CN104152175B - A kind of method being prepared aromatic hydrocarbon by bio oil cut - Google Patents
A kind of method being prepared aromatic hydrocarbon by bio oil cut Download PDFInfo
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Abstract
The invention discloses a kind of method being prepared aromatic hydrocarbon by bio oil cut, bio oil cut and ethanol are mixed to get mixed solution, fixed-bed reactor are entered after atomization, there is catalyzed reaction on a catalyst, reaction product is through condensation and gas-liquid separation, and the product liquid of collection is described aromatic hydrocarbon; In described mixed solution, the massfraction of ethanol is 30 ~ 70%; Described catalyzer is dual-function catalyst Ga
2o
3/ HZSM-5, Ga
2o
3account for 5 ~ 40% of catalyzer total mass; Described catalyzed reaction temperature is 400 ~ 500 DEG C, pressure is 1 ~ 5MPa.By selecting the cut being suitable for preparing aromatic hydrocarbon in bio oil to be raw material in the present invention, carrying out feed by the mode of atomization, overcoming the problem that the continuity of the gas phase coking problem of cut high-temperature evaporation and direct liquid phase feed is poor; And adopt dual-function catalyst Ga
2o
3/ HZSM-5, promotes that in bio oil cut, aldehydes and single phenyl ring phenols, to the conversion of aromatic hydrocarbon, significantly improve the selectivity of aromatic hydrocarbon.
Description
Technical field
The present invention relates to organic synthesis field, be specifically related to a kind of method being prepared aromatic hydrocarbon by bio oil cut.
Background technology
In conjunction with the national conditions that the biomass resource reserves such as China's agriculture and forestry organic waste material are huge, walk the technological line that biomass resource liquid fuelization utilizes, the situation alleviating China's fossil energy shortage is had great importance.Successfully achieve the transformation of solid-state biomass waste to liquid biological oil by fast pyrolysis technology at present.But bio oil is that a kind of moisture content is high, oxygen level is high, viscosity is large, calorific value is low, the organic mixture that pH value is low simultaneously, directly can not be used as power fuel.Therefore the follow-up grade lift technique of bio oil determines that bio oil changes the committed step of process to power fuel.
Oxygen in bio oil can remove with the form of water, carbon monoxide and carbonic acid gas by the modifying process based on solid acid catalyst, thus preparation is based on the liquid aromatic hydrocarbon product of single phenyl ring hydro carbons.This aromatic product is not only the important component of commercial gasoline, can improve the octane value of gasoline, is also important industrial chemicals simultaneously, can produces the downstream chemicals such as synthetic resins.
But there is serious catalyst deactivation and reactor plugs problem in the direct modifying process of total composition bio oil, makes correlative study stagnate.This is on the one hand because bio oil composition is very complicated, macromole carbohydrate wherein and phenol polymer volatility poor, simultaneous reactions activity is low, is easily attached to catalyst surface after entering catalytic bed, cause catalyst deactivation, time serious, also can cause reactor plugs; On the other hand, the overall protium content of bio oil is lower, and oxygen element content is higher, has higher degree of unsaturation simultaneously, is easy to the coke forming low hydrogen-carbon ratio at modification deoxidation process, can cause the problem such as catalyst deactivation and reactor plugs equally.
At present existing investigator is by adopting the typical modelling thing acetic acid of bio oil cut, pyruvic alcohol, cyclopentanone and ethanol concerted reaction; and use solid acid catalyst HZSM-5; the carbon selectivity of aromatic hydrocarbon can be made to reach about 48% (ChineseJournalofCatalysis2014; 35,709-722).But, under this catalyst action, also create more C
3, C
4gaseous hydrocarbons, the concentration in tail gas can reach more than 50%, and this have impact on the selectivity of aromatic hydrocarbon, needs the aromatization strengthened further in modifying process; Meanwhile, also containing the single phenyl ring phenols of part and aldehydes in bio oil cut, this kind of material deoxidation aromizing efficiency under conventional H ZSM-5 catalyzer is lower.
