CN101805629B - Method for producing fuel oil by biomass hydrothermal liquefaction - Google Patents
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Abstract
The invention discloses a method for producing fuel oil by biomass hydrothermal liquefaction. The method is characterized by comprising the following steps: fully mixing a biomass raw material and solvent water (or adding catalyst water solution) to prepare seriflux, wherein a mass ratio of a catalyst to the raw material is 1:10 to 1:50, and the mass ratio of the raw material to water is 1:2 to 1:8; performing a reaction in a slurry bed reactor under a reducing atmosphere; controlling a liquefaction reaction temperature between 300 and 450 DEG C, a reaction pressure between 5 and 30 MPa and reaction time between 5 and 40 minutes; after the reaction, separating a product to obtain the fuel oil, solid residue, water, gas and the like. The method has the advantages of achieving complete biomass conversion, high oil product productivity, obtaining an oil product with a heat value equal to that of standard oil, relieving dependence on fossil energy, contributing to environment protection, lowering production cost and achieving good social and economic benefits.
Description
Technical field
The present invention relates to a kind of method of biomass liquefying made fuel oil, relate in particular to a kind of method of the producing fuel oil by biomass hydrothermal liquefaction under reducing atmosphere, belong to energy conversion field.
Background technology
Biomass are reproducible resources, are also the green energy resources that can realize carbonic acid gas " zero release " simultaneously.In recent years, particularly developed country utilizes the research of technology to become increasingly active to biomass in the world.China is large agricultural country, has abundant biomass resource, but take traditional burning as main at present, and thermo-efficiency is low, and major part is not reasonably utilized.Exploitation biomass liquefying technology not only can make up the deficiency of China's fossil energy, and is conducive to environment protection.The research of current biomass liquefying technology be take rapidly pyrolysing and liquefying as main, this technical matters is simple, easy to operate, but this process temperature required higher (500 ℃ of >), cause energy consumption larger, and general gained oil product oxygen level higher (> 20%), calorific value lower (< 25MJ/kg), can not directly replace oil to use.
Biomass high-pressure liquefaction is to take liquid solvent as medium, and biomass generate the process of a large amount of liquid products and a small amount of gas and solid residue in relatively low temperature (200-500 ℃), the higher lower reaction of pressure (> 5MPa).Compare with pyrolysis liquefaction, high-pressure liquefaction process condition is relatively gentle, gained oil product oxygen level lower (< 18%), calorific value higher (> 30MJ/kg), and subsequent processes is relatively simple.In recent years because this process receives much concern in the superiority aspect liquiefied product quality.The selection of solvent is most important for high-pressure liquefaction process, and people's solvent after deliberation comprises water, hydro carbons (as hexanaphthene), lower alcohols (as methyl alcohol, ethanol, Virahol, butanols), polyalcohols (as ethylene glycol, glycerol), phenols (as phenol), organic acid (as acetic acid, lactic acid), organic bases (as thanomin), ethers (as methyl glycol ether), ketone (as acetone, pimelinketone) etc. at present.Compare with organic solvent, water has good development prospect as a kind of green solvent, and the most water content of biomass is high, and the water of take can be removed drying process from as solvent, reduces energy consumption.Research shows, water can be removed partial oxygen in biomass by conversion reforming reaction, thereby improves oil product calorific value, has the potentiality of industrial application.
Have at present some patented technologies about biomass by hydro-thermal liquefaction process both at home and abroad, as the HTU technology (United States Patent (USP): 4 of Shell Co. Ltd, 670,613), the lignocellulose liquefaction technology (United States Patent (USP): 4 of Japan, 935,567) and the biomass catalyzing and liquefying technology (Chinese patent: 200510109176.1) etc. of Chinese scholar application.In above-mentioned existing patent by Optimizing Technical, add the measures such as basic catalyst to obtain than the good liquefaction oil product of fast pyrogenation quality, but still there is Wood Adhesives from Biomass not exclusively (< 95%), the problems such as liquefaction oil productive rate not high (< 35%), oxygen level higher (12-18%), calorific value lower (30-35MJ/kg), compare and still have certain gap with standard oil calorific value (41.8MJ/kg), the further upgrading processing of still needing could be used as oil substitute.In a word, there is unique advantage in hydro-thermal liquefaction technology aspect Wood Adhesives from Biomass, but current state of the art still has certain defect, needs further this technology to be optimized, and can advance the process of industrial application.
