Refining and purifying process of pyroligneous liquor

Abstract

The invention relates to the technical field of biomass resource utilization, and provides a wood vinegar refining and purifying process which comprises the following steps: adding ethyl acetate into crude wood vinegar for extraction, and performing rotary evaporation and concentration to obtain crude concentrated wood vinegar; adding a sodium bicarbonate aqueous solution into the crude concentrated pyroligneous liquor for extraction to obtain primary refined pyroligneous liquor; adding a composite acid solution into the primary refined pyroligneous liquor, adding ethyl acetate again, extracting, and carrying out rotary evaporation concentration to obtain secondary refined pyroligneous liquor; and adding modified biomass activated carbon into the secondary refined wood vinegar, and carrying out water bath reaction, standing and suction filtration to obtain the refined wood vinegar. The sugar beet pulp is used as a raw material, the crude wood vinegar is prepared by controlling fermentation conditions, and the content of effective components is increased; meanwhile, the crude wood vinegar can be simply, rapidly and effectively refined through the refining and purifying technology, the treatment process is mild in condition, and harmful substances such as tar and the specific smoke flavor of the wood vinegar are effectively removed.

Description

Technical Field

[0001] The invention belongs to the technical field of biomass resource utilization, and in particular relates to a refining and purification process of wood vinegar. Background Art

[0002] With the massive consumption of non-renewable resources, the world pays more and more attention to the development and utilization of renewable resources. Biomass resources are characterized by abundant sources, no pollution, and low cost. Wood vinegar, also known as wood vinegar, mainly refers to a product obtained by pyrolysis of biomass such as waste wood and crop straw under conditions of isolation from air or a small amount of oxygen. The composition of wood vinegar is very complex, containing a large amount of organic matter and a small amount of inorganic matter, among which the organic matter is mainly phenols, acids, ketones, esters, and aldehydes, accounting for 60%-90% of the total mass of wood vinegar organic matter.

[0003] At present, the main methods for refining wood vinegar include static method, activated carbon adsorption method, membrane filtration method, distillation method, organic solvent extraction method, etc. Different refining methods have their own characteristics. For example, although the static method is easy to operate and has low cost, it has a long preparation cycle and large losses; the distillation method and activated carbon adsorption method can extract effective ingredients to a certain extent, but the losses are large; the membrane filtration method has a good refining effect and is well targeted for separating organic components in wood vinegar, but it has the problems of complex operation and high cost. In contrast, the organic solvent extraction method uses the principle of like dissolves like, has a simple process flow, and can effectively enrich the effective ingredients in wood vinegar, thereby greatly improving the extraction efficiency.

[0004] Chinese patent CN 107746721 B discloses a method for refining wood vinegar. By treating crude wood vinegar with a demulsifier, the tiny wood tar droplets in the wood vinegar can be quickly polymerized to form an oil phase, and then separated from the wood vinegar, effectively removing the wood tar component in the wood vinegar. The demulsifier can be an acetal-polyol and polyether composite demulsifier, and a variety of components are available. This invention provides a demulsification method to purify wood vinegar, which reduces the processing cost and does not have the problem of energy consumption. However, the demulsifier formula is complex, and its applicability to crude wood vinegar of different raw materials remains to be verified, and the demulsifier contains some toxic solvents, which may increase environmental risks.

[0005] Therefore, there is an urgent need to develop a refining and purification process for wood vinegar that can effectively remove harmful substances such as smoke smell and tar while ensuring that toxicity can be reduced and environmental risks can be alleviated. Summary of the invention

[0006] In view of the existing technical problems, the purpose of the present invention is to provide a refining and purification process for wood vinegar. The present invention uses beet pulp as a raw material, controls fermentation conditions to prepare crude wood vinegar, and increases the content of effective ingredients; at the same time, the refining and purification process of the present invention can simply, quickly and effectively purify the crude wood vinegar, the treatment process conditions are mild, and harmful substances such as tar can be effectively removed, and the unique smoky taste of wood vinegar can be removed, and the application value is good.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] The present invention provides a refining and purification process for wood vinegar, comprising the following steps:

[0009] S1. Add ethyl acetate to the crude wood vinegar, ultrasonically shake, extract 2-3 times, combine the extracts, and concentrate by rotary evaporation to obtain a crude concentrated wood vinegar;

[0010] S2. Adding an aqueous solution of sodium bicarbonate to the crude concentrated wood vinegar obtained in step S1, extracting 2-3 times, combining the extracts to obtain a primary refined wood vinegar;

[0011] S3. The composite acid is added to the primary refined wood vinegar obtained in step S2, ethyl acetate is added again and ultrasonically shaken, extracted, and concentrated by rotary evaporation to obtain a secondary refined wood vinegar;

[0012] S4. Add modified biomass activated carbon to the secondary refined wood vinegar obtained in step S3, react in a water bath, let stand, and filter to obtain refined wood vinegar.

