CN101851560A - Method for improving quality of bio-oil through ozonization-esterification - Google Patents
Method for improving quality of bio-oil through ozonization-esterification Download PDFInfo
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- CN101851560A CN101851560A CN201010179498A CN201010179498A CN101851560A CN 101851560 A CN101851560 A CN 101851560A CN 201010179498 A CN201010179498 A CN 201010179498A CN 201010179498 A CN201010179498 A CN 201010179498A CN 101851560 A CN101851560 A CN 101851560A
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Abstract
The invention discloses a method for improving the quality of bio-oil through ozonization-esterification, which comprises the following steps: 1. ozonization reaction: introducing ozone into the bio-oil to generate oxidation reaction for obtaining oxidized bio-oil, and stopping the introduction of the ozone when the acid value of the oxidized bio-oil reaches 110 to 130 mg KOH/g; and 2. esterification reaction: simultaneously adding the oxidized bio-oil, normal butanol and catalysts into a reaction kettle with a water segregator, carrying out heating back flowing water segregation until no water is segregated out, stopping the reaction, and obtaining products of the bio-oil after the quality improvement. The acid value is between 10 and 35 mg KOH/g.
Description
Technical field
The invention belongs to the biomass energy source domain, relate generally to the novel method that biomass pyrolysis liquefaction oil upgrading modification prepares oil fuel.
Background technology
Primary energy source based on oil, coal is exhausted just day by day, and biomass energy is to utilize renewable or the round-robin organic substance, comprise that farm crop, trees and other plant and residual body thereof etc. are raw material, carry out the industry that bio-based product, biofuel and bioenergy are produced.Biomass cracked oil by using is the resulting product liquid of the direct pyrolysis liquefaction of biomass, other the energy utilization mode of comparing, biomass cracked oil by using energy density height, convenient transportation.And this pyrolysis oil sulfur-bearing and nitrogen are seldom, can reduce the content of SOx, NOx in the discharging gas greatly, reduced atmospheric pollution; On the other hand, because of it comes from biomass, utilize CO in the process at energy
2Clean quantity discharged is zero.Yet the process of biomass pyrolytic does not reach thermodynamic(al)equilibrium, so the physicochemical property instability of biomass cracked oil by using, mainly showing as biological oil viscosity increases gradually with storage time and temperature.The bio oil calorific value is low in addition, the pH value is low, solid impurity content height.
Because the bio oil thermostability is relatively poor, cause condensation, polyreaction take place in its modifying process easily, make bio oil viscosity increase, stop up reactor pipeline.The condensation reaction that this situation takes place mainly is aldehydes matter and aldehyde material causes.
Summary of the invention
In order to solve the unsettled shortcoming of biomass cracked oil by using physicochemical property that exists in the prior art, the invention provides a kind of method of improving quality of bio-oil through ozonization-esterification, technology is simple, and the modifying bio-oil physicochemical property of production are stable.
Technical scheme of the present invention is: a kind of method of improving quality of bio-oil through ozonization-esterification may further comprise the steps:
The first step, ozonization: ozone fed in the bio oil oxidizing reaction takes place obtain the oxidation bio oil, when the acid number of oxidation bio oil reaches 110～130mgKOH/g, stop to feed ozone;
In second step, esterification: oxidation bio oil, propyl carbinol and catalyzer are joined simultaneously in the reactor of band water trap, reflux is divided water, and when no longer including moisture and go out, stopped reaction, product are the bio oil after the upgrading, and acid number is 10～35mgKOH/g.
Described ozone is provided by ozonizer.
The ozonization temperature is controlled at 0-30 ℃.
In the esterification, the mass ratio m of oxidation bio oil, propyl carbinol and catalyzer
The oxidation bio oil: m
Butanols: m
Catalyzer=100: 50～150: 1～10.
Catalyzer is any one in sulfuric acid, phosphoric acid, sodium pyrosulfate, the sal enixum in the described esterification.
Beneficial effect:
1. reaction conditions gentleness, cleanliness without any pollution in the whole upgrading process.
2. use ozone effectively the aldehyde material in the bio oil to be converted into carboxylic acid in the method for the present invention, reduce the incidence of condensation reaction in the esterification process, effectively improve the thermostability of bio oil.
Description of drawings
Fig. 1 is the gel chromatography molecular weight graphic representation of the product of bio oil, oxidation bio oil, improving quality of bio oil, bio oil direct esterification.
Wherein 1 is that bio oil, 2 is that oxidation bio oil, 3 is that improving quality of bio oil, 4 is the gel chromatography molecular weight curve of the product of bio oil direct esterification.
Embodiment
A kind of method of improving quality of bio-oil through ozonization-esterification may further comprise the steps:
The first step, ozonization: ozone fed in the bio oil oxidizing reaction takes place obtain the oxidation bio oil, when the acid number of oxidation bio oil reaches 110～130mgKOH/g, stop to feed ozone; Described ozone is provided by ozonizer.The ozone flow that ozonizer among the present invention at present can provide is 5g/h.When the amount of bio oil during at 150g, the ozonization time is about 6～20h.The ozonization temperature is controlled at 0-30 ℃.During ozonization, the time that then needs when the flow of ozone is little is relatively length just, and the reaction times that needs when flow is big is just shorter, can be by control ozone flow from by the controlled oxidation time.
