CN111394401A - Method for preparing medium-chain fatty acid by anaerobic fermentation of wood fiber raw material - Google Patents

Method for preparing medium-chain fatty acid by anaerobic fermentation of wood fiber raw material Download PDF

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Publication number
CN111394401A
CN111394401A CN202010156686.9A CN202010156686A CN111394401A CN 111394401 A CN111394401 A CN 111394401A CN 202010156686 A CN202010156686 A CN 202010156686A CN 111394401 A CN111394401 A CN 111394401A
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chain fatty
fermentation
medium
fatty acid
acid
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邢涛
甄峰
孙永明
孔晓英
李连华
杨改秀
李颖
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/64Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6409Fatty acids
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2201/00Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2203/00Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source

Abstract

The invention provides a method for preparing medium-chain fatty acid by anaerobic fermentation of a wood fiber raw material. A method for preparing medium-chain fatty acid by anaerobic fermentation of a wood fiber raw material comprises the following steps: (1) mixing the crushed wood fiber raw material with anaerobic digestion sludge according to the mass ratio of 1: 20-1: 4, adjusting the pH value to 9.0-11.0, adding a methane production inhibitor, and then performing anaerobic fermentation to obtain fermentation liquor containing short-chain fatty acids; (2) continuously carrying out anaerobic fermentation on the fermentation liquor containing the short-chain fatty acid for 10-45 days at the fermentation temperature of 30-40 ℃, and intermittently adding ethanol or lactic acid in the fermentation process to obtain the fermentation liquor containing the medium-chain fatty acid; (3) and carrying out solid-liquid separation on the fermentation liquor containing the medium-chain fatty acid to obtain a supernatant, adjusting the pH of the supernatant to 3.0-6.0, and extracting to obtain the medium-chain fatty acid in the supernatant. The invention can not only consume organic wastes, but also has cleaner conversion process compared with petrochemical-based process, and is a clean and green conversion process.