[0013] The reaction mechanism and effects of the present invention are as follows:

[0014] 1. The present invention uses beet pulp as raw material and combines microbial fermentation and pyrolysis technology to prepare crude wood vinegar. Beet pulp is rich in cellulose, hemicellulose and a small amount of lignin, which can be converted into organic acids and other beneficial compounds in wood vinegar during pyrolysis. Compared with other biomass raw materials such as wood, beet pulp has a lower lignin content, which helps to reduce tar and other by-products produced during pyrolysis from the source.

[0015] On the one hand, two complex enzymes, cellulase and ligninase, are used to decompose the cellulose and lignin components in the beet pulp raw material and convert them into soluble sugars to provide substrates for the fermentation process. On the other hand, the applicant uses a mixed and activated bacterial solution of Bacillus subtilis, yeast, and Acetobacter xylinum for fermentation. The metabolic activities of microorganisms during the fermentation process can produce a variety of organic acids, alcohols, esters and other compounds. These compounds can be converted into components of wood vinegar during the pyrolysis process, increasing the diversity of the products, thereby improving the utilization rate of beet pulp, improving the quality of wood vinegar, and possibly providing better antimicrobial activity and antioxidant properties.

[0016] 2. The present invention uses highland barley straw residue, chitosan and 4-piperidinamide to prepare a modified biomass activated carbon. On the one hand, the present invention uses potassium hydroxide and hydrochloric acid of specific concentrations to prepare highland barley straw residue activated carbon, which increases the specific surface area of ​​activated carbon, enriches the pore structure of activated carbon, and avoids the occurrence of surface pore collapse problems, so that the adsorption and decolorization effect is good. On the other hand, when chitosan is used for decolorization, it can play a good effect on the reduction of color value. However, when chitosan is used alone, the flocculation effect is small, the floccules are loose and not easy to settle, making it difficult to separate wood vinegar from pigments. When chitosan and highland barley straw residue activated carbon materials are cross-linked and composited, the porosity tends to decrease slightly, but the applicant unexpectedly found that the flocculation effect of chitosan and the adsorption effect of activated carbon will have a synergistic effect, so that the decolorization rate of wood vinegar is high and the decolorization effect is good. In addition, the present invention further introduces 4-piperidinecarboxamide, increases the adsorption sites of activated carbon, improves the refining efficiency, and enables the modified biomass activated carbon to remove the smoky smell unique to wood vinegar through selective adsorption, thereby broadening the applicability of wood vinegar; of course, the piperidine structure also brings stability to the modified biomass activated carbon, promotes the recycling and regeneration of activated carbon, reduces resource waste, and has important economic and environmental benefits.

[0017] In some embodiments, the method for preparing the crude wood vinegar in step S1 comprises the following steps:

[0018] (1) mixing Bacillus subtilis, yeast, and Acetobacter xylinum and activating them to obtain a bacterial solution for later use;

[0019] (2) crushing the beet pulp to a particle size of 1-4 cm, soaking it in a citric acid solution for 10-16 hours, filtering out the solid, adding a composite enzyme, cottonseed hulls, sorghum bran and the bacterial solution prepared in step (1), and then adding deionized water until the overall moisture content is 30wt%-40wt%, and fermenting it for 6-8 days in a sealed manner to obtain a beet pulp fermentation product; wherein the composite enzyme is a cellulase and a ligninase in a mass ratio of (2-4):1;

[0020] (3) filtering the fermented beet pulp obtained in step (2), drying to an overall moisture content of 5 wt%-8 wt%, pouring into a reactor, introducing an inert gas, heating to 300-400° C. at a rate of 4-8° C. / min, collecting the distillate, and obtaining a crude wood vinegar solution.

[0021] In some embodiments, the viable count of Bacillus subtilis in step (1) is 1×10 8 ~3×10 8 CFU / g, the number of live yeast cells is 2×10 8 ~5×10 8 CFU / g, the number of viable Acetobacter xylinum was 2×10 7 ~7×10 7 CFU / g, the mass ratio of the three is 1:(4-6):(2-4).

[0022] Preferably, in step (1), the mass ratio of Bacillus subtilis, yeast and Acetobacter xylinum is 1:5:3.

[0023] Preferably, the citric acid solution in step (2) is a citric acid aqueous solution with a mass fraction of 20-40 wt%.

