CN112110447A - Preparation method of yellow wine vinasse-based activated carbon - Google Patents
Preparation method of yellow wine vinasse-based activated carbon Download PDFInfo
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- CN112110447A CN112110447A CN202011006788.9A CN202011006788A CN112110447A CN 112110447 A CN112110447 A CN 112110447A CN 202011006788 A CN202011006788 A CN 202011006788A CN 112110447 A CN112110447 A CN 112110447A
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- yellow wine
- activated carbon
- vinasse
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- lees
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
Abstract
The invention discloses a preparation method of yellow wine vinasse-based activated carbon, which comprises the following steps: (1) preparing slurry liquid with the dosage ratio of the yellow wine vinasse to the hydrochloric acid solution being 1g: 5-20 ml, and hydrolyzing in a water bath to obtain slurry hydrolysate; (2) vacuum drying the hydrolysate to obtain dry yellow wine lees; (3) calcining the dried yellow wine vinasse in nitrogen atmosphere, and cooling to room temperature; (4) and grinding the cooled calcined product, soaking in a chemical activating agent, and performing vacuum drying to obtain the yellow wine vinasse activated carbon. The invention is prepared by a method of hydrolysis, carbonization and activation, which not only can greatly improve the yield of the active carbon, but also can reduce the carbonization temperature and the energy consumption.
Description
Technical Field
The invention relates to the field of vinasse resource utilization, in particular to a preparation method of yellow wine vinasse-based activated carbon.
Background
Yellow wine is used as one of three kinds of brewed wine in China, the total yield of the yellow wine in China in 2019 reaches 320 ten thousand liters, the total yield of the yellow wine needs 160 ten thousand tons of grain when 1kg of rice is used for producing 2L wine, the yield of yellow wine lees is calculated by 30 percent of grain consumption, and the yield of the yellow wine lees can reach about 48 thousand tons. The yellow wine lees contains rich substances such as protein, peptide, amino acid, starch, sugar, cellulose and the like, has wide sources and low price, is an ideal resource for development and utilization, can improve the resource utilization rate if effectively developing and utilizing the wine lees, can reduce and prevent the pollution of the waste wine lees to the environment, and can bring remarkable economic benefit.
At present, along with the enhancement of the awareness of environmental protection and the awareness of recycling waste resources, people gradually realize that yellow wine lees have wide development value, and the comprehensive utilization of yellow wine lees has made certain progress, such as the preparation of seasonings, flavor wine, compound amino acids from yellow wine lees and the like as renewable resources of wine brewing, but the consumption is little or in the experimental stage, because yellow wine is open fermentation, although the yellow wine has good flavor, the production control is not easy to accurately control, the quality difference of the yellow wine lees is too large, and most of the yellow wine lees can only be used as common feed or discarded. At present, the vinasse obtained by fermenting and squeezing Shaoxing yellow wine is added with about 10-15% of rice husk, corncob and the like, and then is distilled in a single distiller to obtain vinasse distilled liquor, and the yellow vinasse obtained by distilling the vinasse is mainly used as a feed raw material. The yellow wine lees has high cellulose content and belongs to coarse feed, so the yellow wine lees can be only used in daily ration of livestock, and the added value is not high.
The active carbon is an important porous material, can be used as an adsorbent, a catalyst carrier, hydrogen storage, an electrode material and the like, and is widely applied to the fields of food industry, chemical industry, environmental protection and the like. The traditional activated carbon generally takes coal as a raw material, the coal is a non-renewable resource, and the raw material of the biomass-based activated carbon is agricultural and forestry waste, such as coconut shells, corncobs, rice husks, bamboo waste and the like, and has the advantages of rich sources, low price and renewability. Therefore, the production and use of biomass-based activated carbon has received much attention in recent years. CN105502393A discloses a macadamia nut shell activated carbon and a microwave heating preparation method thereof, CN105819443B discloses an activated carbon prepared by using waste plant-based biomass and a method thereof, CN106608622A discloses a method for preparing hemp stalk-based activated carbon by using microwaves, CN 109928391A-a modified spirit lees-based activated carbon and a preparation method thereof, CN110980731A discloses a method for preparing a lees activated carbon material with a high specific surface area by using waste lees, and the like.
