CN116283542A - Method for preparing small molecular organic carboxylic acid such as acetic acid based on selective catalytic oxidation method refined wood vinegar - Google Patents

Method for preparing small molecular organic carboxylic acid such as acetic acid based on selective catalytic oxidation method refined wood vinegar Download PDF

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CN116283542A
CN116283542A CN202211091874.3A CN202211091874A CN116283542A CN 116283542 A CN116283542 A CN 116283542A CN 202211091874 A CN202211091874 A CN 202211091874A CN 116283542 A CN116283542 A CN 116283542A
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acetic acid
wood vinegar
organic carboxylic
catalyst
molecular organic
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宋朝霞
谢普凯提·买买提
王洋
许英梅
朱骏
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Dalian Minzu University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/02—Formic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/08—Acetic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/122—Propionic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/06—Oxalic acid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for preparing small molecular organic carboxylic acids such as acetic acid based on refined pyroligneous liquor by a selective catalytic oxidation method, belonging to the field of effective utilization of low-value and waste biomass resources. Mixing wood vinegar with catalyst, introducing O into the mixed liquid 3 /O 2 And (3) mixing the gases, and reacting for 60-240 min to obtain a small molecular organic carboxylic acid solution containing acetic acid. The method of the invention improves the yield of acetic acid, and has the advantages of simple process, high product yield, low cost, high comprehensive utilization rate and environmental protectionIs suitable for large-scale industrial production.

Description

Method for preparing small molecular organic carboxylic acid such as acetic acid based on selective catalytic oxidation method refined wood vinegar
Technical Field
The invention belongs to the field of effective utilization of low-value and waste biomass resources, and particularly relates to a method for preparing small-molecule organic carboxylic acids such as acetic acid by refining pyroligneous liquor based on a selective catalytic oxidation method.
Background
The wood vinegar is dark brown to brown acidic liquid obtained by condensing and separating pyrolysis smoke of agriculture and forestry biomass (waste wood chips, straws and the like). The main component of the wood vinegar is water, and also contains more than 200 organic matters such as organic acids, alcohols, phenols, aldehydes, ketones, esters and the like, wherein the acetic acid content is the largest, and the acetic acid content can reach about 10 percent. Because the wood vinegar has very complex components, especially contains biologically difficult degradation substances such as phenols, aldehydes and the like which are biologically toxic, if the wood vinegar is discharged at will, the wood vinegar has a threat to human health and ecological systems. In fact, wood vinegar is a precious biomass resource, and can be used as a bacteriostatic agent, an insecticide, an antioxidant, a plant growth regulator and the like to be applied to the fields of medicines, foods, pesticides and the like after being processed. When people process and utilize the pyroligneous liquor, the effective chemical components in the pyroligneous liquor are complex and are not easy to separate. Typical separation methods are distillation (CN 103788928A; wang, Z., lin, W., song, W., yao, J.,2010.Preliminary investigation on concentrating of acetol from wood vinegar.Energy Convers.Manag 51,346-349); extraction methods (CN 107338025; li, z, zhang, l, chen, g, wu, l, liu, b, li, y, sun, s, 2018b.A new method for comprehensive utilization of wood vinegar by distillation and liquid-liquid extraction, process biochem.75,194-201; ma, c, song, k, yu, j, yang, l, zhao, c, wang, w, zu, g, zu, y, 2013.Pyrolysis process and antioxidant activity of pyroligneous acid from Rosmarinus officinalis leaves.J.Anal.Appl.Pyrolysis 104,38-47; ma, x, wei, q, zhang, s, shi, l, zhao, z, 2011.Isolation and bioactivities of organic acids and phenols from walnut shell pyroligneous acid.J.Anal.Appl.Pyrolysis 91,338-343); activated carbon adsorption (CN 1657586A) and membrane filtration (Teella, A., huber, G.W., ford, D.M.,2011.Separation of acetic acid from the aqueous fraction of fast pyrolysis bio-oils using nanofiltration and reverse osmosis membranes J.membrane Sci.378, 495-502), and the like. These methods are physical methods, and some high-value chemical substances can be separated and extracted. However, the methods have the defects of complicated operation, high cost, low efficiency and the like, so that the utilization rate of the pyroligneous liquor is reduced, and the large-scale production is not easy to realize. Acetic acid is a very important large-scale chemical raw material, and as the main organic component in the wood vinegar is acetic acid, the content of the other 200 organic components is low, and the separation and purification are difficult.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for preparing small-molecule organic carboxylic acids such as acetic acid by refining pyroligneous liquor based on a selective catalytic oxidation method. The method disclosed by the invention is simple in process, high in product yield, low in cost, high in comprehensive utilization rate, green and environment-friendly, and suitable for large-scale industrial production.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a process for preparing small-molecular organic carboxylic acid (acetic acid) from wood vinegar by selective catalytic oxidization method includes such steps as mixing wood vinegar with catalyst, introducing O to the mixture 3 /O 2 Mixing the gases, and reacting for 60-240 min to obtain a small molecular organic carboxylic acid solution containing acetic acid;
the catalyst comprises at least one of ZSM-5 and TS-1.
