CN1125875C - Cotton oil extracting and detoxicating process - Google Patents
Cotton oil extracting and detoxicating process Download PDFInfo
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- CN1125875C CN1125875C CN 00134351 CN00134351A CN1125875C CN 1125875 C CN1125875 C CN 1125875C CN 00134351 CN00134351 CN 00134351 CN 00134351 A CN00134351 A CN 00134351A CN 1125875 C CN1125875 C CN 1125875C
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- 229920000742 Cotton Polymers 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 50
- QBKSWRVVCFFDOT-UHFFFAOYSA-N gossypol Chemical compound CC(C)C1=C(O)C(O)=C(C=O)C2=C(O)C(C=3C(O)=C4C(C=O)=C(O)C(O)=C(C4=CC=3C)C(C)C)=C(C)C=C21 QBKSWRVVCFFDOT-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000002904 solvent Substances 0.000 claims abstract description 78
- QHOPXUFELLHKAS-UHFFFAOYSA-N Thespesin Natural products CC(C)c1c(O)c(O)c2C(O)Oc3c(c(C)cc1c23)-c1c2OC(O)c3c(O)c(O)c(C(C)C)c(cc1C)c23 QHOPXUFELLHKAS-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229930000755 gossypol Natural products 0.000 claims abstract description 59
- 229950005277 gossypol Drugs 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 235000012343 cottonseed oil Nutrition 0.000 claims abstract description 32
- 239000003921 oil Substances 0.000 claims abstract description 32
- 235000019198 oils Nutrition 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 126
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- 235000007164 Oryza sativa Nutrition 0.000 claims description 39
- 235000009566 rice Nutrition 0.000 claims description 39
- 238000000605 extraction Methods 0.000 claims description 23
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
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- 231100000167 toxic agent Toxicity 0.000 claims description 2
- 239000003440 toxic substance Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
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- 238000004064 recycling Methods 0.000 claims 1
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- KKKMIFGNMFSRKV-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;2-hydroxypropanoic acid;phosphoric acid Chemical compound OP(O)(O)=O.CC(O)C(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O KKKMIFGNMFSRKV-UHFFFAOYSA-N 0.000 description 1
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- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
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- XUYPXLNMDZIRQH-LURJTMIESA-N N-acetyl-L-methionine Chemical compound CSCC[C@@H](C(O)=O)NC(C)=O XUYPXLNMDZIRQH-LURJTMIESA-N 0.000 description 1
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- 235000004279 alanine Nutrition 0.000 description 1
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- LEVWYRKDKASIDU-IMJSIDKUSA-N cystine group Chemical group C([C@@H](C(=O)O)N)SSC[C@@H](C(=O)O)N LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
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Abstract
The present invention relates to a method for extracting and detoxicating cotton seed oil. The method comprises the steps of breaking, shelling, grinding, extracting, filtering, removing solvents, drying and recovering oil and solvents. The present invention adopts two solvents which are mutually insoluble to simultaneously or sequentially process cotton seed kernels, a non-polar phase solvent prepared from low-carbon alkane is used for extracting the oil, a water containing low-carbon alcohol polar phase solvent is used for extracting toxic component gossypol, and the low-carbon alcohol polar phase solvent and/or a pure low-carbon alcohol solvent or a water containing solution thereof are used for respectively washing cotton seed cakes obtained by filtration. The present invention can produce the cotton seed oil with good color and the cotton seed cakes with low gossypol content, high protein content and good flowability, and the present invention has the advantages of reasonable process and good industrial prospect.
Description
The present invention relates to a kind of extraction and poison-removing method of cotton oil, particularly a kind of method that also obtains detoxification meal by cottonseed benevolence extraction edible oil simultaneously.
Cotton is national most important cash crop, and cottonseed is the main byproduct of cotton, is second largest oil crops except that soybean in the world, and the whole world is produced cottonseed per year and surpassed 3,000 ten thousand tons, and China's output accounts for 1/5, fluctuation between ten thousand tons of 500-1000.
Cottonseed is not only a kind of edible oil resource, and its benevolence also is the higher plant protein resource of a kind of nutritive value.But, be deleterious to domestic animal and people because cottonseed benevolence contains the free gossypol of 1.09-2.39%.At present, grease extracting method such as squeezing of generally adopting or pre-press for extracting juice-leaching all can not remove gossypol in the world, therefore the gained Oleum Gossypii semen must could eat through the alkali refining, and cotton cake dregs is owing to contain gossypol, can not directly be used as poultry and livestock feed, general only as the batching of soya-bean cake feed, or as the substratum of edible mushrooms, or the as fertilizer sources use, cause the waste of protein resource in the cotton dregs.
