CN102352270A - Technology for preparing fuel by lightweight fraction obtained by bio-oil gradation - Google Patents
Technology for preparing fuel by lightweight fraction obtained by bio-oil gradation Download PDFInfo
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- CN102352270A CN102352270A CN201110203127XA CN201110203127A CN102352270A CN 102352270 A CN102352270 A CN 102352270A CN 201110203127X A CN201110203127X A CN 201110203127XA CN 201110203127 A CN201110203127 A CN 201110203127A CN 102352270 A CN102352270 A CN 102352270A
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Abstract
The invention discloses a technology for preparing fuel by lightweight fraction obtained by bio-oil gradation, comprising the following steps of: (1) carrying out molecular distillation separation on pretreated bio-oil at the distillation temperature of normal temperature to 200 DEG C and at the distillation pressure of 10 Pa to 1800 Pa so as to obtain bio-oil lightweight fraction, medium weight fraction and heavy fraction; (2) carrying out a catalytic esterification reaction between the bio-oil lightweight fraction obtained from step (1) and alcohol with the volume ratio of the lightweight fraction to alcohol being 1:10-1:1 in the presence of a solid catalyst at normal pressure at the reaction temperature of 80-120 DEG C for 0.5-1.5 hours so as to obtain the ester fuel. The technology provided by the invention helps to solve the problem of bio-oil corrosivity and simultaneously can be used to obtain ester compound enriched liquid fuel.
Description
Technical field
The present invention relates to the refining complete processing of the follow-up classification of a kind of bio oil; Be specifically related to adopt the molecular distillation isolation technique that bio oil is carried out the light ends of cut cutting with the enrichment of acquisition carboxylic acid cpd, and then combine the catalytic esterification technology that it is made with extra care to obtain high-grade liquid fuel.
Background technology
In conjunction with huge national conditions of biomass resource reserves such as China's agriculture and forestry organic waste materials, walk the technological line of biomass resource liquid fuel utilization, the situation of alleviating China's fossil energy shortage is had great importance.Through scientific research for many years, successfully realized of the transformation of solid-state biomass waste through the flash pyrolysis technology to liquid bio oil crude oil.Yet; The bio oil that biomass through pyrolysis obtains is that a kind of outward appearance is brownish black, opaque thickness, the mixture of flowability and irritating smell is arranged; Its polarity is big, moisture content is high, oxygen level is high, viscosity is big, calorific value is low, and the pH value is low simultaneously, can not directly be used as power fuel.Thereby the follow-up grade Study of Lifting of bio oil will be the decision bio oil changes a committed step from process to power fuel.
Corrodibility is one of key obstacle of bio oil power liquid turning sludge into fuel utilization, realize that the higher-grade liquid fuel utilization of bio oil at first need overcome this shortcoming.The catalytic esterification technology is one of bio oil purification techniques, and mainly the interpolation through alcohols realizes the transformation of bio oil internal corrosion property carboxylic acid to the neutral ester compounds.In full component bio oil esterification was refining, complicated composition had brought difficulty for the specific aim modification of product, and the product component after making with extra care simultaneously is complicated, still contains other same clan's compounds such as a large amount of phenols and carbohydrate, and the quality of fuel can not get guaranteeing.This patent at first adopts the molecular distillation isolation technique that bio oil is carried out the carboxylic acid separation, has reduced the corrodibility of remaining bio oil cut on the one hand, has improved its fuel characteristic; Obtain the light ends of carboxylic acid enrichment on the other hand, can obtain the high-quality liquid fuel of ester compound enrichment through the esterification of the sour light ends of richness.
Number of patent application is the molecular clock separation method that 201110089928.8 patent application discloses a kind of bio oil; Comprise: the pretreated bio oil that bio oil crude oil is carried out obtaining after particle and the moisture removal preliminary treatment is through the molecular clock separation process; In vapo(u)rizing temperature is normal temperature to 200 ℃; Distillation pressure is under the 10Pa to 1800Pa; Described molecular clock process is accomplished on the molecular clock appearance; Bio oil at first adds at the hopper of molecular clock appearance; By the vapo(u)rizing temperature of main body evaporimeter control molecular clock process, the distillation pressure that adopts in the adjusting control still-process by vavuum pump.The fugitive constituent that still-process produces is by built-in condenser condenses and collect matter cut in being; The fugitive constituent of difficult condensation is collected during through the lower cold-trap of-30 ℃ or temperature fully, is light ends; The distillation residual component glides with the evaporator evaporation surface and gets into the heavy ends collector unit, obtains heavy ends.
