CN102408901B - Biomass rapid pyrolysis method and device - Google Patents
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Abstract
Description
技术领域 technical field
本发明涉及一种生物质热裂解，尤其是涉及一种生物质快速热裂解的方法及其装置。The invention relates to a kind of pyrolysis of biomass, in particular to a method and a device for fast pyrolysis of biomass.
背景技术 Background technique
随着中国经济的高速发展，能源供应不足的矛盾日趋突出，我国原油依赖进口问题严重。因此，充分立足本国资源开发可替代能源，特别是生物质能源，以减少对石油的依赖，对于保证国家能源安全，实现可持续发展具有重要的意义。生物质能源作为唯一可以转化为液体燃料的可再生能源，是仅次于煤炭、石油和天然气而居于世界能源消费总量第四位的能源，在整个能源系统中占有重要地位。生物质是指一切直接或间接利用绿色植物光合作用形成的有机物质，包括除化石燃料外的植物、动物和微生物及其排泄与代谢物等。生物质快速热裂解是生物质能源应用的重要方面，它能够将生物质原料，如秸秆、木屑、农产品加工废料等，转化为高品位的生物质油，该技术对生物质原料的要求为含水量低于10％和粒径小于2mm。生物质快速热裂解是指在无氧环境下，将生物质快速加热到较高反应温度，引起大分子的分解，产生小分子气体和可凝性挥发分以及少量焦炭的过程，可凝性挥发分被快速冷却成可流动液体，称之为生物质油。生物质油具有刺激性焦味，高密度(～1200kg/m3)，酸性(pH值2.8～3.8)以及较低热值(14～18.5MJ/kg)。生物质油成分复杂，包含酸类、醛类、酮类、呋喃类等上百种化合物，单一的水冷方式将热裂解蒸汽中所有能够冷凝的生物质油集中在一起，不能将生物质油分级收集，不利于生物质油在更广泛的范围内应用，同时，由于水冷冷凝方式换热不佳，导致生物质油产率较低。如中国专利CN200510057216.2公开的《一种生物质热裂解液化的工艺方法及其装置系统》和CN201110006196.1公开的《一种生物质热裂解炉》等，均是采用水冷的方式收集生物质油，这种冷却方式不能够分级收集生物质油，且由于冷凝效果不理想，造成了生物质油产率低。With the rapid development of China's economy, the contradiction of insufficient energy supply has become increasingly prominent, and the problem of my country's crude oil dependence on imports is serious. Therefore, fully based on domestic resources to develop alternative energy, especially biomass energy, to reduce dependence on oil, is of great significance for ensuring national energy security and achieving sustainable development. Biomass energy, as the only renewable energy that can be converted into liquid fuel, ranks fourth in the world's total energy consumption after coal, oil and natural gas, and occupies an important position in the entire energy system. Biomass refers to all organic substances formed directly or indirectly by photosynthesis of green plants, including plants, animals, microorganisms and their excretion and metabolites other than fossil fuels. Biomass rapid pyrolysis is an important aspect of biomass energy application. It can convert biomass raw materials, such as straw, sawdust, and agricultural product processing waste, into high-grade biomass oil. The requirements of this technology for biomass raw materials are The water content is less than 10% and the particle size is less than 2mm. Biomass rapid pyrolysis refers to the process of rapidly heating biomass to a higher reaction temperature in an oxygen-free environment, causing the decomposition of macromolecules, producing small molecular gases, condensable volatiles, and a small amount of coke, and condensable volatiles The fraction is rapidly cooled into a flowable liquid called biomass oil. Biomass oil has a pungent burning smell, high density (~1200kg/m 3 ), acidity (pH value 2.8~3.8) and low calorific value (14~18.5MJ/kg). The composition of biomass oil is complex, including hundreds of compounds such as acids, aldehydes, ketones, furans, etc. The single water cooling method gathers all the condensable biomass oil in the thermal cracking steam, and the biomass oil cannot be classified Collection is not conducive to the application of biomass oil in a wider range. At the same time, due to the poor heat transfer of water-cooled condensation, the yield of biomass oil is low. For example, "A Biomass Thermal Cracking Liquefaction Process and Its Device System" disclosed in Chinese patent CN200510057216.2 and "A Biomass Thermal Cracking Furnace" disclosed in CN201110006196.1, etc., all use water cooling to collect biomass Oil, this cooling method cannot collect biomass oil in stages, and due to the unsatisfactory condensation effect, the yield of biomass oil is low.
