CN101613377A - Biomass supercritical subcritical combined continuous pretreatment and hydrolysis equipment and method - Google Patents
Biomass supercritical subcritical combined continuous pretreatment and hydrolysis equipment and method Download PDFInfo
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Abstract
生物质超临界亚临界组合连续式预处理与水解设备及方法，所述设备包括贮水罐，附有搅拌装置的贮料罐，预加热系统，超临界反应系统，初次冷却系统，亚临界反应系统，最终冷却系统，产物收集系统以及电子控温系统。其工艺步骤是将达到预热温度的水与生物质原料浆液快速混合后注入超临界反应系统使其在超临界条件进行预处理，反应产物经初次冷却系统和减压阀进行冷却和降压后进入亚临界反应系统继续进行水解，从而连续生成并收集可发酵糖。本发明利用超临界法反应迅速、无需催化剂、无产物抑制的优点，实现木质纤维类生物质的连续水解转化并生成可发酵糖，是后续发酵产乙醇等资源化技术的基础，应用前景广阔。
Biomass supercritical subcritical combined continuous pretreatment and hydrolysis equipment and method, the equipment includes a water storage tank, a storage tank with a stirring device, a preheating system, a supercritical reaction system, a primary cooling system, and a subcritical reaction system, final cooling system, product collection system and electronic temperature control system. The process step is to quickly mix the water that has reached the preheating temperature with the biomass raw material slurry and inject it into the supercritical reaction system to pretreat it under supercritical conditions. The reaction product is cooled and depressurized by the primary cooling system and the pressure reducing valve. Enter the subcritical reaction system to continue hydrolysis, so as to continuously generate and collect fermentable sugars. The present invention utilizes the advantages of rapid supercritical reaction, no need for catalysts, and no product inhibition to realize continuous hydrolysis conversion of lignocellulosic biomass and generate fermentable sugars.
Description
技术领域 technical field
本发明涉及一种生物质资源化的超临界亚临界组合连续式预处理与水解专用设备和方法，特别涉及一种木质纤维类生物质超临界亚临界组合连续式预处理与水解设备及方法，属于生物质能源处理及利用技术领域。The present invention relates to a special equipment and method for supercritical subcritical combined continuous pretreatment and hydrolysis of biomass resources, in particular to a supercritical subcritical combined continuous pretreatment and hydrolysis equipment and method for lignocellulosic biomass. The invention belongs to the technical field of biomass energy processing and utilization.
背景技术 Background technique
农作物秸秆是最具开发潜力的生物质能源之一，其资源化技术特别是乙醇化技术已受到了广泛关注。秸秆制取燃料乙醇的瓶颈因素有二：第一，纤维素本身结构决定其水解困难。纤维素是由D-吡喃葡萄糖酐键接而成的线性巨分子，分子间和分子内存在很多氢键，具有高度结晶和难溶性，减小了与催化剂或酶的接触面积，水解困难。第二，木质素包裹作用使纤维素难以水解。木质素是由苯丙烷单元链接的难降解高聚物，常和半纤维素一起填充在细胞壁纤维之间，紧紧包裹着纤维素，使其更难以溶于水解溶剂或与酶接触，加大了其水解的难度。Crop straw is one of the most potential biomass energy sources, and its recycling technology, especially ethanolization technology, has received extensive attention. There are two bottleneck factors in the production of fuel ethanol from straw: first, the structure of cellulose itself determines its difficulty in hydrolysis. Cellulose is a linear macromolecule bonded by D-glucopyranose anhydride. There are many hydrogen bonds between and within the molecule. It is highly crystalline and insoluble, which reduces the contact area with catalysts or enzymes, making it difficult to hydrolyze. Second, lignin encapsulation makes cellulose difficult to hydrolyze. Lignin is a refractory polymer linked by phenylpropane units. It is often filled with hemicellulose between cell wall fibers and tightly wraps cellulose, making it more difficult to dissolve in hydrolysis solvents or contact with enzymes. the difficulty of its hydrolysis.