For reducing the free gossypol content in the cottonseed meal, scientists and engineers have done a lot of work, have applied for some patents.A kind of is doping in commercially available cotton dregs, mainly is FeSO
4, NH
3, inorganicss such as urea are converted in conjunction with gossypol free gossypol, reduce its toxicity, as patent ZL94110717 (1994), and ZL89105899 (1989); Another is to utilize microbial process that the free gossypol in the commercially available cotton dregs is converted in conjunction with gossypol, reduces its toxicity, as patent ZL93117168 (1993).Above-mentioned two kinds of methods all are on the basis of commercially available cotton dregs free gossypol to be converted in conjunction with gossypol.Because poisonous in conjunction with gossypol, therefore clearly, at first, these class methods do not remove gossypol yet, only be to reduce its toxicity; Secondly, they all just handle the dregs of rice, promptly handle having removed greasy dregs of rice product.Present commercially available cotton dregs are obtained by squeezing that comprises high-temperature step or pre-press for extracting juice-lixiviation process, thereby because the injury to the dregs of rice that pyroprocessing is brought, as protein denaturation, nutritive value reduces, the color and taste variation, caking, the drawback that palatability variation etc. are brought owing to pyroprocessing all can't be retrieved.
Another kind of method is not made raw material with the commercially available dregs of rice, but directly uses solvent treatment cottonseed or cottonseed benevolence.Solvent can be single solvent (adds water or do not add water), also can be mixed solvent.R.J.Hron etc. have reported with the ethanol single solvent and have handled the method (JAOCS that cottonseed benevolence obtains Oleum Gossypii semen and detoxification cotton dregs, 71, No4,417 (1994)), the method (ZL92113916.0 (1992)) of Zhu new people report adds acetone or ethane with ethane and adds alcohol mixed solvent and handle cotton benevolence removing gossypol wherein, and the grand grade of Tsing-Hua University's room poem has also been introduced with acetone and added the method (ZL93119443.1 (1993)) that No. 6 petroleum naphthas (being industrial hexane) mixed solvent is handled cottonseed benevolence.
The mixed solvent that the liquid phase that propositions such as Wuxi Liu of light institute compound light are not exclusively dissolved each other with ethanol-petroleum naphtha (being industrial hexane) two coexists counter-current treatment in loop type extractor is pressed the cotton benevolence sheet of embryo to obtain removing cotton phenol cotton dregs (ZL91108214.X (1991)) and has been obtained effect preferably.Regrettably they have adopted the less ethanol polar phase solvent of polarity, more fail to break away from the constraint of traditional cotton benevolence working method, employing is leached cotton benevolence to the little suitable leacher of immiscible two-phase coexistent solvent system, so that cause leaching cycle long, grease and solvent loss are big, and gossypol content is still higher and fail to promote in the product dregs of rice.
The R.J.Rubin of University of Toronto etc. courageously propose with polarity methyl alcohol phase, the mutually incomplete simultaneous two-phase mixed solvent of dissolved two liquid phases of nonpolar hexane comes the breaked poisonous vegetable seed of counter-current treatment, has obtained good vegetable seed detoxification efficiency (USP4460504 (1984)).Then poem grand grade in Tsinghua UnisPlendour Group room has then proposed to handle cotton dregs with removing cotton phenol (ZL94105913.8 (1994)) with methyl alcohol and hexane.With respect to the patent (ZL91108214.X (1991)) of Liu Fuguang, substitute habitual ethanol with methyl alcohol, strengthened the polar phase polarity of solvent greatly, improved detoxification efficiency, purple light has still been continued to use the habitual means such as embryo, leacher leaching of softening, roll unfortunately.Handle the mixed solvent system of immiscible two liquid phases coexistence for fear of leacher, they have adopted two-step approach, promptly two step single solvents are handled, at first, obtain leaching the dregs of rice with the grease in the cottonseed benevolence of industrial hexane (phase) leaching after peeling off, soften, rolling embryo of the saturated mistake of the 80%-95% polar solvent aqueous solution; Gained has taken off the oily leaching dregs of rice and has used the polar solvent aqueous solution of 60%-95% (another phase) to remove gossypol again in leacher, also be the grease of the first step in the nonpolar phase single-solvent extraction cottonseed benevolence, second step removed gossypol in the dregs of rice after deoiling with the polar phase single solvent, to adapt to the requirement of leacher.Obviously, do like this, made the complicated operation change.
