum for-0.08Mpa, distill out unnecessary second alcohol and water, until without distillate, the oil phase obtained is free fatty and phytosterol quality is 7.53g.Collection is handled oil phase well and is taked nitrogen to seal protection in order to experiment use.
Get oil phase (acid number is free fatty and the phytosterol of the 152.32mgKOH/g) 7.53g handled well, ethanol 22.59g, strongly acidic styrene type cation exchange resin catalyst 2.64g puts into there-necked flask, under being warming up to reflux state, react after 9 hours and stop, filtering recovering catalyst, liquid state carries out distillation removing second alcohol and water, continue distillation about 210 DEG C to start to steam fatty-acid ethyl ester, be warming up to 250 DEG C and no longer include distillate, stop distillation, distillate is biodiesel, survey acid number is 2.25mgKOH/g, conversion ratio is 98.5%, collect the remaining slag liquid 5.24g of distillation.Whole reaction, always to inflated with nitrogen in there-necked flask, prevents free-fat acid oxidase.
Get slag liquid 5.24g and put into there-necked flask, add ethyl acetate 13.1g stirring and be warming up to 65 DEG C, after oil phase has dissolved, start average rate cooling of lowering the temperature, within 6 hours, be cooled to curing temperature 10 DEG C, stop stirring insulation slaking 16 hours, the solid-state phytosterol crude product quality that is of collected by centrifugation is 0.365g, and content of phytosterol is 90.4%.
Get crude product phytosterol 0.365g and put into there-necked flask, add ethanol 7.3g stirring and be warming up to 60 DEG C, after sterol has dissolved, start average rate cooling of lowering the temperature, within 6 hours, be cooled to curing temperature 8 DEG C, stop stirring insulation slaking 24 hours, centrifugal drying obtains fine work phytosterol 0.175g, water capacity is 5.5%, and sterol content is 97.6%, and total phytosterol yield is 68.7%.
Embodiment 2
(dry bean dregs: ethanol: NaOH solution mass ratio=1:1:0.2, feed liquid: ethanol: catalyst quality ratio=1:0.5:0.05)
Get pretreated bean dregs 50g and put into there-necked flask, add 50g ethanol and be warming up to 80 DEG C of (reflux state) stirring and dissolving 30min, then in reaction system, the NaOH solution 10g of 5mol/L is dripped with funnel, be added dropwise to complete, react 3 hours under return stirring state, reaction completes, and starts in reaction system, drip hydrochloric acid (mass concentration is 37.5wt%) acidifying and regulates PH=3, stir 10min, repetition measurement PH.To feed liquid centrifugation, collecting precipitation and mother liquor, add water in precipitation and stir 30min, centrifugation again, collecting precipitation and mother liquor, so carry out 3 times, precipitation oven dry shatters and obtains insoluble diedairy fiber 12.3g, insoluble diedairy fiber content is 85.6%, and water capacity is 5.5%, and the yield of insoluble diedairy fiber is 58.5%.
The mother liquor collected leaves standstill and cuts water layer, collecting oil phase repeatedly washes until PH=7, be then heated to 80 DEG C, vacuum for-0.08Mpa, distill out unnecessary second alcohol and water, until without distillate, the oil phase obtained is free fatty and phytosterol quality is 6.54g.Collection is handled oil phase well and is taked nitrogen to seal protection in order to experiment use.
Get oil phase (acid number is free fatty and the phytosterol of the 149.25mgKOH/g) 6.54g handled well, ethanol 3.27g, strongly acidic styrene type cation exchange resin catalyst 0.327g puts into there-necked flask, under being warming up to reflux state, react after 9 hours and stop, filtering recovering catalyst, liquid state carries out distillation removing second alcohol and water, continue distillation about 210 DEG C to start to steam fatty-acid ethyl ester, be warming up to 250 DEG C and no longer include distillate, stop distillation, distillate is biodiesel, survey acid number is 18.36mgKOH/g, conversion ratio is 87.7%, collect the remaining slag liquid 7.23g of distillation.Whole reaction, always to inflated with nitrogen in there-necked flask, prevents free-fat acid oxidase.