目前秸秆预处理和水解的方法主要有酸处理、蒸汽爆破和酶水解。酸处理会导致设备腐蚀、环境污染；蒸汽爆破则会导致大量的木糖损失；酶水解需要至少3种主要的酶同时存在，且不得有抑制性物质，对条件要求严格，酶消耗大、成本高，停留时间需要3天以上。At present, the methods of straw pretreatment and hydrolysis mainly include acid treatment, steam explosion and enzymatic hydrolysis. Acid treatment will lead to equipment corrosion and environmental pollution; steam explosion will lead to a large amount of xylose loss; enzymatic hydrolysis requires the presence of at least three main enzymes at the same time, and no inhibitory substances are required, strict requirements on conditions, high enzyme consumption and high cost High, the residence time needs to be more than 3 days.
超临界法对秸秆进行预处理和水解，是利用水在超临界条件下(374.2℃和22.1MPa以上溶剂化能力增强、电离程度增大(约比常温高3个数量级等性质，使秸秆中纤维素溶解，实现与木质素的完全分离，并利用电离的H+作为催化剂进行水解。极短时间内纤维素即可完成水解并获得低聚糖、葡萄糖等产物，能够解决酸处理腐蚀设备、酶水解生产效率低等技术问题。但葡萄糖在超临界水中分解反应速率很大，迅速即分解为不能进行乙醇发酵的赤藓糖、糠醛等物质。因此，现有的超临界工艺尚不能获得令人满意的可发酵糖转化率。The supercritical method pretreats and hydrolyzes the straw, which utilizes the properties of water under supercritical conditions (374.2°C and above 22.1MPa) to enhance the solvation ability and ionization degree (about 3 orders of magnitude higher than normal temperature), so that the fibers in the straw Dissolving cellulose to achieve complete separation from lignin, and using ionized H+ as a catalyst for hydrolysis. Cellulose can be hydrolyzed in a very short time and products such as oligosaccharides and glucose can be obtained, which can solve the problem of acid treatment corrosion equipment, enzyme hydrolysis Low production efficiency and other technical problems. But the decomposition reaction rate of glucose in supercritical water is very large, and it is quickly decomposed into substances such as erythrose and furfural that cannot be fermented by ethanol. Therefore, the existing supercritical process cannot obtain satisfactory results. conversion rate of fermentable sugars.
然而，当反应温度、压力降低时，葡萄糖的分解速率也呈指数下降，如亚临界水中(如300℃，葡萄糖的分解速率比超临界水中(如400℃降低2个数量级。由于亚临界水密度比超临界水大，其对高聚糖和低聚糖的水解更为有利。因此，可以提出超临界亚临界组合工艺方法，首先秸秆在超临界水中预处理和水解，使纤维素彻底水解为低聚糖，再经过亚临界条件进一步水解为葡萄糖，既利用了超临界法反应迅速、无需催化剂、无产物抑制的优点，又解决了其产物不稳定、条件难控制的技术瓶颈。However, when the reaction temperature and pressure are reduced, the decomposition rate of glucose also decreases exponentially, such as in subcritical water (such as 300 ° C, the decomposition rate of glucose is 2 orders of magnitude lower than that in supercritical water (such as 400 ° C). Due to the subcritical water density Larger than supercritical water, it is more beneficial to the hydrolysis of polysaccharides and oligosaccharides. Therefore, a supercritical subcritical combined process method can be proposed. First, the straw is pretreated and hydrolyzed in supercritical water, so that the cellulose is completely hydrolyzed into Oligosaccharides are further hydrolyzed into glucose under subcritical conditions, which not only utilizes the advantages of rapid reaction, no catalyst, and no product inhibition in the supercritical method, but also solves the technical bottleneck of unstable products and difficult conditions to control.