The objective of the invention is, overcome the weak point of existing cotton oil detoxification, a kind of cotton oil extracting and detoxicating process that industrial prospect is arranged that can obtain the crude oil of the edible Oleum Gossypii semen of high-quality and obtain Cambodia's phenol removal rate cotton dregs simultaneously is provided.
Cotton oil extracting and detoxicating process of the present invention, its process bag Chinese juniper is broken to shell, mill, extract, the recovery of filtration, precipitation drying, oil and solvent, it is characterized in that handling cottonseed benevolence simultaneously or sequentially with two kinds of immiscible solvents, the nonpolar phase solvent-extracted oil of forming by low-carbon alkanes, by the low-carbon alcohol polar phase solvent extraction toxic substance gossypol that contains water, the grouts that filter gained are washed successively with low-carbon alcohol polar phase solvent and/or pure low-carbon alcohol solvent or its aqueous solution.
It is similar that the inventive method and vegetable seed do not have ammonia double liquid phase extraction technology (ZL92107829.2), but its process object difference.Vegetable seed do not have the technical finesse of ammonia double liquid phase extraction to as if vegetable seed, the present invention handle to as if cottonseed/benevolence.The patent (ZL91108214.X (1991)) of the present invention and Liu Fuguang etc. has essential distinction: the cotton benevolence that (1) latter's cottonseed obtains after broken, shelling is still needed and is obtained cotton benevolence embryo and just contact with solvent through softening, roll a plurality of steps such as embryo, and the former cottonseed/benevolence is not made embryo and is just directly contacted with solvent, carries out wet-milling; (2) main component of latter's polar phase solvent is an ethanol, and the former then is a methyl alcohol; (3) latter's solvent is handled cotton benevolence embryo in loop type extractor, and the former is without leacher; (4) the former adopts to mill and further pulverizes cottonseed benevolence, and the latter need not.The present invention also has essential distinction with the patent (ZL94105913.8 (1994)) of Fang Shihong etc.: the patent of (1) latter and Liu Fuguang etc. is the same, the cotton benevolence that cottonseed obtains after broken, shelling is still needed and is obtained cotton benevolence embryo and just contact with solvent through softening, roll steps such as embryo, and the former cottonseed benevolence is not made embryo and is just directly contacted with solvent, carries out wet-milling; (2) latter adopts the two-step approach leaching to handle cotton benevolence embryo, be that the first step is handled cotton benevolence embryo mutually with the nonpolar hexane of homogeneous, the degrease dregs of rice that obtain are the second polarity methyl alcohol phase detoxification that goes on foot with another homogeneous again, and the former can use two-step approach, also can adopt single stage method, preferred single stage method to be to reduce treatment step, promptly with nonpolar hexane mutually and mutually immiscible two liquid phases of polarity methyl alcohol and the breaked cottonseed benevolence of milling constitute liquid-liquid-solid three phase extraction system together and come one to go on foot the extraction treatment chippy cottonseed benevolence of milling; (3) latter is the same with the patent of Liu Fuguang etc., and solvent is handled cotton benevolence embryo in leacher, and the former is without leacher; (4) the former adopts to mill and further pulverizes cottonseed benevolence, and the latter need not.In this uniform solution that defines based on non-polar solvent is nonpolar phase, uniform solution based on hexane is nonpolar hexane phase or hexane phase, uniform solution based on polar solvent is a polar phase, based on the uniform solution of low-carbon alcohol be the polarity low-carbon alcohol mutually or the low-carbon alcohol phase; Uniform solution based on methyl alcohol is polarity methyl alcohol phase or methyl alcohol phase; Definition is leaching with the relative immobilized solid of flowing fluid drip washing with the process of extracting some material, handle to flow or the immobilized solid serves as extraction or liquid-solid extraction with the process of extracting some material with flowing fluid.
The present invention is used for the low-carbon alkanes nonpolar phase solvent of extraction oil and can selects the alkane that contains 5 to 7 carbon atoms for use, industrial hexane commonly used, or be oil No. six.The polarity low-carbon alcohol phase solvent that is used for detoxification can be methyl alcohol phase solvent, ethanol phase solvent, Virahol phase solvent, and preferred material is the methyl alcohol phase solvent.
