CN102199440A - Method for preparing low-acidity and low-oxygen content biological oil by two-section conversion - Google Patents
Method for preparing low-acidity and low-oxygen content biological oil by two-section conversion Download PDFInfo
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- CN102199440A CN102199440A CN2011100984219A CN201110098421A CN102199440A CN 102199440 A CN102199440 A CN 102199440A CN 2011100984219 A CN2011100984219 A CN 2011100984219A CN 201110098421 A CN201110098421 A CN 201110098421A CN 102199440 A CN102199440 A CN 102199440A
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Abstract
The invention discloses a method for preparing low-acidity and low-oxygen content biological oil by the two-stage conversion of biomass, which comprises: allowing biomass granules (which are less than or equal to 1 millimeter) serving as raw materials to enter a fluidized bed reactor from the screw feeder at the speed of 0.005 t/h; cracking in a fluidized bed cracking reactor at the temperature of between 400 and 450 DEG C under the condition that the N2 feed is 1.37 m<3>/hour and under the pressure of between 0.01 and 0.1 MPa; and condensing biological oil steam by a microwave catalyst bed and the upgrading deoxidation of a catalyst under the condition of taking noncondensable gas generated by a cracking reaction as spouted gas and fluidifying gas (a ratio of the spouted gas to the fluidifying gas ranges from 1 to 10) and carrier gas to obtain the low-acidity and low-oxygen content biological oil. When the method is used, steam products can outflow continuously, and the biomass granules serving as the raw materials are circulated in a bed (the retention time of the biomass granules in the reactor is 0.1 to 3 seconds), so that large granules are cracked fully until the granules are diminished to be discharged from a bed layer by the gas. The biomass oil steam cracked by the fluidized bed in the first stage is subjected to catalytic upgrading in a microwave field, so energy consumption is reduced, and the quality of the biological oil is improved.
Description
Technical field
The present invention relates to the method for a kind of bio oil preparation and online upgrading, promptly prepare the method for high-quality liquid fuel with fluidized-bed-two sections cracking conversion systems of microwave reinforced catalytic bed.
Background technology
The energy and environmental problem have become the focus that the whole world is paid close attention at present, and fossil fuel resource is still being played the part of the role of world energy sources pillar and large organic chemical industry's rule of origin.Fossil oil is when promoting the well-being of mankind, and also the environment of depending on for existence to the mankind has caused severe contamination, and fossil oil must exhaust in the near future, and it is imperative to seek its alternate resources.Biomass enlarge and optimize it and utilize the common recognition that has become the whole world as unique renewable energy source that can be converted into liquid fuel.The liquid fuel (being commonly referred to bio oil) that is transformed by biomass cracking is substantially free of sulphur, nitrogen and metal ingredient, environmentally safe.Except from the energy utilization angle is considered, also, can be used as the primary raw materials of many organic chemical industry's products because of containing the organism of abundant higher utility value in the bio oil.By the regulating effect of different catalysts, can realize that different organic highly selectivies generate.In addition because biomass fuel has the carbon dioxide zero discharge characteristics, so clean effectively utilization of biomass resource helps reducing greenhouse gas emission.
Biomass typically refer to terrestrial plant (timber, yule logs, stalk etc.) and waterplant, are a kind of stable renewable energy source resources, and the source is abundant.China is large agricultural country, and large number of biological matter generation of waste materials is arranged every year, and only China's agricultural crop straw output is about 700,000,000 tons every year, and the stock number that can be used as the energy is hundred million tons of 2.8-3.5; The year rational exploitation amount of yule logs is about 1.58 hundred million tons, also has a large amount of waterplant in addition.But these resources are not fully utilized so far, and on-site incineration and contaminate environment, and this has become nationwide problem; China's Oil resource-constrained on the other hand, in continuous increase, development biomass liquefying technology is of great immediate significance to China to the demand of oil product.