Summary of the invention
The object of the invention is to overcome the defect of aforesaid method, and in conjunction with its advantage, provide the technology that a kind of Wood Adhesives from Biomass is complete, oil product productive rate is high, calorific value is high.
Design of the present invention is such: in biomass liquefying process the quality of oil quality and the height of output with the feature of biomass itself, the selection of the character of solvent, processing condition and catalyzer all has relation.
In biomass, organic three major polymers: cellulose, hemicellulose and xylogen form, and wherein the above two are carbohydrate polymer, easily decompose; The latter is aromatic structure, within more difficult minute, transforms.Comparatively speaking, agricultural crop straw contains less xylogen than forestry timber, is easy to transform under similarity condition, and the oil product obtaining contains more fatty compounds.In agricultural crop straw ash content, contain more basic metal, the particularly crops necessary potassium element of growing up simultaneously.The experimental results shows, basic metal has good katalysis to Wood Adhesives from Biomass process.Therefore in the present invention, biomass material tends to select but be not limited to stalk biomass.
Water is as a kind of green solvent, and being applied to biomass high-pressure liquefaction process has many-sided advantage.First, in biomass preprocessing process, the water of take can be removed drying process from as solvent.General fresh biomass water ratio is 20-60%, even if still contain the moisture of 5-20% after exposure in sunshine.In the high-pressure liquefaction process that fast pyrogenation and the organic compound of take are solvent, need dry or processed in advance, the industrial energy that conventionally will consume 20-30%; In hydro-thermal liquefaction process, without dry and processed (only need suitably add water), can save this part energy consumption, thereby reduce production costs.Secondly, in biomass liquefying process, water is not only as solvent but also as reactant participation reaction.With respect to the water under common state, particularly critical and overcritical (stagnation point of water is 374 ℃ to high-temperature high pressure water near, 22.1MPa) under state, density (slightly diminishes, but far above gas), specific inductivity (significantly reducing), ionic product (first becomes large, after diminish), viscosity (diminishing), the character such as spread coefficient (becoming large) will change, now the dissolving power of water will be similar with organic solvent, can dissolve most of organism and nearly all gas completely, thereby breakthrough resistance to mass transfer, for gas and organic reaction provide good location, and effectively prevent coking and the carbon deposit on heterogeneous catalyst surface, inorganics, particularly oxide compound and the salt that for normality water, can dissolve, closely critical and supercritical water declines to a great extent to its dissolving power, thereby can effectively prevent the loss of catalyst metal ion.Water, as reactant, is participated in biomass and secondary organic hydrolysis and reforming reaction directly, effectively improves biomass cracking speed, improves products obtained therefrom quality.Again, in the high-pressure liquefaction process that the organism of take is solvent, oil product is a phase with solvent, and the processes such as rectifying and extraction will expend suitable macro-energy (conventionally can account for the 30-50% of total energy); And take water during as solvent, cooled water and part oil product (particularly hydrocarbon compound) layering, is convenient to separation, can alleviate the follow-up burden that water is processed, thereby saves separation costs; Finally, from application of engineering project, high pressure (pressure is all the time higher than water saturation vapour pressure under relevant temperature) water, without evaporative process, therefore can not consume vaporization heat (evaporation of water latent heat can be greater than intensification sensible heat conventionally), can save this part energy consumption.The high-temperature water that reactor is left in utilization heats into the cold water before reactor, and the mode integrated by energy can be optimized combination to hydro-thermal liquefaction process, can save water coolant and additional heat.
