CN1240811C - Process for hydrogenating oil obtained by fast cracking of bioplasm - Google Patents
Process for hydrogenating oil obtained by fast cracking of bioplasm Download PDFInfo
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- CN1240811C CN1240811C CN 02111203 CN02111203A CN1240811C CN 1240811 C CN1240811 C CN 1240811C CN 02111203 CN02111203 CN 02111203 CN 02111203 A CN02111203 A CN 02111203A CN 1240811 C CN1240811 C CN 1240811C
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- cracked oil
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Abstract
The present invention discloses a hydrogenating method of biomass fast cracking oil, which has the technical scheme that a hydrogen supply solvent is added to a hydrogenating catalyst used in oil refining industry to lower the coking rate under the technological conditions of appropriate reaction temperature, appropriate reaction time, appropriate reaction pressure, etc. so as to enhance properties of biomass fast cracking oil and widen the use range, which provides foundations for the development of biomass resources.
Description
Technical field
The present invention relates to a kind of hydroprocessing process of biomass quick cracked oil.
Background technology
As everyone knows, environment and energy problem will become the focus of 21st century whole world attention, along with oil, Nonrenewable energy resources such as Sweet natural gas and coal exhausted day by day and environmental pollution that they brought serious day by day, the various countries scholar has turned to sight the renewable resources-biomass resource of cleaning one after another.
It is that the purpose biomass flash pyrolysis is technical that the development and utilization of biomass mainly concentrates on to produce liquid fuel, because its higher liquid yield has caused global extensive concern.But because biomass quick cracked oil viscosity, density are bigger, oxygen level higher (40%), particularly its thermolability (being heated to 120 ℃ is that coking becomes the sponge coke body) causes it can not be directly as motor spirit, and because the existence of a large amount of oxygen-containing functional groups in the biomass cracked oil by using, compound such as aldehyde, ketone particularly, even if under normal temperature condition, also polycondensation can take place, cause the difficulty of its storage and transportation.In a word, want to enlarge the use range of biomass cracked oil by using, must make with extra care it.
The most effective solution is to improve the performance of bio-oil by hydrogenation deoxidation.But, just because of the peculiar property of biomass quick cracked oil causes its refining oil and the distillate thereof of being different from, and because the thermolability of biomass cracked oil by using, the processing that causes it is with difficult more.Although various countries are more for the biomass flash pyrolysis technical study, but for making with extra care of biomass quick cracked oil, the achievement that obtains at present is also less, patent has only 4,795,841 1 of United States Patent (USP)s, it has proposed the method for two step hydrotreatments in order to overcome unstable this important limitation of bio-oil.At first between 250 ℃-280 ℃, stablize and then carry out the pyritous Deep Hydrotreating.But just because of the processing of two steps, make byproduct increase, the productive rate that causes purpose product liquid product only is 35%.China also is in blank in the research aspect the processing of biomass quick cracked oil.
Summary of the invention
The objective of the invention is at the unsettled limitation of biomass cracked oil by using, a kind of hydroprocessing process of biomass quick cracked oil is provided, reduce the generation of byproducts such as gas, coke as far as possible, obtain higher liquid yield, produce the replacement liquid fluid fuel of oil, enlarge the use range of biomass quick cracked oil, provide the basis for biomass replace fossil oil.
Design of the present invention:
The inventor finds that after deliberation the hydrotreatment of biomass cracked oil by using exists competing reaction, i.e. the competition of deoxygenation and polyreaction, and biomass cracked oil by using can produce tar in its purified process, and these tar can further coking form coke.This research is taken off the generation that just can avoid coke with its oxygen before being desirably in the cracked oil coking.Therefore, must be that deoxygenation speed is greater than coking rate.Coking rate influence more complicated, but elevated temperature will increase deoxidation speed greatly, and discover that the coke predecessor is that the quantity of tar reduces along with the rising of temperature, therefore carry out the hydrogenation deoxidation reaction in a step and can reach the purpose of improving the cracked oil performance by elevated temperature.
Technical scheme of the present invention is:
Biomass quick cracked oil, catalyzer and hydrogen supply dissolvent are placed in the sealed reactor, feed hydrogen after the displaced air, being pressurized to pressure is 2-15Mpa, and heat temperature raising to 340 is ℃-550 ℃ then, reaction 10-240min.After reaction finished, reaction product was refined raw material oil obtained by fast cracking after cooling.
Wherein said catalyzer is CoMo/Al
2O
3Or NiMo/Al
2O
3, its consumption is the 3-25% of biomass quick cracked oil weight; Described hydrogen supply dissolvent is good with naphthane or perhydronaphthalene, and its consumption is that the 10-150% of biomass quick cracked oil weight is advisable; Preferred 10 ℃ of-50 ℃/min of temperature rise rate.
The hydroprocessing process of biomass quick cracked oil of the present invention has following advantage:
1. deoxidation speed was taken off oxygen before the cracked oil coking greater than coking rate, had reduced the generation of coke.
2. adopt hydrogen supply dissolvent in the reaction, played dilution and hydrogen supply.
3. the catalyzer of applicable industry production enlarges its scope of application.
4. a step finishes, and reduces operation easier, increases the productive rate of purpose product.