基于上述思路，国内外已经开发了生物质的超临界亚临界组合的批式预处理与水解设备和操作方法(Zhao et al.Combined Supercritical and Subcritical Process for CelluloseHydrolysis to Fermentable Hexoses.Environ.Sci.Technol.2009，43(5))，然而，批式预处理与水解装置由于间歇式操作不具有连续性，设备规模难以放大，对能源消耗较大，目前仅限于科学试验与机理研究，不能应用于实际生产。Based on the above ideas, batch pretreatment and hydrolysis equipment and operation methods of supercritical and subcritical combination of biomass have been developed at home and abroad (Zhao et al.Combined Supercritical and Subcritical Process for Cellulose Hydrolysis to Fermentable Hexoses.Environ.Sci.Technol. 2009, 43(5)), however, due to the discontinuity of the batch-type pretreatment and hydrolysis device, it is difficult to enlarge the scale of the equipment and consume a lot of energy. At present, it is limited to scientific experiments and mechanism research, and cannot be applied to practice Production.
发明内容 Contents of the invention
本发明的目的是提供一种生物质超临界亚临界组合连续式预处理与水解设备及方法，旨解决批式预处理与水解的操作不具有连续性，设备规模难以放大，对能源消耗较大的技术缺陷，可实现木质纤维原料的超临界亚临界组合连续预处理与水解，提供一条新型并高效的木质纤维类生物质水解资源化途径，具有广阔的应用前景。The purpose of the present invention is to provide a biomass supercritical subcritical combined continuous pretreatment and hydrolysis equipment and method, aiming to solve the problem that the operation of batch pretreatment and hydrolysis is not continuous, the scale of the equipment is difficult to enlarge, and the energy consumption is relatively large It can realize the supercritical subcritical combined continuous pretreatment and hydrolysis of lignocellulosic raw materials, and provide a new and efficient way of hydrolyzing lignocellulosic biomass resources, which has broad application prospects.
本发明采用以下技术方案：The present invention adopts following technical scheme:
一种用于生物质超临界亚临界组合连续式预处理和水解的设备，其特征在于：所述设备包括贮水罐1，附有搅拌装置的贮料罐2，预加热系统5，超临界反应系统6，初次冷却系统7，亚临界反应系统8，最终冷却系统9，产物收集系统10以及电子控温系统11；所述贮水罐1通过管路经由高压进水泵3与预加热系统5入口相连，预加热系统5出口通过三通与超临界反应系统6入口相连，所述附有搅拌装置的贮料罐2通过管路经由高压进料泵4与超临界反应系统6入口相连，所述超临界反应系统6出口通过管路经由初次冷却系统7和第一减压阀14a与亚临界反应系统8入口相连；所述亚临界反应系统8出口通过管路经由第二减压阀14b和最终冷却系统9与产物收集系统10相连；所述的预加热系统、超临界反应系统、初次冷却系统和亚临界反应系统分别通过测温探头13和信号线与所述的电子控温系统11相连接。A device for biomass supercritical subcritical combined continuous pretreatment and hydrolysis, characterized in that: the device includes a water storage tank 1, a storage tank 2 with a stirring device, a preheating system 5, a supercritical Reaction system 6, primary cooling system 7, subcritical reaction system 8, final cooling system 9, product collection system 10 and electronic temperature control system 11; the water storage tank 1 passes through the pipeline through the high-pressure water inlet pump 3 and the preheating system 5 The inlet is connected, the outlet of the preheating system 5 is connected with the inlet of the supercritical reaction system 6 through a tee, and the storage tank 2 with the stirring device is connected with the inlet of the supercritical reaction system 6 through a pipeline through a high-pressure feed pump 4, so that The outlet of the supercritical reaction system 6 is connected to the inlet of the subcritical reaction system 8 through the primary cooling system 7 and the first decompression valve 14a through the pipeline; the outlet of the subcritical reaction system 8 is passed through the pipeline through the second decompression valve 14b and The final cooling system 9 is connected to the product collection system 10; the described preheating system, supercritical reaction system, primary cooling system and subcritical reaction system are connected with the electronic temperature control system 11 through the temperature measuring probe 13 and the signal line respectively. connect.