针对这个问题，本申请案的生物质油收集系统对热裂解蒸汽采用高压喷淋、水冷和冰冷的三个步骤，能够收集到不同成分的生物质油，且能提高生物质油产率。In response to this problem, the biomass oil collection system of the present application adopts three steps of high-pressure spraying, water cooling and ice cooling for the thermal cracking steam, which can collect biomass oil of different components and increase the yield of biomass oil.
发明内容 Contents of the invention
本发明的目的在于针对现有的冷却方式不能够分级收集生物质油，且由于冷凝效果不理想，造成了生物质油产率低等问题，提供一种不仅可提高生物质油的产率，而且通过分级冷凝获得生物质油，可提高生物质油的应用范围的生物质快速热裂解的方法及其装置。The purpose of the present invention is to solve the problem that the existing cooling method cannot collect biomass oil in stages, and the yield of biomass oil is low due to the unsatisfactory condensation effect, to provide a method that can not only improve the yield of biomass oil, Moreover, the biomass oil is obtained through graded condensation, which can improve the application range of the biomass oil, and the method and device thereof for rapid pyrolysis of biomass.
所述生物质快速热裂解装置设有加料仓、自动给料装置、质量流量仪、气体预热器、热裂解反应器、分离器、生物炭收集器、冷却器、循环泵、激冷塔、塔底暂储罐、第1生物质油收集罐、水冷冷凝器、第2生物质油收集罐、冰水冷凝器、第3生物质油收集罐；所述加料仓的出料口经自动给料装置接热裂解反应器的生物质物料进口，质量流量仪的进口接氮气进口，质量流量仪的出口经气体预热器接热裂解反应器的混合气进口，热裂解反应器的热裂解蒸气生物炭和灰份出口接分离器的进口，分离器的生物炭和灰份出口接生物炭收集器进口，分离器的热裂解蒸气出口接激冷塔的进口，激冷塔的生物质油出口接塔底暂储罐的进口，塔底暂储罐的一路出口接第1生物质油收集罐的进口，塔底暂储罐的另一路出口依次经循环泵和冷却器接激冷塔，激冷塔经水冷冷凝器分别与第2生物质油收集罐和冰水冷凝器连接，冰水冷凝器的出口接第3生物质油收集罐，冰水冷凝器的不可凝性气体出口接质量流量仪的入口。The biomass fast thermal cracking device is equipped with a feeding bin, an automatic feeding device, a mass flow meter, a gas preheater, a thermal cracking reactor, a separator, a biochar collector, a cooler, a circulating pump, a quenching tower, Temporary storage tank at the bottom of the tower, the first biomass oil collection tank, water-cooled condenser, the second biomass oil collection tank, ice water condenser, and the third biomass oil collection tank; the outlet of the feeding bin is automatically fed The feed device is connected to the biomass material inlet of the thermal cracking reactor, the inlet of the mass flow meter is connected to the nitrogen inlet, the outlet of the mass flow meter is connected to the mixed gas inlet of the thermal cracking reactor through the gas preheater, and the thermal cracking steam of the thermal cracking reactor The outlet of biochar and ash is connected to the inlet of the separator, the outlet of biochar and ash of the separator is connected to the inlet of the biochar collector, the outlet of thermal cracking steam of the separator is connected to the inlet of the quenching tower, and the outlet of biomass oil of the quenching tower Connect to the inlet of the temporary storage tank at the bottom of the tower, one outlet of the temporary storage tank at the bottom of the tower is connected to the inlet of the first biomass oil collection tank, and the other outlet of the temporary storage tank at the bottom of the tower is connected to the cooling tower through the circulation pump and cooler in turn, and the excitation The cooling tower is connected to the second biomass oil collection tank and the ice water condenser through the water-cooled condenser, the outlet of the ice water condenser is connected to the third biomass oil collection tank, and the non-condensable gas outlet of the ice water condenser is connected to the mass flow rate instrument entrance.
所述分离器可设第1级分离器和第2级分离器；所述收物炭收集器可设第1级生物炭收集器和第2级生物炭收集器，第1级生物炭收集器设于第1级分离器下端，第2级生物炭收集器设第2级分离器下端。The separator can be provided with a 1st-stage separator and a 2nd-stage separator; the described charcoal collector can be provided with a 1st-stage biochar collector and a 2nd-stage biochar collector, and the 1st-stage biochar collector It is located at the lower end of the first-stage separator, and the second-stage biochar collector is located at the lower end of the second-stage separator.
所述热裂解反应器可采用生物质鼓泡流化床反应器等。The thermal cracking reactor can be a biomass bubbling fluidized bed reactor or the like.
生物质热裂解产生的不可凝性气体作为载气。载热体可采用热稳定性好、导热好、不易粉末化的石英砂。The non-condensable gas produced by pyrolysis of biomass is used as carrier gas. The heat carrier can be quartz sand with good thermal stability, good thermal conductivity, and not easy to powder.
