WO2012155414A1 - 生物质热解液化制备生物质燃料的方法 - Google Patents

生物质热解液化制备生物质燃料的方法 Download PDF

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WO2012155414A1
WO2012155414A1 PCT/CN2011/079512 CN2011079512W WO2012155414A1 WO 2012155414 A1 WO2012155414 A1 WO 2012155414A1 CN 2011079512 W CN2011079512 W CN 2011079512W WO 2012155414 A1 WO2012155414 A1 WO 2012155414A1
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biomass
fuel
oil
pyrolyzed
pyrolysis
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PCT/CN2011/079512
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English (en)
French (fr)
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谭鸿鑫
段占庭
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科威国际技术转移有限公司
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Publication of WO2012155414A1 publication Critical patent/WO2012155414A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention relates to the further development and utilization of biomass raw materials, in particular biomass waste, and in particular to a method for pyrolyzing a biomass raw material to prepare a biomass fuel, the biomass fuel comprising biomass light oil and biomass Diesel and biomass heavy oil.
  • biomass waste in China's industrial background, such as bagasse, distiller's residue, cassava residue, straw, wheat straw, bean stalk, cotton stalk, corn stalk, corn cob, deciduous and sawdust.
  • Material waste usually contains a large amount of macromolecular substances such as lignin, cellulose, hemicellulose and starch which can be further utilized.
  • macromolecular substances such as lignin, cellulose, hemicellulose and starch which can be further utilized.
  • Biomass pyrolysis is a thermochemical process in which macromolecular substances in biomass such as lignin, cellulose, hemicellulose, and starch are thermochemically reacted in the absence of an oxidant or a limited oxidant. Decomposition is converted to biomass oil, charcoal and flammable gases, and the ratio between the products can be varied by controlling thermochemical reaction conditions such as temperature, pressure and residence time, etc., such as air, oxygen, water Or steam, etc.
  • the requirements for the collection and cooling equipment of the bio-oil are high.
  • the temperature at which the pyrolysis product leaves the reactor is generally 400-500X, at which time the pyrolysis products are mostly gaseous, and in the subsequent process, these gaseous products condense together with the solid particles.
  • Contamination on the surface of pipes and equipment causes blockage, which in turn affects process operation
  • the continuous operation is not conducive to the industrialization of the technology, but also affects the process yield.
  • there are still some problems in the biomass pyrolysis technology For example, the production cost of biomass oil is usually higher than that of mineral oil, and the biomass oil cannot be directly used in existing power equipment because Biomass oils are mostly hydrocarbons that are not physically and chemically stable and must be modified and/or refined to be applied.
  • the present invention seeks a method for fractionating biomass at lower pressures and then fractionating the biomass into biomass light oil, biomass diesel, and biomass heavy oil, thereby further utilizing Biomass waste provides a sustainable source of energy. Summary of the invention
  • the present invention provides a method of pyrolyzing liquefied biomass to prepare a biomass fuel, the method comprising, in the presence of a basic catalyst, in a liquid fuel solvent at a pressure of 1-6 atmospheres and at a temperature of 200-300
  • the biomass feedstock particles are pyrolyzed and separated, and the obtained pyrolyzed liquefied products are separated into biomass fuel products of different boiling ranges.
  • the biomass raw material is generally biomass waste, and is specifically selected from the group consisting of bagasse, distiller's residue, cassava residue, straw, wheat straw, bean stalk, cotton stalk, corn stalk, Corn cob, leaves and sawdust.
  • the source of the biomass feedstock is <rich.
  • the biomass material is generally pulverized and sieved to obtain a particle size of less than or equal to about 300 microns (about 50 mesh), preferably less than or equal to about 200 microns (about 70 mesh).
  • the biomass feedstock granules are typically comminuted by mechanical disruption and the sieving is carried out using standard sieves to obtain the desired biomass size granules of a particular particle size range.
  • the biomass raw material if the biomass raw material has an excessively large water content, the biomass raw material is generally dried in advance, for example, by a dryer such as a cyclone, preferably to a water content of less than 10 wt. More preferably, it is dried to a water content of less than 5% by weight to facilitate subsequent comminution and sieving of the biomass feedstock.