In the existing reports of preparing the bio-based activated carbon by using the vinasse, more than all the vinasse is directly carbonized at high temperature and then is physically or chemically activated, and the obtained activated carbon has large specific surface area and good adsorption performance, but the carbonization temperature is high, and the yield of the activated carbon is low and is only 10-20%.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of yellow wine vinasse-based activated carbon, which is prepared by a method of hydrolyzing, carbonizing and activating, so that the yield of the activated carbon can be greatly improved, the carbonization temperature is reduced, and the energy consumption is reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of yellow wine vinasse-based activated carbon comprises the following steps:
(1) weighing yellow wine lees into a conical bottle with a plug, adding hydrochloric acid solution to prepare slurry liquid with the ratio of the yellow wine lees to the hydrochloric acid solution being 1g: 5-20 ml, and hydrolyzing in a water bath kettle at 100 ℃ for 5-10 hours to obtain slurry hydrolysate; the dosage of the slurry liquid can ensure that the vinasse is dispersed more uniformly than the dosage of the slurry liquid prepared by the preparation method, the hydrolysis effect is improved, and the energy consumption of drying can be avoided being increased due to the excessive moisture content of the slurry liquid.
(2) Vacuum drying the hydrolysate at 105 ℃ for 12-24 hours to obtain dry yellow wine vinasse;
(3) calcining the dried yellow wine vinasse for 1-5 hours at 400-600 ℃ in a nitrogen atmosphere, and cooling to room temperature;
(4) and grinding the cooled calcined product, soaking in a chemical activating agent for 12-24 hours, and performing vacuum drying at 105 ℃ to obtain the yellow wine vinasse activated carbon.
In the step (1), the concentration of the hydrochloric acid is 1-6 mol/L. The increase of the hydrochloric acid concentration is beneficial to improving the hydrolysis effect, but the higher the hydrochloric acid concentration is, the less obvious the influence on the hydrolysis effect is, and when the hydrochloric acid concentration is 5-6mol/L, the hydrolysis effect is not different.
In the step (3), the nitrogen flow rate is 100-500 ml/min, and the temperature rise rate is 5-20 ℃/min.
The chemical activators include, but are not limited to, potassium hydroxide, potassium chloride, potassium carbonate, zinc chloride.
The invention has the beneficial effects that:
(1) according to the characteristic that the composition of the yellow wine vinasse mainly comprises protein, cellulose, fat and other macromolecules, the yellow wine vinasse-based activated carbon is prepared by a method of hydrolysis, carbonization and activation, macromolecular substances are hydrolyzed into micromolecular substances (such as amino acid, glucose, fatty acid, glycerol and the like) by utilizing the hydrolysis process, and the generation of N-nitroso compounds, heterocyclic amine compounds, polymers and other substances in the carbonization process is reduced, so that the yield of the activated carbon is greatly improved.
(2) In the hydrolysis process, except for hydrolyzing the protein, macromolecular substances are basically converted into micromolecular substances, so that the generation of substances with higher thermal stability, such as polymers, cyclic aromatic compounds and the like in the carbonization process is reduced, the micromolecular substances are easier to carbonize, the carbonization temperature can be reduced, and the energy consumption is reduced.
Detailed Description
The invention is further described below with reference to specific embodiments:
example 1
Step 1, weighing 10g of yellow wine lees in a conical flask with a plug, adding 200ml of 1mol/L hydrochloric acid solution to prepare slurry, and hydrolyzing in a water bath kettle at 100 ℃ for 10 hours to obtain slurry hydrolysate.
And 2, drying the slurry hydrolysate for 12 hours in vacuum at 105 ℃ to obtain dry yellow wine vinasse.
And 3, continuously heating the dried yellow wine vinasse to 400 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere with a nitrogen flow rate of 100ml/min, calcining for 5 hours, and cooling to room temperature.
