CN114350389A - A process for high-value resource recycling and utilization of aquatic plants - Google Patents
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Abstract
Description
技术领域technical field
本发明属于生态水利和可再生能源领域，特别涉及水草高值资源化回收利用的工艺，该处理河湖中水草（水葫芦、水花生、水浮莲等）工艺适用于不同含水率、原材料不均一的生物质高值资源化利用。The invention belongs to the field of ecological water conservancy and renewable energy, and particularly relates to a process for high-value resource recycling of aquatic plants. The process for treating aquatic plants (water hyacinth, water peanut, water lotus, etc.) Uniform high-value resource utilization of biomass.
背景技术Background technique
随着城市化建设规模的扩大和经济的快速发展，河湖污染日趋严重，大量未经处理或者未经有效处理的生物污水和工农业生产废水排入了江河、湖泊、海洋，加剧了水体的富营养化，导致水草疯长，破坏水体的生态平衡，带来严重的生态环境问题。面对这日益突出的环境问题，物理打捞漂浮在水体表面的水草是解决问题的主要途径。但是打捞上来的水草如何处理处置是河湖治理面临的重要问题。With the expansion of urbanization construction scale and the rapid economic development, the pollution of rivers and lakes is becoming more and more serious. Eutrophication causes aquatic plants to grow wildly, destroys the ecological balance of water bodies, and brings serious ecological and environmental problems. Facing this increasingly prominent environmental problem, physical salvage of aquatic plants floating on the water surface is the main way to solve the problem. However, how to deal with the salvaged aquatic plants is an important issue facing river and lake governance.
在每年的春夏秋季节，水草的日打捞量巨大，高达百万吨，而打捞上来的水草被倾倒到垃圾填埋场、冲沟或者水边洼地，长时间堆放容易腐烂产生异味，经过雨水的冲刷还易产生二次污染的问题。而水草作为生物质的重要组成部分，数量如此巨大的水草意味着蕴藏着巨大的生物质资源，但是由于水草的含水率高、有机质含量高、易腐烂、含有重金属等特点，因此，如何将水草在避免二次污染的基础上充分资源化回收利用，变废为宝，是当前面临的挑战。In the spring, summer and autumn of each year, the daily salvage of aquatic plants is huge, up to one million tons, and the salvaged aquatic plants are dumped into landfills, gullies or waterside depressions, and they are easy to rot and produce peculiar smell after being piled up for a long time. The flushing is also prone to the problem of secondary pollution. Aquatic plants are an important part of biomass. Such a large number of aquatic plants means that they contain huge biomass resources. However, due to the high water content, high organic matter content, perishability, and heavy metal content of aquatic plants, how to use aquatic plants? On the basis of avoiding secondary pollution, it is the current challenge to fully recycle and utilize resources and turn waste into treasure.
特别地，由于水草的含水率高，无论采用哪种处理处置方法，均要考虑对水草进行脱水，但由于水草大部分水是与有机质结合水，所以脱水困难，脱水技术存在一定的问题，从而导致后续资源化利用的手段受到限制。而且目前针对水草的处理处置，也缺少规模化的工艺流程，因此本专利拟提出一种可以实现水草合理高效资源化处置，避免二次污染，实现资源的充分利用。In particular, due to the high moisture content of aquatic plants, dehydration of aquatic plants should be considered no matter which treatment method is adopted. However, since most of the water of aquatic plants is combined with organic matter, dehydration is difficult, and there are certain problems in dehydration technology. The means for subsequent resource utilization are limited. Moreover, there is currently a lack of large-scale technological processes for the treatment and disposal of aquatic plants. Therefore, this patent proposes a method that can realize reasonable and efficient resource disposal of aquatic plants, avoid secondary pollution, and achieve full utilization of resources.
发明内容SUMMARY OF THE INVENTION
解决的技术问题：本申请主要是提出一种水草高值资源化回收利用的工艺，解决现有技术中存在的水草打捞量巨大，含水率高，脱水困难、处理处置困难，资源利用率不高等技术问题，公开一种包括水草深度脱水、气化热解、产物净化收集、产物提质四个流程的工艺。将打捞的水草放置24~48小时，然后切碎，利用脱水剂进行深度脱水，脱水剂分离回收；将获得的固态产物送入无氧或者低氧的回转窑中连续的气化热解；将获得的气体进行冷凝分离净化干燥分别获得合成气和生物油，将获得的固体收集获得生物炭；根据实际需求，对所获得产物进行提质处理，实现了水草的高值资源化利用，并避免了二次污染。Technical problem to be solved: This application mainly proposes a process for high-value resource recycling of aquatic plants, which solves the problems in the prior art that the amount of aquatic plants salvaged is huge, the moisture content is high, the dehydration is difficult, the treatment and disposal are difficult, and the resource utilization rate is not high. The technical problem is to disclose a process including four processes of deep dehydration of aquatic plants, gasification and pyrolysis, product purification and collection, and product quality improvement. The salvaged aquatic plants are placed for 24 to 48 hours, then chopped, deeply dehydrated by using a dehydrating agent, and the dehydrating agent is separated and recovered; the obtained solid product is sent to an oxygen-free or low-oxygen rotary kiln for continuous gasification and pyrolysis; The obtained gas is condensed, separated, purified and dried to obtain syngas and bio-oil, respectively, and the obtained solids are collected to obtain bio-char; according to actual needs, the obtained product is subjected to quality improvement treatment to realize the high-value resource utilization of aquatic plants and avoid secondary pollution.
