CN110964083B - Method and equipment for recovering protein from starch crop processing wastewater - Google Patents

Method and equipment for recovering protein from starch crop processing wastewater Download PDF

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CN110964083B
CN110964083B CN201911236087.1A CN201911236087A CN110964083B CN 110964083 B CN110964083 B CN 110964083B CN 201911236087 A CN201911236087 A CN 201911236087A CN 110964083 B CN110964083 B CN 110964083B
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protein
starch
silicon dioxide
powder
foam
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CN110964083A (en
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刘伟
胡宏海
张泓
张良
刘倩楠
樊月
徐芬
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Institute of Food Science and Technology of CAAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
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    • C07K1/145—Extraction; Separation; Purification by extraction or solubilisation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
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    • C07K1/24—Extraction; Separation; Purification by electrochemical means
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters

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Abstract

The invention provides a method and equipment for recovering protein from starch crop processing wastewater, wherein the method comprises the following steps: (1) adding modified silicon dioxide nano-particles into starch crop processing wastewater, introducing gas to generate foam, drying the foam, and preparing the foam into powder to obtain protein crude extract powder, wherein the modified silicon dioxide nano-particles are obtained by modifying silicon dioxide nano-particles with dodecyl dimethyl betaine; (2) and (3) carrying out frictional electrification treatment on the crude protein extract powder to enable the protein in the crude protein extract powder to be positively charged, and other components to be uncharged or negatively charged, and carrying out protein recovery through charge difference. According to the invention, starch crop processing wastewater is made into foam through modified silicon dioxide, then is made into powder, and is collected after various components in the powder are charged with different charges in a friction charging mode, the recovery rate of protein is above 84%, the content of protein in the recovered powder can reach 91.2%, and meanwhile, the solubility, the emulsibility and the bioactive components of the powder are effectively maintained.

Description

Method and equipment for recovering protein from starch crop processing wastewater
Technical Field
The invention relates to the field of wastewater treatment, in particular to a method and equipment for recovering protein from starch crop processing wastewater.
Background
Starch crops are accompanied by the production of large amounts of organic waste water, such as potatoes, about 20 tons of waste water are discharged per 1 ton of starch produced on average, and the protein content of juice separated from a hydrocyclone (cyclone station) on a potato starch processing production line reaches 0.9-2.1%. The starch crop protein has good foaming and emulsifying properties, and has good application prospect in the food industry. Therefore, the extraction and utilization of starch waste water protein of starch crops become the problems to be solved by the starch production industry of starch crops in view of improving environment and realizing full utilization of resources.
At present, protein extraction in starch processing wastewater of starch crops mainly comprises methods such as concentration, flocculation, precipitation, ion exchange chromatography, enzymolysis, ultrafiltration, dialysis and the like. Equipment and technology for extracting protein from potato starch wastewater (application publication number: CN 200510053212.7A) disclose that zeolite powder and gypsum powder are used as precipitating agents, and a chemical method is used as a main separation method to obtain protein powder. Because a large amount of flocculant is added, the protein cannot be recycled and can only be used as the pretreatment of the subsequent water treatment process. The process for extracting potato protein by a thermal flocculation method (application publication number: CN 105230964A), the process for producing the potato protein (application publication number: CN 105111276A), the method for extracting protein from waste liquid of potato starch processing (application publication number: CN101220078A), the method for treating protein in potato starch production waste water (application publication number: CN 105565543A), the method for recovering protein from waste water after potato starch preparation (application publication number: CN1217890A) and the method and equipment for extracting protein from waste water of potato starch production (application publication number: CN200610003857.4) respectively adopt the thermal flocculation method or the acid thermal flocculation method to separate and precipitate the protein to obtain the potato protein extract, the process is complicated, the using amount of chemical additives is large, the recovered protein is denatured, the purity is low, and the potato protein extract is generally used as animal feed. A method for separating and preparing potato protein powder from potato juice water (application publication No. CN102504011A) separates the technical water of potato starch processing by separating membranes with different molecular weight cut-off to obtain the potato protein powder, but the membrane has high cost, low permeation quantity, easy blockage and frequent cleaning.