And 4, grinding the cooled calcined product, soaking in a KOH solution for 12 hours, and performing vacuum drying at 105 ℃ for 24 hours to obtain the yellow wine vinasse activated carbon. Tests show that the yield of the activated carbon is 47.5 percent, and the specific surface area is 1699m2/g。
Comparative example 1:
step 1, weighing 10g of yellow wine lees, and drying the yellow wine lees at 105 ℃ for 12 hours in vacuum to obtain dry yellow wine lees.
And 2, continuously heating the dried yellow wine vinasse to 400 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere with a nitrogen flow rate of 100ml/min, calcining for 5 hours, and cooling to room temperature.
Step 3, grinding the cooled calcined product, soaking in KOH solution for 12 hours, vacuum drying at 105 ℃ for 24 hours,obtaining the yellow wine vinasse active carbon. The test shows that the yield of the active carbon is 16.5 percent, and the specific surface area is 1038m2/g。
Compared with the yield of the activated carbon in example 1, the yield of the activated carbon prepared in example 1 is 31% higher than that of the activated carbon prepared in comparative example 1, which shows that the yield of the activated carbon can be greatly improved after yellow wine lees are treated by hydrolysis under the condition of the same preparation conditions.
Example 2
Step 1, weighing 100g of yellow wine lees in a conical flask with a plug, adding 500ml of 1mol/L hydrochloric acid solution to prepare slurry, and hydrolyzing in a water bath kettle at 100 ℃ for 10 hours to obtain slurry hydrolysate.
And 2, drying the hydrolysate for 24 hours in vacuum at 105 ℃ to obtain dry yellow wine vinasse.
And 3, continuously heating the dried yellow wine vinasse to 500 ℃ at a heating rate of 10 ℃/min under the nitrogen atmosphere with a nitrogen flow rate of 200ml/min, calcining for 3 hours, and cooling to room temperature.
Step 4, grinding the cooled calcined product into ZnCl2Soaking in the solution for 24 hours, and vacuum drying at 105 deg.C for 24 hours to obtain yellow wine lees activated carbon. The test shows that the yield of the active carbon is 35.6 percent, and the specific surface area is 1163m2/g。
Comparative example 2
Step 1, weighing 100g of yellow wine vinasse, and drying the yellow wine vinasse for 24 hours at 105 ℃ in vacuum to obtain dry yellow wine vinasse.
And 2, continuously heating the dried yellow wine vinasse to 500 ℃ at a heating rate of 10 ℃/min under a nitrogen atmosphere with a nitrogen flow rate of 200ml/min, calcining for 3 hours, and cooling to room temperature.
Step 3, grinding the cooled calcined product into ZnCl2Soaking in the solution for 24 hours, and vacuum drying at 105 deg.C for 24 hours to obtain yellow wine lees activated carbon. The test shows that the yield of the active carbon is 12.8 percent, and the specific surface area is 783m2/g。
Compared with the yield of the activated carbon in the embodiment 2, the yield of the activated carbon prepared in the embodiment 2 is 22.8% higher than that of the activated carbon prepared in the ratio 2, which shows that under the same conditions of other preparation conditions, macromolecular substances are hydrolyzed into micromolecules (such as amino acid, glucose, fatty acid, glycerol and the like) through hydrolysis treatment of yellow wine vinasse, and the generation of substances such as N-nitroso compounds, heterocyclic amine compounds, polymers and the like is reduced, so that the yield of the activated carbon is greatly improved.
Example 3
Step 1, weighing 50g of yellow wine lees in a conical flask with a plug, adding 500ml of 6mol/L hydrochloric acid solution to prepare slurry, and hydrolyzing in a water bath kettle at 100 ℃ for 5 hours to obtain slurry hydrolysate.
And 2, drying the hydrolysate for 24 hours in vacuum at 105 ℃ to obtain dry yellow wine vinasse.
And 3, continuously heating the dried yellow wine vinasse to 600 ℃ at a heating rate of 20 ℃/min under the nitrogen atmosphere with a nitrogen flow rate of 500ml/min, calcining for 3 hours, and cooling to room temperature.
