CN104341273A - Method for preparing 4-ethylphenol by performing catalytic pyrolysis on biomass - Google Patents
Method for preparing 4-ethylphenol by performing catalytic pyrolysis on biomass Download PDFInfo
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- CN104341273A CN104341273A CN201410558325.1A CN201410558325A CN104341273A CN 104341273 A CN104341273 A CN 104341273A CN 201410558325 A CN201410558325 A CN 201410558325A CN 104341273 A CN104341273 A CN 104341273A
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- ethylphenol
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
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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-ethylphenol by performing catalytic pyrolysis on biomass by using a palladium catalyst. The method comprises the following steps: mechanically mixing biomass and a palladium catalyst at 250-380 DEG C under oxygen-free conditions to perform flash pyrolysis, and condensing the pyrolytic gas to obtain a liquid product containing rich 4-thylphenol; and carrying out simple separation purification on the liquid product to obtain the higher-purity 4-ethylphenol. Besides, by using the low-price wide-source biomass as the raw material, the method can obviously lower the production cost of the 4-ethylphenol.
Description
Technical field
What the invention belongs to biomass energy utilizes field, is specifically related to a kind of palladium series catalyst catalyse pyrolysis biomass-making that utilizes for the method for 4-ethylphenol.
Background technology
4-ethylphenol, call p-ethyl phenol, to ethyl phenol or to diethylstilbestrol, there is following structure:
4-ethylphenol is widely used in producing the important source material such as resol, rubber anti-ageing agent, tensio-active agent, and itself is important pesticide intermediate, can be used as a series of top grade of raw material production, low toxicity, less-persistent pesticide.At present, the method preparing 4-ethylphenol mainly comprises natural partition method, ethylbenzene hydrolysis method, alkylation of phenol method etc.Wherein alkylation of phenol method is the most general preparation method, such as Chinese Patent Application No. 201010123979.3 discloses a kind of preparation method of 4-ethylphenol, with diethyl carbonate and phenol for raw material, with modified micropore molecular sieve MCM-22, ZSM-5 or HY for catalyzer, react in ethanol and water mixed solvent, obtain 4-ethylphenol.Although mild condition selectivity of product is high, costly, economy is difficult to ensure the price of its raw material (diethyl carbonate and phenol).
As unique renewable resources containing phenyl ring, the potential alternative fossil resource of biomass prepares phenolic compound as raw material.In biomass pyrolysis process, xylogen decomposition wherein can be formed more than 100 kinds of phenolic product, and this does not wherein have definitely main product.4-ethylphenol general being only present in pyrolysis liquids as wherein a kind of product of minute quantity (even can't detect 4-ethylphenol) in some pyrolysis liquids, and this makes from pyrolysis liquids, be directly separated the extremely difficult realization of 4-ethylphenol.In order to obtain the higher 4-ethylphenol of purity, the selectivity of pyrolytic process to 4-ethylphenol must be improved.Efficient manner introduces suitable catalyzer the most, suppresses Mierocrystalline cellulose and hemicellulose pyrolysis to form volatility organic product on the one hand, promotes that xylogen pyrolysis forms 4-ethylphenol and suppresses xylogen pyrolysis to form other phenolic product simultaneously on the other hand.Although more existing patents (such as, Chinese patent grant number: CN102070408B; Chinese Patent Application No. 201210310261.4) report in biomass pyrolysis process and promote xylogen cracking, thus the main method obtaining phenolic product.But the product liquid obtained is the mixture of organic phenols, and 4-ethylphenol is not primary product wherein, all have similar structure due to aldehydes matter thus cause boiling point close, therefore from this phenol mixture, separating-purifying 4-ethylphenol is still extremely difficult realizes.Therefore, still need to develop further the high efficiency method that catalytic pyrolysis of biomass selectivity prepares 4-ethylphenol at present, can directly obtain the product liquid being rich in 4-ethylphenol by the method.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of palladium series catalyst catalyse pyrolysis biomass-making that utilizes for the method for 4-ethylphenol.