技术方案：Technical solutions:
一种水草高值资源化回收利用的工艺，该工艺包括水草深度脱水、热解气化、产物净化收集、产物提质四个流程的工艺，将打捞的水草放置24~48小时，然后切碎，利用脱水剂进行深度脱水，脱水剂分离回收；将获得的固态产物送入无氧或者低氧的回转窑中连续的气化热解；将获得的气体进行冷凝分离净化干燥分别获得合成气和生物油，将获得的固体收集获得生物炭；根据实际需求，对所获得产物进行提质处理，实现了水草的高值资源化利用，并避免了二次污染，具体包括如下步骤：A process for high-value resource recycling of aquatic plants, the process includes four processes of deep dehydration of aquatic plants, pyrolysis and gasification, product purification and collection, and product quality improvement. The salvaged aquatic plants are placed for 24 to 48 hours, and then chopped. , using a dehydrating agent for deep dehydration, and the dehydrating agent is separated and recovered; the obtained solid product is sent to an oxygen-free or low-oxygen rotary kiln for continuous gasification and pyrolysis; the obtained gas is condensed, separated, purified and dried to obtain synthesis gas and Bio-oil, the obtained solid is collected to obtain biochar; according to the actual demand, the obtained product is upgraded to realize the high-value resource utilization of aquatic plants and avoid secondary pollution, which specifically includes the following steps:
第一步，将打捞的水草预处理自然放置24~48小时，水草含水率降为70-85%，然后切碎至1-5cm，将配置好的脱水剂与预处理后的水草在压力为0.1-0.8Mpa容器中充分以100-500 r/min的速度搅拌40min~60min，当水草的含水率降为5~15%时，停止搅拌，升压至常压，回收利用＞80%的脱水剂，将液固分离，得到固态深度脱水后的水草进入第二步；The first step is to place the salvaged aquatic plants for 24-48 hours naturally, the moisture content of the aquatic plants is reduced to 70-85%, and then chopped to 1-5 cm, and the prepared dehydrating agent and the pretreated aquatic plants are placed under a pressure of Stir in a 0.1-0.8Mpa container at a speed of 100-500 r/min for 40min~60min, when the water content of the aquatic plants drops to 5~15%, stop stirring, increase the pressure to normal pressure, and recycle >80% dehydration agent, the liquid-solid separation is obtained, and the water plants after the solid-state deep dehydration are obtained and enter the second step;
第二步：在封闭的回转窑通入N2，将回转窑中＞95%的空气排出，实现无氧或者低氧状态，并根据产物需要设置反应温度在300~600℃，待达到反应温度后，固态深度脱水后的水草通过螺旋进料器进入回转窑中进行热解气化，并由螺旋进料器控制进料量，水草热解气化的时间为10~30min，供第三步使用；Step 2: Pour N 2 into the closed rotary kiln, and discharge >95% of the air in the rotary kiln to achieve anaerobic or low-oxygen state, and set the reaction temperature at 300~600°C according to the needs of the product, until the reaction temperature is reached After that, the water plants after solid deep dehydration enter the rotary kiln through the screw feeder for pyrolysis and gasification, and the feed amount is controlled by the screw feeder. use;
第三步：将热解气化产生的热解气进行冷凝分离净化干燥分别获得合成气和生物油，收集固体获得生物炭，共第四步使用；The third step: the pyrolysis gas produced by the pyrolysis gasification is condensed, separated, purified and dried to obtain synthesis gas and bio-oil, respectively, and the solid is collected to obtain bio-char, which is used in the fourth step;
第四步：获得产物合成气、生物油和生物炭直接使用或根据实际应用需求进行提质；所述合成气用于回转窑的预热气中、或通过深度净化接入居民的民用燃气管网中、或通过进一步的裂解重整获得更高品质的化学制品；所述生物油通过进一步添加催化剂提质作为生物柴油和乙醇；所述生物炭根据其性质作为土壤改良剂、作为吸附剂吸附重金属污染物、作为燃料，进一步提质部分或完全取代商用活性炭；Step 4: Obtain the product syngas, bio-oil and bio-char for direct use or upgrading according to actual application requirements; the syngas is used in the preheating gas of the rotary kiln, or connected to the residential gas pipe through deep purification In the net, or through further cracking and reforming to obtain higher quality chemicals; the bio-oil is upgraded by further adding catalysts as biodiesel and ethanol; Heavy metal pollutants, as fuel, further upgrading to partially or completely replace commercial activated carbon;
第五步：水草的生物炭直接应用于河湖岸边护堤的材料，过滤、吸附、净化雨水和工农业污水中的重金属污染物，同时由于其吸水性和含有丰富的氮磷，有助于护堤的植物生长，有利于生态护堤的实现。Step 5: The biochar of aquatic plants is directly applied to the material of the embankment on the banks of rivers and lakes to filter, adsorb and purify heavy metal pollutants in rainwater and industrial and agricultural sewage. The growth of plants in the berm is beneficial to the realization of the ecological berm.
