CN102911784A - Extraction method of cottonseed oil - Google Patents

Extraction method of cottonseed oil Download PDF

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CN102911784A
CN102911784A CN201210453335XA CN201210453335A CN102911784A CN 102911784 A CN102911784 A CN 102911784A CN 201210453335X A CN201210453335X A CN 201210453335XA CN 201210453335 A CN201210453335 A CN 201210453335A CN 102911784 A CN102911784 A CN 102911784A
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enzymolysis
oleum gossypii
gossypii semen
oil
puffing
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李杨
江连洲
齐宝坤
王辰
王中江
王胜男
冯红霞
曹亮
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Northeast Agricultural University
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Northeast Agricultural University
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Abstract

The invention relates to an extraction method of cottonseed oil, and belongs to the vegetable oil and fat extraction technology. The extraction method comprises the following steps: crushing cottonseeds and performing wet process extrusion to obtain an extruded material; mixing the extruded material with water to obtain a mixed liquor; grinding the mixed liquor and adding Aclase2.4 L alkaline protease to perform enzymolysis to obtain a enzymolysis liquid; and carrying out enzyme deactivation processing and centrifugal separation on the enzymolysis liquid, so as to obtain the cottonseed oil. Through utilizing an extrusion preprocessing and biological enzyme combined aqueous enzymatic method to separate cottonseed oil and fat, the extraction method has the characteristics of simple required equipment, safety for operation, capability of obtaining high-quality cottonseed oil, high nutritive value and the like.

Description

A kind of extracting method of Oleum Gossypii semen
Technical field
The present invention relates to a kind of extracting method of Vegetable oil lipoprotein, particularly relate to a kind of extracting method for the cottonseed grease, belong to the extraction manufacture field of Vegetable oil lipoprotein.
Background technology
Existing Oleum Gossypii semen extraction process mainly is traditional solvent extraction method at present.There are problems in traditional technology, and, poor transparency dark such as the Oleum Gossypii semen color and luster, oil extracting rate are low.Main is that Oleum Gossypii semen production exists potential safety hazard, and the gossypol that exists with free state in the Oleum Gossypii semen has toxicity, chemical property ripple very alive, and the quality on grease and the dregs of rice in the process of manufacture of Oleum Gossypii semen has certain impact.
Extruding puffing is to utilize fricative heat that material is heated up, and forces material to pass through nib under the effect of extrusion spiral, obtains simultaneously certain pressure.After material was extruded nib, pressure sharply descended, the inner vesicular structure that forms of material, and volume increases, thereby reaches expanded purpose.Utilizing extruding and puffing technology that oil plant is carried out pre-treatment, is the new technology that a kind of grease extracts.After oil plant is expanded, because the gathering of grease in the destroyed and oil plant cell of cell walls, thereby be conducive to the extraction yield of grease.Aqueous enzymatic method is as a kind of novel oil plant extractive technique, be applied to high-quality oil plant extraction and improve the extraction yield of grease.
Not enough for using aqueous enzymatic extraction Oleum Gossypii semen technical study at present, the present invention adopts the wet method extruding-puffing technique that cottonseed is carried out pre-treatment, make free gossypol can with cottonseed in protein fully act on, become bound gossoypol, lose toxicity; Use simultaneously aqueous enzymatic method cottonseed is carried out enzymolysis processing, extract high-quality cottonseed oil, and improve the extraction yield of Oleum Gossypii semen.Therefore, significant for aqueous enzymatic extraction Oleum Gossypii semen technical study.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned the deficiencies in the prior art, and a kind of extracting method of Oleum Gossypii semen is provided, and reaches the purpose that improves Oleum Gossypii semen yield and quality.
A kind of extracting method of Oleum Gossypii semen, the method may further comprise the steps: cottonseed is pulverized laggard row wet method extruding puffing, obtains expanded material, water ratio is 9-11% before the described cotton seed puffing, the nib aperture is 8-16mm, and swelling temperature is 70-90 ℃, and vapor pressure is 0.6-0.8KPa; Expanded material and water are mixed to get mixed solution, amount of water is 6-10:1 with the quality of material ratio, adding Aclase2.4L Sumizyme MP after the mixed solution grinding is carried out enzymolysis obtain enzymolysis solution, described enzyme concentration is the 1.4-2.2 % of quality of material in the mixed solution, hydrolysis temperature 40-60 ℃, enzymolysis time 2.5-4.5 h, enzymolysis pH 8-10; With enzymolysis solution go out enzyme process after under 4500r/min centrifugation 30min, both obtained Oleum Gossypii semen.
