CN101613377A - Biomass supercritical and subcritical combined continuous type pretreatment and hydrolysis equipment and method - Google Patents

Biomass supercritical and subcritical combined continuous type pretreatment and hydrolysis equipment and method Download PDF

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CN101613377A
CN101613377A CN 200910088895 CN200910088895A CN101613377A CN 101613377 A CN101613377 A CN 101613377A CN 200910088895 CN200910088895 CN 200910088895 CN 200910088895 A CN200910088895 A CN 200910088895A CN 101613377 A CN101613377 A CN 101613377A
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supercritical
subcritical
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reaction system
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CN101613377B (en
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王洪涛
岩 赵
陆文静
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清华大学
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/54Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals characterised by the solvent
    • Y02P20/544Supercritical solvents, e.g. supercritical H2O or CO2

Abstract

The invention relates to biomass supercritical and subcritical combined continuous type pretreatment and hydrolysis equipment and a method. The equipment comprises a water storage tank, a material storage tank with a stirring device, a preheating system, a supercritical reaction system, a primary cooling system, a subcritical reaction system, a final cooling system, a product collection system and an electronic temperature controlling system. The method comprises the following processing steps: water reaching preheat temperature and biomass material paste are rapidly mixed and then injected into the supercritical reaction system to be pretreated under supercritical condition; the reaction product is cooled through the primary cooling system and depressurized through a pressure reducing valve and then enters into the subcritical reaction system to be hydrolyzed sequentially, therefore fermentable sugars are continuously generated and collected. The invention utilizes the advantages of the supercritical method that the reaction is rapid, activator is not required and product inhibition does not exit, realizes that the continuous hydrolysis conversion of wood fiber biomass can generate fermentable sugars, is the foundation of subsequent resource recovery technologies, such as ethanol production by fermentation and the like, and has wide application prospect.

Description

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技术领域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。 Continuous pre-treatment equipment and methods with the biomass composition supercritical subcritical continuous hydrolysis pretreatment apparatus and methods Technical Field The present invention relates to one kind of biomass resource supercritical subcritical hydrolysis compositions, more particularly to a wood fiber biomass composition supercritical subcritical continuous hydrolysis pretreatment apparatus and method, processing and use of biomass energy belongs to the technical field. 背景技术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。 BACKGROUND crop straw is one of the most potential for development of biomass energy, resources and technology in particular its ethanol technology has received wide attention. 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。 Bottlenecks straw fuel ethanol is twofold: first, to determine its own structure cellulose hydrolysis difficult. 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。 Cellulose is the D - glucopyranose linear macromolecules bonded anhydride formed by intermolecular hydrogen bond and the molecule in many, having highly crystalline and poorly-soluble, the contact area is reduced, hydrolyzed or enzyme catalyst with difficulty. 第二,木质素包裹作用使纤维素难以水解。 Second, the role of lignin inclusions difficult to hydrolyze cellulose. 木质素是由苯丙垸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。 Lignin is linked phenylpropyl embankment unit refractory polymers, hemicellulose and often filled between the cell wall with the fibers, tightly wrapped cellulose, making it more difficult or dissolved in a solvent into contact with an enzyme hydrolysis, plus big difficulty of 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。 Current methods of pretreatment and hydrolysis of straw main acid treatment, steam explosion and enzymatic hydrolysis. 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。 Acid treatment can cause equipment corrosion, environmental pollution; steam explosion will result in substantial loss of xylose; enzymatic hydrolysis requires at least three key enzymes exist, and may not have inhibitory substances, demanding conditions, a large consumption of enzyme, the cost of high residence time required more than three 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U74.2'C和22. lMPa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。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30(TC ,葡萄糖的分解速率比超临界水中(如40(TC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 Supercritical method straw pretreatment and hydrolysis using water and solvates 22. lMPa U74.2'C more enhanced ability under supercritical conditions, the degree of ionization increases (higher than normal temperature properties such as three orders of magnitude about the dissolving cellulose in straw, to achieve complete separation of lignin, and the use of ionized H- hydrolysis as a catalyst. a very short time to complete the hydrolysis of the cellulose and to obtain oligosaccharides, glucose and other products, the acid treatment can solve corrosion equipment, low productivity enzymatic hydrolysis technical problem, but the decomposition of glucose in supercritical water reaction rate is large, i.e., the rapid decomposition of ethanol fermentation can not be performed erythritol, furfural and other substances. Accordingly, the conventional supercritical process is not yet satisfactory conversion of fermentable sugars. However, when the reaction temperature, the pressure is reduced, the decomposition rate of glucose decline exponentially, as the subcritical water (e.g., 30 (TC, glucose decomposition rate than the supercritical water (e.g. 40 (TC reduced by 2 orders of magnitude due to the subcritical water is denser than supercritical water, hydrolysis of polysaccharides and oligosaccharides are more highly advantageous. Therefore, 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。