作为本发明的一种优选技术方案：所述第一步中脱水剂由80~95%的活性组分与5%~15%的助剂组分在压力为0.1-0.8Mpa条件下充分混合而成。As a preferred technical solution of the present invention: in the first step, the dehydrating agent is fully mixed by 80-95% of the active components and 5%-15% of the auxiliary components under the condition of a pressure of 0.1-0.8Mpa. to make.
作为本发明的一种优选技术方案：所述活性组分为L-DME，且在完成脱水后可实现分离回收。As a preferred technical solution of the present invention: the active component is L-DME, which can be separated and recovered after dehydration is completed.
作为本发明的一种优选技术方案：所述助剂组分为酶。As a preferred technical solution of the present invention: the auxiliary component is an enzyme.
作为本发明的一种优选技术方案：所述酶为裂解酶。As a preferred technical solution of the present invention: the enzyme is a lyase.
作为本发明的一种优选技术方案：所述第二步所述的热解气化反应炉为封闭式的回转窑，回转窑适应水草的不均一性，避免了卡顿和堵塞，实现水草均匀的热解气化，并由螺旋进料器根据反应器的运行情况及时调整水草的进料速率，并起到了密封作用。As a preferred technical solution of the present invention: the pyrolysis gasification reaction furnace described in the second step is a closed rotary kiln, and the rotary kiln adapts to the heterogeneity of aquatic plants, avoids jamming and clogging, and realizes uniform aquatic plants. And the screw feeder adjusts the feeding rate of aquatic plants in time according to the operation of the reactor, and plays a sealing role.
作为本发明的一种优选技术方案：所述第三步所述的合成气、生物油和生物炭根据需要调整反应温度、在反应炉的时间及氧气的含量获得不同质量比的产物，冷凝分离净化干燥。As a preferred technical solution of the present invention: the synthesis gas, bio-oil and bio-char described in the third step are adjusted to the reaction temperature, the time in the reaction furnace and the content of oxygen to obtain products with different mass ratios, condensation and separation Clean and dry.
作为本发明的一种优选技术方案：所述裂解酶为纤维素酶和/或果胶酶。As a preferred technical solution of the present invention: the lyase is cellulase and/or pectinase.
有益效果：本申请所述水草高值资源化回收利用的工艺采用的以上技术方案与现有技术相比，具有以下技术效果：Beneficial effect: Compared with the prior art, the above technical scheme adopted by the process for recycling and utilizing aquatic plants with high value in the present application has the following technical effects:
1、本发明所述的深度脱水，可以通过脱水剂的活性成分和助剂实现在微加压的条件下实现将水草的含水率降低到15%~5%。一方面，此方法相较于机械脱水、干化脱水等方法具有更强的可操作性，更能实现规模化脱水；一方面，其脱水所用的仪器简单，并且脱水剂可以实现80%以上的回收利用率，成本低；另一方面，该方法可以在较低能耗下实现含水率的深度降低，脱水率高。1. The deep dehydration of the present invention can reduce the water content of aquatic plants to 15%~5% under the condition of slight pressure through the active ingredients and auxiliary agents of the dehydrating agent. On the one hand, this method has stronger operability compared with methods such as mechanical dehydration and drying dehydration, and can realize large-scale dehydration; The recycling rate is low, and the cost is low; on the other hand, the method can realize the deep reduction of the water content and the high dehydration rate under the lower energy consumption.
2、本发明所述的热解气化反应炉为封闭式的回转窑，可以满足水草的不均性，防止出现堆积、结块和阻塞，适用于不同种类水草同时多种或一种的热解反应。2. The pyrolysis gasification reaction furnace of the present invention is a closed rotary kiln, which can meet the heterogeneity of aquatic plants, prevent accumulation, agglomeration and blockage, and is suitable for the simultaneous heating of multiple or one type of different types of aquatic plants. solution reaction.
