CN101624530A - Biomass liquefied oil and preparation method thereof - Google Patents
Biomass liquefied oil and preparation method thereof Download PDFInfo
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- CN101624530A CN101624530A CN200910090412A CN200910090412A CN101624530A CN 101624530 A CN101624530 A CN 101624530A CN 200910090412 A CN200910090412 A CN 200910090412A CN 200910090412 A CN200910090412 A CN 200910090412A CN 101624530 A CN101624530 A CN 101624530A
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Abstract
The invention discloses biomass liquefied oil and a preparation method thereof. The preparation method comprises the following steps: placing microalgae into a reaction kettle and pyrolyzing the microalgae to obtain biomass liquefied oil, wherein the microalgae is chlorella pyrenoidosa and/or spirulina platensis; protective atmosphere is arranged in the reaction kettle and is reducing atmosphere or inert atmosphere obtained after a carrier gas is led into the reaction kettle; and catalyst is added in the pyrolysis reaction and is carbonate. The biomass liquefied oil obtained by the method has the characteristics of high yield, calorific value and hydrogen content, low oxygen content, and the like.
Description
Technical field
The present invention relates to biomass engineering and energy field, particularly biomass liquefied oil and preparation method thereof.
Background technology
Because the minimizing day by day of fossil energy and the utilization of fossil energy have brought the aggravation of environmental pollution, scientist focuses on attention in the exploitation and renewable energy source of new forms of energy.In various renewable energy sources, the recycle of biomass energy can not cause Atmospheric CO
2Increase, can not discharge the SO that causes acid rain
2And the ash that burning produces is than the much less that coal combustion produced, and these ash contents can be used as farm crop fertilizer again simultaneously, thereby are paid close attention to widely.As far back as just prediction of the World Food Programme (FAO) in 1993,, will provide the electric power in the whole world 60% and 40% fuel based on the renewable energy source of biomass energy, and its price is lower than fossil oil to the year two thousand fifty.
In numerous biomass, little algae has that biomass is big, growth cycle is short, easily cultivate and contain higher advantages such as lipid, makes it not only in Atmospheric CO
2Recycle in play an important role, but also be the preparation biomass liquid fuel good material.
Summary of the invention
The object of the present invention is to provide biomass liquefied oil and preparation method thereof, the biomass liquefied oil that utilizes this method to obtain has characteristics such as productive rate height, calorific value height, hydrogen content height, oxygen level be low.
The preparation method of biomass liquefied oil provided by the invention is with little algae pyrolysis, obtains biomass liquefied oil.
Described little algae can be the dry little algae that crosses or wet little algae.
Above-mentioned wet little algae is the mixture of little algae and water, and little algae accounts for the 1-100% of wet little algae, does not comprise 100% (mass percent); Preferably, little algae can account for the 10-80% (mass percent) of wet little algae; More preferably, little algae can account for the 20-60% (mass percent) of wet little algae.
Above-mentioned little algae is meant fatty, proteinic little algae, oil yield rate and fat, the Protein content relation of being proportionate.Above-mentioned little algae is Chlorella pyrenoidesa, spirulina plalensis, Phaeodactylum tricornutum and/or Porphyridium cruentum preferably.
Above-mentioned pyrolytic reaction can have protective atmosphere or not have protective atmosphere, and described protective atmosphere is that carrier gas is fed reducing atmosphere or the inert atmosphere that obtains behind the reactor.Feed carrier gas in the reactor, drive air, can avoid the oxygen in raw material and the reactor to react, prevent that the productive rate of biomass liquefied oil from reducing.
The used carrier gas of above-mentioned reducing atmosphere is a reducing gas, and described reducing gas can be hydrogen or carbon monoxide.
The used carrier gas of described inert atmosphere is rare gas element or nitrogen, and this rare gas element can comprise all rare gas elementes.
Above-mentioned pyrolytic temperature of reaction is 230 ℃-600 ℃, 260 ℃-335 ℃ or 285 ℃-300 ℃; The described pyrolytic reaction times is 0-70 minute, does not comprise 0 minute, is preferably 10-30 minute, more preferably 15-23 minute.
Above-mentioned pyrolytic temperature of reaction specifically can be 285 ℃, 290 ℃ or 300 ℃.
