CN107043320B - Method for preparing 4-vinylphenol by catalytic pyrolysis of gramineous biomass - Google Patents
Method for preparing 4-vinylphenol by catalytic pyrolysis of gramineous biomass Download PDFInfo
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- CN107043320B CN107043320B CN201710325263.3A CN201710325263A CN107043320B CN 107043320 B CN107043320 B CN 107043320B CN 201710325263 A CN201710325263 A CN 201710325263A CN 107043320 B CN107043320 B CN 107043320B
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/004—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from plant material or from animal material
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Abstract
The invention belongs to the field of utilization of biomass energy, and particularly relates to a method for preparing 4-vinylphenol by catalytic pyrolysis of gramineous biomass. According to the method, gramineous biomass is used as a raw material, an alkaline catalyst is loaded in a dipping mode, catalytic pyrolysis is carried out at 230-350 ℃ in an inert atmosphere, and a liquid product rich in 4-vinylphenol can be obtained after condensation of pyrolysis gas; the yield of the 4-vinylphenol and the selectivity of the 4-vinylphenol in the organic liquid product are high. The method for preparing the 4-vinylphenol can overcome the defects of low content of the 4-vinylphenol, poor selectivity, high separation and extraction cost and the like in the biological oil obtained by the traditional gramineous biomass pyrolysis liquefaction technology, and has good application prospect.
Description
Technical Field
The invention belongs to the field of utilization of biomass energy, and particularly relates to a method for preparing 4-vinylphenol by catalytic pyrolysis of gramineous biomass.
Background
4-vinylphenol is a colorless crystal with phenol-like chemical and pharmaceutical smell, has mildew and meat fragrance, has sweet fragrance and fragrance of vanilla bean extract when diluted, and is widely used in the industries of synthetic resins, printing inks, synthetic rubbers, essence formulations, petroleum processing, medicines and the like.
Chinese patent application No. 200610042200.9 discloses a preparation method of 4-vinylphenol, which takes p-hydroxybenzaldehyde and malonic acid as raw materials to react in an alkaline catalyst and an aprotic polar organic solvent to obtain 4-vinylphenol; the method has high requirements on reaction conditions and reaction equipment, long reaction period and high production cost.
In addition, chinese patent application No. 201110134872.3 reports a method for preparing 4-vinylphenol from biomass, and although this technique is a method for preparing 4-vinylphenol by pyrolyzing biomass, the pyrolysis reaction time is long, the temperature rise rate is low, and it has a certain inhibition effect on the generation of 4-vinylphenol, so that the yield of 4-vinylphenol in the organic liquid product obtained by this method is low; meanwhile, effective inhibition measures are not taken for the generation of other pyrolysis products except for the 4-vinylphenol in the pyrolysis process, so that the purity of the 4-vinylphenol in a liquid product is lower, and the difficulty and the cost of separation and purification of the 4-vinylphenol are greatly improved.
Therefore, it is a need to provide a novel method for preparing 4-vinylphenol from biomass, which can realize the production of 4-vinylphenol with environmental protection, low cost and high efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing phenol by catalytic pyrolysis of gramineous biomass.
According to the method provided by the invention, gramineous biomass is taken as a raw material, an alkaline catalyst is loaded in a dipping mode, then catalytic pyrolysis reaction is carried out at 230-350 ℃ in an inert atmosphere, pyrolysis gas is collected, and a liquid product rich in 4-vinylphenol is obtained after condensation, and the method comprises the following specific steps:
Crushing a gramineous biomass raw material to a particle size of below 1mm, soaking in an alkaline catalyst solution with the concentration of 0.5-30 wt% for 1-60 min, filtering, drying at 105 ℃ to remove free moisture, and controlling the loading amount of the alkaline catalyst in the raw material to be 0.2-15 wt%; placing the pretreated gramineous biomass material in a pyrolysis reactor, and carrying out pyrolysis reaction at 230-350 ℃ in an inert atmosphere, wherein the heating rate of the pyrolysis reaction is higher than 100 ℃/s, and the pyrolysis reaction time is not more than 50 s; and condensing the pyrolysis gas to obtain a liquid product rich in 4-vinylphenol.