The preferred parameter of described extruding puffing is: water ratio is 10.0% before the cotton seed puffing, and the nib aperture is 12mm, and swelling temperature is 82 ℃, and vapor pressure is 0.7MPa.
The preferred parameter of described enzymolysis is: enzyme concentration be in the mixed solution quality of material 2.1%, 48 ℃ of hydrolysis temperatures, enzymolysis time 3.4h,, enzymolysis pH 9.18.
The inventive method is to adopt extruding-puffing technique that cotton oil is carried out pre-treatment, and the wet method extruding puffing can reduce the free gossypol content in the Oleum Gossypii semen, improves the security of grease; Simultaneously, on the basis of extruding puffing, adopt the enzyme of energy degrading plant oil plant cell or have the enzyme of Degradation to act on oil plant to complex bodys such as lipoprotein, lipopolysaccharides, make grease be easy to from the oil plant solid, discharge, utilize non-oil component (albumen and carbohydrate) to oil and the avidity difference of water, utilize profit proportion difference and oil is separated with non-oil component.In the inventive method, enzyme is except the complex bodys such as the oil plant cell of degrading, decomposition lipoprotein, lipopolysaccharides, can also destroy the lipoprotein membrane that is wrapped in oil droplets that oil plant forms in the processes such as defibrination, reduce the stability of milk sap, thereby improve the free oil yield.
The aqueous enzymatic method that the inventive method utilizes expelling-expansion pretreatment and biological enzyme to combine separates the cottonseed grease, needed equipment is simple, operational safety, can obtain high-quality Oleum Gossypii semen, be of high nutritive value, can obtain low high-quality cottonseed protein and the cottonseed peptide of sex change simultaneously.Through checking and simultaneous test, percent of total oil can reach about 83.28% under extruding-puffing technique condition of the present invention, when selecting under the preferred processing condition, percent of total oil can reach about 87.68%, than directly utilizing aqueous enzymatic extraction Oleum Gossypii semen percent of total oil to improve 16 percentage points.
The inventive method action condition gentle (normal temperature, organic solvent-free, the violent chemical reaction of nothing), the degraded product in the system generally can not react with extract, can effectively protect grease, protein and colloid etc. can utilize the quality of composition.
Expelling-expansion pretreatment of the present invention is produced Oleum Gossypii semen with the aqueous enzymatic method combination technique is compared with traditional oil-producing technique mainly has following technological advantage:
1. simultaneously separating oil and protein from cottonseed;
2. simple, the operational safety of equipment, vegetables oil no solvent residue and less investment;
3. reduced the content of free gossypol in the extrusion pressing puffing process, simultaneously, the color and luster that can avoid wet heat treatment to cause is dark, poor transparency, obtains high-quality Oleum Gossypii semen;
4. can avoid the serious sex change of sesame protein, obtain that the protein denaturation rate is low, the cottonseed protein of high-quality, effectively avoid the waste of cottonseed protein resource;
5. the oil in water emulsion that is obtained by the enzyme process separation need not to process behind breakdown of emulsion and can obtain high-quality oil.
Description of drawings
The process route chart of accompanying drawing 1 the inventive method;
Embodiment
Below in conjunction with accompanying drawing the specific embodiment of the invention is described in detail.
A kind of extracting method of Oleum Gossypii semen, the method may further comprise the steps: cottonseed is pulverized laggard row wet method extruding puffing, obtains expanded material, water ratio is 9-11% before the described cotton seed puffing, the nib aperture is 8-16mm, and swelling temperature is 70-90 ℃, and vapor pressure is 0.6-0.8KPa; Expanded material and water are mixed to get mixed solution, amount of water is 6-10:1 with the quality of material ratio, adding Aclase2.4L Sumizyme MP after the mixed solution grinding is carried out enzymolysis obtain enzymolysis solution, described enzyme concentration is the 1.4-2.2 % of quality of material in the mixed solution, hydrolysis temperature 40-60 ℃, enzymolysis time 2.5-4.5 h, enzymolysis pH 8-10; With enzymolysis solution go out enzyme process after under 4500r/min centrifugation 30min, both obtained Oleum Gossypii semen.