Treating processes of the present invention can be carried out at normal temperatures, also can carry out being lower than under the temperature of solvent boiling point.Milling, to handle can be that to dry grind also can be wet-milling, preferred wet-milling.The content of water if water-content is too high, will cause the protein loss to increase generally at below 25% of polar phase solvent cumulative volume in the polarity low-carbon alcohol phase solvent.The polar phase solvent can contain a little auxiliary, and auxiliary agent can be an alkali metal hydroxide, and preferred sodium hydroxide also can be food acids.Because the auxiliary agent selected for use is all non-volatile, and consumption seldom needn't reclaim, and therefore, can make full use of extraction and wash temperature, the kind of auxiliary agent and concentration in the polar phase solvent, and the combination of factors such as water-content improves removing of gossypol.Grouts wash successively through polarity low-carbon alcohol phase solvent and/or pure low-carbon alcohol or moisture low-carbon alcohol, further improve the gossypol decreasing ratio, finally obtain the grouts of good fluidity, help very much further industrial treatment.
Based on taking all factors into consideration of said temperature, auxiliary agent, solvent comprises water amount, further aspect of the present invention is: (1) is after cottonseed fragmentation, shelling, the pulverizing of further milling of cottonseed benevolence impels easier being extracted of gossypol in the cotton body of gland, and best milling is wet-milling; (2) preferred range of extracting and detoxicating process is a room temperature-50 ℃, and optimum temps is room temperature (10-35 a ℃); (3) auxiliary agent can be a sodium hydroxide, also can be phosphoric acid, food acids, and preferred material is a citric acid; The assistant concentration preferable range is 0.01%-0.5% (weight) in the polar phase solvent, and optimum range is 0.05-0.2% (weight); (4) water (volume) accounts for below 25% of polar phase solvent cumulative volume in the polarity low-carbon alcohol phase solvent.
Industrial feasible flow process of the present invention is seen Fig. 1.Wherein being the main nonpolar hexane phase solvent of forming with the hexane, is the main polarity methyl alcohol phase solvent of forming with methyl alcohol.At first, cottonseed through broken, shell cotton benevolence, cotton benevolence is milled together with the methyl alcohol phase solvent in mill, and slip carries out the double liquid phase extraction process of liquid-liquid-solid three-phase coexistence mutually mutually together with methyl alcohol with hexane in intermittence or successive mixer-settler extractor or the board-like extraction tower of successive.Then, the slip order reaches pure methyl alcohol or its solution washing mutually with methyl alcohol, and refiltered oil from mixing oil, methyl alcohol also are partially recovered mutually and reuse, and all the other carry out recycled.The grouts that washing obtains are through precipitation dried recovered solvent and obtain detoxification meal.
Critical process of the present invention relates to a mill processes, an extraction process, a precipitation drying process.The present invention adopts planetary roller mill (internal diameter 100mm and 140mm) or ball mill (internal diameter 250mm) with the wet-milling mode cotton benevolence of milling, with pulsed sieve plate column (diameter 25mm, high 2000mm), Karr vibration tower (diameter 50mm, high 2500mm), macropore rotating disc contactor (diameter 75mm, high 1300mm), intermittently (50L) or (diameter 400mm continuously, long 2500mm) mixer-settler extractor extraction slip is with the precipitation drying of horizontal continuous oven (diameter 120mm, the long 1000mm) dregs of rice that wet.The combination of these equipment is suitable for industry and amplifies very much.
Typical laboratory scale testing sequence of the present invention is as follows:
The cotton benevolence of 30 grams is placed in the family expenses cooking machine, with the polar phase solvent (being generally 150ml methyl alcohol phase solvent) that contains 0.1% (weight) auxiliary agent (being generally citric acid) and 10% (volume) water wet-milling certain hour (common 2 minutes) together, (during dry grinding, cottonseed benevolence dry grinding earlier 2 minutes, shook together 2 minutes with the polar phase solvent again), left standstill 20 minutes, add hexane again, wet-milling certain hour (common 2 minutes) left standstill 20 minutes, filter, the dregs of rice respectively wash twice with methyl alcohol and hexane, and each 50ml surveys gossypol content behind the room temperature airing, filtrate in separating funnel after the layering, refiltered oil in the hexane phase solvent.