Disclosure of Invention
The invention provides a method and equipment for recovering protein from starch crop processing wastewater, which solves the problems of difficult maintenance of biological activity and high cost in the process of recovering protein from starch crop wastewater in the prior art by collecting crop protein after the starch crop protein is electrified.
In a first aspect, the present invention provides a method for recovering protein from starch crop processing wastewater, comprising:
(1) adding modified silicon dioxide nano particles into starch crop processing wastewater, introducing gas to generate foam, drying the foam, and preparing the foam into powder to obtain protein crude extract powder, wherein the modified silicon dioxide nano particles are obtained by modifying silicon dioxide nano particles through dodecyl dimethyl betaine;
(2) and (3) carrying out frictional electrification treatment on the crude protein extract powder to enable the protein in the crude protein extract powder to be positively charged, and other components to be uncharged or negatively charged, and carrying out protein recovery through charge difference.
The starch crop processing wastewater is wastewater generated in the process of processing starch crops into starch, contains protein, starch, cellulose and other impurities, is made into a foam shape in a foam separation mode, and the silicon dioxide nanoparticles modified by dodecyl dimethyl betaine have stronger hydrophobic activity, can be used as a foam stabilizer to improve the interface adsorption effect of the starch crop protein, can effectively separate the protein, the starch, the cellulose and other impurities in the foam generation process, can enhance the foam drainage efficiency and the starch crop protein recovery efficiency, and has positive influence on the further separation effect of the subsequent protein crude extract powder.
Further, the modification method of the silica nanoparticles comprises the following steps: dispersing silicon dioxide particles in dodecyl dimethyl betaine solution, adjusting the pH value to 4.5-5.5, stirring, centrifuging and freeze-drying; the molar ratio of the silicon dioxide particles to the dodecyl dimethyl betaine is 2: 1-2.5: 1.
During the modification process of the silicon dioxide, the pH value can greatly influence the modification effect, and the excessive pH value causes the modification effect in OH-Under the action of (2), SiO2And H2Formation of Si (OH) by O bonding4Reduction of silica and dodecyl dimethyl beetThe combination of alkali makes it impossible to effectively separate protein from starch, cellulose and other impurities during the process of forming foam. When the pH value is too low, the dodecyl dimethyl betaine is cationic and not easy to be SiO2And carrying out polycondensation reaction.
Further, the concentration of the modified silicon dioxide nano particles is 300-500 mg/L, and the flow rate of the introduced gas is 250-350 mL/min.
The concentration of the silicon dioxide nano particles can fully act with potato protein under the action of air with a certain flow velocity, so that the protein separation efficiency is improved.
Further, the triboelectric charging comprises the following specific steps:
and (3) carrying the crude protein extract powder with dry gas to enter a friction charged tube, wherein after the crude protein extract powder is rubbed with the tube wall of the friction charged tube, protein components are positively charged, and starch and other components are negatively charged or uncharged.
Furthermore, the drying gas is drying air, and the flow rate is 5-7L/min, preferably 5L/min.
The crude protein extract powder is suspended in moving air fluid under the action of a fluidized bed, then dry air carries the crude protein extract powder into a frictional electrification tube at a certain flow rate, after the dry air fully rubs and contacts the tube wall of the electrification tube by controlling the flow rate of powder particles, the protein part is positively charged, starch and other components carry negative charges or no charges, and the separation of protein can be realized through the difference of the charges.
Furthermore, the particle size of the protein crude extract powder is 50 nm-200 nm.
Starch crop foam is at defoaming, the superfine grinding of spray drying powder process back and is obtained albumen crude extract powder, and its particle size also has great influence to the recovery efficiency of albumen, and the too big granule of particle size can lead to being difficult to by electrified copper board collection in the collection process after owing to the influence of its self gravity, and then makes albumen recovery efficiency descend.
Further, the step of preparing the foam into protein crude extract powder specifically comprises the following steps: ultrasonically defoaming the foam, carrying out spray drying, and then carrying out superfine grinding, wherein the spray drying conditions are as follows: the air inlet temperature is 110-120 ℃, the air outlet temperature is 55-65 ℃, the feeding flow is 5-8 mL/min, and the feeding concentration is 15-20 g/100 g.
Furthermore, the processing time of ultrasonic defoaming is 15-20 min, and the power is 40-60W.