The preferred parameter of described extruding puffing is: water ratio is 10.0% before the cotton seed puffing, and the nib aperture is 12mm, and swelling temperature is 82 ℃, and vapor pressure is 0.7MPa.
The preferred parameter of described enzymolysis is: enzyme concentration be in the mixed solution quality of material 2.1%, 48 ℃ of hydrolysis temperatures, enzymolysis time 3.4h, enzymolysis pH 9.18.
The screening experiment of embodiment 1 extruding puffing optimum parameter
1 materials and methods
1.1 material, reagent
Cottonseed Cotton No. 6 of Shandong
The Aclase2.4L Sumizyme MP Denmark novo company
1.2 key instrument equipment
PHS-25 type acidometer Shanghai great achievement instrument plant
Electronic analytical balance Mei Lete-Tuo benefit instrument (Shanghai) Co., Ltd.
Whizzer Beijing Medical Centrifugal Machine Factory
The electric precise stirrer Jintan City, Jiangsu Province high honour instrument manufacturing company limited
Electric-heated thermostatic water bath Yuyao City east electric instrument factory
Semi-automatic azotometer Shanghai Xin Jia Electronics Co., Ltd.
The digestion instrument Shanghai Qianjian Instrument Co., Ltd.
Wet wheeling machine Shanghai Yi Le mechanical ﹠ electronic equipment corporation, Ltd
Soxhlet extractor Tianjin Glass Instrument Factory
Cooking extruder Beijing middle peasant Kang Yuan company
Muffle furnace Guangdong, Shanghai, Shanghai bright scientific instrument company limited
Spectrophotometer The U.S. spectrum in Shanghai reaches Instr Ltd.
1.3 experimental technique
1.3.1 the composition measurement of cottonseed
Determination of moisture is with reference to GB/T 5528-2008; Crude protein content is measured with reference to GB/T 14489.2-2008; Crude fat content is measured with reference to GB/T 5512-2008; The free gossypol assay is with reference to GB 13086-1991.
1.3.2 technical process
See accompanying drawing
1.3.3 calculation formula
Cottonseed oil extracting rate formula is:
Figure 988873DEST_PATH_IMAGE001
2 results and discussion
2.1 the raw material main component sees Table 1.
Table 1 raw material cottonseed main component
Composition (weight percentage) Fat Protein Moisture Free gossypol content
The decortication cottonseed 38.7 22.6 7.4 0.58
2.2 empirical factor level code table
On the basis of single factor research, choosing 5 factors such as material water ratio, nib aperture, swelling temperature, drop temperature, vapor pressure is independent variable(s), take percent of total oil as response value, according to the center combination principle of design, the experiment of design response surface analysis, its level of factor coding schedule sees Table 2.
Table 2 level of factor coding schedule
Figure 968330DEST_PATH_IMAGE002
2.3 response surface experimental establishment and experimental result
This experimental applications response surface optimized method carries out process optimization.Take x1, x2, x3, x4, x5 as independent variable(s), take percent of total oil as response value Y, response surface experimental program and the results are shown in Table 3.Experiment 1-24 is factorial experiment, and 25-36 is 12 center tests, in order to the estimating experiment error.
Table 3 test arrangement and result
2.4 response surface interpretation
Carry out data analysis by statistical analysis software SAS9.1, set up Quadratic response surface regression model as follows:
Y=-1644.76+240.4767x1+24.79583x2+8.823833x3-4.5235x4+672.0833x5-10.61875x12-2.128125x1x2-0.698984x22+0.1788062x2x3-0.067288x32+6.9125x4x5-1048.875x52
X1, x2, x3, x4, x5 are the factor actual value
Regression analysis and the results of analysis of variance see Table 4.