The above-mentioned pyrolytic reaction times is 23 minutes, 20 minutes, 17 minutes or 15 minutes.
React completely in order to accelerate reaction process and to impel, can add catalyzer before pyrolytic reaction begins, the mass ratio of described catalyzer and little algae is (0-20): 100; Described catalyzer is a carbonate; Described carbonate is salt of wormwood or yellow soda ash.
Utilize the biomass liquefied oil of method preparation provided by the invention also to belong within protection scope of the present invention.
Another object of the present invention is to provide the application of biomass liquefied oil as biomass fuel.
Another purpose of the present invention is to provide the application of biomass liquefied oil in preparation diesel oil, gasoline or kerosene.Biomass liquefied oil provided by the invention can be obtained diesel oil, gasoline or kerosene by ordinary method processing.
The preparation method of biomass fuel provided by the invention is to react in liquefying plant by little algae, obtains biomass liquefied oil behind cooling, the unnecessary gas of eliminating.This method prepares the energy input output efficiency that biomass liquefied oil has reached 1: 3.The present invention also has following beneficial effect:
1, utilize little algal biomass liquefaction can obtain high-quality biomass liquefied oil.With timber, agricultural crop straw is that the hydrogen richness of the biomass liquefied oil that obtains of the fast pyrogenation of raw material is 6.2%, oxygen is 37.3%, and the mean value hydrogen richness that the present invention obtains is 8.6%, oxygen level is 12.1%, so the H of little algal biomass liquefaction oil (hydrogen) content is than the biomass liquefying innage of timber or agricultural crop straw, but O (oxygen) content is then lower, and the mol ratio of hydrogen and carbon is 1: (1.5-2.0), therefore the calorific value of little algal biomass liquefaction oil is higher, on average, simultaneously comparatively stable up to 33.92MJ/kg.
2, utilize the biomass liquefied oil of little algal biomass liquefaction preparation to have good benefits in environment.Reaction back waste water becomes fertilizer because containing element such as a large amount of N, P, K, and remaining solid is less than 5.5% of the raw material total solids, and gaseous product is mainly CO
2
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Among the following embodiment, if no special instructions, be ordinary method.
Embodiment one, do not add catalyzer, do not feed carrier gas and prepare biomass liquefied oil
1, (Chlorella pyrenoidosa, dry powder Chick) are purchased the strong bio tech ltd in sky, Binzhou, Shandong, as stand-by sample to collect Chlorella pyrenoidesa.
2, the pyrolysis of chlorella: sealing is pressed in the reactor in 2 risings that the 600g sample changed over to the band stirring rake.Temperature of reaction is 285 ℃, and isothermal reaction began to cool down after 23 minutes, treats that temperature unloads vent valve when being reduced to 35 ℃, takes out the biomass liquefied oil of reaction gained.The sewage that residue contains N, P and K can be used as fertilizer.
Two, the attributional analysis of biomass liquefied oil
1, the calorific value of biomass liquefied oil
The method that (GB/T384-81) provides according to " petroleum products heating-value determination method " detects the calorific value of the biomass liquefied oil of being produced by chlorella, and experiment repeats 3 times, and mean value reaches 33.26MJ/kg.The method of utilizing the step 1 of present embodiment to provide prepares biomass liquefied oil, and its energy input output efficiency reaches 1: 3.
2, the productive rate analysis of biomass liquefied oil
With the biomass liquefied oil of producing by chlorella that obtains quality divided by the total volatile solid(s) (TVS) of raw material, obtain the productive rate of biomass liquefied oil, reach 50%.Wherein, the organism in volatile solid (VS) three kinds of materials of expression (suspended substance in the water sample, colloid and dissolved matter).
The method of calculation of the quality of volatile solid: porcelain crucible is cleaned and calcination 1h in 600 ℃ of retort furnaces, take out cooling, get material sample and place in the crucible, put into then under 105 ± 2 ℃ of the loft drier inherences and be dried to constant weight, what obtain is the quality of total solids, note is made a gram, dried sample is put into retort furnace,, take out cooling and weigh at 600 ℃ of calcination 2h, the quality note that obtains is made the b gram, the solid amount of then always volatilizing=(a-b) restrain.