Specific implementation method
The invention will be further described below by embodiment:
Example one
With the hydrogenation deoxidation is that purpose is carried out hydrotreatment to biomass cracked oil by using:
With the active ingredient is the catalyzer of CoMo, and at stagnation pressure 11.2Mpa, reaction times 60min under the operational condition that temperature of reaction is 360 ℃, can make the oxygen level in the product drop to 2.97wt% by the 41.8wt% of raw material.
Example two
With the hydrocracking is that main purpose is carried out hydrotreatment to biomass cracked oil by using:
With the active ingredient is the catalyzer of CoMo, at stagnation pressure 16Mpa reaction times 60min, under the operational condition that temperature of reaction is 390 ℃, can make intermediate oil (C
5～350 ℃) account for the 88wt% of total liquid yield.
Claims (2)
1, a kind of hydroprocessing process of biomass quick cracked oil, it is characterized in that, the key step of described method is that biomass quick cracked oil, catalyzer and hydrogen supply dissolvent are placed in the sealed reactor, feed hydrogen after the displaced air, being pressurized to pressure is 2～15Mpa, then heat temperature raising to 340 ℃～550 ℃, reacted 10～240 minutes, after reaction finished, reaction product was refined raw material oil obtained by fast cracking after cooling
Wherein said catalyzer is CoMo/Al
2O
3Or NiMo/Al
2O
3, its consumption is 3～25% of a biomass quick cracked oil weight, and described hydrogen supply dissolvent is naphthane or perhydronaphthalene, and the hydrogen supply dissolvent consumption is 10～150% of a biomass quick cracked oil weight.
2, the described hydroprocessing process of claim 1 is characterized in that, wherein temperature rise rate is 10 ℃～50 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02111203 CN1240811C (en) | 2002-03-29 | 2002-03-29 | Process for hydrogenating oil obtained by fast cracking of bioplasm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02111203 CN1240811C (en) | 2002-03-29 | 2002-03-29 | Process for hydrogenating oil obtained by fast cracking of bioplasm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1376766A CN1376766A (en) | 2002-10-30 |
| CN1240811C true CN1240811C (en) | 2006-02-08 |
Family
ID=4741444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02111203 Expired - Fee Related CN1240811C (en) | 2002-03-29 | 2002-03-29 | Process for hydrogenating oil obtained by fast cracking of bioplasm |
Country Status (1)
| Country | Link |
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| CN (1) | CN1240811C (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173177B (en) * | 2007-10-19 | 2012-05-16 | 华东理工大学 | Method and device for on-line catalytic pyrolysis fine purification of biomass |
| CN101831328B (en) * | 2010-05-21 | 2012-12-12 | 张小红 | Green fuel oil and preparation method thereof |
| CN102433153A (en) * | 2011-10-21 | 2012-05-02 | 华东理工大学 | Method for refining biological oil |
| CN103173237B (en) * | 2011-12-23 | 2015-01-21 | 中国林业科学研究院木材工业研究所 | Biomass alcoholysis method and biomass alcoholysis oil preparation method |
| CN103173243B (en) * | 2011-12-23 | 2015-02-18 | 中国林业科学研究院木材工业研究所 | Method for hydrofining biomass alcoholysis heavy oil |
| CN102851062B (en) * | 2012-05-08 | 2014-12-24 | 郑州大学 | Organic-solvent-promoted bio-oil catalytic hydrogenation process method |
| CN103820141B (en) * | 2012-11-16 | 2015-09-30 | 中国科学院大连化学物理研究所 | A kind of biological cracked oil prepares the method for liquid fuel |
| CN103215068B (en) | 2013-05-07 | 2015-06-03 | 武汉凯迪工程技术研究总院有限公司 | Modification method of biomass pyrolysis oil |
| AT515486B1 (en) | 2014-02-24 | 2017-05-15 | Technische Universität Graz | method |
| CN105733627B (en) * | 2016-04-01 | 2018-09-21 | 华中科技大学 | A kind of biomass fast pyrogenation and coal-burning boiler coupled system |
| CN105694944B (en) * | 2016-04-14 | 2017-08-04 | 广西大学 | A kind of method that stearic acid or waste oil catalytic hydrogenation prepares diesel oil distillate |
| CN108435262B (en) * | 2017-12-26 | 2021-04-27 | 中国科学院长春应用化学研究所 | Treatment method of carbon deposition catalyst generated by synthesizing isoprene by olefine aldehyde gas phase method |
| CN109967003A (en) * | 2019-04-26 | 2019-07-05 | 河南百优福生物能源有限公司 | A kind of biomass pyrolysis liquid fluidized bed reactor and its application |
| CN110218573A (en) * | 2019-06-18 | 2019-09-10 | 太原理工大学 | A kind of no catalyst coal base heavy component method for upgrading |
| CN110846070A (en) * | 2019-11-13 | 2020-02-28 | 南阳理工学院 | Method for carrying out hydrogenation modification on crude bio-oil by using elemental metal aluminum as hydrogen source |
| CN113789192A (en) * | 2021-09-22 | 2021-12-14 | 华中科技大学 | Method for inhibiting biological oil from being coked by heating |
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2002
- 2002-03-29 CN CN 02111203 patent/CN1240811C/en not_active Expired - Fee Related
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Granted publication date: 20060208 Termination date: 20110329 |