Furthermore, the pressure of the airflow for superfine grinding and crushing is 0.80-0.95 MPa, the temperature of the airflow is 5-10 ℃, and the rotating speed of a variable frequency motor is 10000-15000 r/min.
Further, the starch crop processing wastewater is wastewater discharged in a process that the starch crop is used for producing starch, and the starch crop is potato or sweet potato, preferably potato.
In a preferred embodiment of the invention, the method for extracting protein from starch crop processing wastewater specifically comprises the following steps:
(1) dispersing silicon dioxide particles in dodecyl dimethyl betaine solution, adjusting the pH value to 4.5-5.5, stirring, centrifuging and freeze-drying; the molar ratio of the silicon dioxide particles to the dodecyl dimethyl betaine is 2: 1-2.5: 1;
(2) adding the modified silicon dioxide nano-particles obtained in the step (1) into starch crop processing wastewater, and introducing gas to generate foam, wherein the concentration of the modified silicon dioxide nano-particles is 300-500 mg/L, and the flow rate of the introduced gas is 250-350 mL/min;
(3) ultrasonically defoaming the foam generated in the step (2), spray-drying, and then carrying out superfine grinding, wherein the particle size of the superfine ground protein crude extract powder is 50-200 nm;
(4) the protein crude extract powder after the superfine grinding is charged positively by friction and electrification, the starch and other components are charged negatively, and the recovery of the protein is carried out by charge difference.
In a second aspect, the present invention provides an apparatus for recovering protein from starch crop processing wastewater, which is applied to the above method, comprising: the device comprises a bubble separation unit, a spray drying and crushing unit and a pneumatic electrostatic friction unit which are connected through pipelines; the pneumatic electrostatic friction unit comprises a fluidized bed and a friction charged pipe;
a stirrer with a stirring blade surface coated with a polytetrafluoroethylene layer is arranged at the bottom of the fluidized bed, and a gas outlet at the top of the fluidized bed is connected with the frictional electrification pipe;
wherein the crude protein extract powder is transported from the spray drying and comminution unit to the fluidized bed by a pipeline; and the mixture is stirred by a stirrer and then is transported to the frictional electrification pipe through a pipeline.
Furthermore, a shunting collection box is further arranged in the pneumatic electrostatic friction unit, and a bottom outlet of the friction charged tube is connected with a top inlet of the shunting collection box.
Furthermore, the upper part of the shunting collection box is provided with an electrified copper plate which is arranged at the left and right intervals with the feeding port in the horizontal projection direction, the voltage of the electrified copper plate is-1 to-3 kV, and the included angle between the electrified copper plate and the feeding port of the shunting collection box is 10 to 20 degrees. The voltage and angle of the charged copper plate can be changed correspondingly according to the types of starch crops so as to achieve the best protein recovery efficiency.
Furthermore, the bottom space between the feeding port and the horizontal projection center of the charged copper plate is divided into four parts along the direction at the bottom of the diversion collecting box, and four spaces B1, B2, B3 and B4 are arranged. The different components in the crude protein extract powder entering the shunting collection box are separated into the four spaces under the action of the charged copper plate according to the difference of charges of the components. When the electrified copperplate stops electrifying, protein particles on the copperplate enter the B4 space under the action of gravity.
The superfine crushed crude protein powder is introduced into a fluidized bed, a stirrer with a polytetrafluoroethylene layer coated on the surface of a blade arranged at the bottom of the fluidized bed is used for stirring, meanwhile, dry gas is introduced into the bottom of the fluidized bed, the crude protein powder enters a friction electrification pipe under the action of the dry gas for friction electrification, the protein is positively charged, the starch and other components are negatively charged or uncharged, and then the charged crude protein powder is introduced into a shunt collection box to realize the recovery of the protein.
The invention provides a method and equipment for recovering protein from starch crop processing wastewater, which have the following beneficial effects:
1. the invention adopts a physical method to recycle the starch crop wastewater after foam pulverization, compared with a flocculation method and acid sedimentation, the air bubble separation method can effectively keep the biological activity of the starch crop protein, meanwhile, the protein recovery rate reaches over 84 percent, the protein purity after recovery can reach 91.2 percent, compared with a membrane filtration method, the air bubble separation method has simple process and supporting equipment, does not need to repeatedly replace or clean accessories, and has lower cost.