Step 4, grinding the cooled calcined product, and grinding the calcined product at K2CO3Soaking in the solution for 12 hours, and vacuum drying at 105 deg.C for 24 hours to obtain yellow wine lees activated carbon. The test shows that the yield of the activated carbon is 28.9 percent, and the specific surface area is 1895m2/g。
Comparative example 3
Step 1, weighing 50g of yellow wine vinasse, and drying the yellow wine vinasse for 24 hours at 105 ℃ in vacuum to obtain dry yellow wine vinasse.
And 2, continuously heating the dried yellow wine vinasse to 900 ℃ at a heating rate of 20 ℃/min under the nitrogen atmosphere with a nitrogen flow rate of 500ml/min, calcining for 3 hours, and cooling to room temperature.
Step 3, grinding the cooled calcined product, and performing K2CO3Soaking in the solution for 12 hours, and vacuum drying at 105 deg.C for 24 hours to obtain yellow wine lees activated carbon. The test shows that the yield of the active carbon is 27.1 percent, and the specific surface area is 1379m2/g。
The results of comparing example 3 with comparative example 3 show that the yields of the two are equivalent, and the specific surface area of the activated carbon in example 3 is larger than that in comparative example 3, which shows that the hydrolysis treatment of the yellow wine vinasse can hydrolyze macromolecular substances in the vinasse into small molecules, and can reduce the generation of substances with higher thermal stability, such as polymers, cyclic aromatic hydrocarbon compounds and the like, in the carbonization process, so that the activated carbon with equivalent yield can be prepared at a relatively lower carbonization temperature, and the obtained activated carbon has larger specific surface area and better adsorption performance.
Example 4
Step 1, weighing 10g of yellow wine lees into a conical flask with a plug, adding 50ml of 4mol/L hydrochloric acid solution to prepare slurry, and hydrolyzing in a water bath kettle at 100 ℃ for 1 hour to obtain slurry hydrolysate.
And 2, drying the hydrolysate at 105 ℃ in vacuum for 12 hours to obtain dry yellow wine vinasse.
And 3, continuously heating the dried yellow wine vinasse to 400 ℃ at a heating rate of 10 ℃/min under the nitrogen atmosphere with a nitrogen flow rate of 200ml/min, calcining for 5 hours, and cooling to room temperature.
And 4, grinding the cooled calcined product, soaking in a KCl solution for 12 hours, and performing vacuum drying at 105 ℃ for 12 hours to obtain the yellow wine vinasse activated carbon. The test shows that the yield of the active carbon is 51.2 percent, and the specific surface area is 1675m2/g。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. The preparation method of the yellow wine lees-based activated carbon is characterized by comprising the following steps: the method comprises the following steps:
(1) weighing yellow wine lees into a conical bottle with a plug, adding hydrochloric acid solution to prepare slurry liquid with the ratio of the yellow wine lees to the hydrochloric acid solution being 1g: 5-20 ml, and hydrolyzing in a water bath kettle at 100 ℃ for 5-10 hours to obtain slurry hydrolysate;
(2) vacuum drying the hydrolysate at 105 ℃ for 12-24 hours to obtain dry yellow wine vinasse;
(3) calcining the dried yellow wine vinasse for 1-5 hours at 400-600 ℃ in a nitrogen atmosphere, and cooling to room temperature;
(4) and grinding the cooled calcined product, soaking in a chemical activating agent for 12-24 hours, and performing vacuum drying at 105 ℃ to obtain the yellow wine vinasse activated carbon.
2. The method for preparing activated carbon based on yellow wine lees as in claim 1, wherein the activated carbon is prepared by the following steps: in the step (1), the concentration of the hydrochloric acid is 1-6 mol/L.
3. The method for preparing activated carbon based on yellow wine lees as in claim 1, wherein the activated carbon is prepared by the following steps: in the step (3), the nitrogen flow rate is 100-500 ml/min, and the temperature rise rate is 5-20 ℃/min.
4. The method for preparing activated carbon based on yellow wine lees as in claim 1, wherein the activated carbon is prepared by the following steps: the chemical activators include, but are not limited to, potassium hydroxide, potassium chloride, potassium carbonate, zinc chloride.
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| CN101811692A (en) * | 2010-05-05 | 2010-08-25 | 吉林大学 | New method for comprehensive utilization of straw resource |
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Application publication date: 20201222 |