基于上述思路,国内外己经丌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禾口操作方法(Zhao et al. Combined Supercritical and Subcritical Process for Cellulose Hydrolysis to Fermentable Hexoscs. Environ. Sci. Techno丄.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。发明内容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 Proposes a combination of supercritical subcritical process for first straw in a supercritical water pretreatment and hydrolysis, hydrolysis of the cellulose oligosaccharides thoroughly, then after subcritical conditions further hydrolyzed to glucose using both the rapid method of supercritical reaction without the catalyst, product inhibition no advantage and solves its unstable products, technical bottlenecks refractory condition. based on the above ideas, at home and abroad have made Ji batch hydrolysis pretreatment apparatus supercritical alkylene critical combinations of biomass Wo opening operation method (Zhao et al. Combined Supercritical and subcritical Process for Cellulose hydrolysis to Fermentable Hexoscs. Environ. Sci. Techno Shang. 2009, 43 (5)), however, batch pre-hydrolysis apparatus, due to intermittent operation is not continuity, it is difficult to enlarge the size of the device, large energy consumption, research and scientific experiments mechanism currently limited, can not be applied to actual production. SUMMARY oF tHE iNVENTION the present invention is to provide a biomass composition supercritical subcritical continuous pre hydrolysis processing apparatus and method, batch operation aims to solve the non-pretreated and hydrolyzed 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。 本发明采用以下技术方案: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l,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IO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 Continuity, it is difficult to enlarge the size of the device, large energy consumption technical defects, may be implemented in combination supercritical subcritical lignocellulosic feedstock pretreatment and hydrolysis continuously provide a novel and efficient hydrolysis of the lignocellulosic material pathway Biomass resources, having broad application prospects the present invention employs the following technical solutions: a combination of supercritical subcritical continuous hydrolysis pretreatment and apparatus for the production of a substance, characterized in that: said apparatus comprises a storage tank L, with stirring means 2 of the storage silo, pre-heating system 5, 6 supercritical reaction systems, the primary cooling system 7, 8 subcritical reaction system, the final cooling system 9, the product collecting system and an electronic temperature control system 11 IO; the water storage tank 1 via a high-pressure pump through the line 3 into the pre-heating system is connected to the inlet 5, a preheating system is connected to the outlet 5 through the inlet 6 and the supercritical reaction system of the three-way, a holding tank with a stirring device 2 via the high-pressure feed via line feed pump 4 and the inlet 6 is connected to a supercritical reaction systems, the supercritical reaction system through the outlet conduit 6 via a primary cooling system 7 and the pressure reducing valve 14a and a first sub- 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IO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。 The reaction system is connected to an inlet sector 8; 8 a subcritical reaction system is connected to the outlet 9 via the IO system of a second product collection and final cooling system pressure reducing valve 14b via line; said preheating system, a supercritical reaction systems, initial subcritical reaction system and cooling system, respectively, and an electronic temperature control system and said signal line 11 is connected through a temperature probe 13. 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。 Technical features of the present invention is further characterized by: the pre-heating system 5 by a pre-heating and pre-heating unit line, it said pre-heating means is provided by a salt bath tank and electric heating rods constituting the bath in the tank, the pre-heating line screw-type coil. 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黄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。 Supercritical reaction system of claim 6 supercritical reaction conduit and supercritical heating unit, the heating means supercritical yellow and the bath tank in a heating rod constituting the electrically salt bath tank, said supercritical reaction with straight line pipe or elbow. 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。 The subcritical reaction the reaction system 8 by a subcritical line and subcritical heating unit, said subcritical heating means consists of a ceramic sleeve and the electric heating rods arranged in the sleeve, the subcritical reaction line screw-type coil. 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。 