Table 4 returns and the results of analysis of variance
Variable Degree of freedom Sum of squares All square The F value Pr>F
x1 1 39.4497 39.4497 11.98225 0.003488
x2 1 92.9447 92.9447 28.23054 0.0001
x3 1 22.7176 22.7176 6.900126 0.019053
x4 1 59.62954 59.62954 18.11156 0.000691
x5 1 65.9685 65.9685 20.03693 0.000444
x12 1 225.5157 225.5157 68.49696 0.0001
x1x2 1 72.46266 72.46266 22.00943 0.00029
x22 1 250.1525 250.1525 75.98002 0.0001
x2x3 1 50.73001 50.73001 15.40847 0.00135
x2x5 1 17.87176 17.87176 5.428274 0.034189
x32 1 90.55215 90.55215 27.50384 0.0001
x42 1 28.33163 28.33163 8.6053 0.010272
x4x5 1 47.78266 47.78266 14.51325 0.001709
x52 1 220.0278 220.0278 66.83008 0.0001
Return 20 1298.602 64.93012 19.72154 0.0001
Residue 15 49.38519 3.292346 ? ?
Lose and intend 6 17.75654 2.959424 0.84211 0.567888
Error 9 31.62865 3.514294 ? ?
Summation 35 1347.988 ? ? ?
As shown in Table 4, linear relationship between equation dependent variable and the independent variable(s) is obvious, this model returns significantly (p<0.001), lose to intend item not significantly (p〉0.05), and this model R2=96.34%, R2Adj=91.45% illustrates that this model and experimental fit are good, linear relationship is remarkable between independent variable(s) and the response value, and the theory that can be used for this reaction is inferred.Can obtain factor contribution rate by the F check is: x2〉x5〉x4〉x1〉x3, i.e. nib aperture〉vapor pressure〉drop temperature〉material water ratio〉swelling temperature.
Application responds face optimizing analytical procedure is analyzed regression model, and seek the optimal response result: material water ratio is 10.0%, and the nib aperture is 12mm, swelling temperature is 82 ℃, drop temperature is 127.7 ℃, and vapor pressure is 0.7MPa, and response surface has optimum value 83.18 ± 1.18%.Under best extruding-puffing technique parameter, the free gossypol content of the Oleum Gossypii semen of extraction is 0.09%.
2.4 confirmatory experiment and simultaneous test
Under the top condition that the response surface analysis method is tried to achieve, namely material water ratio is 10.0%, and the nib aperture is 12mm, swelling temperature is 82 ℃, and drop temperature is 127.7 ℃, and vapor pressure is 0.7MPa, carry out 3 parallel laboratory tests, the mean value of 3 parallel laboratory tests of oil extracting rate is 83.28%.The oil extracting rate predictor is 83.18 ± 1.18%.Experimental value and regression equation predictor that response value is described are coincide good.Directly utilizing aqueous enzymatic extraction Oleum Gossypii semen percent of total oil only is 70.94%.
3 experiment conclusion
Utilize Response surface methodology that the Extruding-expansion Pretreatment parameter of aqueous enzymatic extraction Oleum Gossypii semen is optimized.Having set up corresponding mathematical model is that later pilot scale and suitability for industrialized production provided fundamental basis, and having obtained optimum extruding-puffing technique condition is that material water ratio is 10.0%, and the nib aperture is 12mm, and swelling temperature is 82 ℃, drop temperature is 127.7 ℃, and vapor pressure is 0.7MPa.Through the checking with simultaneous test as can be known under optimum extruding-puffing technique condition percent of total oil can reach about 83.28%, improved 12 percentage points than the percent of total oil that directly utilizes the aqueous enzymatic extraction Oleum Gossypii semen.Under best extruding-puffing technique parameter, the free gossypol content of the Oleum Gossypii semen of extraction is 0.09%.
Embodiment 2 enzymolysis process optimum parameter optimization experiments
Based on embodiment 1 determined best Extruding-expansion Pretreatment, carry out single factor enzymolysis test, determine the scope of each enzymolysis process parameter (hydrolysis temperature, enzymolysis pH, enzyme concentration, solid-liquid ratio, enzymolysis time).Take oil extracting rate as investigating index, carry out response surface and design 5 hydraulic tests of 5 factors.
1.1 material, reagent
Cottonseed Cotton No. 6 of Shandong
The Aclase2.4L Sumizyme MP Denmark novo company
1.2 key instrument equipment
PHS-25 type acidometer Shanghai great achievement instrument plant
Electronic analytical balance Mei Lete-Tuo benefit instrument (Shanghai) Co., Ltd.
