CN102433153A - Method for refining biological oil - Google Patents
Method for refining biological oil Download PDFInfo
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- CN102433153A CN102433153A CN2011103260492A CN201110326049A CN102433153A CN 102433153 A CN102433153 A CN 102433153A CN 2011103260492 A CN2011103260492 A CN 2011103260492A CN 201110326049 A CN201110326049 A CN 201110326049A CN 102433153 A CN102433153 A CN 102433153A
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- oil
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention discloses a method for refining biological oil, which comprises: preparing an oil and water mixture from coarse biological oil in a carbon monoxide and water system by 10 to 60 minutes of catalytic reaction at 250 to 350 DEG C, under 1 to 6Mpa and at a rotation speed of 250 to 750r/min; and separating oil from water to obtain refined oil. When the method is used, the water in the coarse biological oil can be fully utilized, water reacts with carbon monoxide to form hydrogen, and hydrogen is combined with oxygen in the coarse biological oil to form water. In the whole reaction system, the water content is not increased, which is favorable for promoting the reaction and improving refining effect and yield of refined oil.
Description
Technical field
The present invention relates to a kind of method for refining biological oil.
Background technology
Serious day by day along with problem of environmental pollution, the clean renewable energy source of exploitation becomes the task of top priority.Biomass receive countries in the world in recent years day by day and pay attention to as unique renewable energy source that can be converted into liquid fuel.
Prepare in the liquid fuel technology in biomass, the rapidly pyrolysing and liquefying biomass technology has obtained development rapidly since coming out the eighties in last century.But because oily high-moisture (15-30%), rich oxygen content (40-50%), high viscosity, low heat value (the about 16-20MJ/Kg of coarse biometric oil calorific value of coarse biometric; And the general 42MJ/Kg of motor spirit), the strong character such as (the pH value are about 2.5) of acidity has hindered its use as motor spirit.Therefore, the refining problem demanding prompt solution that becomes of coarse biometric oil.
Shortening be high pressure (10-20Mpa with exist under the hydrogen supply dissolvent condition) with Co-Mo, Ni-Mo and oxide compound thereof or with above active constituent loading at Al
2O
3Deng as catalyzer bio oil being carried out unifining on the carrier.The investigator mainly adopts direct shortening mode in the shortening process.But bio oil is in direct shortening process; Oxygen in active ingredient hydrogen and the bio oil in the oxygenatedchemicals combines to generate water, causes the water-content in the bio oil further to increase (coarse biometric oil water cut is about 15-30wt%), and excessive water suppresses the carrying out of hydrogenation reaction; Liquid yield is lower; Carry out so unifining process generally adopts under higher temperatures (350-500 ℃) and the higher pressure (10-20Mpa), in the reaction process coking more serious, capacity usage ratio is relatively low; Required equipment and refining cost are higher, and in the operating process problem of catalyst deactivation and reactor plugs take place easily.
Therefore, overcome the defective in the existing coarse biometric oil catalytic hydrogenation method, just become the technical issues that need to address of the present invention.
Summary of the invention
Technical problem to be solved by this invention is the defective that overcomes in the existing coarse biometric oil catalytic hydrogenation method.Coarse biometric oil refining method of the present invention, it comprises the steps:
Coarse biometric oil, catalyzer, organic solvent mixing are placed in the autoclave reactor, feed CO to autoclave by the CO steel cylinder, in 250-350 ℃, 1-6Mpa, 250-750r/min, catalysis 10-60min gets oil-water mixture, gets treated oil after the oily water separation.
Wherein, used catalyzer is commercial catalysts B206 in treating process, and the weight of catalyzer is the 2%-20% of coarse biometric weight of oil.The B206 catalyzer that preferred Nanjing Chemical Industry Co., Ltd., SINOPEC produces.
Wherein, organic solvent is naphthane or perhydronaphthalene, and itself and the oily mass ratio of coarse biometric are 1: (1-2).
The used coarse biometric oil of the present invention be by wood chip (coming from wood-working factory) at 500 ℃, nitrogen is done the product liquid that obtains through fast pyrolysis under the condition of fluidized gas, is called for short coarse biometric oil.Concrete experimentation is seen a polished big paper, " biomass fluid bed quick cracking preparing liquid fuel ", solar energy journal, 2003,23 (4): 462-467.
Positive progressive effect of the present invention is: through the inventive method to coarse biometric oil catalytic refining after, the water-content in the whole reaction system does not increase, and helps the carrying out that react, and improves refining effect and treated oil productive rate.