Get slag liquid 7.23g and put into there-necked flask, add ethyl acetate 18.08g stirring and be warming up to 65 DEG C, after oil phase has dissolved, start average rate cooling of lowering the temperature, within 6 hours, be cooled to curing temperature 10 DEG C, stop stirring insulation slaking 16 hours, the solid-state phytosterol crude product quality that is of collected by centrifugation is 0.315g, and content of phytosterol is 89.2%.
Get crude product phytosterol 0.315g and put into there-necked flask, add ethanol 6.3g stirring and be warming up to 60 DEG C, after sterol has dissolved, start average rate cooling of lowering the temperature, within 6 hours, be cooled to curing temperature 8 DEG C, stop stirring insulation slaking 24 hours, centrifugal drying obtains fine work phytosterol 0.165g, water capacity is 5.8%, and sterol content is 95.3%, and total phytosterol yield is 63%.
Embodiment 3
(dry bean dregs: ethanol: NaOH solution mass ratio=1:3.5:0.65, feed liquid: ethanol: catalyst quality ratio=1:6:0.5)
Get pretreated dry bean dregs 50g and put into there-necked flask, add 175g ethanol and be warming up to 80 DEG C of (reflux state) stirring and dissolving 30min, then in reaction system, the NaOH solution 32.5g of 5mol/L is dripped with funnel, be added dropwise to complete, react 3 hours under return stirring state, reaction completes, and starts in reaction system, drip hydrochloric acid (mass concentration is 37.5wt%) acidifying and regulates PH=3, stir 10min, repetition measurement PH.To feed liquid centrifugation, collecting precipitation and mother liquor, add water in precipitation and stir 30min, centrifugation again, collecting precipitation and mother liquor, so carry out 3 times, precipitation oven dry shatters and obtains insoluble diedairy fiber 15.1g, insoluble diedairy fiber content is 94.3%, and water capacity is 5.4%, and the yield of insoluble diedairy fiber is 79.17%.
The mother liquor collected leaves standstill and cuts water layer, collecting oil phase repeatedly washes until PH=7, be then heated to 80 DEG C, vacuum for-0.08Mpa, distill out unnecessary second alcohol and water, until without distillate, the oil phase obtained is free fatty and phytosterol quality is 8.05g.Collection is handled oil phase well and is taked nitrogen to seal protection in order to experiment use.
Get oil phase (acid number is free fatty and the phytosterol of the 145.87mgKOH/g) 8.05g handled well, ethanol 48.3g, strongly acidic styrene type cation exchange resin catalyst 4.03g puts into there-necked flask, under being warming up to reflux state, react after 9 hours and stop, filtering recovering catalyst, liquid state carries out distillation removing second alcohol and water, continue distillation about 210 DEG C to start to steam fatty-acid ethyl ester, be warming up to 250 DEG C and no longer include distillate, stop distillation, distillate is biodiesel, survey acid number is 1.88mgKOH/g, conversion ratio is 98.7%, collect the remaining slag liquid 6.15g of distillation.Whole reaction, always to inflated with nitrogen in there-necked flask, prevents free-fat acid oxidase.
Get slag liquid 6.15g and put into there-necked flask, add ethyl acetate 15.4g stirring and be warming up to 65 DEG C, after oil phase has dissolved, start average rate cooling of lowering the temperature, within 6 hours, be cooled to curing temperature 10 DEG C, stop stirring insulation slaking 16 hours, the solid-state phytosterol crude product quality that is of collected by centrifugation is 0.378g, and content of phytosterol is 90.8%.
Get crude product phytosterol 0.378g and put into there-necked flask, add ethanol 7.6g stirring and be warming up to 60 DEG C, after sterol has dissolved, start average rate cooling of lowering the temperature, within 6 hours, be cooled to curing temperature 8 DEG C, stop stirring insulation slaking 24 hours, centrifugal drying obtains fine work phytosterol 0.182g, water capacity is 5.8%, and sterol content is 97.7%, and total phytosterol yield is 71.3%.