Therefore, the catalyzer for this process must be improved, improve the efficiency of corresponding deoxidation and aromatization.In addition, be heated due to bio oil and easily condensation coking occur, the mode of vaporization therefore can not be adopted to carry out feed, need to seek more uniform feed-type under liquid phase state.
Summary of the invention
The invention provides a kind of method being prepared aromatic hydrocarbon by bio oil cut, the cut being suitable for preparing aromatic hydrocarbon in bio oil is selected to be raw material, carry out feed by the mode of atomization, overcome the problem that the continuity of the gas phase coking problem of cut high-temperature evaporation and direct liquid phase feed is poor; And adopt dual-function catalyst Ga
2o
3/ HZSM-5, promotes that in bio oil cut, aldehydes and single phenyl ring phenols, to the conversion of aromatic hydrocarbon, significantly improve the selectivity of aromatic hydrocarbon.
The invention discloses a kind of method being prepared aromatic hydrocarbon by bio oil cut, step is as follows:
Bio oil cut and ethanol are mixed to get mixed solution, and after atomization, enter reactor, on a catalyst catalyzed reaction occurs, reaction product is through condensation and gas-liquid separation, and the product liquid of collection is described aromatic hydrocarbon;
In described mixed solution, the massfraction of ethanol is 30 ~ 70%;
Described catalyzer is dual-function catalyst Ga
2o
3/ HZSM-5;
Described catalyzed reaction temperature is 300 ~ 500 DEG C, reaction pressure is 1 ~ 5MPa.
The preparation method of described bio oil cut is: take biomass as raw material, through 550 DEG C of obtained bio oil of fast pyrogenation reaction, then obtains bio oil cut through molecular distillation technique.
The process that described molecular distillation technique prepares bio oil cut can be that method in CN102206141A is carried out with reference to publication number.
Described biomass are forestry or agricultural wastes, can select common rice husk, rice straw, rosewood wood chip and Cortex Fraxini mandshuricae wood chip etc.
The moiety of the bio oil obtained through pyrolytic reaction mainly contains aldehydes, ketone, acids, phenols, carbohydrate, also comprises other compositions such as a small amount of ester class in addition.In these main components, micromolecular acids, ketone and ester class reactive behavior in modifying process are higher, aldehydes and single phenyl ring phenols relative reactivity lower, and macromolecular carbohydrate and phenol polymer are easy in catalytic bed coking.
Binding molecule distillation technique, optimizes molecular distillation condition, can will be suitable for the component of preparing aromatic hydrocarbon in bio oil, comprises acids and ketone etc. and is enriched to and steams in cut.It is 90 ~ 130 DEG C in distillation temperature, distillation pressure is under the molecular distillation operational condition of 700 ~ 1000Pa, what obtain steams consisting of of cut: carboxylic acid compound content is 32 ~ 38%, ketone compounds content is 39 ~ 46%, aldehyde compound content is 5 ~ 8%, single benzene ring phenolic compound content is 10 ~ 15%, and ester compound content is 1 ~ 3%, not containing macromole carbohydrate and phenol polymer.
Described carboxylic acid compound is one or more of acetic acid, propionic acid and butenoic acid; Ketone compounds is one or more of pyruvic alcohol, oxobutanol, cyclopentenone and methyl cyclopentene ketone; Aldehyde compound is one or more of hydroxy-acetaldehyde, furfural and hydroxymethylfurfural; Single benzene ring phenolic compound is one or more of phenol, methylphenol, methyl catechol, methyl guaiacol and 4, Syringa oblata Lindl. phenol and Vanillin; Ester compound is valerolactone.
Described bio oil cut is compared primeval life oil in modifying process, is had higher reactive behavior.But still containing a certain amount of aldehydes and single phenyl ring phenols in described cut, the efficiency of these compounds to aromatic conversion in single solid acid catalyst modifying process is lower, thus have impact on overall aromatic hydrocarbon productive rate.