Whizzer Beijing Medical Centrifugal Machine Factory
The electric precise stirrer Jintan City, Jiangsu Province high honour instrument manufacturing company limited
Electric-heated thermostatic water bath Yuyao City east electric instrument factory
Semi-automatic azotometer Shanghai Xin Jia Electronics Co., Ltd.
The digestion instrument Shanghai Qianjian Instrument Co., Ltd.
Wet wheeling machine Shanghai Yi Le mechanical ﹠ electronic equipment corporation, Ltd
Soxhlet extractor Tianjin Glass Instrument Factory
Cooking extruder Beijing middle peasant Kang Yuan company
Muffle furnace Guangdong, Shanghai, Shanghai bright scientific instrument company limited
Spectrophotometer The U.S. spectrum in Shanghai reaches Instr Ltd.
1.3 experimental technique
1.3.1 the composition measurement of cottonseed
Determination of moisture is with reference to GB/T 5528-2008; Crude protein content is measured with reference to GB/T 14489.2-2008; Crude fat content is measured with reference to GB/T 5512-2008; The free gossypol assay is with reference to GB 13086-1991.
1.3.2 technical process
See accompanying drawing
1.3.3 calculation formula
Cottonseed oil extracting rate formula is:
Figure 707058DEST_PATH_IMAGE004
2 results and discussion
2.1 the raw material main component sees Table 1.
Table 1 raw material cottonseed main component
Composition (weight percentage) Fat Protein Moisture Free gossypol content
The decortication cottonseed 35.7 22.6 7.4 0.6
2.2 empirical factor level code table
On the basis of carrying out single factor research, choosing hydrolysis temperature, enzymolysis pH, enzyme concentration, solid-liquid ratio, 5 factors of enzymolysis time is independent variable(s), take percent of total oil as response value, according to the center combination principle of design, the experiment of design response surface analysis, its level of factor coding schedule sees Table 6.
Table 6 level of factor coding schedule
Figure 521430DEST_PATH_IMAGE005
2.3 response surface experimental establishment and experimental result
This experimental applications response surface optimized method carries out process optimization.Take x1, x2, x3, x4, x5 as independent variable(s), take percent of total oil as response value Y, response surface experimental program and the results are shown in Table 7.Experiment 1-26 is factorial experiment, and 27-36 is 12 center tests, in order to the estimating experiment error.
Table 7 response surface experimental program and experimental result
Figure 406210DEST_PATH_IMAGE006
2.4 response surface interpretation
Carry out data analysis by statistical analysis software SAS9.1, set up Quadratic response surface regression model as follows:
Y?=?-1781.3?+?39.51667?x1?+161.7833?x2?+?421.3125?x3?+?52.45417?x4?+?17.36083?x5?–?8.058333?x12?+?3.95?x1x2?–?8.25?x1x3?+?1.65?x1x4?–?0.36?x1x5?–?8.758333?x22?–?6.25?x2x3?+?1.7?x2x4?–?0.31?x2x5?–?50.36458?x32?–?4.9375?x3x4?–?1.8375?x3x5?–?3.514583?x42?–?0.1675?x4x5?–?0.085583?x52
X1, x2, x3, x4, x5 are the factor actual value
Regression analysis and the results of analysis of variance see Table 8.
Table 8 returns and the results of analysis of variance
Variable Degree of freedom Sum of squares All square The F value Pr>F
x 1 1 299.6267 299.6267 135.8651 0.0001
x 2 1 48.16667 48.16667 21.84108 0.0003
x 3 1 732.615 732.615 332.2029 0.0001
x 4 1 15.04167 15.04167 6.820615 0.019639
x 5 1 48.735 48.735 22.09879 0.000284
x 1 2 1 129.8735 129.8735 58.89088 0.0001
x 1x 2 1 15.6025 15.6025 7.074924 0.017836
x 1x 3 1 10.89 10.89 4.93805 0.042074
x 1x 4 1 10.89 10.89 4.93805 0.042074
x 1x 5 1 12.96 12.96 5.876687 0.028446
x 2 2 1 153.4168 153.4168 69.56656 0.0001
x 2x 4 1 11.56 11.56 5.24186 0.036966
x 3 2 1 129.8735 129.8735 58.89088 0.0001
x 3x 4 1 15.6025 15.6025 7.074924 0.01783
x 3x 5 1 54.0225 54.0225 24.4964 0.000175
x 4 2 1 395.2735 395.2735 179.236 0.0001
x 4x 5 1 11.2225 11.2225 5.088821 0.039443
x 5 2 1 146.4901 146.4901 66.42567 0.0001
Return 20 2257.722 112.8861 51.188 0.0001
Residue 15 33.07986 2.20532 ? ?