According to method provided by the invention, take biomass as raw material, be that mechanically mixing is carried out in (10: 1) ~ (1: 3) by biomass and palladium series catalyst according to mass ratio, then carry out fast pyrogenation in 250 ~ 380 DEG C under anaerobic, after condensation is carried out to pyrolysis gas, the product liquid being rich in 4-ethylphenol can be obtained.
Preferably, described biomass material is Gramineae biomass.
Preferably, described palladium series catalyst comprises carrier and the metallic palladium of load on carrier, and its concrete preparation method is as follows:
First the Palladous nitrate taking certain mass is dissolved in deionized water, until completely dissolved, a certain amount of support of the catalyst is added in solution, slowly ammoniacal liquor is instilled under the condition stirred, until pH value reaches 9 ~ 10, filter after continuing at room temperature to stir 12h, filter cake is dry at 100 DEG C, finally the solid obtained after drying is reduced under the hydrogen atmosphere keeping certain reduction temperature, obtain the solid catalyst of supported palladium.
Preferred, described support of the catalyst is the arbitrary combination of a kind of or above-mentioned substance in silicon oxide, aluminum oxide, titanium oxide, zirconium white, diatomite, kaolin, porous molecular screen, gac.
Preferred, the mass percent of the metallic palladium of described load on carrier is 0.5% ~ 10%.
Preferred, described drying is that loft drier is dry, and time of drying is 4 ~ 24h.
Preferred, described hydrogen atmosphere is the gas mixture of pure hydrogen or hydrogen and rare gas element.
Preferred, described reduction temperature is 260 ~ 300 DEG C, and soaking time is 2 ~ 4h.
Preferably, under described oxygen free condition refers to that reaction system maintains inertia anaerobic shielding gas environment.
Preferably, the temperature rise rate of described pyrolytic reaction is not less than 100 DEG C/s.
Preferably, the time of described pyrolytic reaction is no more than 60s.
Beneficial effect of the present invention is:
Palladium series catalyst used in the present invention, significantly can promote the formation of 4-ethylphenol in Gramineae biomass pyrolysis process, suppresses Mierocrystalline cellulose, hemicellulose pyrolysis formation volatility organic product simultaneously, and suppresses xylogen pyrolysis to form other phenolic product.Therefore the product liquid composition obtained is comparatively simple, and the purity of 4-ethylphenol is higher, makes its follow-up separating-purifying comparatively easy.In addition, pyrolysis temperature controls at 250 ~ 380 DEG C by the present invention, and under lower pyrolysis temperature, pyrolysis product is less, is beneficial to and controls product composition, improve the selectivity of 4-ethylphenol.Because temperature of reaction is lower, lower to the requirement of equipment and reaction conditions, be beneficial to reduction production cost.
Embodiment
The invention provides a kind of palladium series catalyst catalyse pyrolysis biomass-making that utilizes for the method for 4-ethylphenol, below in conjunction with embodiment, the present invention will be further described.
Percentage composition in following embodiment is mass percentage if no special instructions.
Embodiment 1
Take the Palladous nitrate dihydrate (Pd (NO of 0.50g
3)
22H
2o) be dissolved in 100mL deionized water, be stirred to after dissolving completely, in solution, add 8.00g MCM-41, under the condition stirred, in mixed solution, slowly instill ammoniacal liquor (25%) reach 10 to pH value, then continue at room temperature to stir 12h.Stirring terminates rear filtering solids, dry 3h at solid being placed in 100 DEG C, reduces 3h (temperature programming is 2 DEG C/min) at being then placed in hydrogen (hydrogen 6%, all the other are protection gas nitrogen) atmosphere 280 DEG C.Obtain the Pd/MCM-41 of 8.01g, wherein the charge capacity of Pd is 2%.
Get the above-mentioned catalyzer of 2g, be ground to particle diameter and be less than 0.5mm, getting 10g mao bamboon is raw material, be ground to particle diameter and be less than 0.3mm, will at 280 DEG C, fast pyrogenation 20s under nitrogen atmosphere after both mechanically mixing, the liquid yield 35.8% obtained, by the content of gas chromatographic analysis wherein 4-ethylphenol, calculates and learns that the productive rate of 4-ethylphenol is 1.6%; The content of 4-ethylphenol in organic liquid product (not comprising water) is 10.2%.