Description

Method for preparing medium-chain fatty acid by anaerobic fermentation of wood fiber raw material
The technical field is as follows:
the invention relates to the technical field of waste recycling, in particular to a method for preparing medium-chain fatty acid by anaerobic fermentation of a wood fiber raw material.
Background art:
the wood fiber raw material is the most abundant and sustainable carbon-hydrogen biomass resource, mainly comprises novel biomasses such as straw and other agricultural and forestry wastes and energy herbaceous plants, has the characteristics of wide sources, high yield, stable components and the like, has different characteristics of each component, has the potential of graded utilization, and is a good raw material for preparing biogas or platform compounds through biomass anaerobic conversion. With the continuous development of biomass energy, the conversion of wood fiber raw materials such as straws, energy plants and the like to prepare energy or bio-based products is receiving more and more attention, has important functions on prolonging the modern agricultural industry chain, driving the industrial industry to upgrade, promoting the economic development of rural towns and towns, relieving the ecological environment pressure and improving the energy structure, and is an important component of a major strategic emerging industry for changing the economic development mode.
The anaerobic fermentation technology is one of the most potential lignocellulose biomass resource utilization technologies, and is an effective way for clean energy and resource conversion. At present, the technology for preparing the biogas and the fuel ethanol by utilizing the anaerobic fermentation of the wood fiber raw material is rapidly developed in China, the construction of related bioenergy engineering is accelerated, and the problems of long fermentation period, low conversion efficiency, insufficient expression of product value and the like still exist.
In recent years, in addition to the preparation of biogas by using anaerobic technology, a new idea of preparing Volatile Fatty Acids (VFAs) by anaerobic fermentation, namely a carboxylate platform compound, is proposed in the field of international anaerobic technology aiming at the traditional anaerobic digestion characteristics and self-limitations, and is a promising high-valued utilization approach. Under the condition of limiting or inhibiting the methanogenesis stage, volatile fatty acid is accumulated as an intermediate product in the anaerobic digestion process, and mixed volatile fatty acid mainly comprising small molecular carboxylic acids (SCCAs) such as acetic acid, propionic acid and butyric acid is obtained. However, these small molecular acids have low energy density, strong hydrophilicity and difficult separation and purification, thereby limiting the subsequent resource utilization. Medium-chain carboxylic acids such as caproic acid have higher energy density and higher hydrophobicity than short-chain fatty acids, and subsequent separation and purification are relatively easy. Furthermore, medium-chain fatty acids such as caproic acid can be further processed into biofuels such as diesel oil, chemical materials such as perfumes (perfumes, thickening agents for lubricating oils, rubber processing aids, and the like), food additives, antibacterial agents, and the like, and have higher added values. Market research shows that the price of acetic acid (industrial grade) is about 4000 yuan per ton, and the price of industrial grade caproic acid reaches 2-3 ten thousand yuan per ton. Therefore, the anaerobic biological synthesis of medium-chain fatty acids such as caproic acid from wood fiber raw materials is a very potential resource recycling technology.
The invention content is as follows:
the invention aims to provide a method for preparing medium-chain fatty acid from a wood fiber raw material in an anaerobic manner.
The invention aims to provide a method for preparing medium-chain fatty acid by anaerobic fermentation of a wood fiber raw material, which comprises the following steps:
(1) mixing a wood fiber raw material crushed to be less than 1-2 cm with anaerobic digested sludge according to a mass ratio of 1: 20-1: 4, adjusting the pH value to 9.0-11.0 to obtain a raw material solution, adding a methane production inhibitor into the raw material solution according to the amount of 20-50 mmol per liter of raw material solution, and then performing anaerobic fermentation at the fermentation temperature of 30-55 ℃ for 5-15 days to obtain a weak acid fermentation broth containing short-chain fatty acids;
(2) continuously carrying out anaerobic fermentation on the fermentation liquor obtained in the step (1) for 10-45 days at the fermentation temperature of 30-40 ℃, and intermittently adding ethanol or lactic acid in the fermentation process to obtain fermentation liquor containing medium-chain fatty acids;
(3) and (3) carrying out solid-liquid separation on the fermentation liquor containing the medium-chain fatty acid obtained in the step (2) to obtain a supernatant, adjusting the pH of the supernatant to 3.0-6.0, and extracting to obtain the medium-chain fatty acid in the supernatant.
The stage (step (1)) for producing the short-chain fatty acid by anaerobic fermentation is alkaline under the initial condition, and compared with the traditional fermentation for producing acid, the short-chain fatty acid is increased in acid production rate and is more beneficial to production of caproic acid and caprylic acid. In addition, with the generation of short-chain fatty acid, the pH of the fermentation liquor is gradually reduced to weak acidity, so that the requirement of producing medium-chain fatty acid by fermentation is met, and the pH is prevented from being adjusted again. The two-stage anaerobic fermentation is adopted to convert the wood fiber raw material into the platform compound with higher added value, compared with the traditional anaerobic fermentation of the wood fiber raw material to produce methane or short-chain fatty acid, the product has higher added value and wider application scene.
Preferably, the addition amount of the ethanol or the lactic acid in the step (2) is 0.5-3 g of ethanol or lactic acid added to 100g of fermentation broth, the addition interval time of the ethanol or the lactic acid is 2-20 days, and the addition times are 1-20 times.
Preferably, the extraction method of medium-chain fatty acids in step (3) comprises an extraction method, a membrane separation method or an adsorption method.
Preferably, the medium-chain fatty acid in step (3) is hexanoic acid or octanoic acid.
Preferably, the wood fiber raw material is selected from one or more of crop straws, energy grass and ensiled straws.
Preferably, the methanogenesis inhibitor is sodium 2-bromoethyl sulfonate.
Unless otherwise defined, the present invention is directed to the definitions of terms having the same meaning as commonly understood by one of ordinary skill in the art.