For the research of biomass by hydro-thermal liquefaction, seldom use reducing atmosphere in the past, and caused the Sauerstoffatom in biomass can not effective elimination.We think the subtractive process that biomass cracking and Sauerstoffatom are accelerated in membership that adds of the reducing gas such as hydrogen, thereby improve Wood Adhesives from Biomass rate and oil product calorific value.Under the specified conditions that are solvent at water, carbon monoxide can react with water generation reactive hydrogen atom, and (research shows, this reactive hydrogen atom activity is higher than hydrogen), therefore take carbon monoxide as reducing atmosphere, in biomass by hydro-thermal liquefaction process, will bring into play unique effect.And be expected to utilize synthetic gas to replace expensive pure hydrogen or pure carbon monoxide gas in industrial application, thereby cost-saving.
The selection of catalyzer is very important to biomass by hydro-thermal liquefaction process, and former studies person mostly studies the catalytic process of alkali and metal-salt (as the oxyhydroxide of sodium, potassium or carbonate) thereof, and other catalyzer seldom relates to.We using transition metal (as iron, cobalt, nickel, platinum, palladium etc.) and oxide compound thereof, salt as catalyzer for biomass by hydro-thermal liquefaction process, the effect that also can go well.Simultaneously cheap slag, sulfur-bearing dirty coal etc. also can play katalysis.
The present invention is achieved by the following technical solutions:
A method for producing fuel oil by biomass hydrothermal liquefaction, is characterized in that, described method is:
1) biomass material is crushed and screened to particle diameter and be less than 80 orders;
2) by step 1) biomass material and aqueous solvent be fully mixed into the uniform slurries of composition, biomass material is 1: 2 to 1: 8 with quality ratio;
3) by step 2) mixing solutions under reducing atmosphere, in paste state bed reactor, react, liquefaction reaction temperature is controlled at 300-450 ℃, reaction pressure 3-30MPa, the reaction times (being that the residence time, batch reactor are the time that maintains predetermined reaction conditions for flow reactor) is 5-40min; Reaction finishes product is carried out to separation to obtain oil fuel afterwards.
Wherein, described biomass material is wooden or straw biomass;
Described reducing atmosphere is hydrogen or carbon monoxide;
Described paste state bed reactor is a kind of in stirred autoclave, micro-vibration reaction unit or continuous, semicontinuous tubular type or tank reactor;
The present invention also provides the further prioritization scheme of technique scheme:
The step 2 of technique scheme) be: by step 1) biomass material and aqueous solvent and catalyzer be fully mixed into the uniform slurries of composition, biomass material is 1: 2 to 1: 8 with quality ratio, and catalyzer and biomass material mass ratio are 1: 10 to 1: 50;
Above-mentioned catalyzer is a kind of in homogeneous catalyst, heterogeneous catalyst or iron ore, and homogeneous catalyst is mixed with the aqueous solution, and heterogeneous catalyst, iron ore powder are broken to particle diameter and are less than 160 orders;
Above-mentioned homogeneous catalyst can be in alkali, basic metal, alkaline earth salt a kind of, the transition-metals and their oxides that heterogeneous catalyst is prepared for dipping or coprecipitation method, iron ore is the iron ore that sulphur content is greater than 1%.
After finishing, above-mentioned reaction can obtain gas phase, liquid phase and solid product.Gas is collected, and isolates the reducing gas such as hydrogen, carbon monoxide and recycles, and carbonic acid gas, methane and low molecular hydrocarbon etc. can properly be disposed; Solid phase can utilize the modes such as extracting to collect remaining oil product, and residue ash content can be used as catalyzer, fertilizer or material of construction etc. and is used; Liquid phase is divided into organic phase and water, and in water, oil product can utilize the modes such as extraction, rectifying separated, and residue water can be recycled.
Beneficial effect
Present method is compared with other method, and Wood Adhesives from Biomass rate is high, can approach 100%, and bio oil productive rate can reach 40-60%, and oxygen level can be down to 5-12%, and calorific value can reach 35-45MJ/kg, suitable with standard oil calorific value (41.8MJ/kg), has industrial application potentiality.