  • the basic catalyst may be any suitable basic catalyst commonly used in the art, preferably an alkali or alkaline earth metal base or a salt, more preferably an alkali metal or alkaline earth metal. 5% by weight, preferably 0. 5 to 5% by weight, preferably 0. 5 to 5% by weight, preferably 0. 5 to 5% by weight. .
  • the liquid fuel solvent may be any suitable liquid fuel commonly used in the art, preferably a less expensive non-volatile liquid fuel, and may be a non-volatile oily liquid fuel such as Heavy oil and coal tar and heavy oil components and coal tar components, wherein the heavy oil component such as heavy oil light fraction, the coal tar components such as naphthalene oil, washing oil, eucalyptus oil and diterpenoid oil, preferably using eucalyptus oil and / or washing oil as the liquid fuel solvent, and the weight ratio of the liquid fuel solvent to the biomass raw material particles can be appropriately selected, generally 10: 1 to 3: 1, preferably 8: 1 to 3: 1 Most preferably from 6:1 to 3:1.
  • the biomass feedstock particles may be subjected to pyrolysis liquefaction in any suitable reactor existing in the prior art, and the pyrolysis liquefaction reactor may be, for example, a recycle stream.
  • the bed reactor, the bubbling bed reactor, but preferably a reactor type reactor, is more preferably a stainless steel reaction crucible with a stirring paddle.
  • the biomass material particles are carried at a pressure of from 1 to 6 atmospheres, preferably from 1 to 3 atmospheres, more preferably at atmospheric pressure.
  • Pyrolysis in a stainless steel reactor with a paddle Liquefaction wherein the heating is carried out under stirring to a temperature of 200-300, preferably heating to 215-290X, more preferably heating to 230-280* €, and the stirring speed of the stirring blade is 100-400 rpm, preferably 130 ⁇ 5. 5 ⁇ , ⁇ 0. 6-5 ⁇ , ⁇ 0. It is preferably from 1 to 4 hours.
  • the pyrolysis liquefaction product may be separated into biomass fuel products of different boiling ranges by a separation process such as rectification, and the pyrolysis product may be separated into Biomass light oil, biomass diesel and biomass heavy oil with different boiling range, wherein the biomass light oil can have a boiling range of 110-180X, which is obtained at the top of the distillation column, and the boiling range of biomass diesel can be 180-365 X, produced in the middle side of the rectification column, and the biomass heavy oil can have a boiling range of 365 or more, obtained at the bottom of the rectification column.
  • the biomass light oil may be used to provide heat to the pyrolysis liquefaction process, in particular to provide heat to the stainless steel reaction vessel, thereby at least partially achieving The heat self-sufficiency of the pyrolysis liquefaction process;
  • the biomass diesel has a calorific value of 33-36 MJ/kg, which can be used to replace or partially replace the conventional heavy diesel oil;
  • the biomass heavy oil has a calorific value of 35-38 MJ/ Kg, can be used to replace conventional fuel oil.
  • the conversion of the biomass feedstock particles by pyrolysis liquefaction to produce biomass oil is generally from 70 to 96% by weight, preferably from 75 to 95% by weight.
  • the method for preparing a biomass fuel significantly improves the product yield, the process is relatively simple, and the equipment used is also a common equipment of the prior art, and therefore, the method of the present invention is easy to perform industrial amplification. It can be continuously produced and has good industrialization prospects, which in turn can provide alternative fuels for the fuel market.