The biomass flash pyrolysis technology can obtain very high liquid product yield at present, but product is formed complexity, and oxygen level is very high, and calorific value is lower, and acid strong, these factors are obstacles that bio oil is used as the high-quality liquid fuel.In order to enlarge the range of application of cracked oil, be necessary to improve technology, reduce oxygen level, acidity and improve oil-phase component, thereby improve calorific value and other fuel performance.The research of bio oil deoxidation upgrading at present all is to carry out in two steps, be that the first step is carried out quick cracking to biomass, bio oil steam cooled off obtain thick oil, again bio oil is carried out the higher liquid fuels of method acquisition quality such as hydrogenation deoxidation, though this method obtains certain progress, but this technological line has two main unfavorable factors: the one, need to consume hydrogen, and hydrogen cost height; The 2nd, this method can not effectively reduce the acidity of bio oil.
Summary of the invention
The present invention is the weak point for avoiding prior art to exist, provide a kind of biomass two sections methods that transform the low acid low oxygen content bio oil of preparation, form complexity, the problem that oxygen level height, calorific value is lower, acidity is strong etc. exists to overcome existing biomass cracked oil by using product.
Technical solution problem of the present invention adopts following scheme:
A kind of two sections methods that transform the low acid low oxygen content bio oil of preparation, with the biological particles is raw material, its method is, biomass cracking comprises one section fluidized bed cracking and two periods two steps of microwave cracking, and described one section fluidized bed cracking temperature is 400-450 ℃, air pressure is 0.01-0.1Mpa, described two sections microwave cracking temperature are 450-600 ℃, and air pressure is normal pressure, and microwave frequency is 2400-2500MHz, initial power 0.9-1.1kw, nitrogen flow rate 0.10-0.20m
3/ h, the reaction mass temperature reaches predetermined temperature 400-600 ℃, turns down power at 0.25-0.35kw.
This preparation method also comprises the pre-treatment to the cracking biomass material, at first the cracked biomass material being pulverized is that median size is less than 1mm, again with itself and catalyst solution thorough mixing, through flood, dry naturally, the biomass compound that contains catalyzer of the free water that is removed after the high temperature drying.
In the above-mentioned preprocessing process, described dipping time is 0.5-2 hour, refer to during described high temperature drying temperature be 70-105 ℃ dry 1.5-3 hour down.
Catalytic amount is for being the 9-11wt% of biomass particle quality in the described biomass compound.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention adopts two sections cleavage methods, one section fluidized-bed under comparatively gentle cracking temperature with biomass cracking, produce bio oil steam, this moment, most of split product of fluidized-bed rested on oligose and monose stage, the bio oil steam that produces is then strengthened the deoxidation upgrading in two sections microwave beds, under microwave action, the many organic deoxygenations of cracked oil vapor generation, through condensation, thus preparation high-quality liquid fuel.The present invention reduces acid in the deoxidation upgrading, do not consume simultaneously hydrogen, low molecule organic matter content in the gained product liquid reaches 30-55%, compares to have very with the content liquid in the quick cracking bio oil of fluidized-bed to increase substantially, and the utility value of the calorific value of liquid is higher.
2, the present invention utilizes unique temperature effective that microwave forms in biomass particle, microwave may form what is called " non-thermal effect " to biomass and catalyzer, realize the further cracking of bio oil product,, obtain the bio oil of the low acidic components of low molecule the further chain rupture of macromolecular substance.
3, the present invention carries out pre-treatment to the cracking biomass material, and it is pulverized back and catalyzer thorough mixing, helps the raising of bio oil output.
Description of drawings
Fig. 1 is the inventive method schematic flow sheet.
Number in the figure: 1-hopper, 2-feeding screw, 3-fluidized-bed, 4-cyclonic separator, 5-microwave reactor, 6-microwave catalysis bed, 7-first-stage condenser, 8-secondary condenser.
Below pass through embodiment, and the invention will be further described in conjunction with the accompanying drawings.
Embodiment
One, feedstock production
With biomass material pulverize for median size less than 1mm, dipping is 0.5-2 hour in aqueous catalyst solution, it is the 9-11% of biomass particle quality that catalyst levels should make wherein contained catalytic amount.Dry after fully stirring, again in baking oven 70-105 ℃ dry 1.5-3 hour down, remove free water and be placed in the moisture eliminator as standby material.