本发明的技术特征还在于：所述的预加热系统5由预加热管路和预加热装置组成，所述的预加热装置由盐浴罐和设置在该盐浴罐内的电加热棒构成，所述的预加热管路采用螺旋式盘管。所述的超临界反应系统6由超临界反应管路和超临界加热装置组成，所述的超临界加热装置由盐浴罐和设置在该盐浴罐内的电加热棒构成，所述的超临界反应管路采用直管或弯管。所述的亚临界反应系统8由亚临界反应管路和亚临界加热装置组成，所述的亚临界加热装置由陶瓷套管和设置在该套管内的电加热棒构成，所述的亚临界反应管路采用螺旋式盘管。所述的初次冷却系统7和最终冷却系统9由传输管路和冷却套管构成，所述的冷却套管采用逆流式水冷却套管，所述的传输管路采用直管或螺旋式盘管。The technical feature of the present invention is also that: the described preheating system 5 is composed of a preheating pipeline and a preheating device, and the described preheating device is composed of a salt bath tank and an electric heating rod arranged in the salt bath tank, The preheating pipeline adopts a spiral coil. Described supercritical reaction system 6 is made up of supercritical reaction pipeline and supercritical heating device, and described supercritical heating device is made of salt bath tank and the electric heating rod that is arranged in this salt bath tank, and described supercritical heating device The critical reaction pipeline adopts straight pipe or bent pipe. Described subcritical reaction system 8 is made up of subcritical reaction pipeline and subcritical heating device, and described subcritical heating device is made of ceramic casing and the electric heating rod that is arranged in this casing, and described subcritical reaction The pipeline adopts spiral coil. The primary cooling system 7 and the final cooling system 9 are composed of a transmission pipeline and a cooling jacket, the cooling jacket adopts a counter-flow water cooling jacket, and the transmission pipeline adopts a straight pipe or a spiral coil .
本发明还提供了一种用于生物质超临界亚临界组合连续式预处理和水解的方法，其特征在于该方法包括如下步骤：The present invention also provides a method for combined continuous pretreatment and hydrolysis of biomass supercritical and subcritical, characterized in that the method comprises the following steps:
1)将设备管路各阀门均置于通路，开启电子控温系统11开关对预加热系统5、超临界反应系统6和亚临界反应系统8进行预热，分别设定为350～370℃、370～400℃和200～300℃范围内的指定温度；1) Put all the valves of the equipment pipeline in the passage, turn on the switch of the electronic temperature control system 11 to preheat the preheating system 5, supercritical reaction system 6 and subcritical reaction system 8, respectively set to 350-370°C, Specified temperature in the range of 370～400℃ and 200～300℃;
2)将生物质原料与水按质量比1∶40～1∶20的比例混合置入贮料罐2内，开启贮料罐2的搅拌装置使物料处于均匀悬浊状态；2) Mix the biomass raw material and water into the storage tank 2 according to the mass ratio of 1:40 to 1:20, and turn on the stirring device of the storage tank 2 to keep the material in a uniform suspension state;
3)根据贮料罐中的悬浊液体积，向贮水罐中加入1～4倍体积的水，调节柱高压进水泵和高压进料泵的流量比例为1∶1～4∶1；3) According to the volume of the suspension in the storage tank, add 1 to 4 times the volume of water to the water storage tank, and adjust the flow ratio of the column high-pressure feed water pump and high-pressure feed pump to 1:1-4:1;
4)当预加热系统5、超临界反应系统6和亚临界反应系统8的温度接近预热指定温度时，开启高压进水泵3和高压进料泵4，将贮水罐中的水注入预加热系统，达到预热温度后与由贮料罐经高压进料泵注入的生物质原料浆液快速混合并注入超临界反应系统，反应产物经初次冷却系统和减压阀进行冷却和降压后进入亚临界反应系统；4) When the temperature of the preheating system 5, the supercritical reaction system 6 and the subcritical reaction system 8 is close to the preheating specified temperature, turn on the high-pressure water inlet pump 3 and the high-pressure feed pump 4, and inject the water in the water storage tank into the preheating system, after reaching the preheating temperature, it is quickly mixed with the biomass raw material slurry injected from the storage tank through the high-pressure feed pump and injected into the supercritical reaction system. critical reaction system;