Said primary cooling system 7 and the final transfer line from the cooling system 9 constituting the cooling jacket and the cooling jacket countercurrent water-cooling jacket type, said transport line using a straight tube or 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: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°C 、370〜40(TC和200〜300°C 范围内的指定温度;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;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;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忙料罐经高压进料泵注入的生物质原料浆液快 The present invention also provides a method for generating continuous supercritical subcritical pretreatment and hydrolysis substance combination, characterized in that the method comprises the following steps: 1) the devices are placed in the pipeline for each valve passage, electronically controlled opening temperature system 11 switches preheating system 5, system 6 and the supercritical subcritical reaction the reaction preheating system 8, are set to 350~370 ° C, within the specified 370~40 (TC range of 200~300 ° C and temperature; 2) the biomass feedstock with water at a mass ratio of 1: 40~1: 20 ratio mixture 2 placed in the storage silo, open storage silo stirring device 2 so that the material uniformly in a suspended state; 3) volume of the suspension in the holding tank, ~ 4-fold volume of water was added to the water storage tank, into the high-pressure pump and regulating the high pressure column feed pump flow rate ratio of 1: 1 ~ 4: 1; 4) when the pre- 5 heating system, the reaction temperature of the supercritical and subcritical systems 6 near the reaction system 8 preheating specified temperature, opening the high-pressure pump into a high-pressure feed pump 3 and 4, the water storage tank is injected into the pre-heating systems, pre reached after the temperature of the hot feed tank is a busy high pressure feed pump injection biomass feedstock slurry faster 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;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;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100〜20(TC和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。 And injected into the supercritical mixed reaction system, the reaction product was subjected to primary cooling system and by a pressure reducing valve into the subcritical cooling down and depressurizing system after the reaction; 5) adjusting the first pressure reducing valve 14a and the second pressure reducing valve 14b, the supercritical 6 the reaction system and the reaction system 8 subcritical internal line pressure stabilized at 20~25MPa and 5~15MPa; 6) regulating the primary cooling system 7 and the cooling water flow rate of the final cooling system 9, so that the respective outlet conduit temperature stabilized at 100~20 (TC and 15~50 ° C; 7) inside the device until the flow rate, temperature and pressure have reached the set value, and stabilized, product collection system 10 using the final product was continuously collected and hydrolyzed biomass pretreatment . 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 effects projection of: supercritical and subcritical method responsive methods, without catalyst, no product inhibition, which can also overcome the large amount of the acid catalyst processing technology, and is difficult to recover the enzyme hydrolysis technique slow response, product of inadequate suppression; and through the high pressure feed, temperature and pressure sealing lines and control each reaction stage, hydrolysis pretreatment solution batch operation is not continuous, hard amplifying device, large energy consumption continuous hydrolysis pretreatment and technical defects, can be achieved lignocellulosic biomass and conversion of fermentable sugars, a basic resource technology subsequent fermentation ethanol and the like, has wide application prospect. 附图说明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。 Brief Description of the drawings of the present invention, apparatus and method for continuous super hydrolyzed schematic flow diagram of pre-treatment with a combination of supercritical subcritical. 图中:l一贮水罐;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;9一最终冷却系统;IO —产物收集罐;U —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。 FIG: l a storage tank; 2 - storage silo; 3 - high pressure feed pump; 4- high pressure feed pump; 5 - preheating system; 6 - supercritical reaction systems; 7-- the primary cooling system; 8 - alkylene The reaction system is critical; 9 a final cooling system; IO - product collection tank; U - electronic temperature control box; 12-- gauge; 13-- temperature probe; 14A-a first pressure reducing valve; 14b-second pressure reducing valve; 15-- pressure explosion-proof valve. 具体实施方式下面结合附图和具体实施例对本发明做进一歩详细说明。 DETAILED DESCRIPTION OF THE DRAWINGS Specific embodiments and examples of the present invention is made into a ho described in detail. 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。 1 a schematic view of a combination of supercritical subcritical continuous hydrolysis pretreatment and process flow equipment and structural principles of the present invention. 该设备包括贮水罐l,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入口相迮;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。 The apparatus includes L water tank, holding tank with stirring 2, preheating system 5, 6 supercritical reaction systems, the primary cooling system 7, 8 subcritical reaction system, the final cooling system 9, 10 and an electronic product collection system temperature control system 11, the storage tank 1 via the high-pressure feed pump 3 via line system 5 is connected to the inlet of the pre-heating, pre-heating system 5 and an outlet 6 through a three phase Ze inlet supercritical reaction system; stirring with a the holding tank 2 are connected via a high pressure feed pump 6 inlet valves 4 and supercritical reaction system via line, the supercritical reaction system through the outlet conduit 6 via a primary cooling system 7 and the pressure reducing valve 14a and a first sub- the critical reaction system was connected to an inlet 8; subcritical reaction system is connected to the outlet 8 through a line 14b via the second pressure reducing valve and a cooling system 9 and the final product collection system 10; the pre-heating system, a supercritical reaction systems, initial subcritical reaction system and cooling system, respectively, and an electronic temperature control system and said signal line 11 is connected through a temperature probe 13. 