The alkaline catalyst at least comprises any one of calcium hydroxide, sodium hydroxide, potassium hydroxide or sodium carbonate.
The gramineous biomass comprises at least one of bagasse, corn stalks, bamboo, cotton stalks or rice hulls.
And the inert atmosphere is formed by introducing inert oxygen-free protective gas into a reaction system, wherein the inert oxygen-free protective gas is any one of nitrogen, helium or argon.
The invention has the beneficial effects that:
During the rapid pyrolysis process of specific gramineous biomass (bagasse, corn stalk, bamboo wood, cotton stalk or rice hull), lignin and p-coumaric acid connected with the lignin through ester bonds can generate a plurality of phenolic derivatives, and 4-vinylphenol is an important product. However, the conventional pyrolysis of gramineous biomass has poor selectivity and the content of 4-vinylphenol in the product is low, which makes the separation and purification of 4-vinylphenol based on the conventional pyrolysis liquid product difficult or even impossible. In order to obtain high-yield and high-purity 4-vinylphenol, a proper mode is adopted to regulate and control the pyrolysis reaction process of gramineous biomass, promote a reaction path for generating the 4-vinylphenol and inhibit reaction paths of other organic liquid products, so that the 4-vinylphenol can be prepared at high selectivity.
The invention adopts alkaline catalyst to carry out catalytic pyrolysis on gramineous biomass in inert atmosphere to prepare a liquid product rich in 4-vinylphenol. The used alkaline catalyst can effectively destroy the structure of the biomass cell wall, promote the generation of phenol products and inhibit the pyrolysis reaction of the holocellulose, and has the advantages of common availability and low cost. In the pyrolysis process of biomass of special gramineous plants, lignin containing a structural unit of p-hydroxyphenyl and p-coumaric acid connected with lignin in an ester bond react to form 4-vinylphenol through bond breaking, decarboxylation and the like. After the alkaline catalyst is added, the structure of the cell wall is destroyed, and the precursor of free 4-vinylphenol such as p-coumaric acid and the like is easier to obtain, so that the reaction energy barrier for generating the 4-vinylphenol by pyrolysis is reduced, the 4-vinylphenol is easier to generate, and meanwhile, the pyrolysis reaction of the holocellulose is inhibited by the existence of the alkaline catalyst, so that the selectivity of the 4-vinylphenol is improved.
In addition, the pyrolysis temperature is controlled to be 230-350 ℃, and the pyrolysis reaction temperature required by the gramineous biomass can be effectively reduced after the alkaline catalyst is added. The lower pyrolysis reaction temperature is adopted, on one hand, the pyrolysis products are less, and the selectivity of the 4-vinylphenol is improved; on the other hand, the requirements on equipment and reaction conditions are lower, the production cost is favorably reduced, and the subsequent separation and purification of the 4-vinylphenol are simpler because the purity of the 4-vinylphenol in the liquid product is very high.
Detailed Description
The invention provides a method for preparing 4-vinylphenol by catalytic pyrolysis of gramineous biomass, which is further described by combining a specific embodiment.
The percentages in the following examples are by mass unless otherwise specified.
Example 1
Bagasse (with particle size of 0.1-0.3mm) as Gramineae biomass raw material, soaking in 1.5% calcium hydroxide water solution for 10min, filtering, drying at 110 deg.C for 5 hr as experimental raw material, and loading amount of calcium hydroxide is 0.9%.
Respectively pyrolyzing the experimental raw materials (pretreated bagasse) and the original bagasse (non-pretreated bagasse) by using a pyrolysis reaction device at 250 ℃ and the heating rate of more than 800 ℃/s for 35s under a nitrogen atmosphere to obtain liquid products with the yields of 33.5% and 22.9%, wherein the yields of 4-vinylphenol are calculated to be 6.7% and 2.1% and the yield is improved by 219.0% by analyzing the content of 4-vinylphenol in the liquid products through gas chromatography; the content of 4-vinylphenol in the organic liquid product (containing no water) was 38.9% and 30.4%, increasing the selectivity by 28.0%.
Example 2
Bagasse (with particle size of 0.1-0.3mm) as Gramineae biomass raw material, soaking in 2.0% calcium hydroxide water solution for 10min, filtering, drying at 110 deg.C for 10 hr as experimental raw material, and loading calcium hydroxide amount is 1.2%.