5)调节第一减压阀14a和第二减压阀14b、使超临界反应系统6和亚临界反应系统8内部管路压力分别稳定在20～25MPa和5～15MPa；5) Adjust the first pressure reducing valve 14a and the second pressure reducing valve 14b, so that the internal pipeline pressures of the supercritical reaction system 6 and the subcritical reaction system 8 are stabilized at 20-25MPa and 5-15MPa respectively;
6)调节初次冷却系统7和最终冷却系统9的冷却水流量，使各自出口管路温度分别稳定在100～200℃和15～50℃；6) Adjust the cooling water flow rate of the primary cooling system 7 and the final cooling system 9, so that the respective outlet pipeline temperatures are stabilized at 100-200°C and 15-50°C;
7)待所述设备内流量、温度和压力均达到上述设定值并稳定后，利用产物收集系统10连续收集生物质预处理和水解的最终产物。7) After the flow rate, temperature and pressure in the equipment reach the above-mentioned set values and become stable, use the product collection system 10 to continuously collect the final products of biomass pretreatment and hydrolysis.
本发明与现有技术相比，具有以下优点及突出性效果：利用超临界法和亚临界法反应迅速、无需催化剂、无产物抑制的优点，能够克服酸处理技术催化剂用量大、难回收和酶水解技术反应慢、产物有抑制等不足；并通过高压进料、密封管路和各反应阶段的温度和压力控制，解决批式预处理与水解的操作不连续、设备难放大、能源消耗大的技术缺陷，可实现木质纤维类生物质的连续式预处理与水解转化并生成可发酵糖，是后续发酵产乙醇等资源化技术的基础，应用前景广阔。Compared with the prior art, the present invention has the following advantages and prominent effects: it utilizes the supercritical method and subcritical method to react quickly, without catalyst, and without product inhibition, and can overcome the large amount of catalyst used in acid treatment technology, difficult recovery and enzyme The hydrolysis technology has shortcomings such as slow reaction and product inhibition; and through high-pressure feeding, sealed pipelines, and temperature and pressure control of each reaction stage, it solves the problems of discontinuous operation of batch pretreatment and hydrolysis, difficult expansion of equipment, and large energy consumption Technical defects, it can realize the continuous pretreatment and hydrolysis conversion of lignocellulosic biomass and generate fermentable sugar, which is the basis of resource technology such as subsequent fermentation of ethanol, and has broad application prospects.
附图说明 Description of drawings
附图为本发明超临界亚临界组合连续式预处理与水解设备及方法流程示意图。The accompanying drawing is a schematic flow chart of the supercritical subcritical combined continuous pretreatment and hydrolysis equipment and method of the present invention.
图中：1-贮水罐；2-贮料罐；3-高压进水泵；4-高压进料泵；5-预加热系统；6-超临界反应系统；7-初次冷却系统；8-亚临界反应系统；9-最终冷却系统；10-产物收集罐；11-电子控温箱；12-压力表；13-测温探头；14a-第一减压阀；14b-第二减压阀；15-压力防爆阀。In the figure: 1-water storage tank; 2-storage tank; 3-high-pressure water inlet pump; 4-high-pressure feed pump; 5-preheating system; 6-supercritical reaction system; 7-primary cooling system; 8-sub Critical reaction system; 9-final cooling system; 10-product collection tank; 11-electronic temperature control box; 12-pressure gauge; 13-temperature probe; 14a-first pressure reducing valve; 14b-second pressure reducing valve; 15-Pressure explosion-proof valve.