所述激冷塔是一种使热裂解蒸汽中的生物质油冷凝的装置，在该装置中，通过循环泵将喷淋介质压缩到高压状态，喷入到热裂解蒸汽中，获得冷凝的生物油，密度较大的生物油沉积到塔底暂储罐中，密度较小的喷淋介质流出激冷塔，进入冷却器，释放出在塔内吸收的热量，以供给下次喷淋使用。The quenching tower is a device that condenses the biomass oil in the thermal cracking steam. In this device, the spray medium is compressed to a high-pressure state by a circulation pump and sprayed into the thermal cracking steam to obtain condensed biomass oil. Oil, the denser biological oil is deposited in the temporary storage tank at the bottom of the tower, and the less dense spray medium flows out of the quenching tower and enters the cooler to release the heat absorbed in the tower for the next spraying use.
所述塔底暂储槽不仅收集激冷塔内得到的生物质油，塔底暂储罐顶部还布置有喷淋介质高压喷嘴，保证热解蒸汽在塔底暂储槽内进一步得到冷却，增强换热效果。The temporary storage tank at the bottom of the tower not only collects the biomass oil obtained in the quenching tower, but also has a spray medium high-pressure nozzle on the top of the temporary storage tank at the bottom of the tower to ensure that the pyrolysis steam is further cooled in the temporary storage tank at the bottom to enhance Heat exchange effect.
喷淋介质是指轻质生物质油、甲醇、环己烷、己烷或正十二烷等，对喷淋介质的要求是密度低于生物质油。若喷淋介质能与生物油相溶，则要求它混合在生物质油中不会对生物质油的后续应用造成影响，不过，最好是选择与生物油不相溶的喷淋介质。The spray medium refers to light biomass oil, methanol, cyclohexane, hexane or n-dodecane, etc. The requirement for the spray medium is that the density is lower than that of biomass oil. If the spray medium is compatible with the bio-oil, it is required that its mixing in the bio-oil will not affect the subsequent application of the bio-oil. However, it is best to choose a spray medium that is incompatible with the bio-oil.
所述水冷冷凝器是通过冷凝水的循环流动，与热裂解蒸汽进行间壁式换热。The water-cooled condenser performs partition heat exchange with thermal cracking steam through the circulating flow of condensed water.
所述冰冷冷凝器是指通过冰水混合物与热裂解蒸汽的间接换热，实现生物质油冷凝的装置。The ice-cooled condenser refers to a device that realizes condensation of biomass oil through indirect heat exchange between ice-water mixture and thermal cracking steam.
所述生物质快速热裂解的方法采用所述生物质快速热裂解装置，包括以下步骤：The method for fast pyrolysis of biomass adopts the fast pyrolysis device of biomass, comprising the following steps:
1)通过给料机构把生物质物料送入热裂解反应器内的步骤；1) The step of sending the biomass material into the pyrolysis reactor through the feeding mechanism;
2)在热裂解反应器内对生物质物料进行热裂解和在分离器中将热裂解蒸汽与生物炭和灰份进行气固分离的步骤；2) performing thermal cracking on the biomass material in the thermal cracking reactor and performing gas-solid separation of the thermal cracking steam, biochar and ash in the separator;
3)在激冷塔中对热裂解蒸汽进行喷淋获得一级生物油的步骤；3) The step of spraying the pyrolysis steam in the quenching tower to obtain first-grade bio-oil;
4)在水冷冷凝器中将热裂解蒸汽冷凝获得二级生物油和在冰冷冷凝器中将热裂解蒸汽进一步冷凝获得三级生物油的步骤。4) A step of condensing the pyrolysis steam in a water-cooled condenser to obtain secondary bio-oil and further condensing the pyrolysis steam in an ice-cooled condenser to obtain tertiary bio-oil.
在步骤1)中，所述通过给料机构把生物质物料送入热裂解反应器内的步骤如下：生物质热裂解产生的不可凝性气体作为载气，经预热至500～600℃，从热裂解反应器底部经气体分配器流入，使热载体及生物质物料处于流态化；热裂解反应器提前预热至400～600℃，生物质物料在自动给料装置作用下进入热裂解反应器，并在反应器内以500～1000℃/s的升温速率加热。In step 1), the step of sending the biomass material into the thermal cracking reactor through the feeding mechanism is as follows: the non-condensable gas generated by the thermal cracking of the biomass is used as the carrier gas, preheated to 500-600 °C, Inflow from the bottom of the pyrolysis reactor through the gas distributor to make the heat carrier and biomass material in a fluidized state; the pyrolysis reactor is preheated to 400-600°C in advance, and the biomass material enters the pyrolysis under the action of the automatic feeding device The reactor is heated at a rate of 500-1000°C/s in the reactor.