[0024] In some embodiments, the mass ratio of the complex enzyme, cottonseed hulls, sorghum bran, bacterial liquid and solid in step (2) is (0.03-0.05): (0.2-0.3): (0.05-0.15): (0.2-0.4): 1.

[0025] In some embodiments, the concentration of the sodium bicarbonate aqueous solution in step S2 is 3wt%-5wt%.

[0026] In some embodiments, the composite acid in step S3 is 40wt%-60wt% phosphoric acid aqueous solution and 15wt%-35wt% sulfuric acid aqueous solution, and the volume ratio of the two is (1-2):1.

[0027] In some embodiments, the method for preparing modified biomass activated carbon in step S4 comprises the following steps:

[0028] ① Wash the highland barley straw residue with deionized water for 3-5 times, dry it, add 0.25-0.5mol / L potassium hydroxide aqueous solution to soak it for 10-16h, filter it with suction, dry it, put the alkalized highland barley straw residue into a reactor, pass inert gas, heat it to 500-700℃ and calcine it for 1-2h, grind it after cooling, add 0.2-0.3mol / L hydrochloric acid aqueous solution, heat it to 85-100℃ and stir it for 30-45min, filter it with suction, wash it, dry it, and obtain highland barley straw residue activated carbon;

[0029] ② dissolving chitosan in 5wt%-8wt% acetic acid aqueous solution to obtain a chitosan solution for standby use; adding the highland barley straw residue activated carbon obtained in step ① to the chitosan solution, heating to 35-45° C., stirring for 30-45 min, adding glutaraldehyde, heating to 65-80° C., stirring for 1-2 h, washing, and drying to obtain modified highland barley straw residue activated carbon;

[0030] ③ Add the modified highland barley straw residue activated carbon, 4-piperidinecarboxamide and dimethyl sulfoxide obtained in step ② to a reaction vessel, stir for 1-2 hours, add formaldehyde dropwise, stir for 10-12 hours, add sodium hydroxide, collect the precipitate after suction filtration, wash with deionized water until the pH of the supernatant is neutral, then wash with anhydrous ethanol 1-2 times, and dry to obtain modified biomass activated carbon.

[0031] In some embodiments, the mass ratio of chitosan to highland barley straw residue activated carbon in step ② is (0.6-1):1.

[0032] In some embodiments, the mass ratio of the modified highland barley straw residue activated carbon and 4-piperidinylcarboxamide in step ③ is 1:(0.1-0.4).

[0033] In some embodiments, the mass ratio of the highland barley straw residue, 0.25-0.5 mol / L potassium hydroxide aqueous solution and 0.2-0.3 mol / L hydrochloric acid aqueous solution in step ① is 1:(2-4):(1-3).

[0034] In some embodiments, the mass ratio of the secondary refined wood vinegar to the modified biomass activated carbon in step S4 is 1:(0.05-0.1).

[0035] In some embodiments, the specific conditions for the water bath decolorization in step S4 are: water bath temperature 50-60° C., water bath reaction time 30-60 min, and shaking every 5 min.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] 1. The present invention uses beet pulp as a raw material and improves the quality of crude wood vinegar by controlling fermentation conditions. At the same time, the refining and purification process of the present invention can simply and quickly purify the crude wood vinegar, the treatment process conditions are mild, and harmful substances such as tar and the unique smoky taste of wood vinegar are effectively removed, and the present invention has good application value.

[0038] 2. The present invention combines microbial fermentation and pyrolysis to prepare crude wood vinegar, which has obvious advantages in raw material utilization, product diversity, product quality, environmental friendliness, controllability and application potential.

[0039] 3. The present invention uses highland barley straw residue, chitosan and 4-piperidinecarboxamide to prepare a modified biomass activated carbon. First, the specific surface area of ​​the activated carbon is increased and the pore structure is enriched; second, when chitosan and highland barley straw residue activated carbon materials are cross-linked and composited, a synergistic effect occurs, so that the decolorization effect of wood vinegar is good; third, the introduction of 4-piperidinecarboxamide enhances the stability of the modified biomass activated carbon, and through selective adsorption, the modified biomass activated carbon can remove the unique smoky taste of wood vinegar, thereby broadening the applicability of wood vinegar. DETAILED DESCRIPTION

[0040] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, rather than to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0041] According to the ratios and processes of the raw materials specified in the following examples and comparative examples, the wood vinegar is refined and purified to obtain refined wood vinegar.

