CN104277857B - Bio-crude oil prepared by a kind of algae and raw glycerine co grinding method and method - Google Patents
Bio-crude oil prepared by a kind of algae and raw glycerine co grinding method and method Download PDFInfo
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- CN104277857B CN104277857B CN201410499416.2A CN201410499416A CN104277857B CN 104277857 B CN104277857 B CN 104277857B CN 201410499416 A CN201410499416 A CN 201410499416A CN 104277857 B CN104277857 B CN 104277857B
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- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention belongs to bio-crude oil and preparing technical field thereof, be specifically related to bio-crude oil prepared by a kind of algae and raw glycerine co grinding method and method.Its flow process is: use high-temperature high-pressure reaction kettle, with algae and raw glycerine for raw material, and preparation bio-crude oil.In produce oil process, major control means are the mass ratio of temperature, initial pressure and algae and raw glycerine.After algae and raw glycerine are raw material reaction, product residual oil, through extraction, filtration, distillation, drying, obtains bio-crude oil.Compared with preparing bio-crude oil with algae hydrothermal liquefaction, for Enteromorpha, the present invention can make the productive rate of bio-crude oil bring up to 38.7% by 23.0%, calorific value (HHV) & gt; 35MJ/kg.Gained bio-crude oil is dark thick liquid, good fluidity, and wherein hydrocarbon compound content is up to 45.6%.These invention energy-conserving and environment-protective, simple to operate, both improve productive rate and the quality of bio-crude oil, also make use of biomass resource fully.
Description
Technical field
The invention belongs to bio-crude oil and preparing technical field thereof, be specifically related to bio-crude oil prepared by a kind of algae and raw glycerine co grinding method and method.
Background technology
Along with expanding economy, global fossil fuel resource is day by day exhausted, and environment constantly worsens.In recent years, for solving shortage of resources problem, people try to explore the substitute products of oil always.Biomass have a high potential, and are the renewable energy sources that uniquely can be converted into liquid fuel.
The pressurized liquefied one as biomass thermal chemical transformation technology, is under certain temperature, pressure, utilizes the special effects of different solvents, is liquid fuel or chemical by Wood Adhesives from Biomass.Wood Adhesives from Biomass rate is higher, relatively low to equipment requirements.Biomass are pressurized liquefied can convert solid-state biomass to liquid bio oil, and these bio oil, by after upgrading refining, can use as fuel oil additive by Substitute For Partial fuel oil.Compared with traditional thermo-cracking, the reaction conditions of biomass liquefying is relatively gentle, in the future can commercial scale production, can be used as one of biomass and raw glycerine resources effective utilization approach.
Since 2007, China Yellow Sea and East China Sea bank has broken out extensive green tide.Prolific algae shielded from sunlight, affects the growth of seabed algae; Dead algae also can consume the oxygen in seawater.Also there are some researches show, the chemical substance of algae secretion causes disadvantageous effect to other marine organisms possibly.Alga eruption also can have a strong impact on view, disturbs the carrying out of going sightseeing with aquatic sports.At present, the main Land use systems of these algae is direct landfill, and Fodder making or fertilizer, urgently effectively utilize.(the ZhouD. such as Fudan University Zhou Dong, ZhangL., ZhangS.C., FuH.B., ChenJ.M.2010.HydrothermalliquefactionofmacroalgaeEnterom orphaproliferatobio-oil.Energy & Fuels24:4054 – 4061.) utilize this algae hydrothermal liquefaction of Enteromorpha to produce bio oil, bio oil productive rate is 23.0%, and calorific value is 28.7MJ/kg.
Raw glycerine utilizes the Main By product in ester exchange method production biodiesel process, and its quality accounts for 10% of total product mass in production of biodiesel, every year, to produce a large amount of raw glycerines thus, the main component in raw glycerine is pure glycerin, grease, methyl alcohol, lipid acid and partial salts.At present, the mode of raw glycerine is not effectively utilized.
Chinese patent CN103409473A discloses a kind of for 1, the raw glycerine pretreatment process of ammediol fermentation, comprises and adsorbing raw glycerine with gac, can remove material harmful to fermentation in raw glycerine, without the need to organic solvent, reduce energy consumption and and processing cost.
Chinese patent CN102952000A discloses refining crude glycerin processing method, comprises dilution, desalination, impurity elimination, distillation, and decolouring such as to de-taste at the processing step, and production high-quality refining glycerine, processing method is simple.