具体实施方式 Detailed ways
下面结合附图和具体实施例对本发明做进一步详细说明。The present invention will be described in further detail below in conjunction with the accompanying drawings and specific embodiments.
图1为本发明超临界亚临界组合连续式预处理与水解设备结构原理及方法流程示意图。该设备包括贮水罐1，附有搅拌的贮料罐2，预加热系统5，超临界反应系统6，初次冷却系统7，亚临界反应系统8，最终冷却系统9，产物收集系统10以及电子控温系统11，所述贮水罐1通过管路经由高压进水泵3与预加热系统5入口相连，预加热系统5出口通过三通与超临界反应系统6入口相连；所述附有搅拌的贮料罐2通过管路经由高压进料泵4和阀门与超临界反应系统6入口相连，所述超临界反应系统6出口通过管路经由初次冷却系统7和第一减压阀14a与亚临界反应系统8入口相连；所述亚临界反应系统8出口通过管路经由第二减压阀14b和最终冷却系统9与产物收集系统10相连；所述的预加热系统、超临界反应系统、初次冷却系统和亚临界反应系统分别通过测温探头13和信号线与所述的电子控温系统11相连接。Figure 1 is a schematic diagram of the structural principle and method flow of the supercritical subcritical combined continuous pretreatment and hydrolysis equipment of the present invention. The equipment includes a water storage tank 1, a stirring storage tank 2, a preheating system 5, a supercritical reaction system 6, a primary cooling system 7, a subcritical reaction system 8, a final cooling system 9, a product collection system 10 and electronic A temperature control system 11, the water storage tank 1 is connected to the inlet of the preheating system 5 through a pipeline through a high-pressure water inlet pump 3, and the outlet of the preheating system 5 is connected to the inlet of the supercritical reaction system 6 through a tee; The storage tank 2 is connected to the inlet of the supercritical reaction system 6 through a pipeline through a high-pressure feed pump 4 and a valve, and the outlet of the supercritical reaction system 6 is connected to the subcritical reaction system 6 through a pipeline through a primary cooling system 7 and a first pressure reducing valve 14a. The inlet of reaction system 8 is connected; the outlet of said subcritical reaction system 8 is connected to product collection system 10 through the second decompression valve 14b and final cooling system 9 through pipeline; said preheating system, supercritical reaction system, primary cooling The system and the subcritical reaction system are respectively connected to the electronic temperature control system 11 through a temperature measuring probe 13 and a signal line.