3, the hydrogen content of biomass liquefied oil, oxygen level analysis
According to " method that petroleum industry new technology and standard specifications handbook provide is measured the hydrogen content and the oxygen level of biomass liquefied oil.
Experiment repeats 3 times, and the hydrogen content of the biomass liquefied oil of being produced by chlorella is on average up to 7.8%, than the hydrogen content in the biomass liquefied oil of timber or agricultural crop straw (6.2%) height; The oxygen level average out to 12.7% of the biomass liquefied oil of being produced by chlorella is lower than the oxygen level in the biomass liquefied oil of timber or agricultural crop straw (37.2%).
Embodiment two, not adding catalyzer, is that protective gas prepares biomass liquefied oil with nitrogen
1, collects spirulina plalensis (Spirulina platensis) (bio tech ltd is good in sky, Binzhou, Shandong), as stand-by sample.
2, the pyrolysis of spirulina plalensis: sealing is pressed in the reactor in 2 risings that the 600g sample changed over to the band stirring rake.Nitrogen is fed in the autoclave to drive air, make algae pyrolysis in inert atmosphere, temperature of reaction is 290 ℃, and isothermal reaction began to cool down after 20 minutes, treated that temperature unloads vent valve when being reduced to 35 ℃, takes out biomass liquefied oil.The sewage that residue contains N, P and K can be used as fertilizer.
Two, the attributional analysis of biomass liquefied oil
1, the calorific value of biomass liquefied oil
The method that provides according to embodiment 1 detects the calorific value of the biomass liquefied oil of being produced by spirulina plalensis, and experiment repeats 3 times, and mean value reaches 33.97MJ/kg.The method of utilizing the step 1 of present embodiment to provide prepares biomass liquefied oil, and its energy input output efficiency reaches 1: 3.
2, the productive rate analysis of biomass liquefied oil
The method that provides according to embodiment 1 calculates the productive rate of biomass liquefied oil, reaches 56%.
3, the hydrogen content of biomass liquefied oil, oxygen level analysis
The method that provides according to embodiment 1 is measured the hydrogen content and the oxygen level of biomass liquefied oil.
Experiment repeats 3 times, and the hydrogen content of the biomass liquefied oil of being produced by spirulina plalensis is on average up to 8.1%, than the hydrogen content in the biomass liquefied oil of timber or agricultural crop straw (6.2%) height; The oxygen level of the biomass liquefied oil of spirulina plalensis is 12.0%, and is lower than the oxygen level in the biomass liquefied oil of timber or agricultural crop straw (37.2%).
Embodiment three, adding catalyzer are that carrier gas prepares biomass liquefied oil with hydrogen
One, the preparation of biomass liquefied oil
1, collects the dry powder (ratio of quality is 1: 1) of Chlorella pyrenoidesa and Phaeodactylum tricornutum (Phaeodactylum tricornutum), mix, as stand-by raw material.Wherein, the dry powder of Phaeodactylum tricornutum is with Phaeodactylum tricornutum (purchasing in Chinese Academy of Sciences algae kind storehouse), utilizes methods such as centrifugal, chemical flocculation, filtration to carry out the microalgae cell enrichment, and then carries out the high temperature drying dehydration, obtains the algae powder.
2, the raw material of 600 grams and the catalyzer (yellow soda ash) of 9 grams are sent in the 2 rising pressure reactors of band stirring rake sealing.Drive air in the reactor with hydrogen, yellow soda ash is as catalyzer, and temperature of reaction is 300 ℃, and isothermal reaction is after 17 minutes, and cooling when temperature is reduced to 35 ℃, is unloaded vent valve, obtains the biomass liquefied oil of mixed algae.The sewage that residue contains N, P and K can be used as fertilizer.
Two, the attributional analysis of biomass liquefied oil
1, the calorific value of biomass liquefied oil
The calorific value (method that provides according to embodiment 1 detects) of the biomass liquefied oil of producing by chlorella and spirulina plalensis mixture, experiment repeats 3 times, and mean value reaches 34.01MJ/kg.The method of utilizing the step 1 of present embodiment to provide prepares biomass liquefied oil, and its energy input output efficiency reaches 1: 3.