[0042] In order to facilitate those skilled in the art to implement the present invention, some raw material manufacturers of the embodiments and comparative examples are described as follows:

[0043] Activated carbon: purchased from Henan Senwo Environmental Protection Technology Co., Ltd.;

[0044] Bacillus subtilis: purchased from Chengdu Wanxiang Hongrun Biotechnology Co., Ltd.;

[0045] Yeast: Candida albicans was purchased from Shandong Qilu Chemical Technology Co., Ltd.;

[0046] Acetobacter xylinum: purchased from Shanghai Yaji Biotechnology Co., Ltd.;

[0047] Other raw materials are not specially specified and can be purchased from the market.

[0048] Preparation Example 1

[0049] The preparation method of modified biomass activated carbon A comprises the following steps:

[0050] ① Wash 0.3kg of highland barley straw residue with deionized water 4 times, dry at 80℃ for 5h, add 0.9kg of 0.35mol / L potassium hydroxide aqueous solution and soak for 12h, filter with suction, dry at 80℃ for 7h, put the alkalized highland barley straw residue into a reactor, introduce nitrogen, heat to 600℃ at 10℃ / min, calcine for 1.5h, grind after cooling, add 0.5L of 0.25mol / L hydrochloric acid aqueous solution, heat to 90℃ and stir for 40min, filter with suction, wash with deionized water 3 times, dry at 80℃ for 7h, and obtain highland barley straw residue activated carbon;

[0051] ② Dissolve 0.12 kg of chitosan in 8 L of 6 wt% acetic acid aqueous solution to obtain a chitosan solution for later use; add 0.15 kg of highland barley straw residue activated carbon obtained in step (1) to the chitosan solution, heat to 40 ° C, stir for 40 min, add 1 L of glutaraldehyde, heat to 75 ° C, stir for 1.5 h, wash with anhydrous ethanol and deionized water twice each, and dry at 70 ° C for 6 h to obtain modified highland barley straw residue activated carbon;

[0052] ③ Add 0.1 kg of modified highland barley straw residue activated carbon obtained in step ②, 25 g of 4-piperidinecarboxamide, and 100 ml of dimethyl sulfoxide to a reaction vessel, stir for 1.5 h, add 200 ml of formaldehyde dropwise, stir for 10 h, add 400 ml of 0.2 mol / L sodium hydroxide aqueous solution, collect the precipitate after filtration, wash with deionized water until the pH of the supernatant is neutral, then wash twice with anhydrous ethanol, and dry at 60 ° C for 7 h to obtain modified biomass activated carbon A.

[0053] Preparation Example 2

[0054] The preparation method of modified biomass activated carbon B is the same as that of Preparation Example 1, except that the amount of chitosan added in step ② is 0.18 kg.

[0055] Preparation Example 3

[0056] The preparation method of modified biomass activated carbon C is the same as that of Preparation Example 1, except that the amount of chitosan added in step ② is 0.06 kg.

[0057] Preparation Example 4

[0058] The preparation method of modified biomass activated carbon D is the same as that of Preparation Example 1, except that the amount of 4-piperidinamide added in step ③ is 8 g.

[0059] Preparation Example 5

[0060] The preparation method of modified biomass activated carbon E comprises the following steps:

[0061] ① Wash 0.3kg of highland barley straw residue with deionized water 4 times, dry at 80℃ for 5h, add 0.9kg of 0.35mol / L potassium hydroxide aqueous solution and soak for 12h, filter with suction, dry at 80℃ for 7h, put the alkalized highland barley straw residue into a reactor, introduce nitrogen, heat to 600℃ at 10℃ / min, calcine for 1.5h, grind after cooling, add 0.5L of 0.25mol / L hydrochloric acid aqueous solution, heat to 90℃ and stir for 40min, filter with suction, wash with deionized water 3 times, dry at 80℃ for 7h, and obtain highland barley straw residue activated carbon;

[0062] ② Dissolve 0.12 kg of chitosan in 8 L of 6 wt% acetic acid aqueous solution to obtain a chitosan solution for later use; add 0.15 kg of highland barley straw residue activated carbon obtained in step ① to the chitosan solution, heat to 40 ° C, stir for 40 min, add 1 L of glutaraldehyde, heat to 75 ° C, stir for 1.5 h, wash with anhydrous ethanol and deionized water twice each, and dry at 70 ° C for 6 h to obtain modified biomass activated carbon E.