Embodiment 4
(dry bean dregs: ethanol: NaOH solution mass ratio=1:1:0.65, feed liquid: ethanol: catalyst quality ratio=1:6:0.05)
Get pretreated dry bean dregs 50g and put into there-necked flask, add 50g ethanol and be warming up to 80 DEG C of (reflux state) stirring and dissolving 30min, then in reaction system, the NaOH solution 32.5g of 5mol/L is dripped with funnel, be added dropwise to complete, react 3 hours under return stirring state, reaction completes, and starts in reaction system, drip hydrochloric acid (mass concentration is 37.5wt%) acidifying and regulates PH=3, stir 10min, repetition measurement PH.To feed liquid centrifugation, collecting precipitation and mother liquor, add water in precipitation and stir 30min, centrifugation again, collecting precipitation and mother liquor, so carry out 3 times, precipitation oven dry shatters and obtains insoluble diedairy fiber 13.5g, insoluble diedairy fiber content is 88.9%, and water capacity is 6.5%, and the yield of insoluble diedairy fiber is 65.95%.
The mother liquor collected leaves standstill and cuts water layer, collecting oil phase repeatedly washes until PH=7, be then heated to 80 DEG C, vacuum for-0.08Mpa, distill out unnecessary second alcohol and water, until without distillate, the oil phase obtained is free fatty and phytosterol quality is 6.95g.Collection is handled oil phase well and is taked nitrogen to seal protection in order to experiment use.
Get oil phase (acid number is free fatty and the phytosterol of the 134.89mgKOH/g) 6.95g handled well, ethanol 41.7g, strongly acidic styrene type cation exchange resin catalyst 0.35g puts into there-necked flask, under being warming up to reflux state, react after 9 hours and stop, filtering recovering catalyst, liquid state carries out distillation removing second alcohol and water, continue distillation about 210 DEG C to start to steam fatty-acid ethyl ester, be warming up to 250 DEG C and no longer include distillate, stop distillation, distillate is biodiesel, survey acid number is 15.36mgKOH/g, conversion ratio is 88.6%, collect the remaining slag liquid 6.52g of distillation.Whole reaction, always to inflated with nitrogen in there-necked flask, prevents free-fat acid oxidase.
Get slag liquid 6.52g and put into there-necked flask, add acetone and ethanol (volume ratio is 4/1) mixture 16.3g stirs and is warming up to 50 DEG C, after oil phase has dissolved, start average rate cooling of lowering the temperature, within 5 hours, be cooled to curing temperature 10 DEG C, stop stirring insulation slaking 12 hours, the solid-state phytosterol crude product quality that is of collected by centrifugation is 0.309g, and content of phytosterol is 89.6%.
Get crude product phytosterol 0.309g and put into there-necked flask, add ethanol 6.2g stirring and be warming up to 60 DEG C, after sterol has dissolved, start average rate cooling of lowering the temperature, within 6 hours, be cooled to curing temperature 8 DEG C, stop stirring insulation slaking 24 hours, centrifugal drying obtains fine work phytosterol 0.156g, water capacity is 6.2%, and sterol content is 95.6%, and total phytosterol yield is 59.5%.
Embodiment 5
(dry bean dregs: ethanol: NaOH solution mass ratio=1:3.5:0.2, feed liquid: ethanol: catalyst quality ratio=1:0.5:0.5)
Get pretreated dry bean dregs 50g and put into there-necked flask, add 175g ethanol and be warming up to 80 DEG C of (reflux state) stirring and dissolving 30min, then in reaction system, the NaOH solution 10g of 5mol/L is dripped with funnel, be added dropwise to complete, react 3 hours under return stirring state, reaction completes, and starts in reaction system, drip hydrochloric acid (mass concentration is 37.5wt%) acidifying and regulates PH=3, stir 10min, repetition measurement PH.To feed liquid centrifugation, collecting precipitation and mother liquor, add water in precipitation and stir 30min, centrifugation again, collecting precipitation and mother liquor, so carry out 3 times, precipitation oven dry shatters and obtains insoluble diedairy fiber 12.6g, insoluble diedairy fiber content is 87.2%, and water capacity is 5.8%, and the yield of insoluble diedairy fiber is 60.83%.
