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    • 专利摘要:
    The present invention discloses a method for preparing 4-(3-hydroxyphenyl)-4-oxobutanoic acid from lignin, including the following steps: adding lignin and a catalyst to ethanol; then performing a depolymerization reaction 5 under the condition of supercritical ethanol; and after the reaction, performing rapid cooling to obtain the 4-(3-hydroxyphenyl)-4-oxobutanoic acid, wherein the catalyst includes sepiolite as a carrier and molybdenum and boron as active components supported on the sepiolite. The method of the present invention is simple in process and easy to operate, and avoids inconvenience of operation, environmental pollution and 10 waste of resources caused by using acetic acid and organic compounds as catalysts, the catalyst can be reused, the lignin conversion rate is high, and the selectivity and yield of the monomer 4-(3 -hydroxyphenyl)-4-oxobutanoic acid are high.
    公开号:NL2024500A
    申请号:NL2024500
    申请日:2019-12-18
    公开日:2020-07-07
    发明作者:Chen Mingqiang；Wang Yishuang；Yang Zhonglian；Tang Zhiyuan；Wang Chunsheng；Zhang Han；Wang Jun
    申请人:Univ Anhui Sci & Technology；
    IPC主号:
    专利说明:

    NR. P100376NL00
    METHOD FOR PREPARING 4-(3-HYDROXYPHENYL)-4-OXOBUTANOIC ACID FROM LIGNIN
    BACKGROUND Technical Field The present invention relates to the field of lignin utilization, and in particular to a method for preparing 4-(3-hydroxyphenyl)-4-oxobutanoic acid from lignin. Related Art Lignocellulosic biomass is a rich renewable resource on the earth. Lignocellulose is mainly composed of cellulose, hemicellulose and lignin, and the lignin content is the highest, about 30%. Lignin may be converted to small molecule platforms by lignin degradation technologies to prepare a plurality of secondary compounds which have a wide range of functions and uses. At present, supporting metal elements on a carrier to form a supported solid acid catalyst for catalyzing lignin degradation is an important catalytic conversion path. The main catalytic principle is to use the corresponding B acid sites and L acid sites of the metal elements to selectively break the C-O, C-H and O-H bonds contained in lignin, so as to obtain corresponding small molecule platform compounds (monomers and dimers). Because the metal elements are supported on the carrier, the dispersibility of the metal elements is better, so that the catalytic activity and efficiency are greatly improved. Moreover, the catalyst is environmentally friendly, does not cause pollution, can be recycled and reused, and is a very good green, efficient and economical catalyst. In addition, many of the current substituted phenol and carboxylic acid compounds are not only fine chemical products, but also important agricultural products and pharmaceutical intermediates. The origin, synthesis and preparation thereof have always been research hotspots in the field of organic chemistry. Due to the benzene ring substituent effect, there is a plurality of factors that are difficult to control in the synthesis process, which also brings a series of difficulties to the synthesis. The synthesis and origin of some substituted phenols remain a scientific problem.
    Therefore, the development of green, efficient, economical and highly selective catalysts, as well as a simple and efficient process for the synthesis of substituted aromatic compounds, is the key factors to solve a series of difficult problems in current organic synthesis.
    SUMMARY The technical problem to be solved by the present invention is to provide a method for preparing 4-(3-hydroxyphenyl)-4-oxobutanoic acid from lignin, which 1s simple in process, capable of avoiding environmental pollution and waste of resources, and has high lignin conversion rate and high selectivity and yield of the monomer 4-(3-hydroxyphenyl)-4-oxobutanoic acid.
    In order to solve the above technical problem, the present invention adopts the following technical solution: a method for preparing 4-(3-hydroxyphenyl)-4-oxobutanoic acid from lignin, including the following steps: adding lignin and a catalyst to ethanol; then performing a depolymerization reaction under a condition of supercritical ethanol; and after the reaction, performing rapid cooling to obtain the 4-(3-hydroxyphenyl)-4-oxobutanoic acid, wherein the catalyst includes sepiolite as a carrier and molybdenum and boron as active components supported on the sepiolite.
    Further, in the catalyst, a content of the molybdenum is 5-20 wt.%, a content of the boron is 1-10 wt.%, and the balance 1s the sepiolite.
    Further, a feed mass ratio of the lignin to the catalyst to the ethanol is (0.8-1.2):(0.3-0.7):(28-32).