3、本发明所述的水草高值资源化回收利用的工艺，实现了水草的深度脱水，为水草的后续资源化提供了更多可能，且通过控制回转窑的反应温度、反应时间、氧含量等可以获得不同的气、液、固产物，并且通过进一步提质为其更广阔的应用提供了可能。且针对水草生长的特殊性，可以在河湖岸边就近建厂，产生的生物炭直接应用于护堤，有助于绿色护堤、生态护堤的实现。3. The process of recycling high-value aquatic plants according to the present invention realizes the deep dehydration of aquatic plants, provides more possibilities for the subsequent recycling of aquatic plants, and controls the reaction temperature, reaction time and oxygen content of the rotary kiln. Different gas, liquid and solid products can be obtained, and its wider application can be provided by further upgrading. In view of the particularity of the growth of aquatic plants, plants can be built near the banks of rivers and lakes, and the generated biochar can be directly applied to the berm, which is conducive to the realization of green berms and ecological berms.
附图说明：Description of drawings:
图1为本申请水草高值资源化回收利用的工艺流程图。Fig. 1 is a process flow diagram of the application for high-value resource recycling of aquatic plants.
具体实施方式Detailed ways
下面结合说明书附图对本发明的具体实施方式作进一步详细的说明。The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
实施例1Example 1
一种水草高值资源化回收利用的工艺，该工艺包括水草深度脱水、气化热解、产物净化收集、产物提质四个流程的工艺，将打捞的水草放置24~48小时，然后切碎，利用脱水剂进行深度脱水，脱水剂分离回收；将获得的固态产物送入无氧或者低氧的回转窑中连续的气化热解；将获得的气体进行冷凝分离净化干燥分别获得合成气和生物油，将获得的固体收集获得生物炭；根据实际需求，对所获得产物进行提质处理，实现了水草的高值资源化利用，并避免了二次污染，具体步骤如下：A process for high-value resource recycling of aquatic plants, the process includes four processes of deep dehydration of aquatic plants, gasification and pyrolysis, product purification and collection, and product quality improvement. The salvaged aquatic plants are placed for 24 to 48 hours, and then chopped. , using a dehydrating agent for deep dehydration, and the dehydrating agent is separated and recovered; the obtained solid product is sent to an oxygen-free or low-oxygen rotary kiln for continuous gasification and pyrolysis; the obtained gas is condensed, separated, purified and dried to obtain synthesis gas and Bio-oil, the obtained solid is collected to obtain biochar; according to the actual demand, the obtained product is upgraded to realize the high-value resource utilization of aquatic plants and avoid secondary pollution. The specific steps are as follows:
第一步：选用水葫芦作为原材料，将打捞的水葫芦在自然条件下放置36小时，其含水率降为70-85%，将其切碎到1~5cm，选用95%的活性成分和5%的纤维素酶混合而成的脱水剂，将其与预处理的水葫芦在0.6Mpa反应器中在200r/min混合搅拌40min，然后将液固分离，此时所获得的固态产物即为深度脱水后的水草，其含水率为8%。向回转窑中通过N2，将其中的空气全部排出，并设定反应温度为400℃，待反应温度达到后，设定螺旋进料器，使水草实现均速连续的进料，并在炉内停留30min，将获得热解气化产生的热解气进行冷凝分离净化干燥分别获得合成气和生物油，收集固体获得生物炭，获得的气、液、固质量比为2：1：2，其中合成气一路作为回转窑加热的预热气，一路通过裂解重整制氢，生物油在此作为燃料为回转窑升温提供热量，生物炭作为护堤材料。The first step: choose water hyacinth as raw material, put the salvaged water hyacinth under natural conditions for 36 hours, its moisture content is reduced to 70-85%, chop it to 1~5cm, select 95% active ingredients and 5 % of cellulase is mixed with the dehydrating agent, which is mixed with the pretreated water hyacinth in a 0.6Mpa reactor at 200r/min for 40min, and then the liquid-solid is separated, and the solid product obtained at this time is the depth The water content of the dehydrated aquatic plants is 8%. Pass N 2 into the rotary kiln to discharge all the air in it, and set the reaction temperature to 400°C. After the reaction temperature is reached, set the screw feeder, so that the aquatic plants can be fed at a uniform speed and continuously. After staying for 30min, the pyrolysis gas produced by pyrolysis gasification is condensed, separated, purified and dried to obtain synthesis gas and bio-oil, respectively, and the solid is collected to obtain bio-char. The mass ratio of gas, liquid and solid obtained is 2:1:2, Among them, the syngas is used as the preheating gas heated by the rotary kiln, and the hydrogen is produced by pyrolysis reforming. The bio-oil is used as the fuel to provide heat for the heating of the rotary kiln, and the bio-char is used as the berm material.
最后应说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求范围当中。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be Modifications or equivalent substitutions are made without departing from the spirit and scope of the technical solutions of the present invention, and they should all be included in the scope of the claims of the present invention.
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