University (MatthewTymchyshyn is found in North Carolina, et, al.Directconversionofglycerolintobio-oilviahydrotreatmen tusingsupportedmetalcatalysts.Fuel112 (2013) 193 – 202) there is the report producing bio-crude oil about pig manure and raw glycerine co grinding method, oil yield rate reaches 68.0%, and in raw glycerine, lipid acid improves significantly bio-crude oil productive rate.Canada University of Western Ontario (ShuangningXiu, AbolghasemShahbazi, CarlingtonW.Wallace, LijunWang, DanChengEnhancedbio-oilproductionfromswinemanureco-lique factionwithcrudeglycerol.EnergyConversionandManagement52 (2011) 1004-1009) under catalyst action to the direct thermal treatment of raw glycerine, raw glycerine oil yield rate reaches 40.0%, calorific value is 33.1MJ/kg, is mostly phenols and ketone compounds in oil product.
The present invention achieves efficiency utilization to algae and raw glycerine two kinds resource to be utilized, proposes effective workaround for improving biomass to the transformation efficiency of bio-crude oil and quality.By the temperature in control process, initial pressure, the mass ratio of rotating speed and algae and raw glycerine, thus the bio-crude oil obtaining High-quality high-yield.Algae and raw glycerine co grinding method are converted into liquid fuel, while recycling biomass again and raw glycerine, alleviate energy dilemma, decrease topsoil, protect environment.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, and the bio-crude oil providing a kind of algae and raw glycerine co grinding method to prepare and method.
Algae and raw glycerine co grinding method prepare a method for bio-crude oil, comprise the steps:
1) add in reactor by algae powder and raw glycerine, both mass ratioes are 0:1 ~ 1:6;
2) be filled with rare gas element in reactor and regulate initial pressure, use agitator to stir, start after checking resistance to air loss to heat up, after reaching design temperature, keep certain hour;
3) after reaction terminates, cooling, collects gas, organic solvent extraction, ultrasonic, filtration under diminished pressure, separatory, and distillation is dry, obtains bio-crude oil.
Preferably, step 1) in, algae is Enteromorpha, chlorella, micro-plan ball algae, blue-green algae, one or more in spirulina.
Preferably, step 1) in, reactor is batch reactor or continuous reaction still.
Preferably, step 2) in, initial pressure is 0MPa ~ 8MPa, and agitator speed is 100rpm ~ 800rpm, and design temperature is 240 DEG C ~ 600 DEG C.
Preferably, step 2) in, temperature rise rate is 5 DEG C/min ~ 20 DEG C/min.
Preferably, step 2) in, the hold-time of design temperature is 1min ~ 180min.
Preferably, step 3) in, extraction agent used during extraction is acetone, methylene dichloride, toluene, ether, the one in ethyl acetate.
Preferably, be used as fuel after the gas delivery produced in preparation bio-crude oil process, described gas is one or more in methane, hydrogen, carbon monoxide; The carbonic acid gas produced is used as vegetable fertilizer.
According to bio-crude oil prepared by aforesaid method.
The present invention has the following advantages and beneficial effect:
1. after algae and raw glycerine co grinding method produce bio-crude oil, not only algae obtains utilization, and this material to be utilized of raw glycerine have also been obtained recycling, makes algae and raw glycerine be obtained for increment.
2. bio-crude oil productive rate significantly improves, and for Enteromorpha, when 320 DEG C, Enteromorpha and raw glycerine co grinding method, productive rate is 38.7%, far above productive rate (23.0%) during Enteromorpha hydrothermal liquefaction.
3. bio-crude oil quality significantly improves, for Enteromorpha, when 320 DEG C, Enteromorpha and raw glycerine co grinding method, bio-crude oil calorific value is 35.8MJ/kg, higher than bio oil calorific value (28.7MJ/kg) during Enteromorpha hydrothermal liquefaction, and in the bio-crude oil that obtains of Enteromorpha and raw glycerine co grinding method hydrocarbons content up to 45.6%.
4. the pressurized liquefied superiority with many uniquenesses of biomass: 1) raw material sources are extensive, and most biomass as pressurized liquefied raw material, can comprise all kinds of lignocellulose raw material, industry and sanitary sewage, feces of livestock and poultry etc.2) energy utilization efficiency is high, and in biomass pressure process, water itself can use as solvent, does not need to carry out drying to raw material, thus improves energy utilization efficiency.3) Wood Adhesives from Biomass speed is fast, reacts comparatively complete.4) convenient product separation, is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the embodiment of the present invention.
Embodiment
The present invention's reactor used is batch reactor (4593/HT, 100ml, Parr, USA), and oxygen bomb calorimeter is Parr6200ParrInstrumentCompany (USA).
Below in conjunction with schema the present embodiment be further elaborated and illustrate.
Embodiment 1
Algae and raw glycerine co grinding method prepare a method for bio-crude oil, comprise the steps:
(1) add in reactor by 10g raw glycerine, good seal reactor, pressure initial in reactor is adjusted to 8MPa by logical nitrogen, and agitator speed is 800rpm, and after 10 minutes, pressure is unchanged, then think that resistance to air loss is good.