Embodiment
Mode through embodiment further specifies the present invention below, but does not therefore limit the present invention among the described scope of embodiments.
Used coarse biometric oil is at 500 ℃ by wood chip (coming from wood-working factory) in the following example; Nitrogen is done the product liquid that obtains through fast pyrolysis under the condition of fluidized gas; Concrete experimentation is seen a polished big paper, " biomass fluid bed quick cracking preparing liquid fuel ", solar energy journal; 2003,23 (4): 462-467.
Embodiment 1
Experiment is carried out in autoclave; The mixed solution that at first in reactor drum, adds 100ml coarse biometric oil and naphthane (coarse biometric oil is 2: 1 with the mass ratio of naphthane) before the experiment; Add the B206 catalyzer again, the add-on of catalyzer is the 20wt% of used coarse biometric weight of oil.Feed carbon monoxide then, making the pressure in the reactor drum is 6Mpa, adds 350 ℃ of thermics; Agitator speed is set to 750r/min, and condensation caused room temperature after this state kept 60min, got oil-water mixture; (carbon content is 87.16% in the refining biological oil to get refining biological oil after the separation; Hydrogen richness is 9.64%, and oxygen level is 3.20%), the treated oil productive rate is 87.42%.
Embodiment 2
Experiment is carried out in autoclave; The mixed solution that at first in reactor drum, adds 100ml coarse biometric oil and naphthane (coarse biometric oil is 2: 1 with the mass ratio of naphthane) before the experiment; Add the B206 catalyzer again, the add-on of catalyzer is the 2wt% of used coarse biometric weight of oil.Feed carbon monoxide then, making the pressure in the reactor drum is 6Mpa, adds 350 ℃ of thermics; Agitator speed is set to 750r/min, and condensation caused room temperature after this state kept 60min, got oil-water mixture; (carbon content is 85.63% in the refining biological oil to get refining biological oil after the separation; Hydrogen richness is 9.19%, and oxygen level is 5.18%), the treated oil productive rate is 86.93%.
Embodiment 3
Experiment is carried out in autoclave; The mixed solution that at first in reactor drum, adds 100ml coarse biometric oil and naphthane (coarse biometric oil is 2: 1 with the mass ratio of naphthane) before the experiment; Add the B206 catalyzer again, the add-on of catalyzer is the 2wt% of used coarse biometric weight of oil.Feed carbon monoxide then, making the pressure in the reactor drum is 1Mpa, adds 350 ℃ of thermics; Agitator speed is set to 750r/min, and condensation caused room temperature after this state kept 60min, got oil-water mixture; (carbon content is 81.20% in the refining biological oil to get refining biological oil after the separation; Hydrogen richness is 8.95%, and oxygen level is 9.85%), the treated oil productive rate is 84.14%.
Embodiment 4
Experiment is carried out in autoclave; The mixed solution that at first in reactor drum, adds 100ml coarse biometric oil and naphthane (coarse biometric oil is 2: 1 with the mass ratio of naphthane) before the experiment; Add the B206 catalyzer again, the add-on of catalyzer is the 10wt% of used coarse biometric weight of oil.Feed carbon monoxide then, making the pressure in the reactor drum is 4Mpa, adds 250 ℃ of thermics; Agitator speed is set to 750r/min, and condensation caused room temperature after this state kept 60min, got oil-water mixture; (carbon content is 82.34% in the refining biological oil to get refining biological oil after the separation; Hydrogen richness is 9.15%, and oxygen level is 8.51%), the treated oil productive rate is 80.25%.
Embodiment 5
Experiment is carried out in autoclave; The mixed solution that at first in reactor drum, adds 100ml coarse biometric oil and naphthane (coarse biometric oil is 2: 1 with the mass ratio of naphthane) before the experiment; Add the B206 catalyzer again, the add-on of catalyzer is the 10wt% of used coarse biometric weight of oil.Feed carbon monoxide then, making the pressure in the reactor drum is 4Mpa, adds 350 ℃ of thermics; Agitator speed is set to 250r/min, and condensation caused room temperature after this state kept 60min, got oil-water mixture; (carbon content is 81.64% in the refining biological oil to get refining biological oil after the separation; Hydrogen richness is 7.38%, and oxygen level is 10.98%), the treated oil productive rate is 81.67%.