Because bio oil cut has higher oxygen level and degree of unsaturation, and hydrogen richness is lower, and therefore independent cut is easy to the coke forming low hydrogen-carbon ratio in reaction process.Ethanol can be easier to generate alkene by direct intramolecular dehydration, and alkene (H/C=2) is formed in the process of aromatic hydrocarbon (1≤H/C < 2) in aromizing, hydrogen atom more than needed can be produced, the deoxidation aromatization process of supply bio oil cut, promotes that it is to the conversion of aromatic hydrocarbon.
As preferably, in described mixed solution, the massfraction of ethanol is 50 ~ 60%.Suitable mixing proportion can provide desirable H/C ratio, and can make distillate and ethanol generation concerted reaction, is beneficial to the generation of product aromatic hydrocarbon.
Because bio oil cut has thermo-sensitivity, more than 150 DEG C, under non-catalytic condition, vapour phase condensation reaction easily occurs and directly form coke, the mode being therefore difficult to be vaporized by preheater carries out feed.For the direct feed of liquid form, cut slowly instills catalytic bed with larger drops, cannot realize continuous-feeding; And larger drop by catalyzer time, a part of drop fail catalyst surface vaporization, easily make catalyzer coking.The present invention uses atomizing type to carry out feed to bio oil cut and ethanol, large drop is carried by carrier gas and enters catalytic bed after atomization is broken into fine drop, not only the continuity of feed significantly improves, and fine liquid also more easily fully contacts with catalyzer simultaneously, improves reactant transformation efficiency.After atomization, the optimum grain-diameter of drop depends on catalyst particle size, and size droplet diameter need be less than or close to catalyst particle size, and the drop after can making atomization is like this at catalyst surface fast vaporizing and react, thus effectively prevents catalyzer coking.
For the reaction process based on solid acid catalyst, HZSM-5 is conventional catalyzer.HZSM-5 has abundant acid sites, can promote deoxidation and aromatization, and the shape of selecting of its pore passage structure acts on the formation being also easy to aromatic hydrocarbon simultaneously.Therefore, HZSM-5 has good performance in the modified synergic process promoting acids and ketone and ethanol in bio oil cut.But because its aromatizing capacity is limited, cause the selectivity of C3, C4 gaseous hydrocarbons in modifying process also higher, this catalyzer aldehydes and single phenyl ring phenols conversion aspect in cut is also comparatively difficult, have impact on overall aromatic hydrocarbon selective simultaneously.
In order to strengthen the aromizing effect in modifying process, the present invention has prepared dual-function catalyst Ga
2o
3/ HZSM-5, passes through Ga
2o
3active centre can be formed with the interaction of HZSM-5, the aromizing effect of strengthening intermediate product alkene, and produce more hydrogen atom more than needed by strengthening aromizing effect, promote that in bio oil cut, aldehydes and single phenyl ring phenols are to the conversion of aromatic hydrocarbon, overall aromatic hydrocarbon selective significantly improves.
Described dual-function catalyst Ga
2o
3/ HZSM-5 is prepared by physical mixing processes; Also can adopt pickling process, by flooding corresponding gallium salt, and roasting obtains Ga
2o
3component.As preferably, described dual-function catalyst Ga
2o
3in/HZSM-5, Ga
2o
3content accounts for 5 ~ 25% of catalyzer total mass, and being preferably the silica alumina ratio of 10 ~ 20%, HZSM-5 is 10 ~ 200, and more preferably 25.
In this preparation method, first there is desoxydatoin in reactant, forms intermediate product light olefin, then form aromatic hydrocarbon by the further aromizing of light olefin.At 400 ~ 430 DEG C can there is deoxidation and aromatization in reactant preferably, is therefore suitable temperature of reaction, and the condition 2 ~ 3MPa of pressurization, can promote that gaseous state intermediate product alkene is to the conversion of liquid aromatic hydrocarbon.
As preferably, described reactor adopts fixed-bed reactor.