Further, in the above technical scheme, the ratio of the wood vinegar to the catalyst is 250-500mL:1-5g.
Further, in the technical scheme, the silicon-aluminum ratio of the ZSM-5 is 50-600.
Further, in the above technical solution, O 3 /O 2 O in the mixed gas 3 The concentration of (C) is 90-110mg/L.
Further, in the above technical solution, O 3 /O 2 The gas flow rate of the mixed gas is 150-350mL/min.
Further, in the technical scheme, the content of acetic acid in the small molecule organic carboxylic acid solution is 7-15 wt%.
Ozone is a strong oxidizing agent that selectively attacks electron-rich functional groups (e.g., double bonds, aromatic rings) to break down the polycyclic aromatic hydrocarbon, heterocyclic compounds, and long chain molecular moieties to produce small molecular species. Acetic acid is inert under pure ozone conditions (reaction rate coefficient of about 10 -5 M -1 s -1 ) Even under catalytic ozonation conditions, acetic acid is one of the major intermediates in the oxidation of numerous macromolecular organic species, further oxidation of which is a reaction limiting step. Therefore, the invention can selectively catalyze and oxidize macromolecular organic matters in the wood vinegar liquid to be converted into acetic acid at normal temperature and normal pressure. The selectivity contains two aspects, namely, the reactant has selectivity, namely, macromolecular organic matters in the wood vinegar raw material are oxidized, and acetic acid is limited in oxidation; and secondly, the product has selectivity, namely, macromolecular organic matters are converted into micromolecular organic carboxylic acids such as acetic acid and the like, and are not completely oxidized into carbon dioxide and water.
Advantageous effects of the invention
The invention has the advantages that the simple ozone oxidation is mainly direct oxidation under the acidic condition, and has selectivity, so that the acetic acid in the wood vinegar is not easy to oxidize, and the wood vinegar is kept relatively stable. The MFI type molecular sieve is used as a catalyst, so that the effective combination of adsorption and catalysis can be realized; the catalyst has a pore structure and a larger specific surface area, so the catalyst has catalytic active centers and moderate adsorption performance, is beneficial to the full contact and reaction of macromolecular organic matters such as phenols and the like in wood vinegar liquid and the active centers of the catalyst with ozone, improves the ozone utilization efficiency, and shortens the oxidative degradation reaction time. Meanwhile, as macromolecular organic matters in the pyroligneous liquor are selectively oxidized, degraded and converted into micromolecular organic acids such as acetic acid, the yield of the acetic acid is improved. The method has the advantages of simple process, high product yield, low cost, high comprehensive utilization rate, environmental protection and suitability for large-scale industrial production.
Drawings
FIG. 1 is a schematic diagram of a catalytic ozonation reaction apparatus.
FIG. 2 is a graph showing color change of pyroligneous liquor of example 1 at different catalytic ozonation reaction times. In the figure, the numbers 1 to 7 indicate the reaction times of 0min, 10min, 30min, 60min, 120min, 180min and 240min, respectively.
FIG. 3 is a full view of the UV-visible scans of example 1 for different catalytic ozonation reaction times.
FIG. 4 is a TIC diagram of the organic phase of the wood vinegar as a raw material in example 1. In the figure, the substances represented by the numbers 1 to 6 are acetic acid, 1-hydroxy-2-butanone, 3-buten-2-ol, 2,3, 6-trimethylphenol, guaiacol, and 2, 6-dimethoxyphenol, respectively.
