CN103755528B - A kind of catalytic pyrolysis of biomass prepares the method for phenol - Google Patents
A kind of catalytic pyrolysis of biomass prepares the method for phenol Download PDFInfo
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- CN103755528B CN103755528B CN201410019408.3A CN201410019408A CN103755528B CN 103755528 B CN103755528 B CN 103755528B CN 201410019408 A CN201410019408 A CN 201410019408A CN 103755528 B CN103755528 B CN 103755528B
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Abstract
What the invention belongs to biomass energy utilizes field, is specifically related to a kind of phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making of utilizing for the method for phenol.The present invention first by phosphoric acid salt dip loading in biomass, then with the biomass of impregnation of phosphoric acid salt for raw material, take gac as catalyzer, carry out fast pyrogenation in 280 ~ 450 DEG C under anaerobic by after both mechanically mixing, the product liquid of phenol-rich after condensation is carried out to pyrolysis gas, can be obtained; The productive rate of phenol and the purity in product liquid all higher.In addition, activated-carbon catalyst stable performance, can use through Separation and Recovery Posterior circle, and containing phosphatic solid coke product can activated after prepare gac, for catalyse pyrolysis process.
Description
Technical field
What the invention belongs to biomass energy utilizes field, is specifically related to a kind of phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making of utilizing for the method for phenol.
Background technology
Phenol is a kind of common bulk chemical, be widely used in chemical industry and medical field, can be used for producing Chemicals and the intermediates such as resol, hexanolactam, dihydroxyphenyl propane, Whitfield's ointment, picric acid, Pentachlorophenol, hexanodioic acid, phenolphthalein, also can be used for manufacturing sanitas, sterilant, sterilant and sterilizing agent etc.At present, the output of natural phenol far can not meet the needs in market, has therefore occurred the multiple method preparing phenol, has comprised sulfonated alkali fusion method, Hydrolysis of Chlorobenzene method and cumene method etc.
Lignocellulose-like biomass, as the reproducible resource of one, has the advantages such as source is wide, total amount is large, pollution-free, price is low.In biomass pyrolysis process, the decomposition of xylogen can form multiple phenolic product, comprising phenol; According to the difference of raw material and pyrolytic reaction condition, the productive rate of phenol has obvious difference.But generally speaking, the content of phenol in biomass pyrolytic liquid is no more than 1%, causes its separating-purifying very difficult, and does not have good economy.Therefore, if be that phenol prepared by raw material with biomass, the selectivity of pyrolytic process Pyrogentisinic Acid must be improved.
Prepare aldehydes matter for realizing biomass by selective pyrolysis, the general method adopted is in pyrolytic process, introduce suitable catalyzer.Chinese patent (grant number: CN102070408B) discloses a kind of phosphoric acid salt catalyse pyrolysis biomass-making that utilizes for the method for lightweight phenols organic mixture; Chinese patent application (application number: CN201210310261.4) discloses a kind of coke catalytic pyrolysis biomass-making that utilizes for the method for phenols organic mixture.These two kinds of methods adopt single catalyst to carry out catalyse pyrolysis to biomass respectively, thus selectivity can prepare phenolic product, but the phenolic product obtained is the mixture of the multiple aldehydes matter comprising phenol, in the mixture, phenol is not definitely main product.Because aldehydes matter all has similar structure and close boiling point, therefore from this phenol mixture, separating-purifying phenol remains the thing of very difficulty.Generally speaking, existing document these two kinds of methods disclosed, still successfully cannot realize selectivity pyrolysis and prepare this single product of phenol.Therefore, the high efficiency method that biomass by selective pyrolysis prepares phenol (single product instead of phenols organic mixture) is also needed to seek further.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making of utilizing for the method for phenol.
According to method provided by the invention, first by phosphoric acid salt dip loading in biomass, then with the biomass of impregnation of phosphoric acid salt for raw material, take gac as catalyzer, be that (8:1) ~ (1:4) carries out mechanically mixing by catalyzer and raw material according to mass ratio, under anaerobic, carry out fast pyrogenation reaction in 280 ~ 450 DEG C, collect pyrolysis gas, condensation obtains the product liquid of phenol-rich.
Preferably, described phosphoric acid salt comprises the arbitrary combination of a kind of or above-mentioned substance in Tripotassium phosphate, dipotassium hydrogen phosphate, potassium primary phosphate, tertiary sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC.Preferred, described phosphoric acid salt is Tripotassium phosphate or dipotassium hydrogen phosphate.
