CN114477129A - Modified water coke and its preparation method and use - Google Patents
Modified water coke and its preparation method and use Download PDFInfo
- Publication number
- CN114477129A CN114477129A CN202111342796.5A CN202111342796A CN114477129A CN 114477129 A CN114477129 A CN 114477129A CN 202111342796 A CN202111342796 A CN 202111342796A CN 114477129 A CN114477129 A CN 114477129A
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- water coke
- modified water
- soil
- preparation
- fertilizer
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Classifications
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- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/005—After-treatment of coke, e.g. calcination desulfurization
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
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Abstract
Description
本申请要求享有2020年11月12日向中国国家知识产权局提交的，专利申请号为202011263156.0，发明名称为“改性水焦炭及其制备方法和用途”的在先申请的优先权权益。所述在先申请的全文通过引用的方式结合于本申请中。This application claims to enjoy the priority rights of the prior application submitted to the State Intellectual Property Office of China on November 12, 2020, with the patent application number 202011263156.0 and the invention titled "modified water coke and its preparation method and use". The entire contents of said prior applications are incorporated herein by reference.
技术领域technical field
本发明属于生物质处理与再生利用领域，具体涉及一种改性水焦炭及其制备方法和用途。The invention belongs to the field of biomass treatment and regeneration, and in particular relates to a modified water coke and a preparation method and application thereof.
背景技术Background technique
矿物化肥是当人们发现可溶性的酸性氮磷钾“肥料”，具有刺激植物生长的积极效果而采用的，出自促进农业生产效率的考虑，人们利用了矿藏里的N、P、K(氮、磷、钾)，即从矿石原料加工生产的无机“肥料”，作为促进植物生长的刺激素。但是区域农业的产出一旦严重依赖化肥的“刺激”，该地区的耕作土壤就会偏离生态系统中有机化合物循环的途径而进入土壤质量退化的循环。Mineral fertilizers are used when people find that soluble acidic nitrogen, phosphorus and potassium "fertilizers" have the positive effect of stimulating plant growth. For the purpose of promoting agricultural production efficiency, people use the N, P, K (nitrogen, phosphorus) in the mineral deposits. , potassium), that is, inorganic "fertilizers" produced from ore raw materials, as a stimulant to promote plant growth. However, once the output of regional agriculture relies heavily on the "stimulation" of chemical fertilizers, the cultivated soil in the region will deviate from the organic compound cycle in the ecosystem and enter the cycle of soil quality degradation.
土壤微生物是土壤中最活跃的部分，是土壤中物质转化和养分循环的驱动力，涉及土壤中有机物的分解、腐殖质形成、土壤养分转化和循环等各种过程。而土壤微生物群落、菌群结构又受土壤耕作方式、施肥条件的影响，例如：人口稠密地区对粮食高产的要求，形成了耕地农作物连作这种破坏土壤理化性质的习惯；农作物连作会破坏土壤中微生物的多样性并造成菌群失衡，会引发土壤活性下降和持续的农作物生长障碍。不言而喻，化肥的长期使施用更是严重影响土壤微生物群落、菌群结构的负面因素。这是一种恶性的循环；持续的农作物生长障碍，会形成粮食需求的短缺，粮食短缺加上耕地匮乏，驱动农作物连作和化肥刺激方法的大规模使用，农作物连作和化肥的刺激反过来又推动土壤活性下降、农作物生长障碍的退化循环。即如果在缺乏足够的腐殖质物质的土壤中长期使用无机矿源酸性肥料会造成许多严重的社会、生态问题。因此，亟需开发能够为农业土壤提供“肥料”即生长刺激素的新技术途径。Soil microorganisms are the most active part of soil and are the driving force of material transformation and nutrient cycling in soil, involving various processes such as decomposition of organic matter in soil, humus formation, soil nutrient transformation and cycling. The soil microbial community and bacterial community structure are also affected by soil farming methods and fertilization conditions. For example, the requirements for high grain yield in densely populated areas have formed the habit of continuous cropping of cultivated land, which destroys the physical and chemical properties of soil; continuous cropping will destroy soil. Microbial diversity and resulting imbalances in flora can lead to decreased soil activity and persistent crop failure. It goes without saying that the long-term application of chemical fertilizers is a negative factor that seriously affects the structure of soil microbial communities and flora. This is a vicious cycle; persistent crop growth impediments create a shortage of food demand, which, combined with a lack of arable land, drives continuous cropping and the large-scale use of fertilizer stimulation methods, which in turn drive continuous cropping and fertilizer stimulation. A cycle of degradation in which soil activity declines and crop growth impedes. That is, if the inorganic mineral source acid fertilizer is used for a long time in the soil lacking enough humus material, it will cause many serious social and ecological problems. Therefore, there is an urgent need to develop new technological approaches that can provide "fertilizers", ie, growth-stimulating hormones, to agricultural soils.
