CN114146693A - Grape skin adsorbent for adsorption removal of cadmium ions, preparation method and application thereof - Google Patents
Grape skin adsorbent for adsorption removal of cadmium ions, preparation method and application thereof Download PDFInfo
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- CN114146693A CN114146693A CN202111489233.9A CN202111489233A CN114146693A CN 114146693 A CN114146693 A CN 114146693A CN 202111489233 A CN202111489233 A CN 202111489233A CN 114146693 A CN114146693 A CN 114146693A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/60—Salad dressings; Mayonnaise; Ketchup
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
- A23L5/273—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption using adsorption or absorption agents, resins, synthetic polymers, or ion exchangers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4893—Residues derived from used synthetic products, e.g. rubber from used tyres
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Abstract
The invention discloses a grape skin adsorbent for adsorbing and removing cadmium ions, a preparation method and application thereof, wherein the adsorbent comprises the following components: 35-55 parts of grape skin; 0.5-1 part of pectinase; 0.5-1 part of cellulase; 45-55 parts of water. The method uses grape skin as a main raw material, and the adsorption material capable of adsorbing heavy metal ions cadmium is obtained through the steps of enzymolysis, drying, crushing and the like. The adsorbent can effectively adsorb and remove cadmium ions in an aqueous solution, can add grape-flavor aroma in the solution, and has wide application in aquatic product food processing, particularly in the adsorption and removal of the cadmium ions in the seafood sauce.
Description
Technical Field
The invention belongs to the technical field of food processing, and particularly relates to a grape skin heavy metal adsorbent, a preparation method and application thereof.
Background
Grapes are the most planted fruits in the world, are mainly used for brewing wine, produce about 2500 kiloliters of wine every year, simultaneously produce a large amount of grape pomace waste, cause certain burden on production cost and also cause certain pressure on the environment. The utilization degree of the grape skin residues in China is not high, and the extraction of bioactive substances is mainly focused at present. The grape skin contains rich bioactive substances, especially polyphenols, has obvious antioxidant effect, and can be widely applied in the industries of medicine and health care, food, cosmetics, chemical engineering and the like. The huge pressure brought to the environment by the accumulation of a large amount of peel and slag in the brewing season becomes a problem which is urgently needed to be solved at present. The comprehensive utilization of the grape skin residues is actively promoted, so that the environment can be protected, and huge economic benefits can be created.
Cadmium is widely used in industry as an industrial raw material and a catalyst. In recent years, with the rapid development of fields such as electroplating, metallurgy, chemical engineering, electronic processing, nuclear industry and the like, cadmium pollution in water environment is increasingly serious, and cadmium is listed as one of control pollutants in many countries. The heavy metal cadmium has no biodegradability, is easy to accumulate in organisms, has toxicity and carcinogenicity, and has long half-life and multiple organ injury. Cadmium invades the human body through the respiratory tract and the digestive tract, and causes a series of damages to the lung, the bone, the kidney, the liver, the immunity and the reproductive organs, thereby causing great threat to the health and the environment of human beings.
At present, chemical precipitation, ion exchange, membrane separation, bioremediation and adsorption methods are commonly used for treating cadmium-containing wastewater. The adsorption method is simple to operate, economical and effective, students at home and abroad carry out extensive research on the efficient and low-price biomass byproduct adsorption material, and in recent years, the students adsorb heavy metal ions in water by using rice husks, bamboo charcoal, corncobs, bagasse, shaddock peels and the like, so that the waste is recycled, and a novel green and environment-friendly heavy metal removal method is provided.
With the aggravation of environmental pollution, the phenomenon that heavy metals exceed standards often occurs in marine harvested aquatic products, particularly bivalve and cephalopod. Common adsorption modification processes for wastewater systems may utilize chemicals that are not suitable for use in food production processes. Therefore, a more natural, environment-friendly and low-price adsorbent aiming at the excessive heavy metals in aquatic products is urgently needed to be researched.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an adsorbent which uses grape skin which is a waste product in the wine industry as a raw material, destroys the protective effect of pectin and cellulose on a microstructure through enzyme treatment, exposes relevant adsorption functional groups and increases the specific surface area, and develops the adsorbent which has the adsorption and removal effects on heavy metals.