    Further, reaction conditions of the depolymerization reaction are 270-310°C, 0.4-0.6 MPa of high-purity nitrogen, and a reaction time of the depolymerization reaction is 1-8 h.
    Further, the rapid cooling is achieved by liquid nitrogen or an ice water bath.
    Further, the method further includes a 4-(3-hydroxyphenyl)-4-oxobutanoic acid extraction step, and a specific operation process of the extraction step is: performing solid-liquid separation on a reaction product subjected to the rapid cooling; then performing rotary evaporation on a separated liquid phase product to remove the ethanol and a water phase; then adding a purification solvent; after dissolution, performing filtering treatment; and finally evaporating a soluble liquid phase of a filtrate obtained by the filtering treatment to dryness to obtain the 4-(3-hydroxyphenyl)-4-oxobutanoic acid.
    Further, a temperature condition of the rotary evaporation treatment is 39.5-49.5°C, and a rotation speed condition is 90-120 r/min.
    Further, the purification solvent is ethyl acetate.
    Further, a temperature condition of evaporation to dryness is 32.5-39.5°C.
    Further, a filter used in the filtering treatment is an organic filter with good watertest performance, acid and alkali resistance and oxidation resistance. The beneficial effects of the present invention are: The method of the present invention is simple in process and easy to operate, and avoids inconvenience of operation, environmental pollution and waste of resources caused by using acetic acid and organic compounds as catalysts; and the catalyst can be reused, the lignin conversion rate is high, and the selectivity and yield of the monomer 4-(3-hydroxyphenyl)-4-oxobutanoic acid are high.
    DETAILED DESCRIPTION The present invention is further described below with reference to embodiments. Various raw materials used in the following embodiments, unless otherwise specified, are all commercially available products known in the art. Embodiment 1 Preparation of catalyst A sepiolite raw material was calcinated at 500°C for 4 h, then the sepiolite raw material subjected to the calcinating treatment was taken and added to 5 mol/L nitric acid, stirring and mixing were performed under heating in a 60°C water bath, suction filtration was performed after uniform mixing, a filter cake obtained by suction filtration was washed to neutral with deionized water, and then the filter cake was dried to obtain a solid I. The solid I was placed in a tubular furnace and heated to S00°C at a heating rate of 2°C /min, and then the solid I was roasted in an air atmosphere for 4 h to obtain purified sepiolite. (NH4)sMo7024-4H20 and boric acid were weighed and placed in a 250 mL round bottomed flask, 100 mL of deionized water was added, and a solution I was formed after complete dissolving. The purified sepiolite was weighed and added to the solution I, and then an obtained mixture was placed in a water bath and stirred at a constant temperature of 60°C for 24 h to form a suspension II. Then a temperature of the suspension II was increased to 70°C, the suspension II was slowly evaporated in a metal bath to a slurry state, and then the slurry suspension II was sealed and allowed to stand and age in a sealed state for 48 h at 60°C. Then the suspension II subjected to the sealed aging treatment was evaporated to dryness in the metal bath to obtain a solid cake. Finally, the solid cake was dried for 12 h at 105°C, and then the solid cake was dried, ground and sieved, heated in the tubular furnace to 500°C at a heating rate of 2°C/min, and roasted in the air atmosphere for 4 h to obtain a molybdenum-boron/sepiolite catalyst. By adjusting amounts of the (NH:)sMo7024-4H:O, the boric acid and the purifiedsepiolite, a series of x molybdenum-y boron/sepiolite catalysts (xMo-yB/SEP) were prepared, respectively: 5Mo-9B/SEP, 7Mo-7B/SEP, 10Mo-6B/SEP, 15Mo-5B/SEP, 17Mo-3B/SEP and 20Mo-1B/SEP. Embodiment 2 Preparation of 4-(3-hydroxyphenyl)-4-oxobutanoic acid from lignin
    1.0512 g of alkali lignin and 0.5078 g of a catalyst 5Mo-9B/SEP were added into a 100 mL high pressure reactor, and then 30 mL of absolute ethanol was added to the high pressure reactor. Then, the reactor was charged with 0.5 MPa of high-purity nitrogen. Stirring was performed at 620 rpm for 15 min before reaction, then the temperature was increased from normal temperature 24°C to 290°C at a heating rate of 6°C/min to perform a depolymerization reaction at the temperature for 2 h. Immediately after the reaction, the high pressure reactor was rapidly cooled in an ice-water bath. After reducing to normal temperature, the reactor was opened to take out a reaction product, and then the reaction product was subjected to suction filtration by using a sand core funnel. A liquid phase product obtained by suction filtration was then placed in a rotary evaporator. First, the liquid phase product was evaporated to dryness (for removing the solvent ethanol and a water phase) in a 100 mL distillation flask at the conditions of