Following table 1-table 8 has provided the effect that influences several important factors that cotton powder removes, and table 9, table 10 are respectively tower and dry precipitation test situation.
As shown in Table 1, the effect of wet-milling removing cotton phenol obviously is better than dry grinding.Table 2 shows that best polar phase solvent is the methyl alcohol phase solvent, and according to table 3, the moisture 5%-15% of polar phase solvent is advisable.Table 4, table 5 illustrate that solvent load is big more, the removing cotton phenol effect is good more, the granularity of cotton benevolence removes also influential to gossypol, thin more good more, be excessive solvent ratio, meticulous granularity not only can cause operational difficulty, also can increase energy consumption, molten consumption and facility investment, therefore can only be controlled in the suitable scope.In addition, temperature removes gossypol also considerable influence (table 6), elevated temperature is favourable to removing free gossypol, but higher temperature will impel gossypol quickly with the dregs of rice in amino acid etc. in conjunction with generating in conjunction with gossypol, not only residual a part of toxicity is (also poisonous in conjunction with gossypol, just toxicity is little than free gossypol), combination special and Methionin will reduce the nutritive value of cotton dregs greatly.
Auxiliary agent is to its special effect that removes of gossypol, and different promoter effects is incomplete same.The alkali auxiliary agent is favourable to removing free gossypol, but easily generates in conjunction with gossypol; It is poor slightly that acid additive removes the effect of free gossypol, also can reduce the ability of methanol stripper free gossypol sometimes slightly, but the amount in conjunction with gossypol is lower in the dregs of rice, sees Table 7.Take all factors into consideration, acid additive is comparatively favourable, especially citric acid more better (see Table 7, table 8).Table 9 explanation, the inventive method realizes that by the tower operation industrialization is fully possible.The product dregs of rice reach nontoxic cotton dregs quality standard, are suitable for feed.
Wet dregs of rice precipitation also is a gordian technique in the oilseeds processing, the inside and outside heating of the horizontal stirring at low speed of this process choice continuous oven dregs of rice precipitation that wets, because its hot face is big, general dregs of rice Wen Buhui is above 100 ℃, the nutrition of the dregs of rice can not destroyed, certainly, can use other precipitation device to the greatest extent, cause the downgrade of the dregs of rice as long as it can guarantee that dregs of rice Wen Buhui is too high.Table 10 is wet effects of dregs of rice precipitation of the inside and outside heating of horizontal stirring at low speed continuous oven.By table 10 as seen, effect is unusual ideal.
Table 11 is test results of the cotton dregs that obtain of industrial feasible flow preparation with reference to the accompanying drawings.As can be seen from Table 11, the grouts that the inventive method obtains not only gossypol content are low, and because removed glue, protein content also is much higher than the hexane dregs of rice.Should be noted also that simultaneously the biliquid phase dregs of rice are the same with the low temperature hexane dregs of rice, look shallow is, lightly seasoned, loose, good fluidity, good palatability, is of high nutritive value, and this is that to pass through the commercially available dregs of rice of pyroprocessing at present incomparable.Table 12 is its aminoacids content.By table 12 as seen, each amount of amino acid of the biliquid phase dregs of rice also all is higher than the low temperature hexane dregs of rice basically.
Energy expenditure is that can Technology industrialized another important indicator, and this technology is taked mother liquid recycle, i.e. extraction and (or) the washing mother liquor directly returns extraction and/or washing system and reduces energy expenditure to reduce the methyl alcohol phase mother liquor amount that needs to reclaim without reclaiming.Table 13 is that the methyl alcohol phasor of applying mechanically is to containing the relation of phenol amount in the dregs of rice.Can obviously find out by table 13, it is little that methyl alcohol cover consumption removes influence to free phenol, the cover consumption in addition account for total methyl alcohol phase solvent consumption 83.5% (the fresh methanol phase: methyl alcohol phase mother liquor=1: 5), its free phenol decreasing ratio still can be near the effects of all using the fresh methanol phases.Just have more significantly in conjunction with phenol this moment increases, but still in the scope of allowing.