The invention also aims to provide a preparation method of the adsorbent.
The invention also aims to provide a using method of the adsorbent and application thereof.
It is also an object of the present invention to provide a use of the adsorbent for adsorbing heavy metals.
In order to achieve the purpose, the invention adopts the following technical scheme:
a heavy metal adsorbent comprises the following components: grape skin, pectinase, cellulase and water.
Further, as a preferred embodiment, the heavy metal adsorbent comprises the following components in parts by weight:
35-55 parts of grape skin;
0.5-1 part of pectinase;
0.5-1 part of cellulase;
45-55 parts of water.
Further, as a best embodiment, the heavy metal adsorbent comprises the following components in parts by weight:
50 parts of grape skin;
0.5 part of pectinase;
0.5 part of cellulase;
50 parts of water.
The method for preparing the heavy metal adsorbent comprises the following steps:
s11: cleaning grapes with clear water, stripping and collecting grape skin, adding pure water, pectinase and cellulase, and carrying out full oscillation reaction at a certain temperature to obtain enzyme-treated grape skin;
s12, carrying out ventilation drying on the obtained enzyme-treated grape skin;
s13, crushing and powdering the obtained dried grape skin by using a food processor, and sieving the obtained powder to obtain grape skin powder with the aroma of cooked grapes, namely the adsorbent of heavy metal cadmium.
Further, as a preferred embodiment, the reaction temperature in the step S11 is preferably 25 ℃, and the reaction time with shaking is preferably 1 h.
Further, as a preferred embodiment, the temperature of the air drying in the step S12 is preferably 40 ℃.
Further, as a preferred embodiment, the powder passes through a 200-mesh sieve in the step S13.
Furthermore, the invention also provides application of the adsorbent in adsorbing heavy metal cadmium, in particular to adsorption and removal of heavy metal cadmium in seafood.
A method for adsorbing heavy metal cadmium by a heavy metal adsorbent comprises the following steps:
s21, preparing a cadmium ion standard solution into a liquid containing heavy metal cadmium, and adding 0.6-1.2% by mass of an adsorbent;
s22, adjusting the pH value of the mixed solution to 3-6 after the grape skin adsorbent is added, and oscillating and stirring for 20-120min at 20-50 ℃ to ensure that the adsorption reaction is fully performed; after the reaction is finished, centrifuging and removing the adsorbent to obtain clear liquid;
and S23, analyzing the initial cadmium ion concentration and the absorbed cadmium ion concentration of the mixed solution by ICP-MS, comparing and analyzing, and judging the adsorption capacity of the adsorbent according to the comparison and analysis.
Further, as a preferred embodiment, the addition amount of the adsorbent in the step S21 is preferably 1.0%; the pH value in the step S22 is preferably 6; the oscillation temperature in the S22 is preferably 40 ℃; the oscillation time in S22 is preferably 80 min.
Furthermore, the invention also provides a method for adsorbing heavy metal in the seafood sauce by using the heavy metal adsorbent, and as a preferred embodiment, the heavy metal in the seafood sauce can be heavy metal cadmium.
Further, as a preferred embodiment, the invention provides a method for adsorbing heavy metal cadmium in squid viscera, which comprises the following steps:
s31, taking squid viscera for enzymolysis to prepare sauce, and adding the heavy metal adsorbent;
s32, adjusting the pH value of the mixed solution to which the medium heavy metal adsorbent is added, oscillating and stirring the mixed solution at a certain temperature to fully perform the adsorption reaction, and centrifuging the mixed solution after the reaction is finished to remove the adsorbent to obtain clear solution;
s33: and analyzing the initial cadmium ion concentration of the mixed solution and the absorbed cadmium ion concentration by ICP-MS, and comparing and analyzing to judge the adsorption capacity of the adsorbent.