Embodiment 6
Experiment is carried out in autoclave; The mixed solution that at first in reactor drum, adds 100ml coarse biometric oil and naphthane (coarse biometric oil is 2: 1 with the mass ratio of naphthane) before the experiment; Add the B206 catalyzer again, the add-on of catalyzer is the 10wt% of used coarse biometric weight of oil.Feed carbon monoxide then, making the pressure in the reactor drum is 4Mpa, adds 350 ℃ of thermics; Agitator speed is set to 750r/min, and condensation caused room temperature after this state kept 10min, got oil-water mixture; (carbon content is 84.45% in the refining biological oil to get refining biological oil after the separation; Hydrogen richness is 8.89%, and oxygen level is 6.66%), the treated oil productive rate is 86.34%.
Claims (5)
1. a method for refining biological oil is at CO/H with coarse biometric oil
2In the O system, under organic solvent and catalyst action, carry out catalyzed reaction.
2. the method for claim 1, it is characterized in that: said reaction conditions is temperature of reaction: 250-350 ℃, reaction pressure: 1-6Mpa, rotating speed: 250-750r/min, catalysis 10-60min, oil-water mixture, after the oily water separation treated oil.
3. the method for claim 1, it is characterized in that: described catalyzer is commercial catalysts B206.
4. the method for claim 1, it is characterized in that: wherein the weight of catalyzer is the 2%-20% of coarse biometric weight of oil.
5. the method for claim 1, it is characterized in that: wherein organic solvent is naphthane or perhydronaphthalene, the mass ratio of itself and coarse biometric oil is 1: (1-2).
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| CN2011103260492A CN102433153A (en) | 2011-10-21 | 2011-10-21 | Method for refining biological oil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107810252A (en) * | 2015-06-24 | 2018-03-16 | 卡尔·维尔纳·迪特里希 | Boudouard reaction for the hydrolysis of the combination water that manufactures methane |
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| CN1376766A (en) * | 2002-03-29 | 2002-10-30 | 华东理工大学 | Process for hydrogenating oil obtained by fast cracking of bioplasm |
| CN1990832A (en) * | 2005-12-29 | 2007-07-04 | 中国石油化工股份有限公司 | Quality modified method for hydrocarbon oil |
| WO2009016477A2 (en) * | 2007-08-01 | 2009-02-05 | Nagarjuna Energy Private Limited | A process for producing small molecular weight organic compounds from carbonaceous material |
| CN101565631A (en) * | 2009-06-02 | 2009-10-28 | 华东理工大学 | Method for directly liquefying coal in CO and H2O system |
| CN101676367A (en) * | 2008-09-10 | 2010-03-24 | 赫多特普索化工设备公司 | Improved hydrotreatment process |
| US20100256428A1 (en) * | 2009-04-07 | 2010-10-07 | Gas Technology Institute | Hydropyrolysis of biomass for producing high quality liquid fuels |
| CN101885986A (en) * | 2010-07-16 | 2010-11-17 | 华东理工大学 | Method for refining biological oil |
| WO2010149137A2 (en) * | 2009-06-26 | 2010-12-29 | Hochschule für Angewandte Wissenschaften Hamburg (HAW Hamburg) | Biorefinery method |
-
2011
- 2011-10-21 CN CN2011103260492A patent/CN102433153A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376766A (en) * | 2002-03-29 | 2002-10-30 | 华东理工大学 | Process for hydrogenating oil obtained by fast cracking of bioplasm |
| CN1990832A (en) * | 2005-12-29 | 2007-07-04 | 中国石油化工股份有限公司 | Quality modified method for hydrocarbon oil |
| WO2009016477A2 (en) * | 2007-08-01 | 2009-02-05 | Nagarjuna Energy Private Limited | A process for producing small molecular weight organic compounds from carbonaceous material |
| CN101676367A (en) * | 2008-09-10 | 2010-03-24 | 赫多特普索化工设备公司 | Improved hydrotreatment process |
| US20100256428A1 (en) * | 2009-04-07 | 2010-10-07 | Gas Technology Institute | Hydropyrolysis of biomass for producing high quality liquid fuels |
| CN101565631A (en) * | 2009-06-02 | 2009-10-28 | 华东理工大学 | Method for directly liquefying coal in CO and H2O system |
| WO2010149137A2 (en) * | 2009-06-26 | 2010-12-29 | Hochschule für Angewandte Wissenschaften Hamburg (HAW Hamburg) | Biorefinery method |
| CN101885986A (en) * | 2010-07-16 | 2010-11-17 | 华东理工大学 | Method for refining biological oil |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107810252A (en) * | 2015-06-24 | 2018-03-16 | 卡尔·维尔纳·迪特里希 | Boudouard reaction for the hydrolysis of the combination water that manufactures methane |
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Application publication date: 20120502 |