Preferably, described is be carried in biomass by the phosphoric acid salt of certain mass with the method for incipient impregnation or excessive dipping by phosphoric acid salt dip loading in biomass, and the mass ratio of phosphoric acid salt and biomass is (1:1) ~ (1:50).
Preferably, described biomass are lignocellulose-like biomass raw material, comprise the arbitrary combination of a kind of or above-mentioned substance in farm crop, agricultural waste material, timber or timber waste.Raw material is crushed to below 1mm before use.
Preferably, described gac is black powder or granular decolorizing carbon.Gac, as catalyzer, is crushed to below 1mm before use.
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 40s.
Beneficial effect of the present invention is:
The present invention simultaneously with phosphoric acid salt and gac for catalyzer, by the product liquid of associating catalyse pyrolysis biomass-making for phenol-rich.In biomass pyrolysis process, phosphoric acid salt and gac can both suppress Mierocrystalline cellulose and hemicellulose pyrolysis to form organic product liquid separately; In addition, under both associating katalysis, significantly can promote that xylogen pyrolysis forms phenol, suppress xylogen pyrolysis to generate other phenolic product simultaneously; Therefore, under two kinds of catalyzer associating katalysis, the productive rate of phenol is very high, and the composition of product liquid is comparatively simple, and the purity of phenol is also very high.This associating katalysis and the independent separately katalysis of two kinds of catalyzer completely different (separately separately in catalytic process, the formation of multiple phenolic product can be promoted, thus obtain the mixture of multiple aldehydes matter).Because the purity of phenol in product liquid is very high, the content of other phenolic product is very low, makes its follow-up separating-purifying comparatively simple.In addition, gac is as catalyst performance stabilised, corrosion-free to equipment, environmentally safe, can through the modes such as mechanical separation Separation and Recovery recycling from solid residue after reaction terminates.Again, phosphoric acid salt has good chemical activation effect, containing phosphatic solid coke can after chemical activation direct production gac, as the activated-carbon catalyst needed for the technical program.
Embodiment
The invention provides a kind of phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making of utilizing for the method for phenol, 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
The poplar (particle diameter is 0.1-0.3mm) getting 10g dip loading 5% Tripotassium phosphate is raw material, be that catalyzer carries out mechanically mixing with gac, the mass ratio of poplar and gac is 1:1, then by mixture at 360 DEG C, pyrolysis 20s under nitrogen atmosphere, the liquid product yield obtained is 45.6%, and wherein the productive rate of water is 33.3%, and organic productive rate is 12.3%, by the content of gas chromatographic analysis wherein phenol, calculate and learn that the productive rate of phenol is 7.8%.
Embodiment 2
The poplar (particle diameter is 0.1-0.3mm) getting 20g dip loading 10% dipotassium hydrogen phosphate is raw material, be that catalyzer carries out mechanically mixing with gac, the mass ratio of poplar and gac is 1:2, then by mixture at 350 DEG C, pyrolysis 30s under nitrogen atmosphere, the liquid product yield obtained is 43.1%, and wherein the productive rate of water is 33.7%, and organic productive rate is 9.4%, by the content of gas chromatographic analysis wherein phenol, calculate and learn that the output of phenol is 7.5%.
Embodiment 3
The nut-shell (particle diameter is 0.1-0.3mm) getting 10g dip loading 10% Tripotassium phosphate is raw material, be that catalyzer carries out mechanically mixing with gac, the mass ratio of poplar and gac is 1:1, then by mixture at 380 DEG C, pyrolysis 20s under nitrogen atmosphere, the liquid product yield obtained is 46.2%, and wherein the productive rate of water is 33.0%, and organic productive rate is 13.2%, by the content of gas chromatographic analysis wherein phenol, calculate and learn that the output of phenol is 8.6%.
Embodiment 4
Getting the nut-shell (particle diameter is 0.1-0.3mm) that 20g impregnated of 15% tertiary sodium phosphate is raw material, be that catalyzer carries out mechanically mixing with gac, the mass ratio of poplar and gac is 1:2, then by mixture at 340 DEG C, pyrolysis 30s under nitrogen atmosphere, the liquid product yield obtained is 41.1%, and wherein the productive rate of water is 32.0%, and organic productive rate is 9.1%, by the content of gas chromatographic analysis wherein phenol, calculate and learn that the output of phenol is 7.6%.