[0063] Preparation Example 6

[0064] The preparation method of crude wood vinegar A comprises the following steps:

[0065] (1) Mix 40 g brown sugar with 400 ml sterile water, heat to 50 °C to dissolve the brown sugar completely, cool to room temperature, and add 5 g of sterile water with a viable count of 2 × 10 8 CFU / g of Bacillus subtilis, 25g of live bacteria count is 3.5×10 8 CFU / g of yeast, the number of viable bacteria in 15g is 5×10 7 CFU / g xylinum Acetobacter, put it into a sterile constant temperature incubator, shake and culture it at 30°C for 24 hours to obtain the activated bacterial solution for use;

[0066] (2) 1.2 kg of beet pulp was crushed to a particle size of 3 cm, and soaked in 3.6 L of 30 wt% citric acid solution for 12 h, and the solid was filtered to obtain a solid. 30 g of cellulase and 10 g of ligninase were added to 1 kg of the solid, a layer of non-woven fabric was laid, 250 g of cottonseed hulls, 100 g of sorghum bran and 300 g of the bacterial solution prepared in step (1) were added, and deionized water was added to an overall moisture content of 35 wt%, and the mixture was sealed and fermented at 30° C. and pH 5 for 7 days to obtain a beet pulp fermentation product;

[0067] (3) The beet pulp fermentation product obtained in step (2) is filtered, dried to an overall moisture content of 6.5 wt%, poured into a reactor, introduced with nitrogen, and heated to 350° C. at a rate of 6° C. / min, and the distillate is collected to obtain crude wood vinegar A.

[0068] Preparation Example 7

[0069] The preparation method of crude wood vinegar B is the same as that of Preparation Example 6, except that in step (1), the added amounts of Bacillus subtilis, yeast, and Acetobacter xylinum are 5 g, 5 g, and 15 g, respectively.

[0070] Preparation Example 8

[0071] The preparation method of crude wood vinegar C is the same as that of Preparation Example 6, except that the amount of bacterial liquid added in step (2) is 150 g.

[0072] Preparation Example 9

[0073] The preparation method of crude wood vinegar D is the same as that of Preparation Example 7, except that in step (2), a single 40 g cellulase is used instead of 30 g cellulase and 10 g ligninase.

[0074] Example 1

[0075] A refining and purification process for wood vinegar comprises the following steps:

[0076] S1. 1200 ml of ethyl acetate was added twice to 1000 ml of crude wood vinegar A for extraction, 600 ml was added each time, ultrasonic vibration was performed for 6 min, the layers were allowed to stand, the extracts were combined, and the extracts were concentrated by rotary evaporation to obtain a crude concentrated wood vinegar;

[0077] S2. 450ml of 4wt% aqueous sodium bicarbonate solution was added to 450ml of the crude concentrated wood vinegar obtained in step S1 three times for extraction, 150ml was added each time, ultrasonically shaken for 3min, and the extracts were combined to obtain a primary refined wood vinegar;

[0078] S3. 7.5 ml of 50 wt% aqueous phosphoric acid solution and 5 ml of 25 wt% aqueous sulfuric acid solution were added to 250 ml of the primary refined wood vinegar obtained in step S2, and 300 ml of ethyl acetate was added again and ultrasonically shaken for 5 min, and the extraction was concentrated by rotary evaporation to obtain a secondary refined wood vinegar;

[0079] S4. Add modified biomass activated carbon A to the secondary refined wood vinegar obtained in step S3 at a mass ratio of 1:0.075, set the water bath temperature to 55°C, the water bath reaction time to 45 minutes, shake once every 5 minutes, let stand for 1 hour, and filter to obtain refined wood vinegar.

[0080] Example 2

[0081] A refining and purification process for wood vinegar comprises the following steps:

[0082] S1. 1200 ml of ethyl acetate was added twice to 1000 ml of crude wood vinegar A for extraction, 600 ml was added each time, ultrasonic vibration was performed for 6 min, the layers were allowed to stand, the extracts were combined, and the extracts were concentrated by rotary evaporation to obtain a crude concentrated wood vinegar;

[0083] S2. 450ml of 3wt% aqueous sodium bicarbonate solution was added to 450ml of the crude concentrated wood vinegar obtained in step S1 three times for extraction, 150ml was added each time, ultrasonically shaken for 3min, and the extracts were combined to obtain a primary refined wood vinegar;

[0084] S3. 6.25 ml of 60 wt % aqueous phosphoric acid solution and 6.25 ml of 15 wt % aqueous sulfuric acid solution were added to 250 ml of the primary refined wood vinegar obtained in step S2, and 300 ml of ethyl acetate was added again and ultrasonically shaken for 5 min, and the extraction was concentrated by rotary evaporation to obtain a secondary refined wood vinegar;

[0085] S4. Add modified biomass activated carbon A to the secondary refined wood vinegar obtained in step S3 at a mass ratio of 1:0.05, set the water bath temperature to 50°C, the water bath reaction time to 60 min, shake once every 5 min, let stand for 1 h, and filter to obtain refined wood vinegar.