Free gossypol content % (weight) in table 1 dry grinding, the wet-milling dregs of rice
Dry grinding wet-milling free gossypol 0.108 0.062
Free gossypol content % (weight) in four kinds of polar phase solvent extractions of table 2 dregs of rice
Methanol Virahol acetone free gossypol 0.061 0.181 0.132 0.112
Free gossypol content % (weight) solvent load 23 4.5 6.7 free gossypols 0.046 0.042 0.025 0.021 in the table 3 different moisture content polar phase extracted cake moisture % of free gossypol content (volume) 059 12 15 free gossypol % (weight) 0.007 0.006 0.006 0.007 0.009 table 4 opposed polarity phase solvent consumption (the L/kg cottonseed benevolence) extracted cake
The table 5 wet-milling time (degree of grinding) is to footpath (mm) free gossypol % (weight) in the wet-milling time that influences (second) granularity that removes free gossypol
40 0.65 0.032
60 0.63 0.025
70 0.60 0.025
80 0.55 0.024
90 0.55 0.020
100 0.48 0.023
110 0.45 0.021
120 0.46 0.021
Effect of extracting extraction temperature under table 6 differing temps ℃ 20 30 40 free gossypol % (weight) 0.018 0.010 0.007 are in conjunction with gossypol % (weight) 0.27 0.36 0.47
The different auxiliary agents of table 7 are to removing the influence of gossypol
Auxiliary agent does not have NaOH lactic acid phosphoric acid citric acid free gossypol % (weight) 0.026 0.012 0.036 0.033 0.020 in conjunction with gossypol % (weight) 0.17 0.59 0.16 0.15 0.17
The different assistant concentrations of table 8 influence auxiliary agent NaOH citric acid concentration % 0 0.1 0.2 0.25 0.05 0.1 0.2 0.25 0.3 to what remove gossypol, (weight) free gossypol 0.026 0.01 0.012 0.005 0.015 0.02 0.02 0.017 0.016%, (weight) is in conjunction with gossypol 0.17 0.24 0.59 0.43 0.31 0.33 0.17 0.21 0.26%, (weight)
The test of table 9 tower
The moisture % auxiliary agent of methyl alcohol phase operational condition cotton dregs quality stirring intensity temperature liquid holdup Residual oil free gossypol is in conjunction with gossypol
Mm/min ℃ of % % % % 6.5 citric acids 540 24 29.1 1.14 0.010 0.22
The wet residual molten amount ppm 47.67 94 8 4.03 360 42.66 88 8 4.38 530 43,079 87 6 3.03 700 of the dregs of rice moisture content % temperature ℃ dried dregs of rice of the dried dregs of rice moisture content of stirring velocity rpm % of the dry precipitation test of table 10
Table 11 biliquid phase cotton dregs and low temperature hexane dregs of rice character (%) are relatively
Moisture content ash fat crude protein robust fibre is free in conjunction with hexane methyl alcohol
The gossypol gossypol ppm ppm low temperature hexane dregs of rice 9.04 5.76 2.17 40.85 12.16 0.43 0.21 do not detect-and the biliquid phase dregs of rice 8.69 5.23 1.56 43.12 12.52 0.010 0.14 do not detect 953
What amino acid content amino acid low temperature hexane cotton dregs Two Liquid Phases cotton dregs sky propylhomoserin 3.60 3.80 threonines 1.15 1.24 serines 1.57 1.67 glutamic acid 10.40 10.95 proline 1.01 1.09 glycine 1.66 1.78 alanine 1.53 1.64 cystines 0.77 0.79 valine 1.96 2.12 methionine 0.62 0.61 isoleucine 1.20 1.31 leucines 2.44 2.60 tyrosine 0.91 0.98 phenylalanine 2.36 2.51 lysines 1.87 2.08 histidines 1.09 1.16 arginine 4.67 4.89 tryptophans 0.42 0.46 essential amino acid 12.01 12.93 total amino acids 39.23 41.68 table 13 methyl alcohol phase mother liquor use amount cotton dregs contained the phenol amount in table 12 cotton dregs affects the fresh methanol phase: account for mutually in conjunction with phenol % fresh methanol in the free phenol % dregs of rice in the methyl alcohol phase mother liquor dregs of rice
Total methyl alcohol phase %
1∶0 0.010 0.14 100.0
1∶2 0.014 0.21 33.3
1∶3 0.015 0.25 25.0
1∶5 0.013 0.43 16.5
Claims (13)
1, a kind of cotton oil extracting and detoxicating process, its process comprises fragmentation, shelling, mill, extraction, filter, the precipitation drying, the recovery of oil and solvent, it is characterized in that cottonseed benevolence is in fragmentation, not making embryo after the shelling just directly contacts with solvent, mill, handle cottonseed benevolence simultaneously or sequentially with nonpolar hexane phase solvent and moisture two kinds of immiscible solvents of low-carbon alcohol polar phase solvent less than 25% (volume), by the nonpolar phase solvent-extracted oil, by polar phase solvent extraction toxic substance gossypol, with low-carbon alcohol polar phase solvent and/or pure low-carbon alcohol solvent or its aqueous solution the grouts that filter gained are washed successively, wherein, low-carbon alcohol is a methyl alcohol, ethanol, the Virahol thrin.