Embodiment
Below by embodiment, the present invention is further elaborated, its objective is to be beneficial to better understand content of the present invention and not limit the scope of the invention.
Embodiment mono-: by 2.0g cornstalk powder, it is the micro-vibration reactor of 30ml (Φ 20 * 100mm) that 10.0mL water adds volume, after sealing, with hydrogen exchange, fall the air in reactor, and to maintain hydrogen first pressing be 4.0MPa, in 5min, by sand-bath, be heated to 400 ℃ (now system pressure rises to about 25.0MPa), under this state, keep 35min, rapidly heating source withdrawn, and with ice-water bath by microreactor Quench to room temperature.Product is isolated to oil fuel, and organic total conversion rate is 96.3%, and fuel oil yield is 41.2%, and oxygen level is down to 11.4%, and calorific value is 36.5MJ/kg.
Embodiment bis-: by 2.0g wheat-straw powder, it is the micro-vibration reactor of 30ml (Φ 20 * 100mm) that 8.0mL water adds volume, after sealing, with carbon monoxide, displace the air in reactor, and to maintain first pressing be 4.0MPa, in 5min, by sand-bath, be heated to 390 ℃ (now system pressure rises to about 23.0MPa), under this state, keep 30min, rapidly heating source withdrawn, and with ice-water bath by microreactor Quench to room temperature.Product is isolated to oil fuel, and organic total conversion rate is 97.9%, and fuel oil yield is 42.7%, and oxygen level is down to 10.6%, and calorific value is 37.2MJ/kg.
Embodiment tri-: by 3.0g wheat-straw powder, it is the micro-vibration reactor of 30ml (Φ 20 * 100mm) that 14.0mL water adds volume, after sealing, with carbon monoxide, displace the air in reactor, and to maintain first pressing be 4.0MPa, in 5min, by sand-bath, be heated to 420 ℃ (now system pressure rises to about 24.0MPa), under this state, keep 25min, rapidly heating source withdrawn, and with ice-water bath by microreactor Quench to room temperature.Product is isolated to oil fuel, and organic total conversion rate is 98.5%, and fuel oil yield is 40.3%, and oxygen level is down to 11.8%, and calorific value is 35.9MJ/kg.
Embodiment tetra-: by 20.0g saw dust, it is in the high-pressure stirring reactor of 500ml that 100.0mL adds volume containing the aqueous solution of 2% sodium hydroxide, after sealing, with carbon monoxide, displace the air in reactor, and to maintain hydrogen first pressing be 3.0MPa, be warming up to 378 ℃ (now system pressure rises to about 27.0MPa), under this state, keep 30min, by spiral coil cooling tube in still, material is down to room temperature.Product is isolated to oil fuel, and organic total conversion rate is 99.7%, and fuel oil yield is 44.4%, and oxygen level is down to 9.3%, and calorific value is 39.8MJ/kg.
Embodiment five: by 2.0g transformation catalyst (commercially available product, purchased from the Qingjian River, Jiangsu catalyzer head factory), 20.0g cornstalk powder, it is in the high-pressure stirring reactor of 500ml that 100.0mL water adds volume, after sealing, with carbon monoxide, displace the air in reactor, and to maintain first pressing be 3.0MPa, be warming up to 375 ℃ (now system pressure rises to about 27.0MPa), under this state, keep 20min, by spiral coil cooling tube in still, material is down to room temperature.Product is isolated to oil fuel, and organic total conversion rate is 99.9%, and fuel oil yield is 52.6%, and oxygen level is down to 8.5%, and calorific value is 41.5MJ/kg.
Embodiment six: 2.0g is utilized to nickel, the molybdenum catalyst that ammoniacal liquor and nitrate prepared by coprecipitation method, and (underlying condition is, Ni: Mo atomic ratio is 1: 1, ammoniacal liquor is slightly excessive, 500 ℃ of roasting 4h) transformation catalyst, 18.0g wheat-straw powder, it is in the high-pressure stirring reactor of 500ml that 100.0mL water adds volume, after sealing, with hydrogen, change the air in reactor, and to maintain first pressing be 5.0MPa, be warming up to 375 ℃ (now system pressure rises to about 27.0MPa), under this state, keep 20min, by spiral coil cooling tube in still, material is down to room temperature.Product is isolated to oil fuel, and organic matter transforms substantially completely, and fuel oil yield is 56.1%, and oxygen level is down to 5.9%, and calorific value is 43.8MJ/kg.