FIG. 5 is a TIC diagram of the organic phase extracted after 240min of catalytic ozonation of pyroligneous liquor of example 1. The substances represented by the numbers 1 to 4 in the figure are acetic acid, 1-hydroxy-2-butanone, 2,3, 6-trimethylphenol, and guaiacol, respectively.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Specific examples 1 to 5 used apple branch wood vinegar as a raw material, the stock solution contained 76.6wt% of water, 9.8wt% of acetic acid, and 13.6wt% of other organic matters.
As shown in FIG. 1, a catalytic ozonation reaction apparatus is shown. Comprises an ozone generator, a reactor and an absorber which are connected in sequence. The main structure of the reactor is a sealed reaction tube, and a quartz sand aeration disc is arranged at the bottom of the reaction tube. The bottom of the reaction tube is connected with an ozone generator, the top of the reaction tube is connected with an absorber, and wood vinegar and a catalyst are added into the reaction tube. The bottom of the reaction tube is provided with a sampling port. The absorber is filled with KI solution. The gas conveyed to the reactor by the ozone generator is mixed gas of ozone and oxygen, and parameters such as the proportion of the ozone, the flow rate of the mixed gas and the like can be set according to experimental requirements.
Example 1
To 250mL of apple branch wood vinegar was added 1g of ZSM-5 (SiO 2 /Al 2 O 3 =300) catalyst, which was stirred well at room temperature to reach adsorption equilibrium and charged into the reaction tube. Then introducing mixed gas of ozone and oxygen, wherein the flow rate of the mixed gas is 250mL/min, the ozone concentration is 100mg/L, and the mixed gas passes throughThe quartz sand aeration disc at the bottom of the reactor continuously bubbles into the wood vinegar.
5ml were sampled at given time intervals (10-240 min) of the reaction, and the samples were then separated with a centrifuge. FIG. 2 is a graph of the color change of pyroligneous liquor over time in a catalytic ozonation degradation reaction of example 1. Wherein, the No. 1 is not treated by ozone, and the No. 2-7 is treated by ozone for 10min, 30min, 60min, 120min, 180min and 240min respectively, and the wood vinegar is obviously light after catalyzing the ozone oxidation for 120min, is changed from dark brown to light yellow and is almost colorless after 240min.
The supernatant was diluted and analyzed by an ultraviolet-visible spectrophotometer, and the results are shown in FIG. 3. The organic matter containing conjugated double bond or benzene ring has obvious absorption or characteristic peak in ultraviolet region, and the absorbance value is obviously reduced in the region along with continuous ozone introduction, which indicates that the macromolecular organic matter containing conjugated double bond or benzene ring is degraded. By variation of Colour Number (CN/CN) 0 ) Evaluating the degree of discoloration, wherein CN 0 The color value of the wood vinegar stock solution is CN, and the color value of the wood vinegar stock solution after catalytic ozone oxidation reaction is CN. The calculation formula is that
CN＝(ABS 2 436 +ABS 2 525 +ABS 2 620 )/(ABS 436 +ABS 525 +ABS 620 )
Wherein ABS n (n=436, 525 and 620) refers to absorbance values at 436, 525 and 620 nm.
(Urea, L., collado, S., oliego, P., dliaz, M.,2017.Wet oxidation of the structural sludge fractions.J.Clean.Prod.168,1163-1170.Https:// doi.org/10.1016/j.jclepro.2017.09.033.) after catalytic ozonation for 240min, CN/CN 0 0.08.
At various time intervals, the supernatant was diluted, filtered through a 0.45 μm filter and analyzed for formic acid, acetic acid, propionic acid and oxalic acid content using an ion chromatograph. After 240min of catalytic ozonation, the contents of formic acid, propionic acid and oxalic acid were 1.7wt%,0.4wt% and 1.1wt%, respectively, while the content of acetic acid was 14.2wt%, which was 1.45 times that of the stock solution of wood vinegar.
The apple branch wood vinegar and the catalytic ozonation post-solution of example 1 were respectively subjected to diethyl ether extraction and GC-MS (gas chromatography-mass spectrometry) analysis of the organic phase. FIGS. 4 and 5 are TIC diagrams of the extracted organic phase after 240min of the raw wood vinegar and catalytic ozonation wood vinegar, respectively. From the graph, when the wood vinegar is subjected to catalytic ozonation for 240min, the macromolecular organic matters are almost removed. And the result of the ion chromatography analysis is combined, so that the catalytic ozonation is used for selectively degrading macromolecular organic matters to be converted into small-molecule carboxylic acids such as acetic acid.