(2) reactor is heated to 240 DEG C, temperature rise rate 5 DEG C/min, keeps 180min, stop heating afterwards, question response still is cooled to room temperature.
(3) after reactor is cooled to room temperature, first by collection and confinement of gases, then open reactor, collect product with glass cylinder, with 150ml acetone cleaning kettle, then pour beaker into for one piece.Beaker to be placed in ultrasonic wave ultrasonic 30 minutes.
(4) product after ultrasonic extraction passes through filtration under diminished pressure, liquid phase part after filtration is acetone, bio-crude oil and water, and liquid phase part is poured separating funnel into and left standstill 30 minutes, water bleeds off in lower floor, and bio-crude oil and acetone mixture are poured in extracting bottle and distilled recover acetone.
(5) product after removing acetone puts into loft drier dry 12 hours, obtains bio-crude oil.Bio-crude oil productive rate 58.1%, calorific value is 39.6MJ/kg, hydrocarbon compound content 50.2%.
Embodiment 2
Algae and raw glycerine co grinding method prepare a method for bio-crude oil, comprise the steps:
(1) add in reactor by 5g Enteromorpha powder and 10g raw glycerine, good seal reactor, pressure initial in reactor is adjusted to 6MPa by logical nitrogen, and agitator speed is 600rpm, and after 10 minutes, pressure is unchanged, then think that resistance to air loss is good.
(2) reactor is heated to 320 DEG C, temperature rise rate 12 DEG C/min, keeps 120min, stop heating afterwards, question response still is cooled to room temperature.
(3) after reactor is cooled to room temperature, first gas is bled off, then open reactor, collect product with glass cylinder, with 150ml ethyl acetate cleaning kettle, then pour beaker into for one piece.Beaker to be placed in ultrasonic wave ultrasonic 30 minutes.
(4) product after ultrasonic extraction passes through filtration under diminished pressure, liquid phase part after filtration is ethyl acetate, bio-crude oil and water, and liquid phase part is poured separating funnel into and left standstill 30 minutes, water bleeds off in lower floor, and bio-crude oil and ethyl acetate mixture are poured in extracting bottle to distill and ethyl acetate reclaimed.
(5) product after removing ethyl acetate puts into loft drier dry 12 hours, obtains bio-crude oil.Bio-crude oil productive rate 38.7%, calorific value is 35.8MJ/kg, hydrocarbon compound content 45.6%.
Embodiment 3
Algae and raw glycerine co grinding method prepare a method for bio-crude oil, comprise the steps:
(1) add in reactor by 5g chlorella powder and 20g raw glycerine, good seal reactor, pressure initial in reactor is adjusted to 1MPa by logical nitrogen, and agitator speed is 300rpm, and after 10 minutes, pressure is unchanged, then think that resistance to air loss is good.
(2) reactor is heated to 400 DEG C, temperature rise rate 15 DEG C/min, keeps 60min, stop heating afterwards, question response still is cooled to room temperature.
(3) after reactor is cooled to room temperature, first gas is bled off, then open reactor, collect product with glass cylinder, with 150ml toluene cleaning kettle, then pour beaker into for one piece.Beaker to be placed in ultrasonic wave ultrasonic 30 minutes.
(4) product after ultrasonic extraction passes through filtration under diminished pressure, liquid phase part after filtration is toluene, bio-crude oil and water, and liquid phase part is poured separating funnel into and left standstill 30 minutes, water bleeds off in lower floor, and bio-crude oil and toluene mixture are poured in extracting bottle and distilled toluene recovery.
(5) product after removing toluene puts into loft drier dry 12 hours, obtains bio-crude oil.Bio-crude oil productive rate 42.4%, calorific value is 38.3MJ/kg, hydrocarbon compound content 43.7%.
Embodiment 4
Algae and raw glycerine co grinding method prepare a method for bio-crude oil, comprise the steps:
(1) add in reactor by 5g spirulina powder and 25g raw glycerine, good seal reactor, pressure initial in reactor is adjusted to 2MPa by logical nitrogen, and agitator speed is 100rpm, and after 10 minutes, pressure is unchanged, then think that resistance to air loss is good.
(2) reactor is heated to 500 DEG C, temperature rise rate 20 DEG C/min, keeps 20min, stop heating afterwards, question response still is cooled to room temperature.
(3) after reactor is cooled to room temperature, first gas is bled off, then open reactor, collect product with glass cylinder, with 150ml ether cleaning kettle, then pour beaker into for one piece.Beaker to be placed in ultrasonic wave ultrasonic 30 minutes.