Two, charging
Take by weighing the 1000g standby material, put into feeding screw funnel 1, feeding screw 2 begins charging with the speed charging of 5Kg/h when temperature reaches design temperature.
Three, fluidized bed cracking
The less biomass compound of particle diameter reaches a high temperature rapidly in fluidized-bed 3 and carries out catalytic pyrolysis, fluidized-bed 3 height of bed 1200cm, diameter 150cm, nitrogen flow is 1.37m3/h, at bed internal pressure 0.01-0.1MPa, carries out cracking under 400-450 ℃ the condition, spouted gas is 1-10 with the ratio of fluidized gas, fluidized operating speed 0.5m/s, bed pressure drop 1Kpa, its splitting gas arrives cyclonic separator 4 through pipe-line transportation.
Four, cyclonic separation
Five, microwave cracking
Open microwave reactor 5 (2400-2500MHz), about initial power 0.95-1.1kw, nitrogen flow rate 0.10-0.20m3/h, the reaction mass temperature reaches predetermined temperature 400-600 ℃, turn down power at 0.25-0.35kw, keep the bio oil vapor temperature, treat liquid distillate finish after, can close microwave, stop catalysis.Liquid collecting place the liquid of ice-water bath secondary U-shaped pipe 7 and three grades of U-shaped pipes 8 promptly get the low acid of deoxidation mixed biologic fluid body, the liquid product yield is between 30～55%, general liquid begins to distillate after microwave is opened 2 minutes, no longer includes tangible liquid overhead product after 10 minutes.
With the tobacco rod is raw material, and it is crushed to particle diameter is below the 1mm, and with the catalyzer CaO aqueous solution in the dipping 0.5-2 hour, it is the 9-11% of biomass particle quality that catalyst levels should make wherein contained catalytic amount.Dry after fully stirring, again in baking oven 70-105 ℃ dry 1.5-3 hour down, remove free water.In fluidizer, carry out cracking then, carry out catalytic pyrolysis through microwave reinforced catalytic bed again, and adopt catalyzer that bio oil steam is carried out the catalysis upgrading deoxidation, the cracking and catalyzing time is 10 minutes, cracking condition is: the fluidized bed cracking temperature is 400 ℃, air pressure is 0.01-0.03Mpa, two sections microwave cracking temperature are 450 ℃, air pressure is normal pressure, microwave frequency is 2500MHz, initial power 0.9-1.1kw, nitrogen flow rate 0.10-0.20m3/h, the reaction mass temperature reaches 400 ℃ of predetermined temperature, turns down power at 0.25-0.35kw; Collect product liquid.Do not contain acid compounds in the product liquid, nicotine content is 60.81%, methyl ring propionic acid amide 6.45%, 2-methylbutane 5.75%.
With the wheat stalk is raw material, selects for use MgCl2 to make catalyzer, adopts step similarly to Example 1, in the cleavage step, cracking condition is that the fluidized bed cracking temperature is 450 ℃, air pressure is 0.08-1Mpa, the microwave cracking temperature is 600 ℃, and air pressure is normal pressure, and microwave frequency is 2500MHz, initial power 0.9-1.1kw, nitrogen flow rate 0.10-0.20m3/h, the reaction mass temperature reaches 600 ℃ of predetermined temperature, turns down power at 0.25-0.35kw; Collect product liquid.The yield of product liquid is 48.3%, and the bio oil main component is that furfural and two kinds of material relative concentrations of methyl furfural sum reach 74.42%, also has hydro carbons in addition, as n-heptylacetylene, and dimethyl tetrahydrobenzene (2.76%), decane (1.96%) accounts for 15%.