2, cotton oil extracting and detoxicating process according to claim 1 is characterized in that described low-carbon alcohol is a methyl alcohol.
3, cotton oil extracting and detoxicating process according to claim 1 and 2 is characterized in that the volume of water in the polar phase solvent accounts for the 0-15% of polar phase solvent cumulative volume.
4, cotton oil extracting and detoxicating process according to claim 3 is characterized in that the volume of water in the polar phase solvent accounts for the 5-15% of polar phase solvent cumulative volume.
5, cotton oil extracting and detoxicating process according to claim 1 is characterized in that adopting wet-milling, and the cottonseed that is about to broken shelling is milled with the polar phase solvent.
6, cotton oil extracting and detoxicating process according to claim 1 is characterized in that milling in the cotton dregs treating processes, extraction process carry out being lower than under the temperature of solvent boiling point.
7, cotton oil extracting and detoxicating process according to claim 6 is characterized in that extraction temperature is 20 ℃-40 ℃.
8, cotton oil extracting and detoxicating process according to claim 1 is characterized in that containing in the polar phase solvent sodium hydroxide alkalescence auxiliary agent.
9, cotton oil extracting and detoxicating process according to claim 1 is characterized in that containing in the polar phase solvent food acids acid additive.
10, cotton oil extracting and detoxicating process according to claim 9 is characterized in that containing in the polar phase solvent the acid auxiliary agent of citric acid of 0.05-0.2%.
11, cotton oil extracting and detoxicating process according to claim 1 is characterized in that with tray column or mixer-settler extractor extraction oil.
12, cotton oil extracting and detoxicating process according to claim 1 is characterized in that carrying out dregs of rice temperature with heating continuous oven inside and outside the horizontal stirring at low speed is no more than 100 ℃ low temperature desolventizing drying.
13, cotton oil extracting and detoxicating process according to claim 1, it is characterized in that the polar phase Recycling Mother Solution that will come from extraction, washing is used for extraction, washing, make fresh methanol phase consumption only occupy the 33.3-16.5% of whole extractions, the required polar phase solvent gross weight of washing, promptly in the polar phase solvent of Shi Yonging fresh methanol phase and methyl alcohol mutually the ratio of mother liquor be 1: 2-1: 5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100408543C (en) * | 2006-04-03 | 2008-08-06 | 南京工业大学 | A process for co-producing fatty acid esters, glycerin and vegetable crude protein |
| CN101073376B (en) * | 2007-04-02 | 2011-12-28 | 北京中棉紫光生物科技有限公司 | Method for recovery solvent of cotton-seed protein extraction |
| CN101253929B (en) * | 2008-04-14 | 2010-12-08 | 华中农业大学 | A fast and efficient method for removing gossypol from cottonseed cake |
| GB0822805D0 (en) * | 2008-12-15 | 2009-01-21 | D1 Oils Plc | Methods for detoxifying oil seed crops |
| CN102936534A (en) * | 2012-12-07 | 2013-02-20 | 江南大学 | Process for simultaneously extracting phosphatide, gossypol and pigments from cottonseed oil |
| CN107868695A (en) * | 2016-09-26 | 2018-04-03 | 四川大学 | A kind of preparation method of detoxification jatropha curcas oil |
| CN111018944A (en) * | 2019-12-02 | 2020-04-17 | 晨光生物科技集团股份有限公司 | Method for producing dephenolized cottonseed protein |
| CN112358912B (en) * | 2020-09-29 | 2023-06-23 | 新疆希普生物科技股份有限公司 | Preparation method and application of baked cotton seeds |
| CN114874848B (en) * | 2022-05-31 | 2023-10-20 | 江苏冠军科技集团股份有限公司 | Alkyd resin composition and preparation method and application thereof |
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