所述的预加热系统5由预加热管路和预加热装置组成，预加热管路采用螺旋式盘管，其管径和管长可根据设备规模、流量和预加热温度进行调整；预加热装置由盐浴罐和设置在该盐浴罐内的电加热棒构成，可使预加热管路内的流体维持在260～450℃间的指定温度。超临界反应系统6由超临界反应管路和超临界加热装置组成，超临界反应管路可采用直管或弯管，其管径和管长可根据设备规模、流量和超临界反应条件进行调整；超临界加热装置由盐浴罐和设置在该盐浴罐内的电加热棒构成，可使超临界反应管路内的流体维持260～450℃间的指定温度。亚临界反应系统8由亚临界反应管路和亚临界加热装置组成，亚临界反应管路采用螺旋式盘管，其管径和管长可根据设备规模、流量和亚临界反应条件进行调整；亚临界加热装置由陶瓷套管和设置在该套管内的电加热棒构成，可使亚临界反应管路内的流体维持在30～360℃间的指定温度。初次冷却系统7和最终冷却系统9由传输管路和冷却套管构成，冷却套管采用逆流式水冷却套管，传输管路采用直管或螺旋式盘管，其管径和管长可分别根据超临界反应系统和亚临界反应系统的管径和管长进行调整；通过控制冷却水流量可使传输管路内流体分别快速冷却至15～300℃范围内的指定温度以利于亚临界反应和15～100℃范围内的较低温度以利于产物收集。The preheating system 5 is composed of a preheating pipeline and a preheating device. The preheating pipeline adopts a spiral coil, and its pipe diameter and length can be adjusted according to the equipment scale, flow rate and preheating temperature; the preheating device It consists of a salt bath tank and an electric heating rod installed in the salt bath tank, which can maintain the fluid in the preheating pipeline at a specified temperature between 260 and 450 °C. The supercritical reaction system 6 is composed of a supercritical reaction pipeline and a supercritical heating device. The supercritical reaction pipeline can be a straight pipe or a curved pipe, and its diameter and length can be adjusted according to the equipment scale, flow rate and supercritical reaction conditions. ; The supercritical heating device is composed of a salt bath tank and an electric heating rod installed in the salt bath tank, which can maintain the fluid in the supercritical reaction pipeline at a specified temperature between 260 and 450 °C. The subcritical reaction system 8 is composed of a subcritical reaction pipeline and a subcritical heating device. The subcritical reaction pipeline adopts a spiral coil, and its diameter and length can be adjusted according to the equipment scale, flow rate and subcritical reaction conditions; The critical heating device is composed of a ceramic casing and an electric heating rod arranged in the casing, which can maintain the fluid in the subcritical reaction pipeline at a specified temperature between 30°C and 360°C. The primary cooling system 7 and the final cooling system 9 are composed of a transmission pipeline and a cooling jacket. The cooling jacket adopts a counter-flow water cooling jacket, and the transmission pipeline adopts a straight pipe or a spiral coil. The diameter and length of the pipe can be respectively Adjust according to the pipe diameter and pipe length of the supercritical reaction system and subcritical reaction system; by controlling the flow of cooling water, the fluid in the transmission pipeline can be rapidly cooled to a specified temperature in the range of 15-300°C to facilitate subcritical reaction and A lower temperature in the range of 15-100°C is used to facilitate product collection.
超临界反应系统6、亚临界反应系统8以及亚临界反应系统后的压力可采用压力表12分别监测，量程可为40MPa，并可通过第一减压阀14a和第二减压阀14b分别调节；在预加热系统5和超临界反应系统6之间的管路上设置压力防爆阀15，并通过放空管与贮水罐1连接。工作压力可为40MPa，并不得高于压力表12的量程和所述装置的总设计压力。The pressure behind the supercritical reaction system 6, the subcritical reaction system 8 and the subcritical reaction system can be monitored respectively by a pressure gauge 12, and the range can be 40MPa, and can be adjusted respectively by the first pressure reducing valve 14a and the second pressure reducing valve 14b; A pressure explosion-proof valve 15 is arranged on the pipeline between the preheating system 5 and the supercritical reaction system 6, and is connected with the water storage tank 1 through a vent pipe. The working pressure can be 40MPa, and must not be higher than the range of the pressure gauge 12 and the total design pressure of the device.