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260〜45(TC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260〜45(TC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 5 according to a pre-heating system and pre-heating line pre-heating unit, a pre-heating line spiral type coil, pipe diameter and its length can be adjusted according to the size of the device, flow rate and temperature of the preheating; preheating means the bath tank and electric heating rods arranged in a configuration of the bath tank, the fluid within the preheating can be maintained at 260~45 line (between the predetermined temperature TC.] supercritical reaction system supercritical reaction conduit 6 and supercritical heating unit, a supercritical reaction line can be a straight tube or pipe, pipe diameter and its length can be adjusted according to the size of the device, and a supercritical flow reaction conditions; supercritical heating means is provided by a salt bath tank and in the electric heating rods of the salt bath tank structure, a fluid in a supercritical reaction conduit maintained 260~45 (between the designated temperature TC. subcritical reactor subcritical reaction system by the conduit 8 and subcritical heating unit subcritical reaction using spiral coil tubing, pipe diameter and its length can be adjusted according to the size of the device, flow rate and reactor subcritical conditions; subcritical heating means and a ceramic sleeve disposed within the electrical heating of the sleeve 棒构成,可使亚临界反应管路内的流体维持在30〜36(TC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,传输管路釆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°C范围内的指定温度以利于业临界反应和15〜10(TC范围内的较低温度以利于产物收集。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 Rod structure, a fluid in a subcritical reactor was maintained at 30~36 line (between the predetermined temperature TC. Primary cooling system 7 and the final transfer line from the cooling system 9 constituting the cooling jacket and the cooling tube countercurrent using water-cooling jacket, preclude the transport line, pipe diameter and its length can be adjusted according to the diameter, respectively, the supercritical and subcritical reaction the reaction system and a pipe system with long straight tube or spiral coil; by controlling the cooling water flow It allows the fluid transfer conduit are rapidly cooled to a predetermined temperature within the range of 15~300 ° C to facilitate the reaction and 15~10 industry lower critical temperature in (TC range to facilitate product was collected. 6 supercritical reaction systems, ethylene the critical pressure of the reaction system after the reaction system 8 and the subcritical pressure gauge 12 can be monitored separately, may range 40MPa, and may be adjusted by the first pressure reducing valve 14a and the second pressure reducing valve 14b are respectively: preheating system 5 and the super the reaction system critical path between the tube 6 is provided a pressure explosion-proof valve 15, and a vent pipe is connected through a water tank. working pressure 40MPa may be, and should not exceed the overall design pressure gauge 12 and the measuring range of the apparatus 本发明丁作原理如下: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IO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: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350〜37CTC 、370〜40(TC和200〜30(TC 范围内的指定温度;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 Mingding present principles as follows: the fibers of the wood raw material and water after preheating Biomass supercritical reaction system after the high-pressure feed pump 4 and the high pressure injection pump 6 into the mixing 3, lignocellulosic biomass in supercritical conditions the pretreatment and hydrolysis, the lignocellulosic structures breaking, hydrolysis of soluble oligosaccharides; 7 after passing through the primary cooling system and the first pressure reducing valve 14a, the supercritical temperature and pressure of the reaction product is reduced to subcritical conditions, in addition the reaction continued subcritical system 8 is hydrolyzed to produce fermentable sugars; final product was continuously collected supercritical subcritical pretreatment composition IO hydrolysis in the final product collection system by means of a cooling system 9 which specific steps are as follows: 1) the device tube. each passage way valves are disposed to open the temperature control system 11 switches the electronic preheating system 5, system 6 and the supercritical subcritical reaction the reaction preheating system 8, are set to 350~37CTC, 370~40 (TC and 200~30 (TC within a specified temperature range; 2) the biomass feedstock with water at a mass ratio of 1: 40~1: 20 ratio mixture 2 placed in the storage silo, open stirred holding tank 2 装置使物料处于均匀悬浊状态;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: 1:4) 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;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;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100〜20(TC和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 Means that the material is uniformly suspended state; 3) The volume of the suspension in the holding tank, ~ 4-fold volume of water was added to the water storage tank, a high pressure column feed flow rate ratio adjustment pumps and high pressure feed pumps. 1: 1 ~ 4: 1: 4) when the pre-heating system 5, system 6, the temperature of the supercritical and subcritical reaction the reaction system specified preheat temperature is close to 8, opening the high-pressure pump into a high-pressure feed pump 3 and 4, the reservoir water is injected into the tank pre-heating system, after reaching the preheating temperature by the holding tank via a high pressure feed pump injection biomass feedstock slurry quickly mixed and injected into the supercritical reaction system, the reaction product was the primary cooling system and pressure relief valve after cooling down and depressurizing into the reactor subcritical system; 5) adjusting the first pressure reducing valve 14a and the second pressure reducing valve 14b, the supercritical subcritical reaction the reaction system 6 and system 8 internal line pressure stabilized at 20~ 25MPa and 5~15MPa; cooling water flow 6) regulating the primary cooling system 7 and a final cooling system 9, so that the respective outlet conduit temperature stabilized at 100~20 (TC and 15~50 ° C; 7) to be the device the flow rate, temperature and pressure have reached the set value, and stable 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。 After the set, using the final product was continuously collected product collection system 10 and hydrolysis of biomass pretreatment.