The mother liquor collected leaves standstill and cuts water layer, collecting oil phase repeatedly washes until PH=7, be then heated to 80 DEG C, vacuum for-0.08Mpa, distill out unnecessary second alcohol and water, until without distillate, the oil phase obtained is free fatty and phytosterol quality is 7.26g.Collection is handled oil phase well and is taked nitrogen to seal protection in order to experiment use.
Get oil phase (acid number is free fatty and the phytosterol of the 148.23mgKOH/g) 7.26g handled well, ethanol 3.63g, strongly acidic styrene type cation exchange resin catalyst 3.63g puts into there-necked flask, under being warming up to reflux state, react after 9 hours and stop, filtering recovering catalyst, liquid state carries out distillation removing second alcohol and water, continue distillation about 210 DEG C to start to steam fatty-acid ethyl ester, be warming up to 250 DEG C and no longer include distillate, stop distillation, distillate is biodiesel, survey acid number is 12.68mgKOH/g, conversion ratio is 91.44%, collect the remaining slag liquid 7.06g of distillation.Whole reaction, always to inflated with nitrogen in there-necked flask, prevents free-fat acid oxidase.
Get slag liquid 7.06g and put into there-necked flask, add ethyl acetate 17.65g stirring and be warming up to 60 DEG C, after oil phase has dissolved, start average rate cooling of lowering the temperature, within 6 hours, be cooled to curing temperature 10 DEG C, stop stirring insulation slaking 16 hours, the solid-state phytosterol crude product quality that is of collected by centrifugation is 0.356g, and content of phytosterol is 90.5%.
Get crude product phytosterol 0.356g and put into there-necked flask, add ethanol 7.1g stirring and be warming up to 60 DEG C, after sterol has dissolved, start average rate cooling of lowering the temperature, within 6 hours, be cooled to curing temperature 8 DEG C, stop stirring insulation slaking 24 hours, centrifugal drying obtains fine work phytosterol 0.174g, water capacity is 6.0%, and sterol content is 97.4%, and total phytosterol yield is 67.8%.
Claims (10)
1. a bean dregs method of comprehensive utilization, is characterized in that, comprises the following steps:
1) pretreatment: suppressed by wet bean dregs and dewater, pulverizes filter cake, and then use protease hydrolytic to remove protein in bean dregs, drying process obtains the dry bean dregs that water content is 5-12%;
2) dietary fiber is reclaimed
In dry bean dregs, add ethanol, aqueous slkali carries out basecatalyzed decomposition reaction, reacted rear adjustment pH=3-5, solid, liquid has been separated and is precipitated and mother liquor, drying precipitatedly obtain dietary fiber;
3) biodiesel is prepared
By step 2) in the mother liquor that obtains leave standstill and get oil phase, add water and rinse to neutral, then distillation removing superfluous water and ethanol; In the feed liquid after distillation, add ethanol, macroporous type strongly acidic styrene type cation exchange resin catalyst carries out esterification, in esterification, the mass ratio of feed liquid, ethanol and catalyst is: feed liquid: ethanol: catalyst=1:0.5-6:0.05-0.5; Reacted rear filtering recovering catalyst, liquid phase slowly heats up distillation, and when being warming up to 250 DEG C, distillation obtains biodiesel;
4) phytosterol is reclaimed
Add in remaining slag liquid in broad dose of ethyl acetate, acetone or alcohol after distillation biodiesel one or more, decrease temperature crystalline after slag liquid dissolves, what crystallization went out is solid-stately phytosterol crude product, and mother liquor distillating recovering solvent reuses;
In phytosterol crude product, add ethanol or re-crystallizing in ethyl acetate, insulation, centrifugation obtain fine work phytosterol, and mother liquor distillating recovering solvent reuses.