    42.5°C and 110 r/min. Then ethyl acetate was added to the flask and the flask was shaken in an ultrasonic shaker for 5 min. After dissolution, an obtained solution was taken out and filtered through an organic filter (for separating ethyl acetate insoluble products). A filtrate obtained by the filtering treatment was placed in a distillation flask, and an ethyl acetate soluble liquid phase was evaporated to dryness at the conditions of
    39.5°C and 100 r/min to obtain the 4-(3-hydroxyphenyl)-4-oxobutanoic acid. According to calculations, in the present embodiment, the lignin conversion rate exceeds 91%, the selectivity of the monomer 4-(3-hydroxyphenyl)-4-oxobutanoic acid exceeds 39%, and the yield exceeds 7%. Embodiment 3 Preparation of 4-(3-hydroxyphenyl)-4-oxobutanoic acid from lignin
    1.0122 g of alkali lignin and 0.5042 g of a catalyst 7Mo-7B/SEP were added into a 100 mL high pressure reactor, and then 30 mL of absolute ethanol was added to the high pressure reactor. Then, the reactor was charged with 0.4 MPa of high-purity nitrogen. Stirring was performed at 620 rpm for 15 min before reaction, then the temperature was increased from normal temperature 25°C to 270°C at a heating rate of 6°C/min to perform a depolymerization reaction at the temperature for 3 h. Immediately after thereaction, the high pressure reactor was rapidly cooled in an ice-water bath. After reducing to normal temperature, the reactor was opened to take out a reaction product, and then the reaction product was subjected to suction filtration by using a sand core funnel. A liquid phase product obtained by suction filtration was then placed in a rotary evaporator. First, the liquid phase product was evaporated to dryness (for removing the solvent ethanol and a water phase) in a 100 mL distillation flask at the conditions of
    40.5°C and 108 r/min. Then ethyl acetate was added to the flask and the flask was shaken in an ultrasonic shaker for 6 min. After dissolution, an obtained solution was taken out and filtered through an organic filter (for separating ethyl acetate insoluble products). A filtrate obtained by the filtering treatment was placed in a distillation flask, and an ethyl acetate soluble liquid phase was evaporated to dryness at the conditions of
    40.5°C and 98 r/min to obtain the 4-(3-hydroxyphenyl}-4-oxobutanoic acid. According to calculations, in the present embodiment, the lignin conversion rate exceeds 91%, the selectivity of the monomer 4-(3-hydroxyphenyl)-4-oxobutanoic acid exceeds 38%, and the yield exceeds 7%. Embodiment 4 Preparation of 4-(3-hydroxyphenyl)-4-oxobutanoic acid from lignin
    1.0147 g of alkali lignin and 0.5112 g of a catalyst 10Mo-6B/SEP were added into a 100 mL high pressure reactor, and then 30 mL of absolute ethanol was added to the high pressure reactor. Then, the reactor was charged with 0.6 MPa of high-purity nitrogen. Stirring was performed at 620 rpm for 15 min before reaction, then the temperature was increased from normal temperature 22°C to 280°C at a heating rate of 6°C/min to perform a depolymerization reaction at the temperature for 4 h. Immediately after the reaction, the high pressure reactor was rapidly cooled in an ice-water bath. After reducing to normal temperature, the reactor was opened to take out a reaction product, and then the reaction product was subjected to suction filtration by using a sand core funnel. A liquid phase product obtained by suction filtration was then placed in a rotary evaporator. First, the liquid phase product was evaporated to dryness (for removing the solvent ethanol and a water phase) in a 100 mL distillation flask at the conditions of
    43.5°C and 104 r/min. Then ethyl acetate was added to the flask and the flask was shaken in an ultrasonic shaker for 6 min. After dissolution, an obtained solution was taken out and filtered through an organic filter (for separating ethyl acetate insoluble products). A filtrate obtained by the filtering treatment was placed in a distillation flask, and an ethyl acetate soluble liquid phase was evaporated to dryness at the conditions of
    37.5°C and 105 r/min to obtain the -(3-liyd oxyphenyl}-d-excbuandie acid.