Claims (7)

1.一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 A combination of supercritical subcritical continuous hydrolysis pretreatment and apparatus for the production of a substance, characterized in that: said apparatus comprises a storage tank (1), holding tank with a stirring device (2), pre- The heating system (5), supercritical reaction system (6), the primary cooling system (7), the reaction subcritical system (8), a final cooling system (9), the product collection system (10) and an electronic temperature control system (11) ; said reservoir tank (1) via a high-pressure feed pump (3) and the pre-heating system (5) is connected via an inlet conduit, a pre-heating system (5) connected to the outlet of the three-way supercritical reaction system (6) inlet, with the holding tank (2) is connected via a conduit stirring apparatus via a high-pressure feed pump (4) and the supercritical reaction system (6) inlet, the supercritical reaction system (6) through the outlet conduit via a first cooling system (7) and the first pressure reducing valve (14a) is connected to the reaction system and subcritical (8) inlets; the reactor subcritical system (8) through the outlet conduit via a second pressure reducing valve (14b) and final cooling system (9) and product collection system (10) is connected; said preheating system, the reaction system supercritical, subcritical primary cooling system and the reaction system 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。 Do (13) and an electronic temperature control system (11) and said signal line are connected via temperature probe.
2、 根据权利要求1所述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。 2, according to claim 1 for the biomass composition supercritical subcritical continuous pretreatment and hydrolysis of the apparatus, wherein: said pre-heating system (5) by a pre-heating and pre-heating unit line, It said pre-heating means of the electric heating rods in the bath tank is provided and consists of a salt bath tank, the pre-heating line screw-type coil.
3、 根据权利要求1所述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。 3, a combination of supercritical subcritical continuous pretreatment and hydrolysis of the apparatus 1 for biomass according to claim, wherein: said supercritical reaction system of (6) from the conduit and supercritical reaction was heated supercritical means the composition of the supercritical heating means of the electric heating rods in the bath tank is provided and consists of a salt bath tank, the supercritical reaction with straight line pipe or elbow.
4、 根据权利要求1所述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。 4. The composition as claimed in supercritical subcritical continuous hydrolysis pretreatment and apparatus for the biomass in claim 1, wherein: said subcritical the reaction system (8) is heated by the reaction conduit and subcritical subcritical composition means, said subcritical heating means consists of a ceramic sleeve and the electric heating rods arranged in the sleeve, the subcritical reactor line screw-type coil.
5、 报据权利要求1所述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。 5, a combination of supercritical subcritical continuous pretreatment and hydrolysis of the apparatus 1 for biomass data packets as claimed in claim, wherein: said primary cooling system (7) and a final cooling system (9) by a transfer pipe and constituting passage cooling jacket, said cooling jacket countercurrent water-cooling jacket type, said transport line using a straight tube or a spiral coil.
6、 根据权利要求1所述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: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。 6. The composition as claimed in supercritical subcritical continuous hydrolysis pretreatment and apparatus for the biomass in claim 1, wherein: the pipeline system between the pre-heating (5) and supercritical reaction system (6) a pressure explosion-proof valve (15), and is connected to the water storage tank through the vent tube (1).