With the China fir is raw material, selects for use catalyst Fe 2 (SO4) 3 to make catalyzer, adopts step similarly to Example 1, in the cleavage step, cracking condition is: the fluidized bed cracking temperature is 450 ℃, and air pressure is 0.5Mpa, and the microwave cracking temperature is 500 ℃, air pressure is normal pressure, microwave frequency is 2450MHz, initial power 0.9-1.1kw, nitrogen flow rate 0.10-0.20m3/h, the reaction mass temperature reaches 500 ℃ of predetermined temperature, turns down power at 0.25-0.35kw; Collect product liquid, the bio oil main component is that furfural, methyl furfural, three kinds of material relative concentrations of furans sum reach 83.38%.
Claims (4)
1. one kind two sections transform the methods that acid low oxygen content bio oil is hanged down in preparation, with the biological particles is raw material, it is characterized in that biomass cracking comprises one section fluidized bed cracking and two periods two steps of microwave cracking, described one section fluidized bed cracking temperature is 400-450 ℃, air pressure is 0.01-0.1Mpa, described two sections microwave cracking temperature are 450-600 ℃, and air pressure is normal pressure, and microwave frequency is 2400-2500MHz, initial power 0.9-1.1kw, nitrogen flow rate 0.10-0.20m
3/ h, the reaction mass temperature reaches predetermined temperature 400-600 ℃, turns down power at 0.25-0.35kw.
2. a kind of two sections methods that transform the low acid low oxygen content bio oil of preparation according to claim 1, it is characterized in that, also comprise pre-treatment to biomass material, at first the cracked biomass material being pulverized is that median size is less than 1mm, again with itself and catalyst solution thorough mixing, through flood, dry naturally, the biomass compound that contains catalyzer of the free water that is removed after the high temperature drying.
3. a kind of two sections methods that transform the low acid low oxygen content bio oil of preparation according to claim 2 is characterized in that described dipping time is 0.5-2 hour, and described high temperature drying is meant that being 70-105 ℃ in temperature descended dry 1.5-3 hour.
4. two sections methods that transform the low acid low oxygen content bio oil of preparation according to claim 3 is characterized in that catalytic amount is the 9-11wt% of biomass particle quality in the described biomass compound.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102963866A (en) * | 2012-11-30 | 2013-03-13 | 安徽理工大学 | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis |
| CN104560093A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing fuel oil from biomass |
| CN107557046A (en) * | 2017-11-06 | 2018-01-09 | 耿航宇 | A kind of liquefied method of straw splitting |
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| CN1432625A (en) * | 2002-11-08 | 2003-07-30 | 华东理工大学 | Fast biomass-cracking process of preparing liquid fuel |
| CN100999676A (en) * | 2006-12-31 | 2007-07-18 | 安徽理工大学 | Process of preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis |
| CN100999677A (en) * | 2006-12-31 | 2007-07-18 | 安徽理工大学 | Process of preparing rich furol biological oil by biomass microwave catalytic pyrolysis |
| EP2074192A2 (en) * | 2006-08-16 | 2009-07-01 | Aston University | Biomass pyrolysis |
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- 2011-04-20 CN CN2011100984219A patent/CN102199440A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1432625A (en) * | 2002-11-08 | 2003-07-30 | 华东理工大学 | Fast biomass-cracking process of preparing liquid fuel |
| EP2074192A2 (en) * | 2006-08-16 | 2009-07-01 | Aston University | Biomass pyrolysis |
| CN100999676A (en) * | 2006-12-31 | 2007-07-18 | 安徽理工大学 | Process of preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis |
| CN100999677A (en) * | 2006-12-31 | 2007-07-18 | 安徽理工大学 | Process of preparing rich furol biological oil by biomass microwave catalytic pyrolysis |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102963866A (en) * | 2012-11-30 | 2013-03-13 | 安徽理工大学 | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis |
| CN102963866B (en) * | 2012-11-30 | 2015-01-21 | 安徽理工大学 | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis |
| CN104560093A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing fuel oil from biomass |
| CN104560093B (en) * | 2013-10-22 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of living beings are produced the method for fuel oil |
| CN107557046A (en) * | 2017-11-06 | 2018-01-09 | 耿航宇 | A kind of liquefied method of straw splitting |
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Application publication date: 20110928 |