  • Figure 1 is a flow diagram of a process for the preparation of biomass fuel by pyrolysis liquefaction of biomass feedstock of the present invention. detailed description
  • the method for preparing a biomass fuel by pyrolyzing a liquefied biomass feedstock of the present invention can be carried out as follows:
  • the biomass material such as corn cob
  • the biomass material is dried to a water content of less than 10% by weight and then mechanically broken and sieved using a standard sieve such as 50 mesh to obtain biomass feedstock particles having a particle size of less than or equal to 300 microns;
  • a liquid fuel solvent such as eucalyptus oil and stirring and mixing with the biomass raw material granules in a predetermined ratio, for example, 5:1, and adding a selected basic catalyst such as sodium carbonate, the amount of sodium carbonate added thereto
  • the weight of the biomass raw material particles is, for example, 3 wt%, and is further uniformly mixed;
  • the previously obtained homogenous reaction mixture is added to a stainless steel reaction vessel with a stirring paddle as a pyrolysis liquefaction reactor, which may be an atmospheric pressure reactor or a pressurized reaction vessel with a steam jacket, for example It may be pressurized to a pressure of 1-6 atmospheres, preferably a pressure of 1-3 atmospheres, wherein the heating is heated to a temperature of, for example, 230 to 280 under stirring, and the rotation speed of the stirring blade is, for example, 150 to 300 rpm, and The residence time of the reaction mixture in the reaction vessel is, for example, 1-4 hours;
  • biomass light oil having a boiling range of 110-180 can be obtained from the top of the rectification column, and a boiling range of 180-365 X is taken from the middle side line of the rectification column.
