CN102433153A - Refining method of bio-oil - Google Patents
Refining method of bio-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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- Prior art keywords
- oil
- water
- coarse biometric
- catalyzer
- bio
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- 238000007670 refining Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000012075 bio-oil Substances 0.000 title abstract description 9
- 235000019198 oils Nutrition 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000019476 oil-water mixture Nutrition 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical group C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 abstract description 54
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000004904 shortening Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- -1 catalyzer Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明公开了一种生物油的精制方法。该方法将粗生物油在一氧化碳和水体系中，250-350℃，1-6Mpa，250-750r/min，催化10-60min，得油水混合物，油水分离后得精制油。本发明可以充分利用粗生物油中的水，水与一氧化碳应产生氢气，氢气与粗生物油中的氧结合生成水。整个反应体系中的水含量不增加，有利于反应的进行，提高精制效果和精制油产率。The invention discloses a bio-oil refining method. The method is to place crude bio-oil in a carbon monoxide and water system at 250-350°C, 1-6Mpa, 250-750r/min, catalyze for 10-60min to obtain an oil-water mixture, and to obtain refined oil after oil-water separation. The invention can make full use of water in the crude bio-oil, water and carbon monoxide should generate hydrogen, and hydrogen combines with oxygen in the crude bio-oil to generate water. The water content in the entire reaction system does not increase, which is conducive to the reaction, and improves the refining effect and the refined oil yield.
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).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103260492A CN102433153A (en) | 2011-10-21 | 2011-10-21 | Refining method of bio-oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103260492A CN102433153A (en) | 2011-10-21 | 2011-10-21 | Refining method of bio-oil |
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| Publication Number | Publication Date |
|---|---|
| CN102433153A true CN102433153A (en) | 2012-05-02 |
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| CN2011103260492A Pending CN102433153A (en) | 2011-10-21 | 2011-10-21 | Refining method of bio-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 | The Boudual reaction of the hydrolysis of bound water for the production of 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 | A kind of refining method of 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 | A kind of refining method of biological oil |
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 | The Boudual reaction of the hydrolysis of bound water for the production of methane |
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Application publication date: 20120502 |