Respectively pyrolyzing the experimental raw material (pretreated bagasse) and the original bagasse (non-pretreated bagasse) by using a pyrolysis reaction device at 270 ℃ and a heating rate of more than 1000 ℃/s for 40s under a nitrogen atmosphere to obtain liquid products with yields of 36.7% and 34.6%, wherein the yields of 4-vinylphenol are calculated to be 6.5% and 5.6% and are improved by 16.1% by analyzing the content of 4-vinylphenol in the liquid products through gas chromatography; the content of 4-vinylphenol in the organic liquid product (containing no water) was 33.4% and 29.7%, increasing the selectivity by 12.5%.
Example 3
Bagasse (with particle size of 0.1-0.3mm) as Gramineae biomass raw material, soaking in 6.0% calcium hydroxide water solution for 10min, filtering, drying at 110 deg.C for 5 hr as experimental raw material, and loading calcium hydroxide 4.2%.
Respectively pyrolyzing the experimental raw materials (pretreated bagasse) and the original bagasse (non-pretreated bagasse) by a pyrolysis reaction device at 290 ℃ and at a heating rate of more than 800 ℃/s for 30s in a nitrogen atmosphere to obtain liquid products with yields of 38.1% and 35.8%, wherein the yields of 4-vinylphenol are calculated to be 6.1% and 5.4% and the yield is improved by 13.0% by analyzing the content of 4-vinylphenol in the liquid products through gas chromatography; the content of 4-vinylphenol in the organic liquid product (containing no water) was 29.4% and 27.2%, increasing the selectivity by 8.1%.
Example 4
Using cornstalks (with the grain diameter of 0.1-0.3mm) as a gramineae biomass raw material, soaking the cornstalks in a sodium hydroxide aqueous solution with the concentration of 1.0% for 2min, filtering, and then drying the soaked raw material at 110 ℃ for 5h as an experimental raw material, wherein the loading capacity of sodium hydroxide is 0.6%.
Respectively pyrolyzing the experimental raw material (pretreated cornstalks) and the original cornstalks (not pretreated cornstalks) by adopting a pyrolysis reaction device at 280 ℃ and a heating rate of more than 1000 ℃/s for 35s in a nitrogen atmosphere to obtain liquid products with the yield of 37.9% and 35.5%, analyzing the content of 4-vinylphenol in the liquid products by using gas chromatography, calculating that the yield of 4-vinylphenol is 5.1% and 4.5%, and improving the yield by 13.3%; the content of 4-vinylphenol in the organic liquid product (containing no water) was 27.4% and 24.4%, increasing the selectivity by 12.3%.
Example 5
Using cornstalks (with the grain diameter of 0.1-0.3mm) as a gramineae biomass raw material, soaking the cornstalks in a sodium hydroxide aqueous solution with the concentration of 8.0% for 5min, filtering the soaked raw material, and drying the soaked raw material at 110 ℃ for 5h to serve as an experimental raw material, wherein the loading capacity of sodium hydroxide is 5.3%.
Respectively pyrolyzing the experimental raw materials (pretreated cornstalks) and the original cornstalks (not pretreated cornstalks) by a pyrolysis reaction device at the temperature of 300 ℃ and the heating rate of more than 500 ℃/s for 25s in a nitrogen atmosphere to obtain liquid products with the yield of 38.8% and 37.9%, analyzing the content of 4-vinylphenol in the liquid products by gas chromatography to calculate that the yield of 4-vinylphenol is 4.8% and 4.4%, and the yield is improved by 9.1%; the content of 4-vinylphenol in the organic liquid product (containing no water) was 24.7% and 22.1%, increasing the selectivity by 11.8%.
Example 6
Soaking rice hull (particle size of 0.1-0.3mm) as Gramineae biomass raw material in 2.0% sodium carbonate water solution for 10min, filtering, and drying at 110 deg.C for 5 hr as experiment raw material with sodium carbonate loading of 1.2%.
