CN111635760A - Preparation method and application of wood vinegar rich in phenols - Google Patents
Preparation method and application of wood vinegar rich in phenols Download PDFInfo
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- CN111635760A CN111635760A CN202010614517.5A CN202010614517A CN111635760A CN 111635760 A CN111635760 A CN 111635760A CN 202010614517 A CN202010614517 A CN 202010614517A CN 111635760 A CN111635760 A CN 111635760A
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- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
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Abstract
The invention discloses a preparation method and application of pyroligneous rich in phenols, which comprises the following steps: crushing Chinese fir branches and the like into Chinese fir sawdust with the particle size of 2-5 mm, and drying at 105 ℃ for later use; mixing the dried cedar chips with an acid solution with the mass fraction of 2% according to a certain mass ratio, stirring for 3-5 h at room temperature, filtering, washing with water to be neutral, and drying; then placing the wood vinegar into a vertical tubular furnace, heating the wood vinegar to 400-600 ℃ under the protection of nitrogen, carrying out pyrolysis for 1h, and cooling and condensing pyrolysis gas to obtain crude wood vinegar; standing the crude wood vinegar solution at room temperature in dark place for 1 month, layering, and filtering to obtain upper brown liquid as the wood vinegar solution. The pyroligneous liquor has phenolic substance content up to 58% of total organic substance content, has good antioxidant activity, and can be used as antioxidant. The method has simple process and simple and convenient operation, greatly increases the content of phenolic substances in the pyroligneous liquor by using the pickling pretreatment, improves the antioxidant activity of the pyroligneous liquor, and is beneficial to high-value utilization of the pyroligneous liquor.
Description
Technical Field
The invention belongs to the technical field of biomass energy, and mainly relates to a preparation method and application of pyroligneous liquor rich in phenols.
Background
China contains rich biomass resources. According to statistics, the agricultural and forestry waste biomass resources produced in China each year reach hundreds of millions of tons. The biomass resources are converted into energy and chemicals through thermochemical conversion, which is a main way for utilizing the biomass resources, so that the waste is changed into valuable, the problem of environmental pollution caused by stacking and decomposition of the waste resources is solved, and the sustainable development strategy of China is met.
Pyroligneous liquor is one of the main products produced in the construction of thermochemical conversion utilization of biomass. The main component of the wood vinegar is water, and simultaneously contains a large amount of organic substances, such as acid substances, phenolic substances, ketone substances, aldehyde substances and the like. Due to the existence of a large amount of organic substances, the wood vinegar has antioxidant effect, bacteriostatic effect, plant growth regulating effect and the like, and is widely used as an antioxidant, an insecticide, a plant growth regulator, a soil conditioner and the like.
The wood vinegar has excellent oxidation resistance, and toxicity tests prove that the wood vinegar has good safety, can be used as an antioxidant for food preservation and oxidation resistance, and has wide prospects. The phenolic substances are the main active ingredients of the wood vinegar with oxidation resistance. Therefore, the preparation of the wood vinegar rich in the phenolic substances and the improvement of the antioxidant activity of the wood vinegar are important ways for the efficient and high-value utilization of the wood vinegar.
Disclosure of Invention
The technical problem to be solved is as follows: provides a preparation method and application of pyroligneous rich in phenols. The method has the characteristics of simple process, simple and convenient operation, low cost and easy industrial application. The pyroligneous liquor prepared by the method has high content of phenolic substances and low content of acid substances, has excellent antioxidant activity, and can be used as a natural antioxidant.
The technical scheme is as follows: a method for preparing pyroligneous liquor rich in phenols comprises the following steps: crushing the branches of the Chinese fir into Chinese fir sawdust, and drying for later use; mixing the dried cedar chips with a dilute acid solution, stirring at room temperature for reaction, filtering, washing with water to neutrality, and drying; then heating and pyrolyzing the wood pulp under the protection of nitrogen, and cooling and condensing pyrolysis gas to obtain crude wood vinegar; standing the crude wood vinegar solution at room temperature in dark place, layering, filtering to obtain upper brown liquid as refined wood vinegar solution.
The diluted acid solution is any one of a hydrochloric acid solution, a phosphoric acid solution, a formic acid solution and an acetic acid solution with the mass fraction of 1-4%.
The mass ratio of the cedar chips to the dilute acid solution is 1: 3-10.
The stirring time is 3-5 h.
The pyrolysis temperature is 400-600 ℃.
The wood vinegar obtained by the preparation method of the wood vinegar rich in phenolic substances is applied to an antioxidant.
Has the advantages that:
the preparation method of the wood vinegar liquid has the advantages of low cost, simple process, simple and convenient operation and easy industrial application. The obtained pyroligneous liquor has high content of phenolic substances and low content of acids, has excellent antioxidant activity, and can be used as natural antioxidant.
According to the method, common acid solution is used as a pretreatment reagent, and is stirred at room temperature for pretreatment, so that the chemical structure and pyrolysis behavior of the biomass raw material are changed, and the pyroligneous liquor rich in phenolic substances is prepared, wherein the phenolic substances are more than 50%, and the pyroligneous liquor has excellent antioxidant activity.