Embodiment 2
Catalyzer 5g in Example 1, be ground to particle diameter and be less than 0.5mm, getting 10g bagasse is raw material, be ground to particle diameter and be less than 0.3mm, will at 310 DEG C, fast pyrogenation 15s under nitrogen atmosphere after both mechanically mixing, the liquid yield 39.1% obtained, by the content of gas chromatographic analysis wherein 4-ethylphenol, calculates and learns that the productive rate of 4-ethylphenol is 1.9%; The content of 4-ethylphenol in organic liquid product (not comprising water) is 11.1%.
Embodiment 3
Take the Palladous nitrate dihydrate (Pd (NO of 1.25g
3)
22H
2o) be dissolved in 100mL deionized water, be stirred to after dissolving completely, in solution, add 7.80g SBA-15, under the condition stirred, in mixed solution, slowly instill ammoniacal liquor (25%) reach 9 to pH value, then continue at room temperature to stir 12h.Stirring terminates rear filtering solids, dry 3h at solid being placed in 100 DEG C, reduces 3h (temperature programming is 2 DEG C/min) at being then placed in hydrogen (hydrogen 6%, all the other are protection gas nitrogen) atmosphere 280 DEG C.Obtain the Pd/SBA-15 of 8.05g, wherein the charge capacity of Pd is 5%.
Get the above-mentioned catalyzer of 2g, be ground to particle diameter and be less than 0.5mm, getting 10g mao bamboon is raw material, be ground to particle diameter and be less than 0.3mm, will at 290 DEG C, fast pyrogenation 15s under nitrogen atmosphere after both mechanically mixing, the liquid yield 35.3% obtained, by the content of gas chromatographic analysis wherein 4-ethylphenol, calculates and learns that the productive rate of 4-ethylphenol is 2.2%; The content of 4-ethylphenol in organic liquid product (not comprising water) is 15.2%.
Embodiment 4
Get the catalyzer 5g in above-described embodiment 3, be ground to particle diameter and be less than 0.5mm, getting 10g bagasse is raw material, be ground to particle diameter and be less than 0.3mm, will at 310 DEG C, fast pyrogenation 15s under nitrogen atmosphere after both mechanically mixing, the liquid yield 39.6% obtained, by the content of gas chromatographic analysis wherein 4-ethylphenol, calculates and learns that the productive rate of 4-ethylphenol is 2.5%; The content of 4-ethylphenol in organic liquid product (not comprising water) is 14.5%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within the scope of the present invention.
Claims (10)
1. one kind utilizes palladium series catalyst catalyse pyrolysis biomass-making for the method for 4-ethylphenol, it is characterized in that, take biomass as raw material, be that mechanically mixing is carried out in (10: 1) ~ (1: 3) by biomass and palladium series catalyst according to mass ratio, then carry out fast pyrogenation in 250 ~ 380 DEG C under anaerobic, after condensation is carried out to pyrolysis gas, the product liquid being rich in 4-ethylphenol can be obtained.
2. the palladium series catalyst catalyse pyrolysis biomass-making that utilizes according to claim 1 is for the method for 4-ethylphenol, and it is characterized in that, described biomass material is Gramineae biomass.
3. the palladium series catalyst catalyse pyrolysis biomass-making that utilizes according to claim 1 is for the method for 4-ethylphenol, it is characterized in that, described palladium series catalyst comprises carrier and the metallic palladium of load on carrier, and its concrete preparation method is as follows:
First the Palladous nitrate taking certain mass is dissolved in deionized water, until completely dissolved, a certain amount of support of the catalyst is added in solution, slowly ammoniacal liquor is instilled under the condition stirred, until pH value reaches 9 ~ 10, filter after continuing at room temperature to stir 12h, filter cake is dry at 100 DEG C, finally the solid obtained after drying is reduced under the hydrogen atmosphere keeping certain reduction temperature, obtain the solid catalyst of supported palladium.