    According to calculations, in the present embodiment, the lignin conversion rate exceeds 93%, the selectivity of the monomer 4-(3-hydroxyphenyl)-4-oxobutanoic acid exceeds 43%, and the yield exceeds 8%.
    Embodiment 5 Preparation of 4-(3-hydroxyphenyl)-4-oxobutanoic acid from lignin
    1.0207 g of alkali lignin and 0.5093 g of a catalyst 15Mo-5B/SEP were added into a 100 mL high pressure reactor, and then 30 mL of absolute ethanol was added to the high pressure reactor. Then, the reactor was charged with 0.5 MPa of high-purity nitrogen.
    Stirring was performed at 620 rpm for 15 min before reaction, then the temperature was increased from normal temperature 24°C to 390°C at a heating rate of 6°C/min to perform a depolymerization reaction at the temperature for 5 h. Immediately after the reaction, the high pressure reactor was rapidly cooled in an ice-water bath. After reducing to normal temperature, the reactor was opened to take out a reaction product, and then the reaction product was subjected to suction filtration by using a sand core funnel. A liquid phase product obtained by suction filtration was then placed in a rotary evaporator. First, the liquid phase product was evaporated to dryness (for removing the solvent ethanol and a water phase) in a 100 mL distillation flask at the conditions of
    47.5°C and 106 r/min. Then ethyl acetate was added to the flask and the flask was shaken in an ultrasonic shaker for 6 min. After dissolution, an obtained solution was taken out and filtered through an organic filter (for separating ethyl acetate insoluble products). A filtrate obtained by the filtering treatment was placed in a distillation flask, and an ethyl acetate soluble liquid phase was evaporated to dryness at the conditions of
    35.5°C and 102 r/min to obtain the 4-(3-hydroxyphenyl)-4-oxobutanoic acid.
    According to calculations, in the present embodiment, the lignin conversion rate exceeds 90%, the selectivity of the monomer 4-(3-hydroxyphenyl)-4-oxobutanoic acid exceeds 35%, and the yield exceeds 6%.
    Embodiment 6 Preparation of 4-(3-hydroxyphenyl)-4-oxobutanoic acid from lignin
    1.0168 g of alkali lignin and 0.5121 g of a catalyst 17Mo-3B/SEP were added into a 100 mL high pressure reactor, and then 30 mL of absolute ethanol was added to the high pressure reactor. Then, the reactor was charged with 0.5 MPa of high-purity nitrogen. Stirring was performed at 620 rpm for 15 min before reaction, then the temperature was increased from normal temperature 26°C to 300°C at a heating rate of 6°C/min toperform a depolymerization reaction at the temperature for 6 h. Immediately after the reaction, the high pressure reactor was rapidly cooled in an ice-water bath. After reducing to normal temperature, the reactor was opened to take out a reaction product, and then the reaction product was subjected to suction filtration by using a sand core funnel. A liquid phase product obtained by suction filtration was then placed in a rotary evaporator. First, the liquid phase product was evaporated to dryness (for removing the solvent ethanol and a water phase) in a 100 mL distillation flask at the conditions of
    48.5°C and 120 r/min. Then ethyl acetate was added to the flask and the flask was shaken in an ultrasonic shaker for 6 min. After dissolution, an obtained solution was taken out and filtered through an organic filter (for separating ethyl acetate insoluble products). A filtrate obtained by the filtering treatment was placed in a distillation flask, and an ethyl acetate soluble liquid phase was evaporated to dryness at the conditions of
    38.5°C and 100 r/min to obtain the 4-(3-hydroxyphenyl)-4-oxobutanoic acid. According to calculations, in the present embodiment, the lignin conversion rate exceeds 92%, the selectivity of the monomer 4-(3-hydroxyphenyl)-4-oxobutanoic acid exceeds 37%, and the yield exceeds 6%. Embodiment 7 Preparation of 4-(3-hydroxyphenyl)-4-oxobutanoic acid from lignin
    1.0012 g of alkali lignin and 0.5068 g of a catalyst 20Mo-1B/SEP were added into a 100 mL high pressure reactor, and then 30 mL of absolute ethanol was added to the high pressure reactor. Then, the reactor was charged with 0.5 MPa of high-purity nitrogen. Stirring was performed at 620 rpm for 15 min before reaction, then the temperature was increased from normal temperature 25°C to 310°C at a heating rate of 6°C/min to perform a depolymerization reaction at the temperature for 8 h. Immediately after the reaction, the high pressure reactor was rapidly cooled in an ice-water bath. After reducing to normal temperature, the reactor was opened to take out a reaction product, and then the reaction product was subjected to suction filtration by using a sand core tunnel. A liquid phase product obtained by suction filtration was then placed in a rotary evaporator. First, the liquid phase product was evaporated to dryness (for removing the solvent ethanol and a water phase) in a 100 mL distillation flask at the conditions of
    48.5°C and 90 r/min. Then ethyl acetate was added to the flask and the flask was shaken in an ultrasonic shaker for 6 min. After dissolution, an obtained solution was taken out and filtered through an organic filter (for separating ethyl acetate insoluble products). A filtrate obtained by the filtering treatment was placed in a distillation flask, and an ethylacetate soluble liquid phase was evaporated to dryness at the conditions of 32.5°C and 100 r/min to obtain the 4-(3-hydroxyphenyl)-4-oxobutanoic acid.