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 (8)
1. one kind utilizes phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making for the method for phenol, it is characterized in that, first by phosphoric acid salt dip loading in biomass, then with the biomass of impregnation of phosphoric acid salt for raw material, taking gac as catalyzer, is that (8:1) ~ (1:4) carries out mechanically mixing by catalyzer and raw material according to mass ratio, under anaerobic, carry out fast pyrogenation reaction in 280 ~ 450 DEG C, collect pyrolysis gas, condensation obtains the product liquid of phenol-rich.
2. a kind of phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making of utilizing according to claim 1 is for the method for phenol, it is characterized in that, described phosphoric acid salt comprises the arbitrary combination of a kind of or above-mentioned substance in Tripotassium phosphate, dipotassium hydrogen phosphate, potassium primary phosphate, tertiary sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC.
3. a kind of phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making of utilizing according to claim 1 is for the method for phenol, it is characterized in that, described is be carried in biomass by the phosphoric acid salt of certain mass with the method for incipient impregnation or excessive dipping by phosphoric acid salt dip loading in biomass, and the mass ratio of phosphoric acid salt and biomass is (1:1) ~ (1:50).
4. a kind of phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making of utilizing according to claim 1 is for the method for phenol, it is characterized in that, described biomass are lignocellulose-like biomass raw material, comprise the arbitrary combination of a kind of or above-mentioned substance in farm crop, agricultural waste material, timber or timber waste.
5. a kind of phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making of utilizing according to claim 1 is for the method for phenol, and it is characterized in that, described gac is black powder or granular decolorizing carbon.
6. a kind of phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making of utilizing according to claim 1 is for the method for phenol, it is characterized in that, under described oxygen free condition refers to that reaction system maintains inertia anaerobic shielding gas environment.
7. a kind of phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making of utilizing according to claim 1 is for the method for phenol, and it is characterized in that, the temperature rise rate of described pyrolytic reaction is not less than 100 DEG C/s.
8. a kind of phosphoric acid salt and activated carbon combined catalyse pyrolysis biomass-making of utilizing according to claim 1 is for the method for phenol, and it is characterized in that, the time of described pyrolytic reaction is no more than 40s.
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| CN104341273B (en) * | 2014-10-21 | 2016-11-09 | 华北电力大学 | A kind of catalytic pyrolysis of biomass prepares the method for 4-ethyl-phenol |
| CN106318477B (en) * | 2016-08-22 | 2018-08-07 | 华北电力大学 | A kind of method that catalytic pyrolysis of biomass prepares high-grade liquid fuel |
| CN106517190B (en) * | 2016-10-27 | 2018-05-04 | 陕西科技大学 | A kind of method of catalytic lignin thermal cracking coproduction list phenolic compound and activated carbon |
| CN106946658B (en) * | 2017-03-06 | 2021-02-12 | 华北电力大学 | Method for preparing 4-ethylphenol by catalytically pyrolyzing bagasse with activated carbon |
| CN107604014A (en) * | 2017-10-25 | 2018-01-19 | 深圳大学 | Improve the biologic pretreatment method of maize straw pyrolysis liquefaction aromatic compound yield |
| CN109755596A (en) * | 2019-01-09 | 2019-05-14 | 华北电力大学 | Modified coating luffa electrode material and microbiological fuel cell |
| CN111018674B (en) * | 2020-01-07 | 2022-04-22 | 山东理工大学 | Method for preparing phenol by directionally catalyzing biomass pyrolysis through modified activated carbon |
| CN111068727A (en) * | 2020-01-07 | 2020-04-28 | 山东理工大学 | Method for preparing aromatic hydrocarbon by pyrolyzing wood-plastic composite waste under catalysis of activated carbon |
| CN111849526B (en) * | 2020-07-22 | 2021-03-23 | 中国电力工程顾问集团西北电力设计院有限公司 | Method for co-producing coke and phenol by pyrolyzing biomass |
| CN113372398B (en) * | 2021-05-31 | 2023-11-21 | 河南城建学院 | Preparation method of levoglucosone |
| CN115322076B (en) * | 2022-08-18 | 2024-10-22 | 华北电力大学 | Co-production of phenolic chemicals and CO by pyrolysis of electronic waste plastics2Method for adsorbing carbon material |
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