4. the palladium series catalyst catalyse pyrolysis biomass-making that utilizes according to claim 3 is for the method for 4-ethylphenol, it is characterized in that, described support of the catalyst is the arbitrary combination of a kind of or above-mentioned substance in silicon oxide, aluminum oxide, titanium oxide, zirconium white, diatomite, kaolin, porous molecular screen, gac.
5. the palladium series catalyst catalyse pyrolysis biomass-making that utilizes according to claim 3 is for the method for 4-ethylphenol, it is characterized in that, the mass percent of described load metallic palladium on carrier is 0.5% ~ 10%.
6. the palladium series catalyst catalyse pyrolysis biomass-making that utilizes according to claim 3 is for the method for 4-ethylphenol, it is characterized in that, described drying is that loft drier is dry, and time of drying is 4 ~ 24h.
7. the palladium series catalyst catalyse pyrolysis biomass-making that utilizes according to claim 3 is for the method for 4-ethylphenol, and it is characterized in that, described hydrogen atmosphere is the gas mixture of pure hydrogen or hydrogen and rare gas element.
8. the palladium series catalyst catalyse pyrolysis biomass-making that utilizes according to claim 3 is for the method for 4-ethylphenol, and it is characterized in that, described reduction temperature is 260 ~ 300 DEG C, and soaking time is 2 ~ 4h.
9. the palladium series catalyst catalyse pyrolysis biomass-making that utilizes according to claim 1 is for the method for 4-ethylphenol, it is characterized in that, under described oxygen free condition refers to that reaction system maintains inertia anaerobic shielding gas environment.
10. the palladium series catalyst catalyse pyrolysis biomass-making that utilizes according to claim 1 is for the method for 4-ethylphenol, and it is characterized in that, the temperature rise rate of described pyrolytic reaction is not less than 100 DEG C/s.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694929A (en) * | 2016-02-25 | 2016-06-22 | 中国科学技术大学 | Bio-oil and preparation method thereof |
| CN106810653A (en) * | 2017-01-23 | 2017-06-09 | 广西科学院 | A kind of method of biorefinery Bagasse Lignin base phenolic resin and its application |
| WO2018161280A1 (en) * | 2017-03-06 | 2018-09-13 | 华北电力大学 | Method for preparing 4-ethylphenol by catalytic pyrolysis of bagasse with activated carbon |
Citations (3)
| 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 |
| US20140107306A1 (en) * | 2012-10-17 | 2014-04-17 | Annellotech, Inc. | Chemical intermediates by catalytic fast pyrolysis process |
| CN103755528A (en) * | 2014-01-16 | 2014-04-30 | 华北电力大学 | Method for preparing phenol through catalytic pyrolysis of biomass |
-
2014
- 2014-10-21 CN CN201410558325.1A patent/CN104341273B/en active Active
Patent Citations (3)
| 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 |
| US20140107306A1 (en) * | 2012-10-17 | 2014-04-17 | Annellotech, Inc. | Chemical intermediates by catalytic fast pyrolysis process |
| CN103755528A (en) * | 2014-01-16 | 2014-04-30 | 华北电力大学 | Method for preparing phenol through catalytic pyrolysis of biomass |
Non-Patent Citations (2)
| Title |
|---|
| QIANG LU 等: "Catalytic upgrading of biomass fast pyrolysis vapor with Pd/SBA-15 catalysts", 《INDUSTRIAL ENGINEERING CHEMISTRY RESEARCH》 * |
| 陆强: "生物质选择性热解液化的研究", 《中国博士学位论文全文数据库（电子期刊）工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694929A (en) * | 2016-02-25 | 2016-06-22 | 中国科学技术大学 | Bio-oil and preparation method thereof |
| CN106810653A (en) * | 2017-01-23 | 2017-06-09 | 广西科学院 | A kind of method of biorefinery Bagasse Lignin base phenolic resin and its application |
| CN106810653B (en) * | 2017-01-23 | 2018-11-06 | 广西科学院 | A kind of method and its application of biorefinery Bagasse Lignin base phenolic resin |
| WO2018161280A1 (en) * | 2017-03-06 | 2018-09-13 | 华北电力大学 | Method for preparing 4-ethylphenol by catalytic pyrolysis of bagasse with activated carbon |
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