    According to calculations, in the present embodiment, the lignin conversion rate exceeds 92%, the selectivity of the monomer 4-(3-hydroxyphenyl)-4-oxobutanoic acid exceeds 36%, and the yield exceeds 6%.
    It should be understood that the examples and embodiments described herein are for illustration only and are not intended to limit the present invention. Those skilled in the art can make various modifications or variations according to the present invention, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
    权利要求:
    Claims (10)
    [1]
    A method for preparing 4- (3-hydroxyphenyl) -4-oxobutanoic acid from lignin, comprising the following steps: adding lignin and a catalyst to ethanol; then performing a depolymerization reaction under supercritical ethanol, and after the reaction performing rapid cooling to obtain 4- (3-hydroxyphenyl) -4-oxobutanoic acid, the catalyst comprising sepiolite as a carrier, and molybdenum and boron as active components on the sepiolite.
    [2]
    The process according to claim 1, wherein in the catalyst the proportion of molybdenum is 5 - 20 weight percent, the proportion of boron is 1 - 10 weight percent and the remainder is the sepiolite.
    [3]
    The method of claim 1 or 2, wherein a feed mass ratio of the lignin to the catalyst and to the ethanol (0.8-1.2): (0.3-0.7): (28-32).
    [4]
    The method of claim 1 or 2, wherein the reaction conditions of the depolymerization reaction are 270-310 ° C, 0.4-0.6MPa high purity nitrogen and a reaction time of the depolymerization reaction is 1-8 hours.
    [5]
    The method of claim 1 or 2, wherein the rapid cooling is achieved by liquid nitrogen or an ice water bath.
    [6]
    The method of claim 1 or 2, wherein the method further comprises an extraction step of 4-G3-hydroxyphenyl) -4-oxobutanoic acid, and an operational embodiment of the extraction step is: performing solid-liquid separation on a reaction product subject to rapid cooling, then performing rotary evaporation on a separated liquid phase product to remove the ethanol and an aqueous phase, then adding a purification solvent; after dissolving, performing filtration, and finally evaporating a soluble liquid phase from a filtrate obtained by filtration to dryness to obtain 4- (3-hydroxyphenyl) -4-oxobutanoic acid.
    [7]
    The method of claim 6, wherein a temperature condition of the rotary evaporation is 39.5 - 49.5 ° C and a rotation speed is 90 - 120 rpm.
    [8]
    The method of claim 6, wherein the purification solvent is ethyl acetate.
    [9]
    The method of claim 6, wherein a temperature condition during evaporation to dryness is 32.5 - 39.5 ° C.
    [10]
    The method of claim 6, wherein a filter used in the filtration is an organic filter, having good water test performance, acid resistance, leaching resistance and oxidation resistance. -0-0-0-0-0-
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    引用文献:
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    US5959167A|1997-08-25|1999-09-28|The University Of Utah Research Foundation|Process for conversion of lignin to reformulated hydrocarbon gasoline|
    CN104888787B|2015-06-10|2017-06-23|南京工业大学|A kind of Catalytic lignin depolymerization is catalyst of compound fragrant hydrocarbon and preparation method and application|
    CN107602362A|2017-09-04|2018-01-19|北京林业大学|The method that molybdenum oxide catalyst Catalytic lignin prepares single phenols aromatic compound|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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