Compared with the prior art, the invention has the following advantages:
(1) the target product of the invention is medium-chain fatty acid such as caproic acid or caprylic acid, and the like, and the solubility of the medium-chain fatty acid in the aqueous solution is far less than that of short-chain fatty acid, so compared with the short-chain fatty acid, the difficulty and the cost of the extraction and separation process can be greatly reduced.
(2) The stage of producing the short-chain fatty acid by anaerobic fermentation is carried out under the alkaline condition, compared with the traditional fermentation for producing acid, the short-chain fatty acid fermentation method not only can increase the acid production rate, but also can ensure that the short-chain fatty acid species are more beneficial to the production of caproic acid and caprylic acid. In addition, with the generation of short-chain fatty acid, the pH of the fermentation liquor is gradually reduced to weak acidity, so that the requirement of producing medium-chain fatty acid by fermentation is met, and the pH is prevented from being adjusted again.
(3) The two-stage anaerobic fermentation is adopted to convert the wood fiber raw material into the platform compound with higher added value, compared with the traditional anaerobic fermentation of the wood fiber raw material to produce methane or short-chain fatty acid, the product has higher added value and wider application scene.
(4) The invention adopts a biological method to prepare carboxylic acid platform compounds such as caproic acid and the like, can utilize organic wastes such as straws and the like, has cleaner conversion process, and is a green and clean process compared with the process for preparing the products by utilizing petrochemical raw materials.
Description of the drawings:
FIG. 1 is a schematic process flow diagram of a method for preparing medium-chain fatty acids by anaerobic fermentation of a lignocellulosic feedstock according to the present invention.
The specific implementation mode is as follows:
the following examples are further illustrative of the present invention and are not intended to be limiting thereof. Anaerobic digestion sludge is commercially available.
Example 1:
as shown in figure 1, the method for preparing the caproic acid by the anaerobic fermentation of the corn stalks comprises the following steps:
(1) crushing corn stalks to be less than 2cm, mixing the corn stalks with anaerobic digestion sludge according to a mass ratio of 1:20, adjusting the pH to 11.0 by using sodium hydroxide to obtain a raw material solution, adding 20mmol of 2-bromoethyl sodium sulfonate into the raw material solution per liter of the raw material solution, then feeding the raw material solution into an anaerobic reactor for anaerobic fermentation at the fermentation temperature of 35 ℃, and continuously fermenting for 15 days to obtain a fermentation liquid with the concentration of short-chain fatty acid of 6-8 g/L, wherein the pH is about 5.5;
(2) keeping the fermentation liquor obtained in the step (1) for anaerobic fermentation for 20 days, controlling the fermentation temperature to be 30 ℃, adding ethanol according to the amount of 1g added in every 100g of fermentation liquor on the 2 nd day of fermentation, and obtaining the fermentation liquor rich in caproic acid after 15-20 days, wherein the caproic acid concentration is detected to be 6 g/L by gas chromatography;
(3) and (3) carrying out solid-liquid separation on the fermentation liquor obtained in the step (2), adjusting the pH value of the supernatant to 6.0, and extracting the caproic acid by using a membrane separation method.
Example 2:
as shown in figure 1, the method for preparing hexanoic acid and octanoic acid by the anaerobic fermentation of hybrid pennisetum comprises the following steps:
(1) crushing fresh hybrid pennisetum alopecuroides to be less than 1cm, mixing the crushed fresh hybrid pennisetum alopecuroides with anaerobic digested sludge according to the mass ratio of 1:10, adjusting the pH to 10.0 by using sodium hydroxide to obtain a raw material solution, adding 50 mmol/L of 2-bromoethyl sodium sulfonate into the raw material solution per liter of the raw material solution, and then performing anaerobic fermentation at the fermentation temperature of 55 ℃ for 10 days to obtain a fermentation liquid with the concentration of short-chain fatty acid of 10-12 g/L;
(2) continuously carrying out anaerobic fermentation on the fermentation liquor obtained in the step (1), wherein the fermentation temperature is 40 ℃, adding ethanol every 2 days from the 2 nd day of fermentation, wherein the adding amount of the ethanol every time is 0.5g of ethanol added into every 100g of fermentation liquor, obtaining fermentation liquor rich in caproic acid and caprylic acid after 40-45 days, and the concentration of the caproic acid and the caprylic acid respectively reaches 6 g/L and 1.5 g/L through gas chromatography detection;
(3) and (3) carrying out solid-liquid separation on the fermentation liquor obtained in the step (2), adjusting the pH value of the supernatant to 3.0, and extracting caproic acid and caprylic acid in the fermentation liquor by using an extraction method.
Example 3:
as shown in figure 1, the method for preparing hexanoic acid by anaerobic fermentation of silage corn stalks comprises the following steps:
(1) smashing silage corn stalks to be less than 2cm, mixing the smashed silage corn stalks with anaerobic digestion sludge according to the mass ratio of 1:4, adjusting the pH value to 9.0 by using potassium hydroxide to obtain a raw material solution, adding 50mmol of 2-bromoethyl sodium sulfonate into each liter of the raw material solution, and then performing anaerobic fermentation at the fermentation temperature of 30 ℃ for 5 days to obtain a fermentation liquid with the concentration of short-chain fatty acids of 8-10 g/L;
(2) continuously carrying out anaerobic fermentation on the fermentation liquor obtained in the step (1), wherein the fermentation temperature is 30 ℃, adding lactic acid according to the amount of 3g of lactic acid added in every 100g of fermentation liquor on the 2 nd day of fermentation, and fermenting for 10-15 days to obtain fermentation liquor rich in caproic acid, wherein the caproic acid concentration is 3-5 g/L detected by gas chromatography;
(3) and (3) carrying out solid-liquid separation on the fermentation liquor obtained in the step (2), adjusting the pH value of the supernatant to 6.0, and extracting the caproic acid by using an adsorption method.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, simplifications, etc., which are made without departing from the spirit and principle of the present invention, should be regarded as being equivalent to the replacement of the above embodiments, and are included in the scope of the present invention.