2, the productive rate analysis of biomass liquefied oil
The method that provides according to embodiment 1 is calculated the productive rate of the biomass liquefied oil of being produced by the algae mixture, reaches 55%.
3, the hydrogen content of biomass liquefied oil, oxygen level analysis
The method that provides according to embodiment 1 is measured hydrogen content, the oxygen level of biomass liquefied oil, experiment repeats 3 times, the hydrogen content of the biomass liquefied oil of being produced by the algae mixture is on average up to 8.9%, than 6.2% height of the hydrogen content in the biomass liquefied oil of timber or agricultural crop straw; Oxygen level by the biomass liquefied oil of algae mixture production is 11.7%, and is lower than the oxygen level in the biomass liquefied oil of timber or agricultural crop straw 37.2%.
Embodiment four, adding catalyzer are that carrier gas prepares biomass liquefied oil with the helium
One, the preparation of biomass liquefied oil
1, collects the dry powder of Porphyridium cruentum (Porohyridium cruentum) and spirulina plalensis (S.platensis) respectively, mix (ratio of quality is 3: 1), add water then, make the little algae in the raw material account for 30% (mass percent).Wherein, the dry powder of Porphyridium cruentum is with Porphyridium cruentum (purchasing in Chinese Academy of Sciences algae kind storehouse), carries out the microalgae cell enrichment through methods such as centrifugal, chemical flocculation, filtrations, and then carries out the high temperature drying dehydration, obtains dry powder.
2, the catalyzer (salt of wormwood) of the raw materials of 800 grams and 42 grams are sent into 2 of band stirring rake raise to press in the reactors (also be catalyzer and the ratio of the consumption of little algae is 42: 800*0.3=17.5: 100), sealing.Drive air in the reactor with helium, salt of wormwood is as catalyzer, and temperature of reaction is 300 ℃, and constant temperature is after 15 minutes, and cooling when temperature is reduced to 35 ℃, is unloaded vent valve, obtains the biomass liquefied oil of mixed algae.The sewage that residue contains N, P and K can be used as fertilizer.
Two, the attributional analysis of biomass liquefied oil
Every indexs such as calorific value, hydrogen content and oxygen level of the biomass liquefied oil of being produced by the algae mixture are identical with embodiment three, be productive rate be 54%.
Claims (10)
1, the preparation method of biomass liquefied oil is with little algae pyrolysis, obtains biomass liquefied oil.
2, method according to claim 1 is characterized in that: described little algae is Chlorella pyrenoidesa, spirulina plalensis, Phaeodactylum tricornutum and/or Porphyridium cruentum.
3, method according to claim 1 and 2 is characterized in that: described pyrolysis is carried out under protective atmosphere, and described protective atmosphere is that carrier gas is fed reducing atmosphere or the inert atmosphere that obtains behind the reactor.
4, method according to claim 3 is characterized in that: the used carrier gas of described reducing atmosphere is a reducing gas, and described reducing gas is hydrogen or carbon monoxide; The used carrier gas of described inert atmosphere is rare gas element or nitrogen.
5, according to the arbitrary described method of claim 1-4, it is characterized in that: described pyrolytic temperature of reaction is 230 ℃-600 ℃, 260 ℃-335 ℃ or 285 ℃-300 ℃; The described pyrolytic reaction times is 0-70 minute, does not comprise 0 minute, is preferably 10-30 minute, more preferably 15-23 minute.
6, method according to claim 5 is characterized in that: described pyrolytic temperature of reaction is 285 ℃, 290 ℃ or 300 ℃; The described pyrolytic reaction times is 23 minutes, 20 minutes, 17 minutes or 15 minutes.
7, according to the arbitrary described method of claim 1-6, it is characterized in that: add catalyzer in the described pyrolytic reaction, described catalyzer is (0-20) with the ratio of the quality of little algae: 100; Described catalyzer is a carbonate; Described carbonate is salt of wormwood or yellow soda ash.
8, the biomass liquefied oil of the arbitrary described method preparation of claim 1-7.
9, the described biomass liquefied oil of claim 8 is as the application of biomass fuel.
10, the application of the described biomass liquefied oil of claim 8 in preparation diesel oil, gasoline or kerosene.