Respectively pyrolyzing the experimental raw material (pretreated rice hull) and the original rice hull (non-pretreated rice hull) by adopting a pyrolysis reaction device at 270 ℃, at a heating rate of more than 100 ℃/s for 30s in a nitrogen atmosphere to obtain liquid products with the yield of 35.8% and 34.2%, analyzing the content of 4-vinylphenol in the liquid products by using gas chromatography, calculating that the yield of 4-vinylphenol is 3.3% and 3.1%, and improving the yield by 6.5%; the content of 4-vinylphenol in the organic liquid product (containing no water) was 19.6% and 18.5%, increasing the selectivity by 5.9%.
Example 7
Taking a mixture of bagasse, bamboo and cotton stalks (with the particle size of 0.1-0.3mm) as a gramineae biomass raw material, wherein the ratio of the bagasse to the bamboo to the cotton stalks is 1: 1: 1, soaking in 3.0 percent calcium hydroxide aqueous solution for 5min, filtering, and drying the soaked raw material at 110 ℃ for 5h to obtain an experimental raw material, wherein the loading amount of calcium hydroxide is 1.8 percent.
Respectively pyrolyzing the experimental raw materials (pretreated mixture) and the original mixture (untreated bagasse, bamboo wood and cotton stalks) by a pyrolysis reaction device at 280 ℃ and a heating rate of more than 800 ℃/s for 35s in a nitrogen atmosphere to obtain liquid products with the yields of 37.1% and 35.7%, wherein the yields of 4-vinylphenol are calculated to be 5.6% and 4.9% and are improved by 14.3% by analyzing the content of 4-vinylphenol in the liquid products by gas chromatography; the content of 4-vinylphenol in the organic liquid product (containing no water) was 28.4% and 24.8%, increasing the selectivity by 14.5%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (3)
1. The method for preparing 4-vinylphenol by catalytic pyrolysis of gramineous biomass is characterized in that gramineous biomass is used as a raw material, the gramineous biomass comprises at least one of bagasse, corn stalks, bamboo wood, cotton stalks or rice hulls, the raw material is crushed to the particle size of less than 1mm, the raw material is soaked in an alkaline catalyst solution with the concentration of 0.5-30 wt% for 1-60 min and then filtered, and the raw material is dried at the temperature of 100-110 ℃ to remove free moisture, and the loading capacity of the alkaline catalyst in the raw material is controlled to be 0.2-15 wt%; placing the pretreated raw materials into a pyrolysis reactor, and carrying out pyrolysis reaction at 230-350 ℃ in an inert atmosphere, wherein the heating rate of the pyrolysis reaction is higher than 100 ℃/s, and the pyrolysis reaction time is not more than 50 s; condensing the pyrolysis gas to obtain the liquid product rich in 4-vinylphenol.
2. The method for preparing 4-vinylphenol according to claim 1, wherein the alkaline catalyst comprises at least one of calcium hydroxide, sodium hydroxide, potassium hydroxide or sodium carbonate.
3. The method for preparing 4-vinylphenol according to claim 1, wherein the inert atmosphere is inert oxygen-free shielding gas introduced into the reaction system, and the inert oxygen-free shielding gas is any one of nitrogen, helium or argon.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249864A (en) * | 2011-05-23 | 2011-11-23 | 中国科学技术大学 | Preparation method of 4-vinylphenol |
| CN102838453A (en) * | 2012-08-28 | 2012-12-26 | 华北电力大学 | Method to prepare phenolic organic mixture preparation by means of catalytic pyrolysis of biomass through coke |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249864A (en) * | 2011-05-23 | 2011-11-23 | 中国科学技术大学 | Preparation method of 4-vinylphenol |
| CN102838453A (en) * | 2012-08-28 | 2012-12-26 | 华北电力大学 | Method to prepare phenolic organic mixture preparation by means of catalytic pyrolysis of biomass through coke |
Non-Patent Citations (3)
| Title |
|---|
| Fast pyrolysis product distribution of biopretreated corn stalk by methanogen;Tipeng Wang等;《Bioresource Technology》;20140727;第169卷;第812-815页 * |
| Yan-Chao Qu等.Selective Production of 4‑Vinylphenol by Fast Pyrolysis of Herbaceous Biomass.《Ind. Eng. Chem. Res.》.2013,第52卷 * |
| 禾本科生物质选择性热解制备4-乙烯基苯酚的研究;叶小宁;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20160215(第02期);全文 * |
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