Claims (6)

1. A method for preparing medium-chain fatty acid by anaerobic fermentation of a wood fiber raw material is characterized by comprising the following steps:
(1) mixing the crushed wood fiber raw material with anaerobic digestion sludge according to the mass ratio of 1: 20-1: 4, adjusting the initial pH value of fermentation to 9.0-11.0, adding 20-50 mmol/L of a methane production inhibitor, and then performing anaerobic fermentation at the fermentation temperature of 30-55 ℃ for 5-15 days to obtain weak acid fermentation liquor containing short-chain fatty acids;
(2) continuously carrying out anaerobic fermentation on the fermentation liquor obtained in the step (1) for 10-45 days at the fermentation temperature of 30-40 ℃, and intermittently adding ethanol or lactic acid in the fermentation process to obtain fermentation liquor containing medium-chain fatty acids;
(3) and (3) carrying out solid-liquid separation on the fermentation liquor containing the medium-chain fatty acid obtained in the step (2) to obtain a supernatant, adjusting the pH of the supernatant to 3.0-6.0, and extracting to obtain the medium-chain fatty acid in the supernatant.
2. The method for preparing medium-chain fatty acids by anaerobic fermentation of lignocellulosic materials as claimed in claim 1, wherein the ethanol or lactic acid is added in an amount of 0.5-3 g per 100g of fermentation broth in step (2), the ethanol or lactic acid is added at intervals of 2-20 days, and the addition frequency is 1-20 times.
3. The method for preparing medium-chain fatty acids by anaerobic fermentation of lignocellulosic feedstocks as claimed in claims 1 or 2, wherein the extraction process of medium-chain fatty acids in step (3) comprises extraction, membrane separation or adsorption.
4. The method for preparing medium-chain fatty acids by anaerobic fermentation of lignocellulosic feedstocks according to claim 1 or 2, wherein the medium-chain fatty acids of step (3) are caproic acid or caprylic acid.
5. The method for preparing medium-chain fatty acids from lignocellulosic feedstocks by anaerobic fermentation according to claim 1 or 2, wherein the lignocellulosic feedstocks are selected from one or more of crop straw, energy grass and silage straw.
6. The method of claim 1 or 2, wherein the methanogenic inhibitor is sodium 2-bromoethylsulfonate.
CN202010156686.9A 2020-03-09 2020-03-09 Method for preparing medium-chain fatty acid by anaerobic fermentation of wood fiber raw material Pending CN111394401A (en)

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CN116640808A (en) * 2023-07-27 2023-08-25 中国农业科学院农业环境与可持续发展研究所 Method for changing methane fermentation into medium-chain fatty acid fermentation

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