  • the steam thus at least partially achieves the self-sufficiency of heat in the pyrolysis liquefaction process of the present invention.

Description

生物质热解液化制备生物质燃料的方法 技术领域
本发明涉及对生物质原料、 特别是生物质废弃物的进一步开 发和利用， 具体涉及将生物质原料热解液化以制备生物质燃料的 方法， 所述生物质燃料包括生物质轻油、 生物质柴油和生物质重 油。 背景技术
在我国的产业背景下存在有大量的生物质废弃物， 具体例如 甘蔗渣、 酒糟渣、 木薯渣、 稻草、 麦秆、 豆秆、 棉秆、 玉米秆、 玉米芯、 落叶及木屑等， 这些生物质废弃物中通常含有大量的可 进一步利用的大分子物质如木质素、纤维素、半纤维素和淀粉等。 近年来， 在绿色低碳的大背景下， 对这些生物质废弃物的进一步 开发和利用越来越受到关注。
生物质热解是一种热化学方法， 其中在不存在氧化剂或只提 供有限氧化剂的条件下， 通过热化学反应使生物质中的大分子物 质如木质素、 纤维素、 半纤维素和淀粉等分解转化为生物质油、 炭和可燃性气体， 并且可以通过控制热化学反应条件如温度、 压 力和停留时间等来改变所述产物之间的比例， 此处所述氧化剂如 空气、 氧气、 水或蒸汽等。
在现有技术中， 由于生物质热解过程会产生焦油， 因此对生 物油的收集和冷却设备的要求都很高。 例如， 在生物质快速热解 过程中， 热解产物离开反应器的温度一般为 400- 500X ， 此时热 解产物大多为气态， 在后续过程中， 这些气态产物冷凝后会与固 体颗粒一起在管道及设备表面上结垢造成堵塞， 进而影响过程操 作的连续进行， 不利于所述技术产业化， 同时也会影响过程收率。 另外， 在现有技术中， 生物质热解技术还存在一些问题， 例 如， 生物质油的生产成本通常比矿物油高， 而且， 生物质油不能 直接用于现有的动力设备， 这是因为生物质油大多是物理和化学 性质均不太稳定的碳氢化合物，必须经过改性和 /或精制处理才能 应用。
基于现有技术的情况， 本发明寻求一种在较低压力下在较低 油， 然后将生物质 分馏 ^到生物质轻油、 生^质柴油和生物质 重油的方法， 从而可进一步利用所述生物质废弃物， 提供了一种 可持续发展的能量来源。 发明内容
本发明提供一种热解液化生物质以制备生物质燃料的方法， 所述方法包括在碱性催化剂存在下在液体燃料溶剂中在 1-6个大 气压的压力下和在 200- 300 的温度下使生物质原料颗粒热解液 化，和将获得的热解液化产物分离成不同沸程的生物质燃料产品。
在本发明的制备生物质燃料的方法中， 所述生物质原料一般 为生物质废弃物， 具体选自甘蔗渣、 酒糟渣、 木薯渣、 稻草、 麦 秆、 豆秆、 棉秆、 玉米秆、 玉米芯、 落叶及木屑等。 因此， 对于 本发明的方法而言， 所述生物质原料的来源还是 »丰富的。
在本发明的制备生物质燃料的方法中， 所述生物质原料一般 经粉碎和筛分处理得到粒度小于或等于约 300微米（约 50目）、优 选小于或等于约 200微米（约 70目）的生物质原料颗粒，粉碎一般 通过机械破碎进行， 而筛分则利用标准筛进行， 以获得所需要的 特定粒度范围的生物质原料颗粒。 在本发明的制备生物质燃料的方法中， 如果所述生物质原料 含水量过大， 则一般预先干燥所述生物质原料， 例如利用旋风等 干燥机进行干燥， 优选干燥至水含量低于 10wt%， 更优选干燥至 水含量低于 5wt%, 从而利于所述生物质原料后续的粉碎和筛分处 理。
在本发明的制备生物质燃料的方法中， 所述碱性催化剂可以 为本领域常用的任何合适的碱性催化剂， 优选为碱金属或碱土金 属的碱或盐， 更优选为碱金属或碱土金属的碳酸盐， 最优选为碳 酸钠、 碳酸钟和碳酸钙， 和所述碱性催化剂的用量为所述生物质 原料颗粒总重量的 0. 2-5wt%, 优选为 0. 5- 3wt%。
在本发明的制备生物质燃料的方法中， 所述液体燃料溶剂可 以为本领域常用的任何合适的液体燃料， 优选价格比较便宜的不 易挥发的液体燃料， 具体可以为不易挥发的油性液体燃料如重油 和煤焦油及重油组分和煤焦油组分， 其中所述重油组分如重油轻 馏分， 所述煤焦油组分如萘油、 洗油、 蒽油和二蒽油， 优选使用 蒽油和 /或洗油作为所述液体燃料溶剂，和所述液体燃料溶剂与所 述生物质原料颗粒的重量比可以适当选择， 一般为 10: 1至 3: 1 , 优选为 8: 1至 3: 1 , 最优选为 6: 1至 3: 1。