2. The whole set of process for extracting and separating the starch crop protein has high extraction and separation efficiency, simplified equipment, high automation degree and no pollution, and can be widely used for extracting and recovering the protein in starch processing wastewater of potatoes and the like and other various protein-rich liquids.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of an apparatus for recovering protein from starch crop processing wastewater according to example 2 of the present invention;
wherein:
1: an air compressor; 2: a rotameter; 3: a delivery pump; 4: a feed inlet; 5: a starch crop processing wastewater storage tank; 6: a foam separator; 7: a foam collector; 8: a gas cylinder; 9: an air wetting bottle; 10: a discharge outlet; 11: an air filter; 12: a blower; 13: an air heater; 14: a spray head; 15: a drying tower; 16: a cyclone separator; 17: an induced draft fan; 18: a dust remover; 19: an ultrasonic bubble remover; 20: a material pump; 21: an ultrafine pulverizer; 22: a material pump; 23: a fluidized bed; 24: a triboelectric charging tube; 25: a charged copper plate; 26: a voltmeter; 27: a dryer; 28: a high pressure air storage tank; 29: a flow controller; 30: and a shunting collection box.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a method for recovering protein from starch crop processing wastewater, which comprises the following steps:
(1) dispersing silicon dioxide particles in dodecyl dimethyl betaine solution, adjusting the pH to 4.9, stirring, centrifuging and freeze-drying; the molar ratio of the silicon dioxide particles to the dodecyl dimethyl betaine is 2: 1;
(2) adding the modified silicon dioxide nano-particles obtained in the step (1) into starch crop processing wastewater, introducing gas to generate foam, wherein the concentration of the silicon dioxide nano-particles is 500mg/L, and the flow rate of the introduced gas is 250 mL/min;
(3) ultrasonically defoaming the foam generated in the step (2), spray-drying, and then carrying out superfine grinding, wherein the particle size of the superfine ground protein crude extract powder is 100 nm.
(4) The protein crude extract powder after the superfine grinding is charged positively by friction and electrification, the starch and other components are charged negatively, and the recovery of the protein is carried out by charge difference.
Further, step (4) may be implemented by: the dry gas with the flow rate of 5L/min is used for carrying the crude protein extract powder into a friction electrostatic tube, and after the crude protein extract powder is rubbed with the tube wall of the friction electrostatic tube, protein components are positively charged, and starch and other components are negatively charged or uncharged.
Example 2
FIG. 1 provides an apparatus for recovering protein from starch crop processing wastewater for performing the method of example 1, and as shown in FIG. 1, the starch crop protein extraction apparatus includes:
a bubble separation unit, a spray drying and crushing unit and a pneumatic electrostatic friction unit;
the air bubble separation unit comprises a starch crop processing wastewater storage tank 5, a foam separator 6 and a foam collector 7, wherein the starch crop processing wastewater storage tank 5 is provided with a feed inlet 4 and a discharge outlet 10, and the starch crop processing wastewater is transported to the foam separator 6 through a pipeline by a feed delivery pump 3; the foam separator 6 is formed by connecting an upper part of an oval sphere and a lower part of a cylinder together, the air inlet end is connected with an air compressor 1, an air bottle 8, a rotor flow meter 2 and an air wetting bottle 9 which are sequentially connected for controlling the air inlet speed, the generated foam is conveyed to a foam collector 7 through a pipeline, and the foam collector 7 conveys the foam to an ultrasonic foam remover 19 through a pipeline.
The spray drying and crushing unit comprises an ultrasonic bubble remover 19, a drying tower 15 and an ultrafine crusher 21, wherein the air inlet end of the drying tower 15 is connected with an air filter 11, a blower 12 and an air heater 13 which are sequentially connected for controlling the air inlet speed and temperature, the ultrasonic bubble remover 19 outputs foams under the regulation and control of a material pump 20, and the foams enter the drying tower 15 through a spray head 14 under the promotion of air inlet to prepare protein crude extract powder in a spray drying mode; the discharge gate end of drying tower 15 is equipped with cyclone 16 and is used for carrying out the air current to protein crude extract powder and grades, and cyclone 16 is equipped with draught fan 17 outward, and draught fan 17 links to each other with dust remover 18, and starch crop that starch crop powder and drying tower output that separate out through cyclone 16 all carry out the superfine grinding of different degrees according to the different air current grades of powder in superfine grinder 21.