本发明工作原理如下：使木质纤维类生物质原料和预热后的水通过高压进料泵4和高压进水泵3混合后注入超临界反应系统6，使木质纤维类生物质在超临界条件下进行预处理和水解，打破木质纤维结构，水解生成可溶性低聚糖；之后通过初次冷却系统7和第一减压阀14a，使超临界反应产物的温度和压力降低至亚临界条件，进而在亚临界反应系统8内继续水解，生成可发酵糖；最后通过9最终冷却系统于10产物收集系统连续收集超临界亚临界组合预处理与水解的产物。其具体操作步骤如下：The working principle of the present invention is as follows: the lignocellulosic biomass raw material and the preheated water are mixed through the high-pressure feed pump 4 and the high-pressure water inlet pump 3 and then injected into the supercritical reaction system 6, so that the lignocellulosic biomass is mixed under supercritical conditions. Carry out pretreatment and hydrolysis, break the lignocellulosic structure, hydrolyze and generate soluble oligosaccharide; After that, through the primary cooling system 7 and the first decompression valve 14a, the temperature and pressure of the supercritical reaction product are reduced to subcritical conditions, and then in the subcritical condition The hydrolysis continues in the critical reaction system 8 to generate fermentable sugars; finally, the final cooling system at 9 and the product collection system at 10 continuously collect the products of supercritical subcritical combined pretreatment and hydrolysis. The specific operation steps are as follows:
1)将设备管路各阀门均置于通路，开启电子控温系统11开关对预加热系统5、超临界反应系统6和亚临界反应系统8进行预热，分别设定为350～370℃、370～400℃和200～300℃范围内的指定温度；1) Put all the valves of the equipment pipeline in the passage, turn on the switch of the electronic temperature control system 11 to preheat the preheating system 5, supercritical reaction system 6 and subcritical reaction system 8, respectively set to 350-370°C, Specified temperature in the range of 370～400℃ and 200～300℃;
2)将生物质原料与水按质量比1∶40～1∶20的比例混合置入贮料罐2内，开启贮料罐2的搅拌装置使物料处于均匀悬浊状态；2) Mix the biomass raw material and water into the storage tank 2 according to the mass ratio of 1:40 to 1:20, and turn on the stirring device of the storage tank 2 to keep the material in a uniform suspension state;
3)根据贮料罐中的悬浊液体积，向贮水罐中加入1～4倍体积的水，调节柱高压进水泵和高压进料泵的流量比例为1∶1～4∶1；3) According to the volume of the suspension in the storage tank, add 1 to 4 times the volume of water to the water storage tank, and adjust the flow ratio of the column high-pressure feed water pump and high-pressure feed pump to 1:1-4:1;
4)当预加热系统5、超临界反应系统6和亚临界反应系统8的温度接近预热指定温度时，开启高压进水泵3和高压进料泵4，将贮水罐中的水注入预加热系统，达到预热温度后与由贮料罐经高压进料泵注入的生物质原料浆液快速混合并注入超临界反应系统，反应产物经初次冷却系统和减压阀进行冷却和降压后进入亚临界反应系统；4) When the temperature of the preheating system 5, the supercritical reaction system 6 and the subcritical reaction system 8 is close to the preheating specified temperature, turn on the high-pressure water inlet pump 3 and the high-pressure feed pump 4, and inject the water in the water storage tank into the preheating system, after reaching the preheating temperature, it is quickly mixed with the biomass raw material slurry injected from the storage tank through the high-pressure feed pump and injected into the supercritical reaction system. critical reaction system;
5)调节第一减压阀14a和第二减压阀14b、使超临界反应系统6和亚临界反应系统8内部管路压力分别稳定在20～25MPa和5～15MPa；5) Adjust the first pressure reducing valve 14a and the second pressure reducing valve 14b, so that the internal pipeline pressures of the supercritical reaction system 6 and the subcritical reaction system 8 are stabilized at 20-25MPa and 5-15MPa respectively;
6)调节初次冷却系统7和最终冷却系统9的冷却水流量，使各自出口管路温度分别稳定在100～200℃和15～50℃；6) Adjust the cooling water flow rate of the primary cooling system 7 and the final cooling system 9, so that the respective outlet pipeline temperatures are stabilized at 100-200°C and 15-50°C;
7)待所述设备内流量、温度和压力均达到上述设定值并稳定后，利用产物收集系统10连续收集生物质预处理和水解的最终产物。7) After the flow rate, temperature and pressure in the equipment reach the above-mentioned set values and become stable, use the product collection system 10 to continuously collect the final products of biomass pretreatment and hydrolysis.
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