Example 2
To 500mL of apple branch wood vinegar was added 2g of ZSM-5 (SiO 2 /Al 2 O 3 =560) catalyst, which is stirred well at room temperature to reach adsorption equilibrium and filled into reaction tubes. Then introducing mixed gas of ozone and oxygen, wherein the flow rate of the mixed gas is 300mL/min, the ozone concentration is 100mg/L, and the mixed gas is continuously bubbled into pyroligneous liquor through a quartz sand aeration disc at the bottom of the reactor. After 240min of catalytic ozonation, the total content of formic acid, propionic acid and oxalic acid is 3.0wt% and the content of acetic acid is 13.5wt%, which is 1.38 times of the content of acetic acid in the wood vinegar stock solution.
Example 3
To 200mL of apple branch wood vinegar was added 1g of ZSM-5 (SiO 2 /Al 2 O 3 =50) catalyst, which was stirred well at room temperature to reach adsorption equilibrium and charged into the reaction tube. Then introducing mixed gas of ozone and oxygen, wherein the flow rate of the mixed gas is 200mL/min, the ozone concentration is 100mg/L, and the mixed gas is continuously bubbled into pyroligneous liquor through a quartz sand aeration disc at the bottom of the reactor. After 240min of catalytic ozonation, the total content of formic acid, propionic acid and oxalic acid is 3.1wt%, and the content of acetic acid is 13.8wt% which is 1.41 times that of the raw wood vinegar liquid.
Example 4
5g of TS-1 catalyst is added into 500mL of apple branch wood vinegar, and the mixture is fully and uniformly stirred at room temperature to reach adsorption equilibrium and is filled into a reaction tube. Then introducing mixed gas of ozone and oxygen, wherein the flow rate of the mixed gas is 350mL/min, the ozone concentration is 90mg/L, and the mixed gas is continuously bubbled into pyroligneous liquor through a quartz sand aeration disc at the bottom of the reactor. After 240min of catalytic ozonation, the total content of formic acid, propionic acid and oxalic acid is 3.1wt%, and the content of acetic acid is 14.0wt% which is 1.43 times that of the raw wood vinegar liquid.
Example 5 (comparative example)
The operation was substantially the same as in example 1, except that no catalyst was added. After 240min of catalytic ozonation, the total content of formic acid, propionic acid and oxalic acid is 2.8wt% and the content of acetic acid is 12.5wt%, which is 1.28 times that of the raw wood vinegar liquid. CN/CN 0 At 0.25, the discoloration is slower than in the case of catalyst addition.
Specific examples 6 to 10 use oak wood vinegar as a raw material, the stock solution contains 85.6wt% of water, 6.1wt% of acetic acid and 8.3wt% of other organic matters.
Example 6
To 500ml of oak vinegar, 2g of ZSM-5 (SiO 2 /Al 2 O 3 =300) catalyst, which was stirred well at room temperature to reach adsorption equilibrium and charged into the reaction tube. Then introducing mixed gas of ozone and oxygen, wherein the flow rate of the mixed gas is 300mL/min, the ozone concentration is 100mg/L, and the mixed gas is continuously bubbled into pyroligneous liquor through a quartz sand aeration disc at the bottom of the reactor. Along with the extension of ozone introducing time, the color of the wood vinegar is gradually changed from dark brown to light yellow, and the wood vinegar is nearly colorless after 180 min. After 180min of catalytic ozonation, the total content of formic acid, propionic acid and oxalic acid is 2.1wt%, and the content of acetic acid is 8.1wt% which is 1.32 times of the content of acetic acid in the wood vinegar stock solution.
Example 7
To 250ml of oak vinegar, 1g of ZSM-5 (SiO 2 /Al 2 O 3 =560) catalyst, which is stirred well at room temperature to reach adsorption equilibrium and filled into reaction tubes. Then introducing mixed gas of ozone and oxygen, wherein the flow rate of the mixed gas is 200mL/min, the ozone concentration is 100mg/L, and the mixed gas is continuously bubbled into pyroligneous liquor through a quartz sand aeration disc at the bottom of the reactor. After 180min of catalytic ozonation, the total content of formic acid, propionic acid and oxalic acid was 2.0wt%, while acetic acid containedThe amount is 7.8wt% and is 1.28 times of the acetic acid content in the wood vinegar stock solution.