The pneumatic electrostatic friction unit comprises a fluidized bed 23, a friction charged pipe 24 and a shunt collection box 30, a dryer 27 is connected to the feeding end of the fluidized bed 23, a high-pressure air storage tank 28 and a flow controller 29 are used for regulating and controlling air inflow, protein crude extract powder after superfine grinding is counted into the fluidized bed 23 under the pushing of the air inflow through a material pump 22, the protein crude extract powder is suspended in the air through a stirrer wrapped by a PTFE coating inside the fluidized bed 23, then the dry air carries the protein crude extract powder to enter the friction charged pipe 24, the protein crude extract powder and the pipe wall carry charges after friction, protein components in the protein crude extract powder carry positive charges, starch and other components are uncharged or negatively charged, and the protein crude extract powder enters the shunt collection box 30 along with dry gas after being charged.
Furthermore, the crude protein extract powder vertically enters from a feeding port at the top of the shunting collection box 30, the upper part of the shunting collection box 30 is provided with an electrified copper plate 25 which is arranged at left and right intervals with the feeding port in the horizontal projection direction, the electrified voltage is-1 to-3 kV, the included angle between the electrified copper plate and the feeding port is 10 to 20 degrees, and a voltmeter 26 is connected with the electrified copper plate 25 to regulate the voltage.
Further, the bottom space of the horizontal projection center of the feed inlet and the charged copper plate is divided into four parts along the direction by the bottom of the diversion collection box 30, four spaces B1, B2, B3 and B4 are arranged, the space B1 is closest to the position where the charged protein crude extract powder enters, and the space B4 is farthest.
The different components in the crude protein extract powder entering the shunting collection box 30 are separated into the four spaces after being acted by the charged copper plate 25 according to the difference of the charges of the components, for example, the positively charged protein powder is acted by the charged copper plate and then the locus is deviated, and falls into the B4 space which is closer to the copper plate, and the negatively charged starch powder is acted by the charged copper plate and then the locus is deviated, and falls into the B1 space which is farther from the copper plate.
Example 3
This example provides a method for recovering protein from starch crop processing wastewater, which, with reference to fig. 1, includes the following specific steps:
(1) in the bubble separation unit, potato processing wastewater containing modified silicon dioxide nanoparticles in a starch crop processing wastewater storage tank 5 enters a foam separator 6 through a delivery pump 3, wherein the concentration of the modified silicon dioxide nanoparticles is 500 mg/L. Gas generated by the air compressor 1 sequentially passes through the gas cylinder 8 and the air moistening cylinder 9, the flow rate of the gas is controlled to be 250mL/min by the rotor flow meter 2, foam is generated by the potato processing wastewater in the foam separator 6 under the action of the gas, and the foam flows into the spray drying and crushing unit through continuous expansion and contraction.
The preparation method of the modified silicon dioxide nano-particles comprises the following steps: dispersing 2.2mol/L silicon dioxide particles in 1mol/L dodecyl dimethyl betaine solution, adjusting the pH of the solution to 4.9 by 0.1mol/L HCl, stirring at a constant speed for 12h, centrifuging at 6000rpm, collecting precipitate, and freeze-drying to obtain the modified silicon dioxide nanoparticles.
(2) In the spray drying and crushing unit, foam of the potato processing wastewater is defoamed by an ultrasonic defoaming device 19, the treatment time is 20min, and the power is 40W. Then, the powder is prepared by a spray drying mode through a drying tower 15, the air inlet temperature is 110-120 ℃, the air outlet temperature is 65 ℃, the feeding flow is 8mL/min, and the feeding concentration is 20g/100 g; and then crushing for 2 times by using an ultrafine crusher 21 to obtain potato protein crude extract powder, wherein the airflow pressure is 0.80MPa, the airflow temperature is 5 ℃, the rotating speed of a variable frequency motor is 10000r/min, and the particle size of the ultrafine crushed potato protein crude extract powder is 100 nm.