Summary of the invention
For solving the corrodibility defective of bio oil; This patent has proposed the technology that light ends that a kind of bio oil classification obtains prepares fuel; Selection through molecular distillation separating technology operating mode; Compound in the bio oil is carried out selective enrichment, and then combine separate fraction to adopt corresponding process for refining to carry out the preparation of fuel.This novel process has solved the biological oil separating difficult problem of thermo-sensitivity simultaneously, and rich sour bio oil light ends is provided simultaneously, so that further adopt catalytic esterification technology to obtain the liquid fuel of ester class enrichment.
The invention provides the technology that light ends that a kind of bio oil classification obtains prepares fuel, comprising:
(1) with pretreated bio oil through the molecular distillation sepn process, be normal temperature to 200 ℃ in distillation temperature, distillation pressure is under the 10Pa to 1800Pa, obtains bio oil light ends, middle matter cut and heavy ends;
Bio oil is generally produced by biomass through pyrolysis such as forestry waste, agricultural wastes, herbaceous biomass and waterplant and is obtained.Selected biomass are after preprocessor such as super-dry, fragmentation and screening; Choose the material of particle diameter at 0.4mm-0.6mm; In the biomass fluid bed fast pyrolysis liquefaction test system of band spray condensation, carry out thermo-cracking; Cracking temperature is 400 ℃-600 ℃, and the liquid that condensation obtains is bio oil.Described forestry waste, agricultural wastes, herbaceous biomass or waterplant can be selected common pinus sylvestris var. mongolica, rosewood, rice husk, rice straw or marine alga etc. for use; The moiety of gained bio oil mainly contains alcohols, aldehydes, ketone, acids, phenols, carbohydrate, also comprises other compositions such as a spot of furans, ester and hydro carbons in addition.The composition of bio oil own is very complicated, comprises hundreds of micromolecular compounds, also contains the inadequate macromolecular cleavage xylogen of cracking simultaneously.
The pre-treatment of bio oil and molecular distillation process number are 201110089928.8 with reference to application for a patent for invention, and denomination of invention is " a kind of molecular distillation separation method of bio oil ".Carry out molecular distillation through the molecular distillation appearance, obtained bio oil light ends, middle matter cut and heavy ends respectively.
Described molecular distillation process is accomplished on the molecular distillation appearance, and the molecular distillation appearance is mainly by the feed hopper of band heat insulation function, form with the vaporizer body of built-in condenser and cold-trap and vacuum system.The molecular distillation appearance adopts commercial equipment, and the unit type that different companies produces is different, but the principle of institute's foundation all is the same with the own characteristic of instrument, all applicable to the present invention.
(2) with resulting bio oil light ends in the step (1), under normal pressure, light ends is 1 with the volume ratio of alcohol: 10-1: 1; Temperature of reaction is 80-120 ℃; Reaction times is 0.5-1.5 hour, adopts solid acid catalyst to carry out catalytic esterification, obtains neutral ester class A fuel A; Described alcohols comprises unitary fatty alcohol, binary aliphatic alcohol or ternary aliphatic alcohol; Preferably, described unitary fatty alcohol is C
1-C
6Positive structure or isomery alcohol; More preferably, described unitary fatty alcohol is ethanol or propyl alcohol, and described binary aliphatic alcohol is terepthaloyl moietie or butyleneglycol, and described ternary aliphatic alcohol is glycerin.It is CN101856620 that described solid acid catalyst adopts the application for a patent for invention publication No., " catalyzer of a kind of modified solid acid catalyst and preparation thereof " disclosed solid catalyst.
The invention provides a kind of novel process of bio oil high efficiency separation, having broken in the past, all bio oil components all adopt single process for refining, the unconspicuous deadlock of refining effect.Adopt technology of the present invention, will cause the corrosive carboxylic acid of bio oil to carry out separation and concentration, utilization catalytic esterification technology is carried out grade and is promoted, and to obtain the liquid fuel of ester class enrichment, this liquid fuel has the potentiality of power train in vehicle application fuel.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is the analysis of spectra of the esterification products cut of the embodiment of the invention 3 acquisitions.
Fig. 3 is the esterification products composition diagram that the embodiment of the invention 3 obtains.