[0086] Example 3

[0087] A refining and purification process for wood vinegar comprises the following steps:

[0088] S1. 1200 ml of ethyl acetate was added twice to 1000 ml of crude wood vinegar A for extraction, 600 ml was added each time, ultrasonic vibration was performed for 6 min, the layers were allowed to stand, the extracts were combined, and the extracts were concentrated by rotary evaporation to obtain a crude concentrated wood vinegar;

[0089] S2. 450ml of 5wt% aqueous sodium bicarbonate solution was added to 450ml of the crude concentrated wood vinegar obtained in step S1 three times for extraction, 150ml was added each time, ultrasonically shaken for 3min, and the extracts were combined to obtain a primary refined wood vinegar;

[0090] S3. 8.3 ml of 40 wt % aqueous phosphoric acid solution and 4.2 ml of 35 wt % aqueous sulfuric acid solution were added to 250 ml of the primary refined wood vinegar obtained in step S2, and 300 ml of ethyl acetate was added again and ultrasonically shaken for 5 min, and the extraction was concentrated by rotary evaporation to obtain a secondary refined wood vinegar;

[0091] S4. Add modified biomass activated carbon A to the secondary refined wood vinegar obtained in step S3 at a mass ratio of 1:0.1, set the water bath temperature to 60°C, the water bath reaction time to 30 minutes, shake once every 5 minutes, let stand for 1 hour, and filter to obtain refined wood vinegar.

[0092] Example 4

[0093] A refining and purification process for wood vinegar, the specific implementation method is the same as that of Example 1, except that the concentration of the sodium bicarbonate aqueous solution in step S2 is 6wt%.

[0094] Example 5

[0095] A process for refining and purifying wood vinegar, the specific implementation method is the same as that of Example 1, except that in step S4, the mass ratio of the secondary refined wood vinegar to the modified biomass activated carbon A is 1:0.03.

[0096] Example 6

[0097] A process for refining and purifying wood vinegar, the specific implementation method is the same as that of Example 1, except that in step S4, the mass ratio of the secondary refined wood vinegar to the modified biomass activated carbon A is 1:0.2.

[0098] Example 7

[0099] A refining and purification process for wood vinegar, the specific implementation method is the same as that of Example 1, except that an equal amount of crude wood vinegar B is used to replace crude wood vinegar A.

[0100] Example 8

[0101] A refining and purification process for wood vinegar, the specific implementation method is the same as that of Example 1, except that an equal amount of crude wood vinegar C is used to replace crude wood vinegar A.

[0102] Example 9

[0103] A refining and purification process for wood vinegar, the specific implementation method is the same as that of Example 1, except that an equal amount of crude wood vinegar D is used to replace crude wood vinegar A.

[0104] Example 10

[0105] A refining and purification process for wood vinegar, the specific implementation method is the same as that of Example 1, except that an equal amount of modified biomass activated carbon B is used to replace the modified biomass activated carbon A.

[0106] Embodiment 11

[0107] A refining and purification process for wood vinegar, the specific implementation method is the same as that of Example 1, except that an equal amount of modified biomass activated carbon C is used to replace the modified biomass activated carbon A.

[0108] Example 12

[0109] A refining and purification process for wood vinegar, the specific implementation method is the same as that of Example 1, except that an equal amount of modified biomass activated carbon D is used to replace the modified biomass activated carbon A.

[0110] Embodiment 13

[0111] A refining and purification process for wood vinegar, the specific implementation method is the same as that of Example 1, except that an equal amount of modified biomass activated carbon E is used to replace the modified biomass activated carbon A.

[0112] Comparative Example 1

[0113] A refining and purification process for wood vinegar, the specific implementation method is the same as that of Example 1, except that an equal amount of commercially available activated carbon is used to replace the modified biomass activated carbon A.

[0114] Effect evaluation:

[0115] The refined wood vinegar of Examples 1-13 and Comparative Example 1 was tested and analyzed, and the specific results are shown in Tables 1 and 2.

[0116] Performance Testing:

[0117] (1) Decolorization test: The obtained refined wood vinegar was observed, and the colors were divided into reddish brown, yellowish brown, yellow, beige, and almost colorless from dark to light.

[0118] (2) Taste: The taste of the refined wood vinegar was identified as strong smoky taste, smoky taste, slight smoky taste, and no smoky taste.

[0119] Table 1

[0120]

[0121]

[0122] From the results in Table 1, it can be seen that the wood vinegar obtained in Examples 1-3 is almost clear, has high transparency, has no smoky smell, and has good application value.