(3) In the pneumatic electrostatic friction unit, potato protein crude extract powder enters a fluidized bed 23 through a material pump, dry air (200kPa) in a high-pressure air storage tank 28 passes through a dryer 27 and is vertically introduced into the fluidized bed, the flow rate of the dry gas in the fluidized bed is 5L/min, a stirrer wrapped by a PTFE coating in the fluidized bed enables the starch protein crude extract powder to be suspended in the air, and the starch protein crude extract powder enters a friction charging pipe 24 under the action of the dry gas to charge particles, the charging property of the particles is related to the composition and the structure of the particles, wherein the potato protein is positively charged, and the starch and other substances are uncharged or negatively charged. The shunting collection box contains an electrified copper plate 25 with the electrified voltage of-1 kV, and the angle between the electrified copper plate 25 and the bottom of the collection box is 20 degrees. The potato protein crude extract powder enters a diversion collecting box from a fluidized bed under the action of air flow, the motion trail of the powder is changed according to the charged property of the powder under the action of an electric field, part of potato protein is collected on a charged copper plate, and the other part of potato protein, starch granules and other components enter different spaces at the bottom of the collecting box (B1, B2, B3 and B4). When the electrified copperplate stops electrifying, protein particles on the copperplate enter the B4 space under the action of gravity.
Example 4
This example provides a method for recovering potato protein from potato processing wastewater, the detailed steps of which are described in example 3, except that the voltage of the charged copper plate is-3 kV.
Comparative example 1
This example provides a method for recovering potato protein from potato processing wastewater, the detailed steps of which are described in example 3, except that the potato processing wastewater in the froth separation unit does not contain modified silica nanoparticles.
Comparative example 2
The comparative example provides a method for recovering potato protein from potato processing wastewater, and the detailed steps are shown in comparative example 1, except that the voltage of the charged copper plate is-3 kV.
Comparative example 3
This example provides a method for recovering potato protein from potato processing wastewater, the detailed steps of which are described in example 3, except that the concentration of modified silica nanoparticles in the potato processing wastewater in the froth separation unit is 100 mg/L.
Comparative example 4
This example provides a method for recovering potato protein from potato processing wastewater, the detailed procedure of which is described in example 3, except that the modified silica nanoparticles in potato processing wastewater in the froth separation unit are silica nanoparticles modified with cocamidopropyl betaine.
Experimental example 1
This experimental example potato protein recovered by the methods of examples 3, 4 and comparative examples 1 to 4 was examined by the following procedure:
1. potato protein concentration determination
Using the BCA protein quantification kit for analysis, 2000. mu.g/mL protein standard solutions were diluted to 1000, 500, 250 and 125. mu.g/mL, respectively. An appropriate amount of BCA working solution was prepared by adding 50 volumes of BCA reagent a to 1 volume of BCA reagent B. Respectively adding 25 mu L of standard substance and a sample with a proper concentration range into micropores of a 96-well plate, respectively adding 200 mu L of BCA working solution, fully and uniformly mixing, incubating at 37 ℃ for 30min, and then measuring the light absorption value at 550 nm.
2. Bubble separation potato protein recovery rate
Potato protein recovery ═ (concentration of potato protein in suspension x volume of suspension-concentration of potato protein in foam drainage x volume of foam drainage)/(concentration of potato protein in suspension x volume of suspension) x 100%
3. The antioxidant activity of potato protein is determined by enzymolysis of potato protein into polypeptide.
(1) The potato protein solution was pretreated (90 ℃ C., 10min) from the supernatant. Adjusting pH to 8.0, and adding papain. Taking out 1mL of enzyme digestion product at the 5 th hour in the enzyme digestion process, and inactivating the enzyme in boiling water bath for 10 min. The pH was adjusted to 11.0 and alkaline protease was added. Taking out 1mL of enzyme digestion product in the 5h of the enzyme digestion process, and inactivating the enzyme in boiling water bath for 10min to obtain the polypeptide product. The degree of hydrolysis was calculated by the pH-stat method, i.e., the Degree of Hydrolysis (DH) was calculated based on the amount of NaOH consumed during the hydrolysis.