Further, as a preferred embodiment, the mass fraction of the heavy metal adsorbent in the step S31 is 1.0%.
Further, as a preferred embodiment, the pH value in step S32 is 6, the temperature is preferably 40 ℃, and the oscillation time is preferably 100 min.
Furthermore, the grape skin is heated and dried to release a large amount of benzaldehyde serving as a flavor component, and the obtained grape skin powder has strong grape fragrance and can achieve the effects of removing fishy smell and enhancing flavor in the process of removing heavy metal adsorption of aquatic food.
Furthermore, the grape skin contains phenolic compounds such as resveratrol and the like, and has the effect of preventing cardiovascular diseases and the like; also contains antioxidant components such as anthocyanin, and can provide more nutrition and functional health promotion effects for the product.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention takes the grape skin as the main raw material, improves the adsorption capacity of the grape skin powder through enzyme treatment, is beneficial to the reutilization of the industrial wastes of the wine in China, and reduces the pressure on the environment. Furthermore, the protection effect of pectin and cellulose on the microstructure is destroyed by pectinase and cellulase, so that adsorption related functional groups are exposed, the specific surface area is increased, and the adsorption efficiency is improved.
(2) In order to fully utilize the adsorption structure of the grape skin, pectinase and cellulase are used, so that the porosity of the grape skin powder is improved, and the defect of weak adsorption capacity of natural grape skin powder is overcome; secondly, the addition amount of the adsorbent, the adsorption pH, the adsorption time and the adsorption temperature during adsorption are optimized so as to achieve the optimal adsorption efficiency and benefit; third, grape skins have a pleasant aroma and a higher nutritional value, and can provide additional benefits to aquatic products and their processed products compared to traditional adsorbents.
(3) The grape skin is heated and dried, so that a large amount of benzaldehyde serving as a flavor component is released, the obtained grape skin powder has strong grape fragrance, and the effects of removing fishy smell and enhancing flavor can be achieved in the process of removing heavy metal adsorption of aquatic food. Compared with the traditional adsorbent, the invention has the advantages of environmental protection, solves the environmental pressure of a large amount of wastes in the grape processing industry, and provides additional value for aquatic food processing by utilizing the flavor and the nutritional value of grape skins.
(4) According to the process method and the optimized adsorption method, the marine products and the processed products thereof with excessive heavy metal cadmium can remove cadmium ions and obtain grape fragrance and partial functional nutrient substances.
Drawings
The invention is further illustrated by the following examples and combinations.
FIG. 1 is an adsorbent of grape skin powder prepared in example 1;
FIG. 2 is a flow chart of the preparation and adsorption process of the grape skin adsorbent material provided by the present invention;
FIG. 3 is a graph showing the effect of different amounts of adsorbent added on the removal rate of cadmium ions;
FIG. 4 is a graph of the effect of different pH on cadmium ion removal;
FIG. 5 is a graph of the effect of different adsorption temperatures on cadmium ion removal rate;
FIG. 6 is a graph showing the effect of different adsorption times on cadmium ion removal rate;
FIG. 7 is an SEM image of grape skin adsorbent powder at 2000 times;
FIG. 8 is a SEM electron micrograph of grape skin adsorbent powder at 5000 times;
FIG. 9 is an SEM image of natural grape skin powder at 2000 times;
FIG. 10 is a SEM electron microscope image of 5000 times of natural grape skin powder;
FIG. 11 is a comparison of infrared absorption spectra of grape skin adsorbent powder and natural grape skin powder.
Detailed Description
The invention will now be described in further detail with reference to the drawings, which are simplified schematic drawings illustrating the basic idea of the invention only in a schematic way, and examples, which thus show only the constructions that are relevant to the invention.
Unless otherwise specified, reagents and materials used in the examples of the present invention are commercially available.