在本发明的制备生物质燃料的方法中， 所述生物质原料颗粒 可以在现有技术中已有的任何合适的反应器中进行热解液化， 所 述热解液化反应器可以为例如循环流化床反应器、鼓泡床反应器， 但优选为反应釜类反应器， 进一步优选为带有搅拌桨的不锈钢反 应蚤。
更优选地， 在本发明的制备生物质燃料的方法中， 所述生物 质原料颗粒在 1-6个大气压的压力下、 优选 1-3个大气压的压力 下、 更优选在大气压下在带有搅拌桨的不锈钢反应釜中进行热解 液化， 其中在搅拌的条件下加热升温至 200- 300 , 优选加热升 温至 215- 290X , 更优选加热升温至 230- 280*€,和搅拌桨的转速 为 100- 400转 /分，优选为 130- 350转 /分， 更优选为 150- 300转 / 分，和所述反应混合物在所述反应釜内的停留时间为 0. 6-5小时， 优选为 0. 8-4. 5小时， 更优选为 1-4小时。
在本发明的制备生物质燃料的方法中， 所述热解液化产物可 以通过精馏等分离过程分离成为不同沸程的生物质燃料产品， 所 塔等， 和所述热解液化产物可以分离成不同沸程的生物质轻油、 生物质柴油和生物质重油， 其中生物质轻油的沸程范围可以为 110-180X ,在精馏塔的塔顶得到，生物质柴油的沸程范围可以为 180-365 X ,在精馏塔的中部侧线采出，和生物质重油的沸程范围 可以为 365 以上， 在精馏塔的塔底得到。
优选地， 在本发明的制备生物质燃料的方法中， 所述生物质 轻油可用于为所述热解液化过程提供热量， 具体可以为所述不锈 钢反应釜提供热量， 从而可至少部分实现所述热解液化过程的热 量自给； 所述生物质柴油的热值为 33-36MJ/kg, 可用于替代或部 分替代常规的重质柴油； 和所述生物质重油的热值为 35-38MJ/kg, 可用于替代常规的燃料油。
在本发明的制备生物质燃料的方法中， 所述生物质原料颗粒 热解液化产生生物质油的转化率一般为 70-96wt% , 优选为 75-95wt%。
按照本发明， 所述制备生物质燃料的方法明显提高了产物收 率， 工艺过程相对简单， 且所使用的设备也均为现有技术的常用 设备， 因此， 本发明的方法容易进行工业放大， 可连续生产， 具 备良好的产业化前景， 进而可以为燃料市场提供代选燃料。 附图说明
图 1为本发明的由生物质原料热解液化制备生物质燃料的方 法的流程图。 具体实施方式
参照图 1 , 本发明的热解液化生物质原料以制备生物质燃料 的方法可以按照如下过程进行：
将生物质原料如玉米芯干燥至水含量低于 10wt%, 然后经机 械破碎和利用例如 50 目的标准筛筛分得到粒度小于或等于 300 微米的生物质原料颗粒；
选择液体燃料溶剂例如蒽油并与所述生物质原料颗粒按规定 比例例如 5: 1在容器内搅拌混合， 并向其中加入所选择的碱性催 化剂如碳酸钠， 碳酸钠的加入量以所述生物质原料颗粒的重量计 为例如 3wt%, 并进一步混合均匀；
将前面获得的均勾的反应混合物加入作为热解液化反应器的 带有搅拌桨的不锈钢反应釜中， 所述反应釜可以为带有蒸汽夹套 的常压反应釜或加压反应釜， 例如可以加压至 1-6个大气压的压 力下、 优选 1-3个大气压的压力下， 其中在搅拌条件下加热升温 至例如 230- 280 , 搅拌桨的转速为例如 150- 300转 /分， 和所述 反应混合物在所述反应釜内的停留时间为例如 1-4小时； 和
从所述反应釜中连续采出热解液化的产物即生物质油， 将采 出的生物质油泵送入精馏塔进行精馏， 从而得到不同沸程的生物 质燃料；
具体地， 可以从精馏塔的塔顶得到沸程范围为 110- 180 的 生物质轻油， 从精馏塔中部侧线采出沸程范围为 180-365 X的生 物质柴油， 和从精馏塔塔底得到沸程范围为 365 以上的生物质 重油， 并且其中所述生物质轻油可用于为所述不锈钢反应釜提供 热量， 例如可用于产生加热所述反应釜的蒸汽， 从而可至少部分 实现本发明的热解液化过程的热量自给。
通过如下实施例进一步描述本发明的方法， 但所述实施例不 用于限制本发明的范围。 实施例
实施例 1 甘蔗渣的热解液化