Example 8
To 300ml of oak vinegar, 2g of ZSM-5 (SiO 2 /Al 2 O 3 =50) catalyst, which was stirred well at room temperature to reach adsorption equilibrium and charged into the reaction tube. Then introducing mixed gas of ozone and oxygen, wherein the flow rate of the mixed gas is 150mL/min, the ozone concentration is 110mg/L, and the mixed gas is continuously bubbled into pyroligneous liquor through a quartz sand aeration disc at the bottom of the reactor. After 180min of catalytic ozonation, the total content of formic acid, propionic acid and oxalic acid is 1.9wt%, and the content of acetic acid is 7.7wt% which is 1.26 times of the content of acetic acid in the wood vinegar stock solution.
Example 9
To 250ml of oak vinegar, 1g of TS-1 catalyst was added, and the mixture was stirred well at room temperature to reach adsorption equilibrium and placed in a reaction tube. Then introducing mixed gas of ozone and oxygen, wherein the flow rate of the mixed gas is 250mL/min, the ozone concentration is 100mg/L, and the mixed gas is continuously bubbled into pyroligneous liquor through a quartz sand aeration disc at the bottom of the reactor. After 180min of catalytic ozonation, the total content of formic acid, propionic acid and oxalic acid is 2.0wt% and the content of acetic acid is 7.9wt%, which is 1.3 times of the content of acetic acid in the wood vinegar stock solution.
Example 10 (comparative example)
The operation was substantially the same as in example 6, except that no catalyst was added. After 180min of catalytic ozonation, the total content of formic acid, propionic acid and oxalic acid is 1.7wt%, and the content of acetic acid is 7.1wt% which is 1.16 times that of the acetic acid in the wood vinegar stock solution. CN/CN 0 At 0.20, the discoloration is slower than in the case of catalyst addition.
The analysis results are shown in tables 1 and 2.
It can be seen that the reaction effect of adding molecular sieve catalyst in examples 1-4,6-9, respectively, is significantly better than that of comparative examples 5 and 10 without catalyst. The molecular sieve catalysts promote the reaction of adsorbed organic matters and ozone, and accelerate the rupture of unsaturated bonds (aromatic groups or conjugated double bonds) of chromophoric groups in an organic conjugated system to generate carboxylic acid with small molecular weight such as acetic acid. Meanwhile, the acetic acid in the wood vinegar is not easy to degrade under the acidic condition even in the presence of ozone and a molecular sieve catalyst, so that a higher acetic acid yield is obtained.
TABLE 1
Figure BDA0003837359350000081
TABLE 2
Figure BDA0003837359350000091
The above-described embodiments are provided for illustration and description of the present invention only and are not intended to limit the invention to the embodiments described. In addition, those skilled in the art will appreciate that the present invention is not limited to the embodiments described above, and that many variations and modifications are possible in light of the teachings of the invention, which variations and modifications are within the scope of the invention as claimed.

Claims (6)

1. A process for preparing small-molecular organic carboxylic acid (acetic acid) from wood vinegar by selective catalytic oxidization method includes such steps as mixing wood vinegar with catalyst, introducing O to the mixture 3 /O 2 Mixing the gases, and reacting for 60-240 min to obtain a small molecular organic carboxylic acid solution containing acetic acid;
the catalyst comprises at least one of ZSM-5 and TS-1.
2. The method according to claim 1, wherein the ratio of the pyroligneous liquor to the catalyst is 250-500mL:1-5g.
3. The method of claim 1, wherein the ZSM-5 has a silica to alumina ratio of 50 to 600.
4. The method according to claim 1, wherein O 3 /O 2 O in the mixed gas 3 The concentration of (C) is 90-110mg/L.
5. The method according to claim 1, wherein O 3 /O 2 The gas flow rate of the mixed gas is 150-350mL/min.
6. The method of claim 1, wherein the acetic acid content of the small molecule organic carboxylic acid solution is 7wt% to 15wt%.
CN202211091874.3A 2022-09-07 2022-09-07 Method for preparing small molecular organic carboxylic acid such as acetic acid based on selective catalytic oxidation method refined wood vinegar Pending CN116283542A (en)

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