Detailed description of the preferred embodiments
A method for adsorbing heavy metal by a heavy metal adsorbent comprises the following steps:
(1) cleaning grapes with clear water, stripping off and collecting 50g of grape skin, adding 50g of pure water, 0.5g of pectinase and 0.5g of cellulase, and carrying out full oscillation reaction at 25 ℃ for 1h to obtain enzyme-treated grape skin;
(2) carrying out ventilation drying on the grape skin subjected to enzyme treatment at 40 ℃;
(3) crushing and powdering the obtained dried grape skin by using a food processor, and sieving the obtained powder with a 200-mesh sieve to obtain grape skin powder with the aroma of cooked grapes, namely the adsorbent of heavy metal cadmium;
(4) preparing a cadmium ion standard solution into a liquid containing heavy metal cadmium, and adding a grape skin adsorbent with the mass fraction of 1.0%;
(5) adjusting the pH value of the mixed solution to 6 after the grape skin adsorbent is added, and oscillating and stirring the mixed solution for 100min at the temperature of 40 ℃ to ensure that the adsorption reaction is fully performed; after the reaction is finished, centrifuging and removing the adsorbent to obtain clear liquid.
(6) And analyzing the initial cadmium ion concentration of the mixed solution and the absorbed cadmium ion concentration by ICP-MS, and comparing and analyzing to judge the adsorption capacity of the adsorbent.
Comparative examples 1 to 3: the amounts of grape skin adsorbent added were respectively modified to 0.6%, 0.8%, and 1.2% based on example 1.
Comparative examples 4 to 6: in addition to example 1, the pH of the mixture was adjusted to 3, 4, and 5, respectively.
Comparative examples 7 to 9: on the basis of example 1, the adsorption temperatures were adjusted to 20 ℃, 30 ℃ and 50 ℃.
Comparative examples 10 to 14: on the basis of example 1, the adsorption time was changed to 20, 40, 60, 80 and 120min, respectively.
Second, testing the adsorption effect
The removal rate of heavy metal cadmium is taken as an index, the concentration of cadmium ions in the liquid is measured by adopting ICP-MS, and the influence of the addition amount, the pH value, the adsorption temperature and the adsorption time of the grape skin adsorbent on the adsorption rate is measured, and the result is shown in figures 3-6.
As can be seen from fig. 3, the adsorption effect of the adsorbent of the present invention gradually increases with the increase of the addition amount of the adsorbent, and the addition of 1.0% of the adsorbent can be considered as a preferred process condition in view of cost and efficiency.
As can be seen from fig. 4, the adsorbents of the present invention have different adsorption efficiencies under different pH conditions, and obtain a better adsorption effect at pH 6, and from the viewpoint of time and cost for adjusting pH, pH 6 can be used as a better process condition.
As can be seen from FIG. 5, the adsorption efficiency of the adsorbent of the present invention is temperature dependent, and the efficiency is optimized at 40 deg.C, and 40 deg.C is selected as the preferred process condition for efficiency and cost.
As can be seen from FIG. 6, the cadmium ions adsorbed by the adsorbent of the present invention are gradually increased in 20-120min, but the adsorption increase speed is gradually slowed down with the increase of time, and 100min is adopted as the preferred process condition in view of efficiency and cost.
Third, application example
The method for preparing the sauce by adsorbing the squid viscera by using the adsorbent prepared in the example 1 comprises the following process steps: (1) taking squid viscera for enzymolysis to prepare sauce, and adding 1.0 mass percent of grape skin adsorbent;
(2) adjusting the pH value of the mixed solution to 6 after the grape skin adsorbent is added, and oscillating and stirring the mixed solution for 100min at the temperature of 40 ℃ to ensure that the adsorption reaction is fully performed; after the reaction is finished, centrifuging and removing the adsorbent to obtain clear liquid.
(3) And analyzing the initial cadmium ion concentration of the mixed solution and the absorbed cadmium ion concentration by ICP-MS, and comparing and analyzing to judge the adsorption capacity of the adsorbent.