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Cited By (9)
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| CN103060075A (en) * | 2012-12-18 | 2013-04-24 | 河南理工大学 | Method for preparing biological oil through catalytic liquefaction of microalgae |
| CN103059895A (en) * | 2012-12-07 | 2013-04-24 | 河南理工大学 | Method for preparing bio-oil through hydrothermal liquefaction of enteromorpha clathrata |
| CN103484234A (en) * | 2013-09-18 | 2014-01-01 | 河南理工大学 | Method for preparing biological oil through catalyzing and liquefying microalgae |
| CN103789076A (en) * | 2013-12-20 | 2014-05-14 | 浙江省海洋开发研究院 | Method for preparing bio-oil by using blue algae |
| CN103980928A (en) * | 2014-04-17 | 2014-08-13 | 张德者 | Biomass oil and preparation method thereof |
| CN104004597A (en) * | 2014-05-14 | 2014-08-27 | 中国科学院广州能源研究所 | Method for modification of biomass pyrolytic oil lightweight components/water phase by using in-situ hydrogenation reaction |
| CN104087350A (en) * | 2010-07-26 | 2014-10-08 | 蓝宝石能源公司 | Process for the recovery of oleaginous compounds from biomass |
| CN104998644A (en) * | 2014-04-17 | 2015-10-28 | 中国人民大学 | Catalyst for producing biomass oil through hydrothermal liquefaction, preparation method and applications thereof |
| CN106316727A (en) * | 2016-08-30 | 2017-01-11 | 许畅 | Porous and granular ANFO (ammonium nitrate fuel oil) and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104087350A (en) * | 2010-07-26 | 2014-10-08 | 蓝宝石能源公司 | Process for the recovery of oleaginous compounds from biomass |
| CN103059895A (en) * | 2012-12-07 | 2013-04-24 | 河南理工大学 | Method for preparing bio-oil through hydrothermal liquefaction of enteromorpha clathrata |
| CN103059895B (en) * | 2012-12-07 | 2015-07-22 | 河南理工大学 | Method for preparing bio-oil through hydrothermal liquefaction of enteromorpha clathrata |
| CN103060075A (en) * | 2012-12-18 | 2013-04-24 | 河南理工大学 | Method for preparing biological oil through catalytic liquefaction of microalgae |
| CN103484234A (en) * | 2013-09-18 | 2014-01-01 | 河南理工大学 | Method for preparing biological oil through catalyzing and liquefying microalgae |
| CN103484234B (en) * | 2013-09-18 | 2015-10-07 | 河南理工大学 | The catalytic liquefaction of a kind of micro-algae prepares the method for bio oil |
| CN103789076A (en) * | 2013-12-20 | 2014-05-14 | 浙江省海洋开发研究院 | Method for preparing bio-oil by using blue algae |
| CN103980928A (en) * | 2014-04-17 | 2014-08-13 | 张德者 | Biomass oil and preparation method thereof |
| CN104998644A (en) * | 2014-04-17 | 2015-10-28 | 中国人民大学 | Catalyst for producing biomass oil through hydrothermal liquefaction, preparation method and applications thereof |
| CN103980928B (en) * | 2014-04-17 | 2016-01-20 | 张德者 | bio-oil and preparation method thereof |
| CN104998644B (en) * | 2014-04-17 | 2017-09-22 | 中国人民大学 | Hydrothermal liquefaction produces catalyst of bio-oil and preparation method and application |
| CN104004597A (en) * | 2014-05-14 | 2014-08-27 | 中国科学院广州能源研究所 | Method for modification of biomass pyrolytic oil lightweight components/water phase by using in-situ hydrogenation reaction |
| CN104004597B (en) * | 2014-05-14 | 2016-03-30 | 中国科学院广州能源研究所 | A kind ofly add in-place H-H reaction is utilized to carry out the method for upgrading to biomass pyrolysis oil light component/aqueous phase |
| CN106316727A (en) * | 2016-08-30 | 2017-01-11 | 许畅 | Porous and granular ANFO (ammonium nitrate fuel oil) and preparation method thereof |
| CN106316727B (en) * | 2016-08-30 | 2018-10-02 | 许畅 | A kind of porous particulated ammonium oil explosive and preparation method thereof |
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Application publication date: 20100113 |