(4) product after ultrasonic extraction passes through filtration under diminished pressure, liquid phase part after filtration is ether, bio-crude oil and water, and liquid phase part is poured separating funnel into and left standstill 30 minutes, water bleeds off in lower floor, and bio-crude oil and ether mixtures are poured in extracting bottle to distill and reclaimed by ether.
(5) product after removing ether puts into loft drier dry 12 hours, obtains bio-crude oil.Bio-crude oil productive rate 63.2%, calorific value is 37.6MJ/kg, hydrocarbon compound content 41.2%.
Embodiment 5
Algae and raw glycerine co grinding method prepare a method for bio-crude oil, comprise the steps:
(1) add in reactor by micro-for 5g plan ball algae powder and 30g raw glycerine, good seal reactor, pressure initial in reactor is adjusted to 1MPa by logical nitrogen, and agitator speed is 100rpm, and after 10 minutes, pressure is unchanged, then think that resistance to air loss is good.
(2) reactor is heated to 600 DEG C, temperature rise rate 10 DEG C/min, keeps 1min, stop heating afterwards, question response still is cooled to room temperature.
(3) after reactor is cooled to room temperature, first gas is bled off, then open reactor, collect product with glass cylinder, with 150ml methylene dichloride cleaning kettle, then pour beaker into for one piece.Beaker to be placed in ultrasonic wave ultrasonic 30 minutes.
(4) product after ultrasonic extraction passes through filtration under diminished pressure, liquid phase part after filtration is methylene dichloride, bio-crude oil and water, and liquid phase part is poured separating funnel into and left standstill 30 minutes, water bleeds off in lower floor, and bio-crude oil and dichloromethane mixture are poured in extracting bottle to distill and reclaimed by methylene dichloride.
(5) product after removing methylene dichloride puts into loft drier dry 12 hours, obtains bio-crude oil.Bio-crude oil productive rate 46.3%, calorific value is 38.9MJ/kg, hydrocarbon compound content 47.1%.
Claims (6)
1. algae and raw glycerine co grinding method prepare a method for bio-crude oil, it is characterized in that, comprise the steps:
1) add in reactor by algae powder and raw glycerine, both mass ratioes are 0:1 ~ 1:6;
2) be filled with rare gas element in reactor and regulate initial pressure, use agitator to stir, start after checking resistance to air loss to heat up, after reaching design temperature, keep certain hour;
3), after reaction terminates, cooling, collects gas, organic solvent extraction, filters, dry, obtains bio-crude oil;
Step 2) in, initial pressure is 0MPa ~ 8MPa, and agitator speed is 100rpm ~ 800rpm, and design temperature is 240 DEG C ~ 600 DEG C, and the hold-time of design temperature is 1min ~ 180min, temperature rise rate is 5 DEG C/and min ~ 20 DEG C/min.
2. a kind of algae according to claim 1 and raw glycerine co grinding method prepare the method for bio-crude oil, it is characterized in that, step 1) in, algae is Enteromorpha, chlorella, micro-plan ball algae, blue-green algae, one or more in spirulina.
3. a kind of algae according to claim 1 and raw glycerine co grinding method prepare the method for bio-crude oil, it is characterized in that, step 1) in, reactor is batch reactor or continuous reaction still.
4. a kind of algae according to claim 1 and raw glycerine co grinding method prepare the method for bio-crude oil, it is characterized in that, step 3) in, extraction agent used during extraction is acetone, methylene dichloride, toluene, ether, the one in ethyl acetate.
5. a kind of algae according to claim 1 and raw glycerine co grinding method prepare the method for bio-crude oil, it is characterized in that, the gas produced in preparation bio-crude oil process is one or more in methane, hydrogen, carbon monoxide, carbonic acid gas.
6. the bio-crude oil that described in claim 1-5 any one claim prepared by method.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011024989A1 (en) * | 2009-08-31 | 2011-03-03 | 株式会社ワンワールド | Process for production of liquefied material from glycerin-type solid material |
| CN103450920A (en) * | 2013-09-13 | 2013-12-18 | 中国农业大学 | Method for increasing heavy oil yield by treating biological crude oil with ultrasonic wave |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011024989A1 (en) * | 2009-08-31 | 2011-03-03 | 株式会社ワンワールド | Process for production of liquefied material from glycerin-type solid material |
| CN103450920A (en) * | 2013-09-13 | 2013-12-18 | 中国农业大学 | Method for increasing heavy oil yield by treating biological crude oil with ultrasonic wave |
Non-Patent Citations (2)
| Title |
|---|
| Enhanced bio-oil production from swine manure co-liquefaction with crude glycerol;Shuangning Xiu等;《Energy Conversion and Management》;20100918;第1004-1009页 * |
| 藻类生物质水热液化制备生物油的研究进展;陈裕鹏 等;《石油学报（石油加工）》;20140831;第756-763页 * |
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