在步骤2)中，所述在热裂解反应器内对生物质物料进行热裂解的步骤如下：生物质物料在热裂解反应器内进行热裂解后，热裂解蒸汽、生物炭和灰份离开热裂解反应器进入两级固体分离器，在分离器下端的集碳罐中收集到生物炭和灰份。In step 2), the step of thermally cracking the biomass material in the thermal cracking reactor is as follows: after the biomass material is thermally cracked in the thermal cracking reactor, the thermal cracking steam, biochar and ash leave the heat The pyrolysis reactor enters the two-stage solid separator, and biochar and ash are collected in the carbon collection tank at the lower end of the separator.
在步骤3)中，所述在激冷塔中对热裂解蒸汽进行喷淋获得一级生物油的步骤如下：不含有生物炭和灰份的热裂解蒸汽进入激冷塔，使用喷淋介质对热裂解蒸汽进行喷淋。本案使用的激冷塔是内循环式，以轻质生物质油、甲醇、环己烷、己烷或正十二烷作为喷淋介质，在循环泵作用下，将喷淋介质增加到一定压力，从激冷塔的高压喷嘴喷出，使流入的热裂解蒸汽冷凝成生物质油，获得第一级生物质油。In step 3), the step of spraying the pyrolysis steam in the quenching tower to obtain the first-grade bio-oil is as follows: the pyrolysis steam that does not contain biochar and ash enters the quenching tower, and the spray medium is used to Pyrolysis steam is sprayed. The quenching tower used in this case is an internal circulation type, with light biomass oil, methanol, cyclohexane, hexane or n-dodecane as the spray medium, and the spray medium is increased to a certain pressure under the action of the circulation pump , which is ejected from the high-pressure nozzle of the quenching tower to condense the inflowing pyrolysis steam into biomass oil to obtain the first-grade biomass oil.
在步骤4)中，所述在水冷冷凝器中将热裂解蒸汽冷凝获得二级生物油的步骤如下：热裂解蒸汽离开激冷塔后，进入水冷换热器，经冷却后获得第二级生物质油；热裂解蒸汽离开水冷换热器后，流入到冰冷换热器，进一步冷凝获得第三级生物质油。随后的热裂解蒸汽为不可凝性气体，作为载气引回到热裂解反应器底部。In step 4), the step of condensing the thermal cracking steam in the water-cooled condenser to obtain the secondary bio-oil is as follows: after the thermal cracking steam leaves the quenching tower, it enters the water-cooled heat exchanger, and obtains the second-level bio-oil after being cooled. Substance oil; after the thermal cracking steam leaves the water-cooled heat exchanger, it flows into the ice-cooled heat exchanger, and is further condensed to obtain the third-grade biomass oil. The subsequent thermal cracking steam is a non-condensable gas, which is introduced back to the bottom of the thermal cracking reactor as a carrier gas.
所述生物质是指一切直接或间接利用绿色植物光合作用形成的有机物质，包括除化石燃料外的植物、动物和微生物及其排泄与代谢物等。本发明对生物质原料的要求为含水量低于10％和粒径小于2mm。The biomass refers to all organic substances formed by photosynthesis of green plants directly or indirectly, including plants, animals, microorganisms and their excretion and metabolites other than fossil fuels. The requirement of the present invention for the biomass raw material is that the water content is less than 10% and the particle size is less than 2mm.
由于给料机构外部包裹冷却水套，因此杜绝了因热裂解反应器的导热影响而使部分生物质物料在未进入反应器之前发生热裂解的情况发生。Since the feeding mechanism is wrapped with a cooling water jacket, the thermal cracking of some biomass materials before entering the reactor is prevented due to the heat conduction effect of the thermal cracking reactor.