The present invention collects the flaxen oil-phase product obtained, and wherein aromatic hydrocarbon content is close to 100%.In reaction process, the transformation efficiency of reactant reaches more than 95%, and aromatic hydrocarbon carbon selectivity reaches more than 58%, and wherein single phenyl ring hydrocarbon content is 60 ~ 75%, and heterocycle and polynuclear hydrocarbon class content are 25 ~ 40%.Described single phenyl ring hydro carbons is several in benzene,toluene,xylene, trimethylbenzene, ethyl methyl benzene, dimethyl-ethyI benzene and durene, and heterocycle and polynuclear hydrocarbon class are several in indane, methyl indan, naphthalene and methylnaphthalene.
The beneficial effect of present invention process is embodied in:
1. the present invention can realize the transformation of bio oil cut to aromatic hydrocarbon, the aromatic hydrocarbon obtained is not only the important component of gasoline, also be important industrial chemicals simultaneously, the method has the potentiality that alternative conventional petroleum refining process produces aromatic hydrocarbon, has active effect for the situation alleviating China's oil shortage of resources.
2. the present invention is to have the bio oil molecular distillation cut of sound response activity for raw material, by promoting that it is to the conversion of aromatic hydrocarbon with the modified synergic of ethanol, contributing to the formation suppressing coke, improving the stability of modifying process.
3. the present invention adopts atomised form to carry out feed, overcomes the problem that the continuity of the gas phase coking problem of cut high-temperature evaporation and direct liquid phase feed is poor.
4. the present invention has prepared the dual-function catalyst Ga with higher deoxidation and aromatization activity
2o
3/ HZSM-5, method for preparing catalyst is simple, and can promote that cut is to the transformation in planta of aromatic hydrocarbon, aromatic hydrocarbon carbon selectivity is higher.
Embodiment
Embodiment 1
With agricultural wastes rice husk for bio oil prepared by raw material, and steam cut by molecular distillation acquisition, the service temperature of molecular distillation is 90 DEG C, and working pressure is 800Pa, and concrete operation step is the method in CN102206141A with reference to publication number.In this cut, acids content is 38%, and flavonoid content is 45%, and aldehyde content is 6%, and single phenyl ring phenols content is 10%, and ester class content is 1%, not containing macromole carbohydrate and phenol polymer.
10%Ga is prepared with physical mixing processes
2o
3/ HZSM-5 catalyzer.Concrete preparation method is: 1g gallium oxide powder and 9gHZSM-5 (Si/Al=25) powder are carried out physical mixed, powder after mixing is carried out compressing tablet crushing and screening, obtaining particle diameter is 40 ~ 60 object particles, then activates 5 hours at 550 DEG C in retort furnace, obtains 10%Ga
2o
3/ HZSM-5 catalyzer.
Steam cut and ethanol carries out blending by above-mentioned, ethanol blending massfraction is 50%.On fixed-bed reactor, filling 10%Ga
2o
3/ HZSM-5 (Si/Al=25) catalyzer 2g, reactant carries out feed through atomization, and sample introduction mass velocity is 6g/h, is 400 DEG C in temperature of reaction, and reaction pressure is 2MPa.Reaction process Raw transformation efficiency is 98%, and aromatic hydrocarbon carbon selectivity is 62%, and wherein single phenyl ring hydrocarbon content is 72%, and heterocycle and polynuclear hydrocarbon class content are 28%.
Embodiment 2
The method identical with embodiment 1 is adopted to prepare bio oil cut.
15%Ga is prepared with physical mixing processes
2o
3/ HZSM-5 catalyzer.Concrete steps are with embodiment 1, and difference is that 1.5g gallium oxide powder and 8.5gHZSM-5 (Si/Al=25) powder are carried out physical mixed.
Bio oil cut and ethanol are carried out blending, and ethanol blending massfraction is 60%.On fixed-bed reactor, filling 15%Ga
2o
3/ HZSM-5 (Si/Al=25) catalyzer 2g, reactant carries out feed through atomization, and sample introduction mass velocity is 6g/h, is 430 DEG C in temperature of reaction, and reaction pressure is 3MPa.Reaction process Raw transformation efficiency is 99%, and aromatic hydrocarbon carbon selectivity is 66%, and wherein single phenyl ring hydrocarbon content is 75%, and heterocycle and polynuclear hydrocarbon class content are 25%.