[0123] Compared with Example 1, Example 4 changes the concentration of the sodium bicarbonate aqueous solution, which may cause incomplete separation of substances and is not conducive to subsequent adsorption and decolorization.

[0124] Compared with Example 1, Examples 5-6 changed the mass ratio of the secondary refined wood vinegar and the modified biomass activated carbon A, which would affect the adsorption effect and result in incomplete adsorption and decolorization.

[0125] Compared with Example 1, when preparing crude wood vinegar, Example 7 changes the mass ratio of Bacillus subtilis, yeast, and Acetobacter xylinum, Example 8 changes the mass ratio of complex enzyme, cottonseed hull, sorghum bran, bacterial liquid and solid, and Example 9 uses a single cellulase, all of which will cause a decrease in the content of total organic active ingredients in refined wood vinegar and affect the color and taste of refined wood vinegar to varying degrees.

[0126] Compared with Example 1, when preparing modified biomass activated carbon, Examples 10-11 changed the mass ratio of chitosan and highland barley straw residue activated carbon. Example 10 would cause a significant reduction in the porosity, and Example 11 would cause a weakening of the flocculation effect of chitosan, which would in turn lead to a weakening of the adsorption and decolorization effect; Example 12 changed the mass ratio of modified highland barley straw residue activated carbon and 4-piperidinecarboxamide, and Example 13 did not introduce 4-piperidinecarboxamide. Comparative Example 1 used commercially available activated carbon instead of modified biomass activated carbon A, which all resulted in a reduction in adsorption sites, a decrease in the stability of activated carbon, and a weakening of the adsorption and decolorization effect.

[0127] Application testing:

[0128] 3 kg of the refined wood vinegar obtained in Examples 1-3, 3 kg of urea, 3 kg of potassium dihydrogen phosphate, 3 kg of fulvic acid, 0.2 kg of potassium diphenylurea sulfonate, and 2.5 kg of ethylenediaminetetraacetic acid were prepared to prepare corresponding fertilizers 1-3; the refined wood vinegar obtained in Example 1 was replaced with commercially available wood vinegar to prepare fertilizer 4;

[0129] 100 cotton plants were randomly selected and divided into 5 groups. 50 insects were added to each group for testing during the cotton boll period. Fertilizers 1-4 and commercially available ordinary fertilizers were used to spray the cotton leaves (the mass ratio of fertilizer to water was 1:300), respectively. The number of live insects, the number of buds, and the boll detachment rate were measured in clear, windless, and a few cloudless weather. Among them, wood vinegar was purchased from Shijiazhuang Hongsen Activated Carbon Co., Ltd., and ordinary fertilizers were purchased from Hebei Nuo Shou Agricultural Technology Co., Ltd.

[0130] Table 2

[0131] Serial number Number of live insects / head Number of buds Cotton boll detachment rate / % Fertilizer 1 0 11 58.2 Fertilizer 2 0 10 63.4 Fertilizer 3 0 11 60.7 Fertilizer 4 5 8 68.6 Ordinary fertilizer 13 6 72.1

[0132] As can be seen from Table 2, the fertilizers 1-3 prepared from the refined wood vinegar provided by the present invention can not only promote the growth of plants and increase the number of cotton buds, but also prevent diseases and insect pests, reduce the risk of cotton pathogens infecting plants, and thus obtain higher economic value; Fertilizer 4 prepared from ordinary commercially available refined wood vinegar, due to the relatively low refined purity in the wood vinegar, affects the plant's absorption of the fertilizer, so the quality of cotton applied with the fertilizer is not high; cotton applied with ordinary fertilizers has a weak ability to resist diseases and insect pests because no anti-disease drugs similar to wood vinegar ingredients are applied, thereby affecting plant growth.

[0133] The above is only a preferred embodiment of the present invention and does not constitute any form of limitation to the present application. Although the present application is disclosed as above in the preferred embodiment, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution.

Claims

1. A refining and purification process for wood vinegar, characterized in that: The following steps are included: S1. Add ethyl acetate to the crude wood vinegar, ultrasonically shake, extract 2-3 times, combine the extracts, and concentrate by rotary evaporation to obtain a crude concentrated wood vinegar; S2. Adding an aqueous solution of sodium bicarbonate to the crude concentrated wood vinegar obtained in step S1, extracting 2-3 times, combining the extracts to obtain a primary refined wood vinegar; S3. The composite acid is added to the primary refined wood vinegar obtained in step S2, ethyl acetate is added again and ultrasonically shaken, extracted, and concentrated by rotary evaporation to obtain a secondary refined wood vinegar; S4. Add modified biomass activated carbon to the secondary refined wood vinegar obtained in step S3, react in a water bath, let stand, and filter to obtain refined wood vinegar.