Taking the concentration of heavy metal cadmium as an index, the initial cadmium ion concentration of the sauce prepared from squid viscera is 24.50mg/L, the cadmium ion concentration after adsorption is 5.41mg/L, and the removal rate reaches 77.92%
Scanning by SEM electron microscope and infrared absorption spectrum
Fig. 7 and 8 are SEM electron microscope scans of the grape skin adsorbent material for adsorbing heavy metal cadmium in water prepared by the present invention, and fig. 9 and 10 are SEM electron microscope scans of natural grape skin powder; as can be seen from the comparison between fig. 7 and 8 and fig. 9 and 10, in the grape skin adsorbing material for adsorbing heavy metal cadmium ions in water prepared by the invention, compared with natural grape skin powder, the grape skin adsorbing material has a rougher surface, a more complex pore structure, more adsorbable and accommodating space and stronger adsorption capacity due to enzyme treatment; as can be seen from FIG. 11, the vibration of the enzyme-treated grape skin powder was enhanced at 3440, 1062 and 540cm-1 in the infrared absorption spectrum, which indicates that the increase of the hydroxyl group and phenolic hydroxyl group, the increase of the carboxyl group and the increase of the amino group have an effect of improving the adsorption ability.
In light of the foregoing description of the preferred embodiment of the present invention, it is to be understood that various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The heavy metal adsorbent is characterized by comprising the following components: grape skin, pectinase, cellulase and water.
2. The heavy metal adsorbent according to claim 1, comprising the following components in parts by weight:
35-55 parts of grape skin;
0.5-1 part of pectinase;
0.5-1 part of cellulase;
45-55 parts of water.
3. The heavy metal adsorbent according to claim 2, comprising the following components in parts by weight:
50 parts of grape skin;
0.5 part of pectinase;
0.5 part of cellulase;
50 parts of water.
4. A method for preparing a heavy metal adsorbent according to any one of claims 1 to 3, comprising the steps of:
s11: cleaning grapes with clear water, stripping and collecting grape skin, adding pure water, pectinase and cellulase, and carrying out full oscillation reaction at a certain temperature to obtain enzyme-treated grape skin;
s12, carrying out ventilation drying on the obtained enzyme-treated grape skin;
s13, crushing and powdering the obtained dried grape skin by using a food processor, and sieving the obtained powder to obtain grape skin powder with the aroma of cooked grapes, namely the adsorbent of heavy metal cadmium.
5. The preparation method according to claim 4, wherein the reaction temperature in the step S11 is preferably 25 ℃, and the reaction time with shaking is preferably 1 h; the temperature of the air drying in the step S12 is preferably 40 ℃; the powder in step S13 was passed through a 200 mesh screen.
6. Use of a heavy metal adsorbent according to any one of claims 1-3 for adsorbing heavy metals.
7. The use according to claim 6, wherein the heavy metal adsorbent is used for adsorbing the heavy metal cadmium.
8. The method for adsorbing the heavy metal cadmium by using the heavy metal adsorbent according to any one of claims 1 to 3, wherein the method comprises the following steps:
s21, preparing a cadmium ion standard solution into a liquid containing heavy metal cadmium, and adding 0.6-1.2% by mass of an adsorbent;
s22, adjusting the pH value of the mixed solution to 3-6 after the grape skin adsorbent is added, and oscillating and stirring for 20-120min at 20-50 ℃ to ensure that the adsorption reaction is fully performed; after the reaction is finished, centrifuging and removing the adsorbent to obtain clear liquid;
and S23, analyzing the initial cadmium ion concentration and the absorbed cadmium ion concentration of the mixed solution by ICP-MS, comparing and analyzing, and judging the adsorption capacity of the adsorbent according to the comparison and analysis.
9. The method for adsorbing heavy metal cadmium by using the heavy metal adsorbent according to claim 9, wherein the addition amount of the adsorbent in the step S21 is preferably 1.0%; the pH value in the step S22 is preferably 6; the oscillation temperature in the S22 is preferably 40 ℃; the oscillation time in S22 is preferably 80 min.
10. Use of a heavy metal adsorbent according to any one of claims 1-3 for cadmium ion removal in seafood sauce.
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