Embodiment
Embodiment 1
(1) Preparation of Catalyst
Adopt patent CN101856620 disclosed method to produce solid acid catalyst, be used for the esterification of light ends.Step 1: get tetra-n-butyl titanate 25.58g, ethanol 20ml places the 250ml beaker to stir; Get ethanol 20ml, vitriol oil 1.04g and distilled water 4ml and mix and place separating funnel, splash into fast in the above-mentioned beaker, stir and obtain titanium colloidal sol.With titanium colloidal sol room temperature ageing 24 hours, 120 mesh sieves were ground in 110 ℃ of oven dry, obtained TiO
2Powder.Step 2: according to SiO
2With TiO
2Mass ratio takes by weighing 4g SiO at 2: 3
2, 6g TiO
2, carrying out mechanically mixing, and add an amount of ethanol continuation stirring, the stirring and drying said mixture obtains uniform SiO
2With TiO
2Mixture adds 0.6g La
2O
3Powder; Mix, carry out incipient impregnation, left standstill 5 hours after stirring fully with the sulfuric acid of 1mol/L; Change the interior 400 ℃ of roastings of retort furnace 6 hours over to after stirring drying; The solid naturally cooling is got above-mentioned solid, washes with 50 ℃ of deionized waters; Treat that the suction filtration liquid pH value is at 3 o'clock; Stop to wash, stir dry back and move into the interior 400 ℃ of roastings of retort furnace 2 hours, naturally cooling obtains La
3+-SO
4 2-/ 60%TiO
2-40%SiO
2Catalyzer.
(2) bio oil produce, pre-treatment with separate
With forestry waste Cortex Fraxini mandshuricae wood chip is raw material; After preprocessor such as super-dry, fragmentation and screening; Choose the material of particle diameter at 0.4mm-0.6mm; In the biomass fluid bed fast pyrolysis liquefaction test system of band spray condensation, carry out thermo-cracking; Cracking temperature is 400 ℃-600 ℃, and the liquid that condensation obtains is Cortex Fraxini mandshuricae thermo-cracking bio oil.Adopt the method for patent of invention 201110089928.8 that bio oil is separated, distillation temperature is 80 ℃, distillation pressure 340pa.6.3% light ends and 27% middle matter cut have been obtained.Middle matter cut has good flowability, and presents deep yellow.Heavy ends is an aterrimus, and calorific value is 22.3MJ/kg.
(3) cut is refining
Get the light ends that obtains in the 40ml step (2); Drop in the reaction kettle of 500ml; Add the propyl alcohol of 150ml and the solid acid catalyst of 3g step (1) gained again; 110 ℃ with non-pressurized condition under the reaction 1h after; Through gas-chromatography and mass spectrometric hyphenated technique product is analyzed; Ester compound content in the refining after product of esterification is 26%, and the content of acid is reduced to 2.2%.
Embodiment 2
Choosing the pinus sylvestris var. mongolica wood chip is raw material, prepares the pinus sylvestris var. mongolica bio oil with embodiment 1 identical mode, and carries out particle and moisture removal pre-treatment.Adopt embodiment 1 identical method that bio oil is carried out pre-treatment and separated, 100 ℃ of distillation temperatures, distillation pressure 1200pa.Do not occur the coking situation in this sepn process, and to have obtained mass percent be 5.2% light ends, 24.6% middle matter cut.Wherein the light ends pale blue is green, contains micromolecular compounds such as acetate, and the pH value is 2.13; Middle matter cut is an incarnadine, and higher furfural and phenol content are arranged; Heavy ends is an aterrimus, and pH is 5.2, and calorific value is 21.4MJ/kg.
Get the light ends of 40ml above-mentioned steps gained; Drop in the reaction kettle of 500ml; Add the propyl alcohol of 180ml and the solid acid catalyst of 3g embodiment 1 gained again; 90 ℃ with non-pressurized condition under the reaction 1.2h after; The esterification treating process has generated a large amount of ester class components such as propyl acetate; The content of ester compound is 28%, and the content of acid is reduced to 1.5%.
Embodiment 3
Choosing rice husk is raw material, prepares the rice husk bio oil with embodiment 1 identical mode, and carries out particle and moisture removal pre-treatment.Adopt embodiment 1 identical method that bio oil is carried out pre-treatment and separated, 130 ℃ of distillation temperatures, distillation pressure 600pa, this experimentation have obtained mass percent and have been respectively 6.3% and 35.1% light ends and middle matter cut.Light ends and middle matter cut all have good flowability, and heavy ends normal temperature current downflow property is poor slightly, and the heavy ends calorific value is 24.2MJ/kg.