与现有技术相比，本发明具有以下突出优点：Compared with the prior art, the present invention has the following outstanding advantages:
1)在生物质油激冷塔内，热裂解蒸汽中几乎全部的重质生物质油和一部分轻质生物质油组分实现冷凝，这是由于高压的喷淋介质通过与热解蒸汽直接接触换热，能够增强热裂解蒸汽的换热效果，远比单纯的间壁式水冷冷凝器获得的生物质油产率高；1) In the biomass oil quenching tower, almost all of the heavy biomass oil and a part of the light biomass oil components in the pyrolysis steam are condensed, because the high-pressure spray medium directly contacts with the pyrolysis steam Heat exchange can enhance the heat exchange effect of thermal cracking steam, which is far higher than the yield of biomass oil obtained by simple partitioned water-cooled condensers;
2)塔底暂储槽不仅收集激冷塔内得到的生物质油，激冷塔顶部还布置有喷淋介质高压雾化喷嘴，保证热解蒸汽在塔底暂储槽内进一步得到冷却，增强换热效果；2) The temporary storage tank at the bottom of the tower not only collects the biomass oil obtained in the quenching tower, but also arranges spray medium high-pressure atomizing nozzles on the top of the quenching tower to ensure that the pyrolysis steam is further cooled in the temporary storage tank at the bottom of the tower, enhancing Heat exchange effect;
3)生物质油的分级收集还能够获得具有明显区别的生物质油组分，便利于后续的生物质油提质提纯，增加生物质油的应用范围；3) The graded collection of biomass oil can also obtain clearly differentiated biomass oil components, which is convenient for subsequent biomass oil upgrading and purification, and increases the application range of biomass oil;
4)本发明使用的生物质热裂解反应器为鼓泡流化床反应器，具有技术成熟，工业上易于放大等优点，因此，采用本发明使用的生物质油收集系统，不需要对现有设备进行较大改动。4) The biomass pyrolysis reactor used in the present invention is a bubbling fluidized bed reactor, which has the advantages of mature technology and easy industrial scale-up. Therefore, the biomass oil collection system used in the present invention does not need to The equipment undergoes major changes.
附图说明 Description of drawings
图1为本发明所述生物质快速热裂解装置实施例的结构组成示意图。在图1中，各标记为：加料仓1、自动给料装置2、氮气进口3、质量流量仪4、气体预热器5、流化床反应器6、第1旋风分离器7、第1生物炭收集器8、第2旋风分离器9、第2生物炭收集器10、冷却器11、循环泵12、激冷塔13、塔底暂储罐14、第1生物质收集油罐15、水冷冷凝器16、第2生物质收集油罐17、冰水冷凝器18、第3生物质油罐19、不可凝性气体20。Fig. 1 is a schematic diagram of the structure and composition of an embodiment of the rapid pyrolysis device for biomass according to the present invention. In Figure 1, each mark is:
图2为本发明生物质快速热裂解装置实施例的激冷塔的结构示意图。在图2中，各标记为：热解蒸汽入口21，高压喷嘴22、23，液位标尺24，冷凝介质出口25，热解蒸汽出口26。Fig. 2 is a structural schematic diagram of a quenching tower of an embodiment of a biomass rapid pyrolysis device of the present invention. In FIG. 2 , each mark is: pyrolysis steam inlet 21 , high-pressure nozzles 22 , 23 ,
具体实施方式 Detailed ways
以下实施例将结合附图对本发明作进一步的说明。The following embodiments will further illustrate the present invention in conjunction with the accompanying drawings.
参见图1，本发明所述生物质快速热裂解装置实施例设有加料仓1、自动给料装置2、质量流量仪4、气体预热器5、热裂解反应器6、分离器、生物炭收集器、冷却器11、循环泵12、激冷塔13、塔底暂储罐14、第1生物质油收集罐15、水冷冷凝器16、第2生物质油收集罐17、冰水冷凝器18和第3生物质油收集罐19；所述加料仓1的出料口经自动给料装置2接热裂解反应器6的生物质物料进口，质量流量仪4的进口接氮气进口3，质量流量仪4的出口经气体预热器5接热裂解反应器6的混合气进口，热裂解反应器6的热裂解蒸气生物炭和灰份出口接分离器的进口，分离器的生物炭和灰份出口接生物炭收集器进口，分离器的热裂解蒸气出口接激冷塔13的进口，激冷塔13的生物质油出口接塔底暂储罐14的进口，塔底暂储罐14的一路出口接第1生物质油收集罐15的进口，塔底暂储罐14的另一路出口依次经循环泵12和冷却器11接激冷塔13，激冷塔13经水冷冷凝器16分别与第2生物质油收集罐17和冰水冷凝器18连接，冰水冷凝器18的出口接第3生物质油收集罐19，冰水冷凝器18的不可凝性气体出口接质量流量仪4的入口。Referring to Fig. 1, the embodiment of biomass fast pyrolysis device of the present invention is provided with
所述分离器设第1级分离器7和第2级分离器9；所述收物炭收集器设第1级生物炭收集器8和第2级生物炭收集器10，第1级生物炭收集器8设于第1级分离器7下端，第2级生物炭收集器10设第2级分离器9下端。The separator is provided with the first-
所述热裂解反应器可采用生物质鼓泡流化床反应器等。The thermal cracking reactor can be a biomass bubbling fluidized bed reactor or the like.