Detailed Description
A method for preparing pyroligneous liquor rich in phenols comprises the following steps:
crushing Chinese fir branches and the like into Chinese fir sawdust with the particle size of 2-5 mm, and drying at 105 ℃ for later use; mixing the dried cedar chips with an acid solution with the mass fraction of 2% according to a certain mass ratio, stirring for 3-5 h at room temperature, filtering, washing with water to be neutral, and drying; then placing the wood vinegar into a vertical tubular furnace, heating the wood vinegar to 400-600 ℃ under the protection of nitrogen, carrying out pyrolysis for 1h, and cooling and condensing pyrolysis gas to obtain crude wood vinegar; standing the crude wood vinegar solution at room temperature in dark place for 1 month, layering, and filtering to obtain upper brown liquid as refined wood vinegar solution.
Preferably, the method comprises the following steps:
the acid solution used for pretreatment is any one of hydrochloric acid solution, phosphoric acid solution, formic acid solution and acetic acid solution with the mass fraction of 2%, and the hydrochloric acid solution is the optimal solution;
the mass ratio of the cedar wood chips to the 2% acid solution is 1 (7-10).
The stirring time is 3-5 h.
The pyrolysis temperature is 400-600 ℃.
Example 1:
crushing Chinese fir branches and the like into Chinese fir sawdust with the particle size of 2-5 mm, and drying at 105 ℃ for later use; mixing the dried cedar chips with a hydrochloric acid solution with the mass fraction of 2% according to the mass ratio of 1:7, stirring for 4 hours at room temperature, filtering, washing with water to be neutral, and drying; then placing the wood vinegar into a vertical tubular furnace, heating the wood vinegar to 550 ℃ under the protection of nitrogen, pyrolyzing the wood vinegar for 1 hour, and cooling and condensing pyrolysis gas to obtain crude wood vinegar; standing the crude wood vinegar solution at room temperature in dark place for 1 month, layering, and filtering to obtain upper brown liquid as refined wood vinegar solution (No. 1).
Example 2:
crushing Chinese fir branches and the like into Chinese fir sawdust with the particle size of 2-5 mm, and drying at 105 ℃ for later use; mixing the dried cedar chips with a hydrochloric acid solution with the mass fraction of 2% according to the mass ratio of 1:10, stirring for 3 hours at room temperature, filtering, washing with water to be neutral, and drying; then placing the wood vinegar into a vertical tubular furnace, heating the wood vinegar to 450 ℃ under the protection of nitrogen for pyrolysis for 1h, and cooling and condensing pyrolysis gas to obtain crude wood vinegar; standing the crude wood vinegar solution at room temperature in dark place for 1 month, layering, and filtering to obtain upper brown liquid as refined wood vinegar solution (2 #).
Example 3:
crushing Chinese fir branches and the like into Chinese fir sawdust with the particle size of 2-5 mm, and drying at 105 ℃ for later use; mixing the dried cedar chips with a phosphoric acid solution with the mass fraction of 2% according to the mass ratio of 1:10, stirring for 3 hours at room temperature, filtering, washing to be neutral, and drying; then placing the wood vinegar into a vertical tubular furnace, heating the wood vinegar to 450 ℃ under the protection of nitrogen for pyrolysis for 1h, and cooling and condensing pyrolysis gas to obtain crude wood vinegar; standing the crude wood vinegar solution at room temperature in dark place for 1 month, layering, and filtering to obtain upper brown liquid as refined wood vinegar solution (No. 3).
Example 4:
crushing Chinese fir branches and the like into Chinese fir sawdust with the particle size of 2-5 mm, and drying at 105 ℃ for later use; mixing the dried cedar chips with a formic acid solution with the mass fraction of 2% according to the mass ratio of 1:9, stirring for 4 hours at room temperature, filtering, washing with water to be neutral, and drying; then placing the wood vinegar into a vertical tubular furnace, heating the wood vinegar to 450 ℃ under the protection of nitrogen for pyrolysis for 1h, and cooling and condensing pyrolysis gas to obtain crude wood vinegar; standing the crude wood vinegar solution at room temperature in dark place for 1 month, layering, and filtering to obtain upper brown liquid as refined wood vinegar solution (No. 4).
Example 5:
crushing Chinese fir branches and the like into Chinese fir sawdust with the particle size of 2-5 mm, and drying at 105 ℃ for later use; mixing the dried cedar chips with an acetic acid solution with the mass fraction of 2% according to the mass ratio of 1:8, stirring for 5 hours at room temperature, filtering, washing with water to be neutral, and drying; then placing the wood vinegar into a vertical tubular furnace, heating the wood vinegar to 550 ℃ under the protection of nitrogen, pyrolyzing the wood vinegar for 1 hour, and cooling and condensing pyrolysis gas to obtain crude wood vinegar; standing the crude wood vinegar solution at room temperature in dark place for 1 month, layering, and filtering to obtain upper brown liquid as refined wood vinegar solution (No. 5).