Second step, esterification: press mass ratio m
The oxidation bio oil: m
Butanols: m
Catalyzer=100: 50～150: 1～10 ratio, take by weighing oxidation bio oil, propyl carbinol and catalyzer, then, join simultaneously in the reactor of band water trap.Reflux is divided water, and temperature of reaction remains on about 120 ℃.Reaction until after stopped reaction when no longer including moisture and going out, this process approximately needs 3～8 hours, the product that obtains is the bio oil after the upgrading, acid number is 10～35mgKOH/g.Catalyzer is any one in sulfuric acid, phosphoric acid, sodium pyrosulfate, the sal enixum in the described esterification.
Embodiment 1:
Take by weighing the 150g bio oil, the mensuration acid number is 45.4mgKOH/g, ozone is fed oxidizing reaction takes place in the bio oil, and 20 ℃ of controlled temperature, ozone generation flow are 5g/h, continues to feed reaction 10h.Record product acid number 118.4mgKOH/g after the oxidation.With 100g oxidation bio oil and 100g propyl carbinol, 5g sulfuric acid joins in the reactor of band water trap.Reflux is divided water, and temperature of reaction remains on about 120 ℃.React when no longer including moisture after about 5 hours and going out, stopped reaction, product are the bio oil after the upgrading, acid number 14.5mgKOH/g.
Embodiment 2:
Take by weighing the 150g bio oil, the mensuration acid number is 45.4mgKOH/g, ozone is fed oxidizing reaction takes place in the bio oil, and 0 ℃ of controlled temperature, ozone generation flow are 5g/h, continues to feed reaction 6h.Record product acid number 112.8mgKOH/g after the oxidation.With 100g oxidation bio oil and 100g propyl carbinol, 5g sulfuric acid joins in the reactor of band water trap.Reflux is divided water, and temperature of reaction remains on about 120 ℃.React when no longer including moisture after about 5 hours and going out, stopped reaction, product are the bio oil after the upgrading, acid number 15.7mgKOH/g.
Embodiment 3:
Take by weighing the 150g bio oil, the mensuration acid number is 45.4mgKOH/g, ozone is fed oxidizing reaction takes place in the bio oil, and 30 ℃ of controlled temperature, ozone generation flow are 5g/h, continues to feed reaction 20h.Record product acid number 126.3mgKOH/g after the oxidation.With 100g oxidation products and 100g propyl carbinol, 5g sulfuric acid joins in the reactor of band water trap.Reflux is divided water, and temperature of reaction remains on about 120 ℃.React when no longer including moisture after about 5 hours and going out, stopped reaction, product are the bio oil after the upgrading, acid number 14.7mgKOH/g.
Embodiment 4:
Take by weighing the 150g bio oil, the mensuration acid number is 45.4mgKOH/g, ozone is fed oxidizing reaction takes place in the bio oil, and 20 ℃ of controlled temperature, ozone generation flow are 5g/h, continues to feed reaction 10h.Record product acid number 118.4mgKOH/g after the oxidation.With 100g oxidation bio oil and 50g propyl carbinol, 1g sulfuric acid joins in the reactor of band water trap.Reflux is divided water, and temperature of reaction remains on about 120 ℃.React when no longer including moisture after about 6 hours and going out, stopped reaction, product are the bio oil after the upgrading, acid number 23.4mgKOH/g.
Embodiment 5:
Take by weighing the 150g bio oil, the mensuration acid number is 45.4mgKOH/g, ozone is fed oxidizing reaction takes place in the bio oil, and 20 ℃ of controlled temperature, ozone generation flow are 5g/h, continues to feed reaction 10h.Record product acid number 118.4mgKOH/g after the oxidation.With 100g oxidation bio oil and 150g propyl carbinol, 10g sulfuric acid joins in the reactor of band water trap.Reflux is divided water, and temperature of reaction remains on about 120 ℃.React when no longer including moisture after about 4 hours and going out, stopped reaction, product are the bio oil after the upgrading, acid number 13.8mgKOH/g.
Embodiment 6:
Take by weighing the 150g bio oil, the mensuration acid number is 45.4mgKOH/g, ozone is fed oxidizing reaction takes place in the bio oil, and 20 ℃ of controlled temperature, ozone generation flow are 5g/h, continues to feed reaction 10h.Record product acid number 118.4mgKOH/g after the oxidation.With 100g oxidation bio oil and 100g propyl carbinol, 5g phosphoric acid joins in the reactor of band water trap.Reflux is divided water, and temperature of reaction remains on about 120 ℃.React when no longer including moisture after about 6 hours and going out, stopped reaction, product are the bio oil after the upgrading, acid number 33.8mgKOH/g.