7、 一种采用如权利要求1所述设备的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歩骤:1)将设各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°C、 370〜 °C和200〜300。 7. A use of apparatus as claimed in claim 1 said method biomass supercritical subcritical continuous composition for pretreatment and hydrolysis, characterized in that the method comprises the step ho: 1) The set of all the valves conduit are placed passage opening electronic temperature control system (11) for preheating the switching system (5), supercritical reaction system (6) and subcritical reaction system (8) is preheated, are set to 350~370 ° C , 370~ ° C and 200-300. C范围内的指定温度;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;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;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;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;6) 调节初次冷却系统 C within a predetermined temperature range; 2) the biomass feedstock with water at a mass ratio of 1: 40~1: 20 ratio mixture stirring device placed in holding tank) (2, opening the storage silo (2) of the material even in a suspended state; 3) the volume of the suspension in the holding tank, ~ 4-fold volume of water was added to the holding tank, and adjusting the high pressure pump into the high pressure column feed pump feed flow rate ratio is 1: 1 ~ 4: 1; 4) when the temperature of the pre-heating system (5), supercritical reaction system (6) and subcritical reaction system (8) is close to the specified preheat temperature, high pressure feed pump opening (3) and the high pressure feed a pump (4), the water storage tank preheating the water injection system, and after reaching a preheating temperature holding tank via a high pressure feed pump injection biomass feedstock slurry quickly mixed and injected into the supercritical reaction system, the reaction product was after the primary cooling system and the cooling down and depressurizing into the pressure reducing valve subcritical reactor system; 5) adjusting the first pressure reducing valve (14a) and a second pressure relief valve (14b), supercritical reaction system (6) and sodium critical the reaction system (8) inside the line pressure is stabilized at 20~25MPa and 5~15MPa; 6) adjusting the primary cooling system 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100〜20(TC和i5〜5(TC;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(IO) 连续收集生物质预处理和水解的最终产物。 7) and a final cooling system (9) of the cooling water flow rate, so that the respective stable temperatures outlet line (TC and i5~5 (TC in 100~20; 7) within the device to be flow, temperature and pressure have reached the above-described after the setting and stabilization by product collection system (IO) the final product is continuously collected biomass pretreatment and hydrolysis.
CN2009100888958A 2009-07-21 2009-07-21 Biomass supercritical and subcritical combined continuous type pretreatment and hydrolysis equipment and method CN101613377B (en)

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WO2014019043A2 (en) 2012-08-01 2014-02-06 Centro Nacional De Pesquisa Em Energia Em Materias - Cnpem Simultaneous conversion method for sugar cane bagasse using uhtst reactors
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US9783565B2 (en) 2011-11-08 2017-10-10 Renmatix, Inc. Liquefaction of biomass at low pH
US9963555B2 (en) 2011-12-30 2018-05-08 Renmatix, Inc. Compositions comprising lignin
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US10053745B2 (en) 2010-01-19 2018-08-21 Renmatix, Inc. Production of fermentable sugars and lignin from biomass using supercritical fluids
CN102859066A (en) * 2010-01-19 2013-01-02 瑞恩麦特克斯股份有限公司 Production of fermentable sugars and lignin from biomass using supercritical fluids
US9359651B2 (en) 2010-01-19 2016-06-07 Renmatix, Inc. Production of fermentable sugars and lignin from biomass using supercritical fluids
CN105525043A (en) * 2010-01-19 2016-04-27 瑞恩麦特克斯股份有限公司 Production of fermentable sugars and lignin from biomass using supercritical fluids
CN101886143A (en) * 2010-07-13 2010-11-17 大连理工大学 Method for preparing reducing sugar by hydrolyzing biomass with super-critical/sub-critical water in two steps
US9738943B2 (en) 2010-11-01 2017-08-22 Renmatix, Inc. Process for controlled liquefaction of a biomass feedstock by treatment in hot compressed water
WO2012060767A1 (en) * 2010-11-01 2012-05-10 Reac Fuel Ab Process for controlled liquefaction of a biomass feedstock by treatment in hot compressed water
US9783565B2 (en) 2011-11-08 2017-10-10 Renmatix, Inc. Liquefaction of biomass at low pH
US9963555B2 (en) 2011-12-30 2018-05-08 Renmatix, Inc. Compositions comprising lignin
WO2014019043A2 (en) 2012-08-01 2014-02-06 Centro Nacional De Pesquisa Em Energia Em Materias - Cnpem Simultaneous conversion method for sugar cane bagasse using uhtst reactors
US10059730B2 (en) 2013-03-15 2018-08-28 Renmatix, Inc. High purity lignin, lignin compositions, and higher structured lignin
CN103570526A (en) * 2013-11-21 2014-02-12 青岛科技大学 Novel biomass supercritical/subcritical hydrolysis reactor

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