Embodiment seven: by 2.0g Hubei sulfurous iron ore, 20.0g cornstalk powder, it is in the high-pressure stirring reactor of 500ml that 100.0mL water adds volume, after sealing, with hydrogen, change the air in reactor, and to maintain first pressing be 5.0MPa, be warming up to 381 ℃ (now system pressure rises to about 27.0MPa), under this state, keep 30min, by spiral coil cooling tube in still, material is down to room temperature.Product is isolated to oil fuel, and organic total conversion rate is 99.9%, and fuel oil yield is 49.8%, and oxygen level is down to 6.2%, and calorific value is 42.5MJ/kg.
Embodiment eight: by 20.0g saw dust, it is in the high-pressure stirring reactor of 500ml that 100.0mL adds volume containing the aqueous solution of 1.5% ferrous sulfate, after sealing, with carbon monoxide, displace the air in reactor, and to maintain hydrogen first pressing be 4.0MPa, be warming up to 380 ℃ (now system pressure rises to about 27.0MPa), under this state, keep 30min, by spiral coil cooling tube in still, material is down to room temperature.Product is isolated to oil fuel, and organic total conversion rate is 99.2%, and fuel oil yield is 46.3%, and oxygen level is down to 7.4%, and calorific value is 40.3MJ/kg.
Embodiment nine: by 5.0g Huainan brown coal, 20.0g Cotton Stalk powder, it is in the high-pressure stirring reactor of 500ml that the 110.0mL aqueous solution adds volume, after sealing, with carbon monoxide, displace the air in reactor, and to maintain hydrogen first pressing be 4.0MPa, be warming up to 360 ℃ (now system pressure rises to about 26.0MPa), under this state, keep 30min, by spiral coil cooling tube in still, material is down to room temperature.Product is isolated to oil fuel (not deducting gelatin liquefaction products obtained therefrom in computation process), and organic total conversion rate is 98.3%, and fuel oil yield is 57.8%, and oxygen level is down to 7.7%, and calorific value is 39.5MJ/kg.
Embodiment ten: by 0.5gPt/Al
2o
3catalyzer (commercially available product; purchased from Shanghai Chemical Research Inst); 5.0g Cotton Stalk powder mixes and packs in the semicontinuous reaction tubes that volume is 20mL, with high-pressure hydraulic pump and gas topping-up pump, in proportion water and CO (carbon monoxide converter) gas is passed into preheater, enters subsequently reactor.By back pressure valve Controlling System pressure, be 25.0MPa, utilizing electric furnace to maintain reactor temperature is 400 ℃ (now system pressure rises to about 26.0MPa), under this state, keeps 30min, by reactor aftercooler, material is cooled to room temperature.Product is isolated to oil fuel, and organic total conversion rate approaches 100%, and fuel oil yield is 59.2%, and oxygen level is down to 5.5%, and calorific value is 44.6MJ/kg.
Claims (5)
1. a method for producing fuel oil by biomass hydrothermal liquefaction, is characterized in that, described method comprises the steps:
1) biomass material is crushed and screened to particle diameter and be less than 80 orders;
2) by step 1) biomass material and aqueous solvent be fully mixed into the uniform slurries of composition, biomass material and quality are than being 1:2 to 1:8;
3) by step 2) mixing solutions under reducing atmosphere, in paste state bed reactor, react, liquefaction reaction temperature is controlled at 300-450 ℃, reaction pressure 3-30MPa, the reaction times is 5-40min; Reaction finishes product is carried out to separation to obtain oil fuel afterwards;
Wherein, described biomass material is wooden or straw biomass;
Described reducing atmosphere is hydrogen or carbon monoxide;
In the described reaction times, be the residence time for flow reactor, is the time that maintains predetermined reaction conditions for batch reactor.