Embodiment 3
With agricultural wastes rice straw for bio oil prepared by raw material, and steam cut by molecular distillation acquisition, the service temperature of molecular distillation is 110 DEG C, and working pressure is 700Pa, and concrete operation step is the method in CN102206141A with reference to publication number.In this cut, acids content is 34%, and flavonoid content is 42%, and aldehyde content is 8%, and single phenyl ring phenols content is 14%, and ester class content is 2%, not containing macromole carbohydrate and phenol polymer.
Steam cut and ethanol carries out blending by above-mentioned, ethanol blending massfraction is 50%.On fixed-bed reactor, load catalyzer 2g in the same manner as in Example 2.Reactant carries out feed through atomization, and sample introduction mass velocity is 6g/h, is 400 DEG C in temperature of reaction, and reaction pressure is 3MPa.Reaction process Raw transformation efficiency is 98%, and aromatic hydrocarbon carbon selectivity is 61%, and wherein single phenyl ring hydrocarbon content is 71%, and heterocycle and polynuclear hydrocarbon class content are 29%.
Embodiment 4
The method identical with embodiment 3 is adopted to prepare bio oil cut.
20%Ga is prepared with physical mixing processes
2o
3/ HZSM-5 catalyzer.Concrete steps are with embodiment 1, and difference is that 2g gallium oxide powder and 8gHZSM-5 (Si/Al=25) powder are carried out physical mixed.
Bio oil cut and ethanol are carried out blending, and described cut is identical with embodiment 3, and ethanol blending massfraction is 60%.On fixed-bed reactor, filling 20%Ga
2o
3/ HZSM-5 (Si/Al=25) catalyzer 2g, reactant carries out feed through atomization, and sample introduction mass velocity is 6g/h, is 430 DEG C in temperature of reaction, and reaction pressure is 2MPa.Reaction process Raw transformation efficiency is 98%, and aromatic hydrocarbon carbon selectivity is 63%, and wherein single phenyl ring hydrocarbon content is 72%, and heterocycle and polynuclear hydrocarbon class content are 28%.
Embodiment 5
With forestry waste Cortex Fraxini mandshuricae wood chip for bio oil prepared by raw material, and steam cut by molecular distillation acquisition, the service temperature of molecular distillation is 130 DEG C, and working pressure is 1000Pa, and concrete operation step is the method in CN102206141A with reference to publication number.In this cut, acids content is 32%, and flavonoid content is 46%, and aldehyde content is 5%, and single phenyl ring phenols content is 15%, and ester class content is 2%, not containing macromole carbohydrate and phenol polymer.
Steam cut and ethanol carries out blending by above-mentioned, ethanol blending massfraction is 50%.On fixed-bed reactor, load catalyzer 2g in the same manner as in Example 2, reactant carries out feed through atomization, and sample introduction mass velocity is 6g/h, is 400 DEG C in temperature of reaction, and reaction pressure is 2MPa.Reaction process Raw transformation efficiency is 96%, and aromatic hydrocarbon carbon selectivity is 62%, and wherein single phenyl ring hydrocarbon content is 69%, and heterocycle and polynuclear hydrocarbon class content are 31%.
Embodiment 6
Bio oil cut and ethanol are carried out blending, and described cut is identical with embodiment 5, and ethanol blending massfraction is 60%.On fixed-bed reactor, load catalyzer 2g in the same manner as in Example 4, reactant carries out feed through atomization, and sample introduction mass velocity is 6g/h, is 430 DEG C in temperature of reaction, and reaction pressure is 3MPa.Reaction process Raw transformation efficiency is 97%, and aromatic hydrocarbon carbon selectivity is 65%, and wherein single phenyl ring hydrocarbon content is 70%, and heterocycle and polynuclear hydrocarbon class content are 30%.