生物质热裂解产生的不可凝性气体作为载气。载热体可采用热稳定性好、导热好、不易粉末化的石英砂。The non-condensable gas produced by pyrolysis of biomass is used as carrier gas. The heat carrier can be quartz sand with good thermal stability, good thermal conductivity, and not easy to powder.
所述激冷塔是一种使热裂解蒸汽中的生物质油冷凝的装置，在该装置中，通过循环泵将喷淋介质压缩到高压状态，喷入到热裂解蒸汽中，获得冷凝的生物油，密度较大的生物油沉积到塔底暂储罐中，密度较小的喷淋介质流出激冷塔，进入冷却器，释放出在塔内吸收的热量，以供给下次喷淋使用。The quenching tower is a device that condenses the biomass oil in the thermal cracking steam. In this device, the spray medium is compressed to a high-pressure state by a circulation pump and sprayed into the thermal cracking steam to obtain condensed biomass oil. Oil, the denser biological oil is deposited in the temporary storage tank at the bottom of the tower, and the less dense spray medium flows out of the quenching tower and enters the cooler to release the heat absorbed in the tower for the next spraying use.
所述塔底暂储槽不仅收集激冷塔内得到的生物质油，塔底暂储罐顶部还布置有喷淋介质高压喷嘴，保证热解蒸汽在塔底暂储槽内进一步得到冷却，增强换热效果。The temporary storage tank at the bottom of the tower not only collects the biomass oil obtained in the quenching tower, but also has a spray medium high-pressure nozzle on the top of the temporary storage tank at the bottom of the tower to ensure that the pyrolysis steam is further cooled in the temporary storage tank at the bottom to enhance Heat exchange effect.
喷淋介质是指轻质生物质油、甲醇、环己烷、己烷或正十二烷等，对喷淋介质的要求是密度低于生物质油。若喷淋介质能与生物油相溶，则要求它混合在生物质油中不会对生物质油的后续应用造成影响，不过，最好是选择与生物油不相溶的喷淋介质。The spray medium refers to light biomass oil, methanol, cyclohexane, hexane or n-dodecane, etc. The requirement for the spray medium is that the density is lower than that of biomass oil. If the spray medium is compatible with the bio-oil, it is required that its mixing in the bio-oil will not affect the subsequent application of the bio-oil. However, it is best to choose a spray medium that is incompatible with the bio-oil.
所述水冷冷凝器是通过冷凝水的循环流动，与热裂解蒸汽进行间壁式换热。The water-cooled condenser performs partition heat exchange with thermal cracking steam through the circulating flow of condensed water.
所述冰冷冷凝器是指经冰水混合物与热裂解蒸汽的间接换热，实现生物质油冷凝的装置。The ice-cooled condenser refers to a device that realizes condensation of biomass oil through indirect heat exchange between ice-water mixture and thermal cracking steam.
实现所述发明目的的生物质热裂解液化工艺方法步骤包括：通过给料机构把生物质物料送入热裂解反应器内的步骤，在热裂解反应器内对生物质物料进行热裂解的步骤，在分离器中将热裂解蒸汽与生物炭和灰份进行气固分离的步骤，在激冷塔中对热裂解蒸汽进行喷淋获得一级生物油的步骤，在水冷冷凝器中将热裂解蒸汽冷凝获得二级生物油的步骤，在冰冷冷凝器中将热裂解蒸汽进一步冷凝获得三级生物油的步骤。The steps of the biomass pyrolysis liquefaction process method for realizing the purpose of the invention include: the step of sending the biomass material into the pyrolysis reactor through the feeding mechanism, and the step of pyrolyzing the biomass material in the pyrolysis reactor, The step of separating the pyrolysis steam from the biochar and ash in the separator for gas-solid separation, the step of spraying the pyrolysis steam in the quenching tower to obtain the first-grade bio-oil, and the step of separating the pyrolysis steam in the water-cooled condenser A step of condensing to obtain secondary bio-oil, and a step of further condensing thermal cracking steam in an ice-cooled condenser to obtain tertiary bio-oil.
所述生物质是指一切直接或间接利用绿色植物光合作用形成的有机物质，包括除化石燃料外的植物、动物和微生物及其排泄与代谢物等。本发明对生物质原料的要求为含水量低于10％和粒径小于2mm。The biomass refers to all organic substances formed by photosynthesis of green plants directly or indirectly, including plants, animals, microorganisms and their excretion and metabolites other than fossil fuels. The requirement of the present invention for the biomass raw material is that the water content is less than 10% and the particle size is less than 2mm.