(2) Measurement of DPPH radical scavenging ability of Potato Polypeptides Each tube was loaded as follows: tubes A1 are 1.5mL of DPPH anhydrous methanol solution and 1.5mL of anhydrous methanol, tubes A2 are 1.5mL of DPPH anhydrous methanol solution and 1.5mL of sample solutions with different degrees of hydrolysis, and tubes A3 are 1.5mL of sample solutions with different degrees of hydrolysis and 1.5mL of anhydrous methanol solution; shaking up forcibly; standing and reacting for 30min at the dark place at room temperature; adding the reaction mixed solution into a cuvette after 30min, and measuring absorbance values of A1, A2 and A3 at a wavelength of 517nm of an ultraviolet spectrophotometer by taking anhydrous methanol as a reference; the clearance rate of the proteolysis sample to be tested to DPPH free radical is calculated according to the following formula: SA (%) [ 1- (a 2-A3)/a 1] × 100%.
The test results are as follows:
TABLE 1 Effect of different treatment modalities on Potato protein in wastewater from Potato starch processing
Figure BDA0002304909480000111
The effect of different treatment methods on potato protein in potato starch processing wastewater is compared in table 1, and it can be seen from table 1 that the recovery rate of potato protein from bubble separation is significantly reduced in comparative examples 1 and 2 compared to examples 2 and 3 without adding modified silica nanoparticles to the bubble separation treatment. The reduction of the potato protein recovery efficiency and the separation efficiency due to the excessively low concentration of the modified silica nanoparticles in comparative example 3, and the use of the cocamidopropyl betaine-modified silica in comparative example 4 also resulted in the reduction of the potato protein-adsorbing effect of the modified silica.
TABLE 2 Effect of different treatment modalities on antioxidant Activity of Potato proteolytic Polypeptides in Potato starch processing wastewater
Figure BDA0002304909480000121
From table 2, it can be seen that the potato proteins of examples 2 and 3 have significantly higher degrees of hydrolysis and DPPH radical scavenging rates than those of comparative examples 1 to 4 after hydrolysis, indicating that the protein activities are less affected, further indicating that the specific conditions of using dodecyl dimethyl betaine modified silica nanoparticles as foam stabilizers in the bubble separation unit and triboelectric charging have a significant effect on the biological activities of the potato proteins.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (7)

1. A method for recovering protein from starch crop processing wastewater, comprising:
(1) adding modified silicon dioxide nanoparticles into starch crop processing wastewater, introducing gas to generate foam, drying the foam, and preparing the foam into powder to obtain protein crude extract powder, wherein the particle size of the protein crude extract powder is 50 nm-200 nm, and the modified silicon dioxide nanoparticles are obtained by modifying silicon dioxide nanoparticles with dodecyl dimethyl betaine;
the modification method of the silicon dioxide nano-particles comprises the following steps: dispersing silicon dioxide particles in dodecyl dimethyl betaine solution, adjusting the pH value to 4.5-5.5, stirring, centrifuging and freeze-drying to obtain the silicon dioxide particle material; the molar ratio of the silicon dioxide particles to the dodecyl dimethyl betaine is 2: 1-2.5: 1;
the concentration of the modified silicon dioxide nano particles is 300-500 mg/L;
(2) and (3) carrying out frictional electrification treatment on the crude protein extract powder to enable the protein in the crude protein extract powder to be positively charged, and other components to be uncharged or negatively charged, and carrying out protein recovery through charge difference.
2. The method according to claim 1, wherein the flow rate of the introduced gas is 250 to 350 mL/min.
3. The method according to claim 1, wherein the triboelectric charging is carried out by the following steps:
and (3) carrying the crude protein extract powder with dry gas to enter a friction electrification tube, wherein after the crude protein extract powder is rubbed with the tube wall of the friction electrification tube, protein components are positively charged, and starch and other components are negatively charged or uncharged.
4. The method according to claim 3, wherein the drying gas is dry air and the flow rate is 5-7L/min.
5. The method according to claim 4, wherein the flow rate of the drying gas is 5L/min.
6. The method of any one of claims 1 to 5, wherein the starch crop processing wastewater is wastewater discharged from a process in which a starch crop is used to produce starch, the starch crop being potato or sweet potato.
7. The method of claim 6, wherein the starch crop is potato.
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