Get the light ends of 40ml above-mentioned steps gained; Drop in the reaction kettle of 500ml; Add the propyl alcohol of 120ml and the solid acid catalyst of 3g embodiment 1 gained again; 100 ℃ with non-pressurized condition under the reaction 1.2h after; In conjunction with gas-chromatography and mass spectrometry analysis product has been carried out the qualitative and quantitative analysis; The spectrogram of the refining after product of esterification as shown in Figure 2, the content of the ester compounds such as propyl acetate in the refined products is up to 31%, the content of carboxylic acid was about for 2.7% (forming as shown in Figure 3).
Claims (3)
1. the light ends that obtains of a bio oil classification prepares the technology of fuel, comprising:
(1) with pretreated bio oil through the molecular distillation sepn process, be normal temperature to 200 ℃ in distillation temperature, distillation pressure is under the 10Pa to 1800Pa, obtains bio oil light ends, middle matter cut and heavy ends;
(2) with resulting bio oil light ends in the step (1), under normal pressure, light ends is 1 with the volume ratio of alcohol: 10-1: 1; Temperature of reaction is 80-120 ℃; Reaction times is 0.5-1.5 hour, adopts solid acid catalyst to carry out catalytic esterification, obtains the ester class A fuel A.
2. the light ends that bio oil classification according to claim 1 obtains prepares the technology of fuel, it is characterized in that: described alcohols comprises unitary fatty alcohol, binary aliphatic alcohol or ternary aliphatic alcohol, and described unitary fatty alcohol is C
1-C
6Positive structure or isomery alcohol, described binary aliphatic alcohol is terepthaloyl moietie or butyleneglycol, described ternary aliphatic alcohol is glycerin.
3. the light ends that bio oil classification according to claim 2 obtains prepares the technology of fuel, it is characterized in that: described unitary fatty alcohol is ethanol or propyl alcohol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851072A (en) * | 2012-07-30 | 2013-01-02 | 东南大学 | Method for refining waste paperboard pyrolytic oil |
| CN105176695A (en) * | 2015-07-17 | 2015-12-23 | 合肥工业大学 | Method for in situ esterification of bio-oil through friction catalysis by using graphene oxide |
| CN105753654A (en) * | 2016-02-04 | 2016-07-13 | 浙江大学 | Separation method of bio-oil molecular distillation heavy fraction |
| GB2535797A (en) * | 2015-02-27 | 2016-08-31 | Future Blends Ltd | Process for removal of water and light organics from pyrolysis oil |
Citations (2)
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| CN100465249C (en) * | 2006-12-28 | 2009-03-04 | 浙江大学 | Method for preparing biodiesel oil |
| CN100513521C (en) * | 2006-09-28 | 2009-07-15 | 张海军 | Preparation method of biological diesel oil |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100513521C (en) * | 2006-09-28 | 2009-07-15 | 张海军 | Preparation method of biological diesel oil |
| CN100465249C (en) * | 2006-12-28 | 2009-03-04 | 浙江大学 | Method for preparing biodiesel oil |
Non-Patent Citations (1)
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| 姚燕 等: "生物油轻质馏分加氢试验研究", 《工程热物理学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851072A (en) * | 2012-07-30 | 2013-01-02 | 东南大学 | Method for refining waste paperboard pyrolytic oil |
| GB2535797A (en) * | 2015-02-27 | 2016-08-31 | Future Blends Ltd | Process for removal of water and light organics from pyrolysis oil |
| GB2535797B (en) * | 2015-02-27 | 2019-10-23 | Future Blends Ltd | Process for removal of water and light organics from pyrolysis oil |
| CN105176695A (en) * | 2015-07-17 | 2015-12-23 | 合肥工业大学 | Method for in situ esterification of bio-oil through friction catalysis by using graphene oxide |
| CN105753654A (en) * | 2016-02-04 | 2016-07-13 | 浙江大学 | Separation method of bio-oil molecular distillation heavy fraction |
| CN105753654B (en) * | 2016-02-04 | 2018-07-17 | 浙江大学 | A kind of separation method of bio oil molecular distillation heavy end |
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| CN102352270B (en) | 2014-08-13 |
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