Lose and intend 6 16.98386 2.830644 1.582741 0.256993
Summation 35 2290.802 ? ? ?
As shown in Table 8, linear relationship between equation dependent variable and the independent variable(s) is obvious, this model returns significantly (p<0.0001), lose to intend item not significantly (p〉0.05), and this model R2=98.56%, R2Adj=96.63%, illustrates that this model and experimental fit are good, linear relationship is remarkable between independent variable(s) and the response value, and the theory that can be used for this reaction is inferred.Can obtain factor contribution rate by the F check is: x3〉x1〉x5〉x2〉x4, i.e. enzyme concentration〉enzymolysis time〉hydrolysis temperature〉enzymolysis pH〉solid-liquid ratio.
Application responds face optimizing analytical procedure is analyzed regression model, and working as enzymolysis time as can be known is 3.4h, and enzymolysis pH is 9.18, and enzyme concentration is 2.1%, and solid-liquid ratio is 1:7.9, and hydrolysis temperature is 48 ℃, and response surface has optimum value 86.38 ± 0.89%.
2.4 confirmatory experiment and simultaneous test
Under the top condition that the response surface analysis method is tried to achieve, namely enzymolysis time is 3.4h, and enzymolysis pH is 9.18, and enzyme concentration is 2.1%, and solid-liquid ratio is 1:7.9, and hydrolysis temperature is 48 ℃, carries out 3 parallel laboratory tests, and the mean value of 3 parallel laboratory tests of oil extracting rate is 87.68%.Experimental value and regression equation predictor that response value is described are coincide good.Directly utilizing aqueous enzymatic extraction Oleum Gossypii semen percent of total oil only is 70.94%.
3. experiment conclusion
Utilize Response surface methodology that the aqueous enzymatic extraction parameter of expelling-expansion pretreatment cottonseed is optimized.Having set up corresponding mathematical model is that later pilot scale and suitability for industrialized production provided fundamental basis, and obtained optimum enzymolysis process condition for being 3.4h when enzymolysis time, enzymolysis pH is 9.18, and enzyme concentration is 2.1%, solid-liquid ratio is 1:7.9, and hydrolysis temperature is 48 ℃.Through the checking with simultaneous test as can be known under optimum enzymolysis process condition oil extracting rate can reach about 87.68%, improved 16 percentage points than the percent of total oil that directly utilizes the aqueous enzymatic extraction Oleum Gossypii semen.

Claims (3)

1. the extracting method of an Oleum Gossypii semen, it is characterized in that the method may further comprise the steps: cottonseed is pulverized laggard row wet method extruding puffing, obtain expanded material, water ratio is 9-11% before the described cotton seed puffing, the nib aperture is 8-16mm, swelling temperature is 70-90 ℃, and vapor pressure is 0.6-0.8KPa; Expanded material and water are mixed to get mixed solution, amount of water is 6-10:1 with the quality of material ratio, adding Aclase2.4L Sumizyme MP after the mixed solution grinding is carried out enzymolysis obtain enzymolysis solution, described enzyme concentration is the 1.4-2.2 % of quality of material in the mixed solution, hydrolysis temperature 40-60 ℃, enzymolysis time 2.5-4.5 h, enzymolysis pH 8-10; With enzymolysis solution go out enzyme process after under 4500r/min centrifugation 30min, both obtained Oleum Gossypii semen.
2. the extracting method of a kind of Oleum Gossypii semen according to claim 1 is characterized in that the preferred parameter of described extruding puffing is: water ratio is 10.0% before the cotton seed puffing, and the nib aperture is 12mm, and swelling temperature is 82 ℃, and vapor pressure is 0.7MPa.
3. the extracting method of a kind of Oleum Gossypii semen according to claim 1 is characterized in that the preferred parameter of described enzymolysis is: enzyme concentration be in the mixed solution quality of material 2.1%, 48 ℃ of hydrolysis temperatures, enzymolysis time 3.4h,, enzymolysis pH 9.18.
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Application publication date: 20130206