Example 6:
crushing Chinese fir branches and the like into Chinese fir sawdust with the particle size of 2-5 mm, and drying at 105 ℃ for later use; mixing the dried cedar chips with an acetic acid solution with the mass fraction of 2% according to the mass ratio of 1:10, stirring for 3 hours at room temperature, filtering, washing with water to be neutral, and drying; then placing the wood vinegar into a vertical tubular furnace, heating the wood vinegar to 450 ℃ under the protection of nitrogen for pyrolysis for 1h, and cooling and condensing pyrolysis gas to obtain crude wood vinegar; standing the crude wood vinegar solution at room temperature in dark place for 1 month, layering, and filtering to obtain upper brown liquid as refined wood vinegar solution (No. 6).
Comparative example:
crushing Chinese fir branches and the like into Chinese fir sawdust with the particle size of 2-5 mm, and drying at 105 ℃ for later use; then placing the wood vinegar into a vertical tubular furnace, heating the wood vinegar to 450 ℃ under the protection of nitrogen for pyrolysis for 1h, and cooling and condensing pyrolysis gas to obtain crude wood vinegar; standing the crude wood vinegar solution at room temperature in dark place for 1 month, layering, and filtering to obtain the upper brown liquid as refined wood vinegar solution (comparative example).
The method for analyzing and testing the content of the phenolic substances and the antioxidant activity of the prepared pyroligneous liquor comprises the following steps:
(1) the components and relative contents of the pyroligneous liquor are analyzed by adopting GC-MS: 1) GC conditions were as follows: the chromatographic column adopts a quartz capillary column with the thickness of 30m multiplied by 0.25mm multiplied by 0.25 mu m, the carrier gas is He gas, the flow rate is 1.6mL/min, the injection port temperature is 280 ℃, the temperature rising program of the chromatographic column is 50 ℃ for 2min, the temperature rising speed is 5 ℃/min to 280 ℃ for 20min, the split ratio is 100:1, and the sample injection amount is 0.2 mu L. 2) MS conditions: the ionization source EI has the temperature of 230 ℃, the electron bombardment energy of 70eV and the scanning mass range (m/Z) of 50-500.
(2) The antioxidant activity of the wood vinegar is evaluated by measuring the DPPH clearance rate and the OH clearance rate of the wood vinegar:
1) DPPH clearance assay: 1.0mL of the sample was mixed with 3.0mL of a solution of DPPH in absolute ethanol (0.1mmol/L) in a cuvette. After shaking, the mixture was left at room temperature for 15 minutes, and the absorbance at 517nm was measured with a spectrophotometer (A)i) (ii) a Measurement A with 1mL of absolute ethanol as a control instead of the sample0(ii) a Determination of A with a mixture of 1mL of sample and 3mL of absolute solutionj. DPPH clearance (R)DPPH·) The calculation formula is as follows:
2) determination of OH clearance: adding 1.0mL of sample into a colorimetric tube, and sequentially adding 1.0mL of FeSO4Solution (1mmol/L), 1.0mL H2O2The solution (1mmol/L) was mixed with 2.0mL of salicylic acid solution (3 mmol/L). Shaking, storing at room temperature for 30min, and measuring absorbance A at 510nmi。A0Measurement with distilled water instead of the sample, AjThe salicylic acid was replaced by distilled water. OH clearance (R)·OH) Calculated from the following formula:
TABLE 1 preparation of phenolic content and antioxidant Activity of pyroligneous liquor
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. The preparation method of the pyroligneous liquor rich in phenolic substances is characterized by comprising the following steps: crushing the branches of the Chinese fir into Chinese fir sawdust, and drying for later use; mixing the dried cedar chips with a dilute acid solution, stirring at room temperature for reaction, filtering, washing with water to neutrality, and drying; then heating and pyrolyzing the wood pulp under the protection of nitrogen, and cooling and condensing pyrolysis gas to obtain crude wood vinegar; standing the crude wood vinegar solution at room temperature in dark place, layering, filtering to obtain upper brown liquid as refined wood vinegar solution.
2. The method for preparing pyroligneous acid rich in phenolic substances according to claim 1, wherein the diluted acid solution is any one of a hydrochloric acid solution, a phosphoric acid solution, a formic acid solution and an acetic acid solution with a mass fraction of 1-4%.
3. The method for preparing wood vinegar rich in phenolic substances according to claim 1, wherein the mass ratio of the cedar wood chips to the dilute acid solution is 1: 3-10.
4. The method for preparing pyroligneous liquor rich in phenolic substances according to claim 1, wherein the stirring time is 3-5 hours.
5. The method for preparing pyroligneous liquor rich in phenolic substances according to claim 1, wherein the pyrolysis temperature is 400-600 ℃.
6. The use of the pyroligneous liquor obtained by the method for producing a pyroligneous liquor rich in phenolic compounds according to any one of claims 1 to 5 as an antioxidant.
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| CN202010614517.5A CN111635760A (en) | 2020-06-30 | 2020-06-30 | Preparation method and application of wood vinegar rich in phenols |
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