Embodiment 7:
Take by weighing the 150g bio oil, the mensuration acid number is 45.4mgKOH/g, ozone is fed oxidizing reaction takes place in the bio oil, and 20 ℃ of controlled temperature, ozone generation flow are 5g/h, continues to feed reaction 10h.Record product acid number 118.4mgKOH/g after the oxidation.With 100g oxidation bio oil and 100g propyl carbinol, the 5g sodium pyrosulfate joins in the reactor of band water trap.Reflux is divided water, and temperature of reaction remains on about 120 ℃.React when no longer including moisture after about 6 hours and going out stopped reaction.Catalyzer filtered and recycled, filtrate are the bio oil after the upgrading, acid number 22.3mgKOH/g.
Embodiment 8:
Take by weighing the 150g bio oil, the mensuration acid number is 45.4mgKOH/g, ozone is fed oxidizing reaction takes place in the bio oil, and 20 ℃ of controlled temperature, ozone generation flow are 5g/h, continues to feed reaction 10h.Record product acid number 118.4mgKOH/g after the oxidation.With 100g oxidation bio oil and 100g propyl carbinol, the 5g sal enixum joins in the reactor of band water trap.Reflux is divided water, and temperature of reaction remains on about 120 ℃.React when no longer including moisture after about 6 hours and going out stopped reaction.Catalyzer filtered and recycled, filtrate are the bio oil after the upgrading, acid number 20.8mgKOH/g.
Embodiment 9-12:
The oxidation bio oil that bio oil, the first step ozonization are obtained, second step bio oil and the product of bio oil direct esterification after the esterification upgrading carries out gel chromatography (molecular weight) and measures.
As shown in Figure 1, from the result, the molecular weight of the bio oil after the oxidation bio oil generation esterification upgrading that the first step ozonization obtains and protista oil base are originally identical, about 5500; And inoxidized bio oil molecular weight after esterification has reached 19000.Illustrate by oxidizing reaction, obviously improved the stability of bio oil in modifying process, reduced the generation of polyreaction.
Claims (5)
1. the method for an improving quality of bio-oil through ozonization-esterification is characterized in that, may further comprise the steps:
The first step, ozonization: ozone fed in the bio oil oxidizing reaction takes place obtain the oxidation bio oil, when the acid number of oxidation bio oil reaches 110～130mgKOH/g, stop to feed ozone;
In second step, esterification: oxidation bio oil, propyl carbinol and catalyzer are joined simultaneously in the reactor of band water trap, reflux is divided water, and when no longer including moisture and go out, stopped reaction, product are the bio oil after the upgrading, and acid number is 10～35mgKOH/g.
2. the method for improving quality of bio-oil through ozonization-esterification according to claim 1 is characterized in that described ozone is provided by ozonizer.
3. the method for improving quality of bio-oil through ozonization-esterification according to claim 1 is characterized in that the ozonization temperature is controlled at 0-30 ℃.
4. the method for improving quality of bio-oil through ozonization-esterification according to claim 1 is characterized in that, in the esterification, and the mass ratio m of oxidation bio oil, propyl carbinol and catalyzer
The oxidation bio oil: the m fourth
Alcohol: m
Catalyzer=100: 50～150: 1～10.
5. the method for improving quality of bio-oil through ozonization-esterification according to claim 1 is characterized in that catalyzer is any one in sulfuric acid, phosphoric acid, sodium pyrosulfate, the sal enixum in the described esterification.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109234021A (en) * | 2018-09-26 | 2019-01-18 | 西安科技大学 | A kind of preparation method of medical ozone carburetion |
| CN111320231A (en) * | 2020-02-26 | 2020-06-23 | 江苏大学 | System and method for upgrading algae bio-oil based on CdS ultrasonic coupling photocatalysis |
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| CN1156717A (en) * | 1996-11-26 | 1997-08-13 | 厦门大学 | Process for producing n-butyl acetate |
| CN101045682A (en) * | 2006-03-28 | 2007-10-03 | 中国石油化工集团公司 | Method for retrieving organic acid, ester from cyclic ethane oxidation liquid |
| CN101113349A (en) * | 2006-07-27 | 2008-01-30 | 上海中油企业集团有限公司 | Method for producing biodiesel with convenient post-treatment |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156717A (en) * | 1996-11-26 | 1997-08-13 | 厦门大学 | Process for producing n-butyl acetate |
| CN101045682A (en) * | 2006-03-28 | 2007-10-03 | 中国石油化工集团公司 | Method for retrieving organic acid, ester from cyclic ethane oxidation liquid |
| CN101113349A (en) * | 2006-07-27 | 2008-01-30 | 上海中油企业集团有限公司 | Method for producing biodiesel with convenient post-treatment |
Non-Patent Citations (1)
| Title |
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| 《江苏大学学报》 20100331 储金宇，等 臭氧氧化处理长江低含油量压载水试验 221-224 1-5 第31卷, 第2期 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109234021A (en) * | 2018-09-26 | 2019-01-18 | 西安科技大学 | A kind of preparation method of medical ozone carburetion |
| CN109234021B (en) * | 2018-09-26 | 2021-10-08 | 陕西福科原力健康科技有限公司 | Preparation method of medical ozonized oil |
| CN111320231A (en) * | 2020-02-26 | 2020-06-23 | 江苏大学 | System and method for upgrading algae bio-oil based on CdS ultrasonic coupling photocatalysis |
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