2. A refining and purification process for wood vinegar according to claim 1, characterized in that: The method for preparing the crude wood vinegar described in step S1 comprises the following steps: (1) mixing Bacillus subtilis, yeast, and Acetobacter xylinum and activating them to obtain a bacterial solution for later use; (2) crushing the beet pulp to a particle size of 1-4 cm, soaking it in a citric acid aqueous solution for 10-16 hours, filtering out the solid, adding a composite enzyme, cottonseed hulls, sorghum bran and the bacterial solution prepared in step (1), and then adding deionized water until the overall moisture content is 30wt%-40wt%, and fermenting it for 6-8 days in a sealed manner to obtain a beet pulp fermentation product; wherein the composite enzyme is a cellulase and a ligninase in a mass ratio of (2-4):1; (3) filtering the fermented beet pulp obtained in step (2), drying to an overall moisture content of 5 wt%-8 wt%, pouring into a reactor, introducing an inert gas, heating to 300-400° C. at a rate of 4-8° C. / min, collecting the distillate, and obtaining a crude wood vinegar solution.

3. A refining and purification process for wood vinegar according to claim 2, characterized in that: The viable number of Bacillus subtilis in step (1) is 1×10 8 ~3×10 8 CFU / g, the number of live yeast cells is 2×10 8 ~5×10 8 CFU / g, the number of viable Acetobacter xylinum was 2×10 7 ~7×10 7 CFU / g, the mass ratio of the three is 1:(4-6):(2-4).

4. A refining and purification process for wood vinegar according to claim 2, characterized in that: The mass ratio of the complex enzyme, cottonseed hull, sorghum bran, bacterial liquid and solid in step (2) is (0.03-0.05):(0.2-0.3):(0.05-0.15):(0.2-0.4):

1.

5. A refining and purification process for wood vinegar according to claim 1, characterized in that: The concentration of the sodium bicarbonate aqueous solution in step S2 is 3wt%-5wt%.

6. A refining and purification process for wood vinegar according to claim 1, characterized in that: The composite acid in step S3 is 40wt%-60wt% phosphoric acid aqueous solution and 15wt%-35wt% sulfuric acid aqueous solution, and the volume ratio of the two is (1-2):

1.

7. A refining and purification process for wood vinegar according to claim 1, characterized in that: The method for preparing the modified biomass activated carbon in step S4 comprises the following steps: ① Wash the highland barley straw residue with deionized water for 3-5 times, dry it, add 0.25-0.5mol / L potassium hydroxide aqueous solution to soak it for 10-16h, filter it with suction, dry it, put the alkalized highland barley straw residue into a reactor, pass inert gas, heat it to 500-700℃ and calcine it for 1-2h, grind it after cooling, add 0.2-0.3mol / L hydrochloric acid aqueous solution, heat it to 85-100℃ and stir it for 30-45min, filter it with suction, wash it, dry it, and obtain highland barley straw residue activated carbon; ② dissolving chitosan in 5wt%-8wt% acetic acid aqueous solution to obtain a chitosan solution for standby use; adding the highland barley straw residue activated carbon obtained in step ① to the chitosan solution, heating to 35-45° C., stirring for 30-45 min, adding glutaraldehyde, heating to 65-80° C., stirring for 1-2 h, washing, and drying to obtain modified highland barley straw residue activated carbon; ③ Add the modified highland barley straw residue activated carbon, 4-piperidinecarboxamide and dimethyl sulfoxide obtained in step ② to a reaction vessel, stir for 1-2 hours, add formaldehyde dropwise, stir for 10-12 hours, add sodium hydroxide, collect the precipitate after suction filtration, wash with deionized water until the pH of the supernatant is neutral, then wash with anhydrous ethanol 1-2 times, and dry to obtain modified biomass activated carbon.

8. A refining and purification process for wood vinegar according to claim 7, characterized in that: The mass ratio of chitosan and highland barley straw residue activated carbon in step ② is (0.6-1):

1.

9. A refining and purification process for wood vinegar according to claim 7, characterized in that: The mass ratio of the modified highland barley straw residue activated carbon and 4-piperidinylcarboxamide in step ③ is 1:(0.1-0.4).

10. A refining and purification process for wood vinegar according to claim 1, characterized in that: The mass ratio of the secondary refined wood vinegar and the modified biomass activated carbon in step S4 is 1:(0.05-0.1).

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