由于给料机构外部包裹冷却水套，因此杜绝了因热裂解反应器的导热影响而使部分生物质物料在未进入反应器之前发生热裂解的情况发生。Since the feeding mechanism is wrapped with a cooling water jacket, the thermal cracking of some biomass materials before entering the reactor is prevented due to the heat conduction effect of the thermal cracking reactor.
所述生物质热裂解工艺过程如下：The biomass pyrolysis process is as follows:
1)生物质热裂解产生的不可凝性气体作为载气，经预热至500～600℃，从热裂解反应器底部经气体分配器流入，使热载体及生物质物料处于流态化；热裂解反应器提前预热至400～600℃，生物质物料在自动给料装置作用下进入热裂解反应器，并在反应器内以500～1000℃/s的升温速率加热；1) The non-condensable gas produced by pyrolysis of biomass is used as carrier gas, which is preheated to 500-600°C, and flows in from the bottom of the pyrolysis reactor through the gas distributor, so that the heat carrier and biomass materials are in a fluidized state; The pyrolysis reactor is preheated to 400-600°C in advance, and the biomass material enters the pyrolysis reactor under the action of the automatic feeding device, and is heated at a heating rate of 500-1000°C/s in the reactor;
2)生物质物料在热裂解反应器内进行热裂解后，热裂解蒸汽、生物炭和灰份离开热裂解反应器进入两级固体分离器，在分离器下端的集碳罐中收集到生物炭和灰份；2) After the biomass material is pyrolyzed in the pyrolysis reactor, the pyrolysis steam, biochar and ash leave the pyrolysis reactor and enter the two-stage solid separator, and the biochar is collected in the carbon collection tank at the lower end of the separator and ash;
3)不含有生物炭和灰份的热裂解蒸汽进入激冷塔，使用喷淋介质对热裂解蒸汽进行喷淋。本案使用的激冷塔是内循环式，以轻质生物质油、甲醇、环己烷、己烷或正十二烷作为喷淋介质，在循环泵作用下，将喷淋介质增加到一定压力，从激冷塔的高压喷嘴喷出，使流入的热裂解蒸汽冷凝成生物质油，获得第一级生物质油；3) The pyrolysis steam that does not contain biochar and ash enters the quenching tower, and sprays the pyrolysis steam with a spray medium. The quenching tower used in this case is an internal circulation type, with light biomass oil, methanol, cyclohexane, hexane or n-dodecane as the spray medium, and the spray medium is increased to a certain pressure under the action of the circulation pump , which is ejected from the high-pressure nozzle of the quenching tower to condense the inflowing pyrolysis steam into biomass oil to obtain the first-grade biomass oil;
4)热裂解蒸汽离开激冷塔后，进入水冷换热器，经冷却后获得第二级生物质油；热裂解蒸汽离开水冷换热器后，流入到冰冷换热器，进一步冷凝获得第三级生物质油；4) After the thermal cracking steam leaves the quenching tower, it enters the water-cooled heat exchanger, and after cooling, the second-grade biomass oil is obtained; after the thermal cracking steam leaves the water-cooled heat exchanger, it flows into the ice-cooled heat exchanger, and is further condensed to obtain the third grade biomass oil;
5)随后的热裂解蒸汽为不可凝性气体，作为载气引回到热裂解反应器底部。5) The subsequent thermal cracking steam is a non-condensable gas, which is introduced back to the bottom of the thermal cracking reactor as a carrier gas.
以下给出具体实施例：Provide specific embodiment below:
实施例1Example 1
生物质储存在加料仓中，在自动给料装置的作用下，从流化床反应器的中部进入反应器内部，不可凝性气体与氮气混合，在质量流量仪控制下进入气体预热器，预热后的气体从流化床反应器的底部进入反应器内，使生物质物料和热载体处于流化状态，生物质物料在热裂解反应器内进行热裂解后，热裂解蒸汽、生物炭和灰份离开热裂解反应器进入两级分离器，在分离器下端的生物炭收集器中收集到生物炭和灰份，不含有生物炭和灰份的热裂解蒸汽进入激冷塔，通过冷凝介质对热裂解蒸汽进行喷淋，得到的生物质油沉积到塔底暂储罐中，并在生物质油收集罐中收集，随后，热裂解蒸汽进入水冷冷凝器和冰冷冷凝器，冷凝的生物质油分别流入2个生物质油罐。Biomass is stored in the feeding bin. Under the action of the automatic feeding device, it enters the reactor from the middle of the fluidized bed reactor. The non-condensable gas is mixed with nitrogen and enters the gas preheater under the control of the mass flow meter. The preheated gas enters the reactor from the bottom of the fluidized bed reactor, so that the biomass material and the heat carrier are in a fluidized state. After the biomass material is pyrolyzed in the pyrolysis reactor, the pyrolysis steam, biochar and ash leave the thermal cracking reactor and enter the two-stage separator, and the biochar and ash are collected in the biochar collector at the lower end of the separator, and the thermal cracking steam without biochar and ash enters the quenching tower and is condensed The medium sprays the thermal cracking steam, and the obtained biomass oil is deposited in the temporary storage tank at the bottom of the tower and collected in the biomass oil collection tank. Then, the thermal cracking steam enters the water-cooled condenser and the ice-cooled condenser, and the condensed biomass oil The material oil flows into 2 biomass oil tanks respectively.