2. bean dregs method of comprehensive utilization according to claim 1, it is characterized in that, step 1) in proteolytic condition be: protease with suppress the bean dregs mass ratio after dewatering and be: 0.2-0.8:100, protease is neutral protein matter enzyme, hydrolysis is 30 ~ 50 DEG C in temperature, and pH=6.5 ~ 7.5 time are carried out.
3. bean dregs method of comprehensive utilization according to claim 1, is characterized in that, step 1) in bean dregs filter cake be crushed to 100-150 order.
4. bean dregs method of comprehensive utilization according to claim 1, is characterized in that, step 2) carry out at 80 DEG C.
5. bean dregs method of comprehensive utilization according to claim 1, is characterized in that, step 2) in, described aqueous slkali is the NaOH solution of 5mol/L, dry bean dregs: ethanol: NaOH solution=1:1-3.5:0.2-0.65, and described ratio is mass ratio.
6. bean dregs method of comprehensive utilization according to claim 1, is characterized in that, step 2) in regulate the acid of pH to be the hydrochloric acid of mass fraction 37.5%.
7. bean dregs method of comprehensive utilization according to claim 1, it is characterized in that, step 2) concrete operations condition is: centrifugal use filter cloth order number is 500 orders, and centrifugal speed is 5000rpm/min, the drying time is 30min/ pot, and baking temperature controls at 65 ~ 75 DEG C.
8. bean dregs method of comprehensive utilization according to claim 1, is characterized in that, step 3) carry out under the protection of nitrogen sealing liquid face.
9. bean dregs method of comprehensive utilization according to claim 1, is characterized in that, step 3) described in slowly heat up that to distill the liquid that first steams be water and ethanol removing; Continue to heat up, about 210 DEG C start to steam fatty-acid ethyl ester; Be warming up to 250 DEG C and no longer include distillate, stop distillation, distillate is biodiesel.
10. bean dregs method of comprehensive utilization according to claim 1, is characterized in that, step 4) crystallization solid-liquid ratio is 1:2.5 when preparing phytosterol crude product, curing temperature 10 DEG C, 16 hours curing times.
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| CN105728431A (en) * | 2016-02-24 | 2016-07-06 | 齐芳 | Cleaning technology for vinasse |
| CN105859813A (en) * | 2016-05-10 | 2016-08-17 | 武汉工程大学 | Process for recovering steroids from residues in biological fermentation based androstenedione production |
| CN107266515A (en) * | 2017-07-10 | 2017-10-20 | 桂林融通科技有限公司 | A kind of method that phytosterol is extracted from corn stigma |
| IT201600116065A1 (en) * | 2016-11-17 | 2018-05-17 | Green Oleo Srl | PROCESS FOR THE PURIFICATION OF THE INSAPONIFIABLE FRACTION OF VEGETABLE OILS |
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| CN102154400A (en) * | 2010-12-10 | 2011-08-17 | 广西大学 | Method for preparing dietary fiber from bean dregs serving as raw material by combining steam explosion and enzymolysis |
| CN104652158A (en) * | 2015-03-20 | 2015-05-27 | 陕西科技大学 | Preparation technology of bean dreg micro-fibrillated cellulose |
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| JP2009013268A (en) * | 2007-07-04 | 2009-01-22 | Univ Kinki | Method for cleaning biodiesel fuel |
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| CN105728431A (en) * | 2016-02-24 | 2016-07-06 | 齐芳 | Cleaning technology for vinasse |
| CN105859813A (en) * | 2016-05-10 | 2016-08-17 | 武汉工程大学 | Process for recovering steroids from residues in biological fermentation based androstenedione production |
| CN105859813B (en) * | 2016-05-10 | 2017-12-26 | 武汉工程大学 | A kind of technique that steroidal compounds are reclaimed from the leftover bits and pieces of biological fermentation process production androstenedione |
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| CN107266515A (en) * | 2017-07-10 | 2017-10-20 | 桂林融通科技有限公司 | A kind of method that phytosterol is extracted from corn stigma |
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