将一定量的甘蔗渣干燥至水含量低于 10wt%， 然后粉碎并筛 分获得 30克 50 目（300微米）以下的固体颗粒； 将所述固体颗粒 与 120克洗油以及 1克 Na2C03在容器中搅拌混合均勾； 将所得反 应混合物加入到 0. 5升的不锈钢反应釜中， 在搅拌条件下加热升 温至 230 X , 所采用的搅拌转速为 300转 /分， 反应混合物在反应 釜内的停留时间为 3小时， 热解液化得到的生物质油经过精馏分 离得到生物质轻油 3. 45克、 生物质柴油 75克和生物质重油 70 克。 经计算可知， 该实施例中热解液化的产物收率约为 98. 97%。 另外， 经测量， 所得到的三种生物燃料的热值均为 36MJ/kg。 实施例 2 玉米芯的热解液化
将一定量的玉米芯干燥至水含量低于 10wt%， 然后粉碎并筛 分获得 30克 70 目（200微米）以下的固体颗粒； 将所述固体颗粒 与 120克蒽油以及 1. 2克 CaC03在容器中搅拌混合均匀； 将所得 反应混合物加入到 0. 5升的不锈钢反应釜中， 在搅拌条件下加热 升温至 所采用的搅拌转速为 200转 /分， 反应混合物在反 应釜内的停留时间为 2. 5小时， 热解液化得到的生物质油经过精 馏分离得到生物质轻油 3. 05克、 生物质柴油 70克和生物质重油 74克。经计算可知，该实施例中热解液化的产物收率约为 98. 03%。 另外， 经测量， 所得到的三种生物燃料的热值均为 35MJ/kg。 实施例 3 棉秆的热解液化
将一定量的棉秆干燥至水含量低于 10wt%, 然后粉碎并筛分 获得 30克 60 目（250微米）以下的固体颗粒； 将所述固体颗粒与 120克洗油以及 0. 6克 K2C03在容器中搅拌混合均勾； 将所得反应 混合物加入到 0. 5升的不锈钢反应釜中， 在搅拌条件下加热升温 至 2401C , 所采用的搅拌转速为 350转 /分， 反应混合物在反应釜 内的停留时间为 4小时， 热解液化得到的生物质油经过精馏分离 得到生物质轻油 2. 95克、 生物质柴油 69克和生物质重油 72克。 经计算可知，该实施例中热解液化的产物收率约为 95. 97%。另外， 经测量， 所得到的三种生物燃料的热值均为 37MJ/kg。

Claims

1. 一种热解液化生物质原料以制备生物质燃料的方法， 所述 方法包括在碱性催化剂存在下在液体燃料溶剂中在 1-6个大气压 的压力下和在 200- 300X的温度下使生物质原料颗粒热解液化， 和将获得的热解液化产物分离成不同沸程的生物质燃料产品。
2. 权利要求 1的方法， 其中所述生物质原料为选自甘蔗渣、 酒糟渣、 木薯渣、 稻草、 麦秆、 豆秆、 棉秆、 玉米秆、 玉米芯、 落叶及木屑的生物质废弃物。
3. 权利要求 1或 2的方法， 其中将所述生物质原料预先干燥 至水含量低于 10wt%, 优选低于 5wt%， 和所述生物质原料颗粒的 粒度小于或等于约 300微米， 优选小于或等于约 200微米。
4. 权利要求 1-3任一项的方法， 其中所述碱性催化剂为碱金 属或碱土金属的碳酸盐， 优选为碳酸钠、 碳酸钾和碳酸钙， 和所 述碱性催化剂的用量为所述生物质原料颗粒总重量的 0. 2-5wt%, 优选为 0. 5- 3wt%。
5. 权利要求 1-4任一项的方法， 其中所述液体燃料溶剂选自 重油和煤焦油及重油组分和煤焦油组分， 优选选自蒽油和洗油， 和所述液体燃料溶剂与所述生物质原料颗粒的重量比为 10: 1 至 3: 1 , 优选为 8: 1至 3: 1 , 最优选为 6: 1至 3: 1。
6. 权利要求 1-5任一项的方法，其中所述热解原料颗粒在 1-3 个大气压的压力下、 优选在大气压下在带有搅拌桨的不锈钢反应 釜中进行热解液化， 其中在搅拌条件下加热升温至 215- 优选加热升温至 230- 280 , 和搅拌桨的转速为 100- 400转 /分， 优选为 130- 350转 /分， 更优选为 150- 300转 /分。
7. 权利要求 6的方法， 其中所述反应混合物在所述反应釜内 的停留时间为 0. 6-5小时， 优选为 0. 8-4. 5小时， 更优选为 1-4 小时。
8. 权利要求 1-7任一项的方法， 其中所述热解液化产物通过 精馏进行分离， 和所述不同沸程的生物质燃料产品包括沸程范围 为 110- 180*€的生物质轻油、沸程范围为 180- 365 的生物质柴油 和沸程范围为 365 X以上的生物质重油。
9. 权利要求 8的方法， 其中利用所述生物质轻油为热解液化 过程提供热量。
PCT/CN2011/079512 2011-05-16 2011-09-09 生物质热解液化制备生物质燃料的方法 WO2012155414A1 (zh)

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