实施例2Example 2
参见图2，从固体分离器过来的热解蒸汽从热解蒸汽入口21进入到激冷塔内，此时，喷淋介质在循环泵12的作用下从高压喷嘴22喷入，部分热解蒸汽冷凝成生物质油，未冷凝的热解蒸汽、生物质油、喷淋介质一起流入到塔底暂储槽14，部分喷淋介质还从塔底暂储槽14顶部喷入，使得从热解蒸汽出口26流出的热解蒸汽进一步冷凝成生物质油。Referring to Fig. 2, the pyrolysis steam coming from the solid separator enters the quenching tower from the pyrolysis steam inlet 21. At this time, the spray medium is injected from the high-pressure nozzle 22 under the action of the
实施例3Example 3
在建立的1kg/h的实验室规模的生物质热裂解反应器中，使用松树木屑作为生物质物料，在500℃反应温度，0.83s的物料停留时间的反应条件下，只采用三级水冷冷凝器收集生物质油的方式，生物质油产率仅为45％，而采用激冷塔、水冷和冰冷的多级冷凝器收集生物质油的方式，生物质油产率达到64.5％。In the established 1kg/h laboratory-scale biomass pyrolysis reactor, pine wood chips are used as the biomass material, under the reaction conditions of 500°C reaction temperature and 0.83s material residence time, only three-stage water-cooled condensation is used. The bio-oil yield is only 45% when the bio-oil is collected by the condenser, but the bio-oil yield reaches 64.5% when the bio-oil is collected by the quenching tower, water cooling and ice-cooled multi-stage condenser.
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| US9035116B2 (en) * | 2012-08-07 | 2015-05-19 | Kior, Inc. | Biomass feed system including gas assist |
| CN103131453B (en) * | 2013-03-11 | 2015-07-01 | 北京神雾环境能源科技集团股份有限公司 | Pyrolytic evaluation device for carbon-containing substances |
| CN103691429B (en) * | 2014-01-03 | 2015-06-10 | 北京林业大学 | Catalyst for rapid pyrolysis and liquefaction of biomass as well as preparation method and application thereof |
| CN104031671B (en) * | 2014-06-30 | 2016-03-02 | 厦门大学 | A kind of biomass pyrolytic prepares the method for bio oil |
| CN106244177A (en) * | 2016-07-27 | 2016-12-21 | 大港油田集团有限责任公司 | A kind of straw Continuous Heat cracking technology and cracking apparatus thereof |
| CN108018054A (en) * | 2016-10-28 | 2018-05-11 | 杨晓林 | A kind of organic waste cracking system and treatment process |
| CN106635114B (en) * | 2016-12-06 | 2018-09-18 | 青岛理工大学 | Device and method for realizing co-production of catalytic cracking oil gas by waste rubber powder in fluidized state |
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| CN1390915A (en) * | 2002-06-07 | 2003-01-15 | 浙江大学 | Biomass integrated thermocracking equipment for preparing liquid fuel |
| CN101531910A (en) * | 2008-03-11 | 2009-09-16 | 广州迪森热能技术股份有限公司 | System for rapidly pyrolysing and liquefying biomass |
| CN101602953A (en) * | 2009-07-22 | 2009-12-16 | 丁赤民 | The purification system of straw quick thermal cracking products |
| CN101602954A (en) * | 2009-07-22 | 2009-12-16 | 丁赤民 | The method of manufacturing fuel through straw quick thermal cracking and fuel product thereof |
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| CN1390915A (en) * | 2002-06-07 | 2003-01-15 | 浙江大学 | Biomass integrated thermocracking equipment for preparing liquid fuel |
| CN101531910A (en) * | 2008-03-11 | 2009-09-16 | 广州迪森热能技术股份有限公司 | System for rapidly pyrolysing and liquefying biomass |
| CN101602953A (en) * | 2009-07-22 | 2009-12-16 | 丁赤民 | The purification system of straw quick thermal cracking products |
| CN101602954A (en) * | 2009-07-22 | 2009-12-16 | 丁赤民 | The method of manufacturing fuel through straw quick thermal cracking and fuel product thereof |
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