Embodiment 7
With forestry waste rosewood wood chip for bio oil prepared by raw material, and steam cut by molecular distillation acquisition, the service temperature of molecular distillation is 90 DEG C, and working pressure is 1000Pa, and concrete operation step is the method in CN102206141A with reference to publication number.In this cut, acids content is 35%, and flavonoid content is 39%, and aldehyde content is 8%, and single phenyl ring phenols content is 15%, and ester class content is 3%, not containing macromole carbohydrate and phenol polymer.
Steam cut and ethanol carries out blending by above-mentioned, ethanol blending massfraction is 50%.On fixed-bed reactor, load catalyzer 2g in the same manner as in Example 2, reactant carries out feed through atomization, and sample introduction mass velocity is 6g/h, is 400 DEG C in temperature of reaction, and reaction pressure is 3MPa.Reaction process Raw transformation efficiency is 95%, and aromatic hydrocarbon carbon selectivity is 58%, and wherein single phenyl ring hydrocarbon content is 65%, and heterocycle and polynuclear hydrocarbon class content are 35%.
Embodiment 8
Bio oil cut and ethanol are carried out blending, and described cut is identical with embodiment 7, and ethanol blending massfraction is 60%.On fixed-bed reactor, load catalyzer 2g in the same manner as in Example 4, reactant carries out feed through atomization, and sample introduction mass velocity is 6g/h, is 430 DEG C in temperature of reaction, and reaction pressure is 2MPa.Reaction process Raw transformation efficiency is 95%, and aromatic hydrocarbon carbon selectivity is 60%, and wherein single phenyl ring hydrocarbon content is 68%, and heterocycle and polynuclear hydrocarbon class content are 32%.
Claims (6)
1. prepared a method for aromatic hydrocarbon by bio oil cut, it is characterized in that, step is as follows:
Bio oil cut and ethanol are mixed to get mixed solution, and after atomization, enter reactor, on a catalyst catalyzed reaction occurs, reaction product is through condensation and gas-liquid separation, and the product liquid of collection is described aromatic hydrocarbon;
The preparation method of described bio oil cut is: take biomass as raw material, and through the obtained bio oil of fast pyrogenation reaction, then obtain bio oil cut through molecular distillation technique, distillation temperature is 90 ~ 130 DEG C, and distillation pressure is 700 ~ 1000Pa; In described bio oil cut, carboxylic acid compound content is 32 ~ 38%, and ketone compounds content is 39 ~ 46%, aldehyde compound content is 5 ~ 8%, single benzene ring phenolic compound content is 10 ~ 15%, and ester compound content is 1 ~ 3%, not containing macromole carbohydrate and phenol polymer;
In described mixed solution, the massfraction of ethanol is 30 ~ 70%;
Described catalyzer is dual-function catalyst Ga
2o
3/ HZSM-5;
Described catalyzed reaction temperature is 300 ~ 500 DEG C, reaction pressure is 1 ~ 5MPa.
2. the method being prepared aromatic hydrocarbon by bio oil cut according to claim 1, is characterized in that, in described mixed solution, the massfraction of ethanol is 50 ~ 60%.
3. the method being prepared aromatic hydrocarbon by bio oil cut according to claim 1, is characterized in that, described dual-function catalyst Ga
2o
3in/HZSM-5, Ga
2o
3account for 5 ~ 25% of catalyzer total mass.
4. the method being prepared aromatic hydrocarbon by bio oil cut according to claim 3, is characterized in that, described Ga
2o
3the silica alumina ratio accounting for 10 ~ 20%, HZSM-5 of catalyzer total mass is 10 ~ 200.
5. the method being prepared aromatic hydrocarbon by bio oil cut according to claim 4, is characterized in that, the silica alumina ratio of HZSM-5 is 25.
6. the method being prepared aromatic hydrocarbon by bio oil cut according to claim 1, is characterized in that, described catalyzed reaction temperature is 400 ~ 430 DEG C, reaction pressure is 2 ~ 3MPa.
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| CN110205205B (en) * | 2019-05-28 | 2020-10-20 | 浙江大学 | Catalytic hydrogenation saturation method for phenol-rich bio-oil fraction |
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