2. the method for producing fuel oil by biomass hydrothermal liquefaction as claimed in claim 1, is characterized in that, described paste state bed reactor is for being selected from stirred autoclave, micro-vibration reaction unit, a kind of in continuous, semicontinuous tubular type or tank reactor.
3. a method for producing fuel oil by biomass hydrothermal liquefaction, is characterized in that, described method comprises the steps:
1) biomass material is crushed and screened to particle diameter and be less than 80 orders;
2) by step 1) biomass material and water and catalyzer be fully mixed into the uniform slurries of composition, the mass ratio of biomass material and water is 1:2 to 1:8, the mass ratio of catalyzer and biomass material is 1:10 to 1:50;
3) by step 2) mixing solutions under reducing atmosphere, in paste state bed reactor, react, liquefaction reaction temperature is controlled at 300-450 ℃, reaction pressure 3-30MPa, the reaction times is 5-40min; Reaction finishes product is carried out to separation to obtain oil fuel afterwards;
Wherein, described biomass material is wooden or straw biomass;
Described reducing atmosphere is hydrogen or carbon monoxide;
In the described reaction times, be the residence time for flow reactor, is the time that maintains predetermined reaction conditions for batch reactor;
Described paste state bed reactor is for being selected from stirred autoclave, micro-vibration reaction unit, a kind of in continuous, semicontinuous tubular type or tank reactor.
4. the method for producing fuel oil by biomass hydrothermal liquefaction as claimed in claim 3, it is characterized in that, described catalyzer is a kind of in homogeneous catalyst, heterogeneous catalyst or iron ore, and homogeneous catalyst is mixed with the aqueous solution, and heterogeneous catalyst, iron ore powder are broken to particle diameter and are less than 160 orders.
5. the method for producing fuel oil by biomass hydrothermal liquefaction as claimed in claim 4, it is characterized in that, described homogeneous catalyst is to be selected from a kind of in alkali, basic metal, alkaline earth salt, a kind of in the oxide compound of dipping or the transition metal prepared of coprecipitation method or transition metal of heterogeneous catalyst, iron ore is that sulphur content is greater than a kind of in 1% iron ore.
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Cited By (1)
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Families Citing this family (42)
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| CN110747001B (en) * | 2018-12-04 | 2021-11-09 | 北京三聚环保新材料股份有限公司 | Secondary biomass conversion process |
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| CN116420830A (en) * | 2023-04-19 | 2023-07-14 | 江西金糠新材料科技有限公司 | Method and system for preparing food-grade rice hull vinegar, rice hull vinegar beverage and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012387A (en) * | 2007-02-01 | 2007-08-08 | 淮北中润生物能源技术开发有限公司 | Technique for manufacturing liquid fuel from highly effective cellulose biomass |
| CN101407727A (en) * | 2008-10-29 | 2009-04-15 | 扬州大学 | Method for preparing biomass liquefied oil by biomass catalytic liquefaction |
| CN101619227A (en) * | 2008-06-30 | 2010-01-06 | 淮北中润生物能源技术开发有限公司 | Direct liquifying method of cellulose biomass |
-
2010
- 2010-03-22 CN CN201010128949.1A patent/CN101805629B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012387A (en) * | 2007-02-01 | 2007-08-08 | 淮北中润生物能源技术开发有限公司 | Technique for manufacturing liquid fuel from highly effective cellulose biomass |
| CN101619227A (en) * | 2008-06-30 | 2010-01-06 | 淮北中润生物能源技术开发有限公司 | Direct liquifying method of cellulose biomass |
| CN101407727A (en) * | 2008-10-29 | 2009-04-15 | 扬州大学 | Method for preparing biomass liquefied oil by biomass catalytic liquefaction |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3509752A4 (en) * | 2016-09-09 | 2020-04-15 | Nulife Greentech Inc. | Extraction of liquid hydrocarbon fraction from carbonaceous waste feedstock |
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