据估计：整个中国大陆的湿生物质固废、有机液体废弃残渣所含的能源总共约90MToe(百万吨油当量，相当于63亿桶油)，对应的各种废弃物的比例如下：约55.5％即50MToe(百万吨油当量)左右的农业废弃物残渣，约33.3％即30MToe(百万吨油当量)的林业废弃残渣和约11.1％即10MToe(百万吨油当量)的食物残渣。除了林业残余物(它们是多种用途的优质原料)外，市政和农业湿废物(如污泥和餐厨、厨余)目前完全未进入再生资源开发，已成为主要的城市环境污染源。虽然，一般除了用作动物的饲料外，现有液体残渣的处理方法就主要是：焚化(占60％以上)、填埋、堆肥、厌氧消化四种。所以人们目前除了无害化、减量处理之外仅通过提高燃烧效率从这些液体残渣(包括污水污泥和消化液)中回收含(碳)能源。It is estimated that the total energy contained in wet biomass solid waste and organic liquid waste residues in mainland China is about 90MToe (million tons of oil equivalent, equivalent to 6.3 billion barrels of oil), and the corresponding proportions of various wastes are as follows: about 55.5% is about 50MToe (million tons of oil equivalent) agricultural waste residues, about 33.3% is about 30MToe (million tons of oil equivalent) forestry waste residues and about 11.1% is about 10MToe (million tons of oil equivalent) food residues. Except for forestry residues, which are high-quality raw materials for a variety of purposes, municipal and agricultural wet wastes (such as sludge and kitchen and kitchen waste) have not entered the development of renewable resources at all, and have become major sources of urban environmental pollution. Although, in addition to being used as animal feed, the existing liquid residue treatment methods are mainly: incineration (accounting for more than 60%), landfill, composting, and anaerobic digestion. Therefore, people currently recover (carbon) energy from these liquid residues (including sewage sludge and digestive juice) by improving combustion efficiency in addition to harmless and weight-reducing treatment.
由于焚烧余热回收过程在本质上不属于有机物高效能源转化的途径(因为湿生物质焚烧转化为电能的过程中，其中超过三分之二的生物质能伴随着热能耗散和焚烧加热的二氧化碳排放，而消耗在生物质转化前的干燥阶段)，所以即使目前最流行的WastetoEnergy的电厂，也无法避免对环境有害排放、无法在经济上实现湿生物质残渣处理和处置独立可行的商业逻辑，所以液体或湿生物质固废的处置和回收变得越来越困难。Since the waste heat recovery process of incineration is not a way of efficient energy conversion of organic matter in essence (because in the process of converting wet biomass incineration into electricity, more than two-thirds of the biomass energy is accompanied by thermal energy dissipation and carbon dioxide emissions from incineration heating. , while the consumption is in the drying stage before biomass conversion), so even the most popular WastetoEnergy power plant can not avoid harmful emissions to the environment, and cannot economically realize the independent and feasible business logic of wet biomass residue treatment and disposal, so Disposal and recycling of liquid or wet biomass solid waste is becoming more and more difficult.
因此，如何实现湿生物质或有机液体残渣资源的“清洁”再生，而不需要以当今昂贵且低效的焚化方式转化为热能进行处理利用，并能够有效地对湿有机废物进行含碳有机化合物方向的重组，高效地将低质量的湿生物质、有机液体残留废弃物升级为高价值的各种碳源材料的资源和碳基化合物产品成为亟待解决的技术问题。Therefore, how to achieve "clean" regeneration of wet biomass or organic liquid residue resources without the need to convert it into thermal energy for treatment and utilization by today's expensive and inefficient incineration methods, and to efficiently regenerate wet organic waste with carbon-containing organic compounds The reorganization of direction and the efficient upgrading of low-quality wet biomass and organic liquid residual waste into high-value resources of various carbon source materials and carbon-based compound products have become technical problems that need to be solved urgently.
发明内容SUMMARY OF THE INVENTION
为了改善上述技术问题，本发明提供一种改性水焦炭，所述改性水焦炭为具有海绵状结构的稳定碳化合物。In order to improve the above technical problems, the present invention provides a modified water coke, which is a stable carbon compound with a sponge-like structure.
根据本发明的实施方案，所述改性水焦炭具有持水性能(也称保水性能)。According to an embodiment of the present invention, the modified water coke has water-holding properties (also referred to as water-holding properties).
根据本发明的实施方案，所述改性水焦炭(在任何pH下)不溶于水。According to an embodiment of the present invention, the modified water coke (at any pH) is insoluble in water.
根据本发明的实施方案，所述改性水焦炭具有耐酸和耐碱的特性，即既不溶于碱(高pH)，也不溶于酸(低pH)。According to an embodiment of the present invention, the modified water coke has acid and alkali resistance properties, ie is neither soluble in alkali (high pH) nor acid (low pH).
根据本发明的实施方案，所述改性水焦炭具有与胡敏素类似的碳结构和碳稳定性能。类比天然胡敏素在土壤中的特性，我们视其为自水焦炭改性而得到的“人工胡敏素”。According to an embodiment of the present invention, the modified water coke has a carbon structure and carbon stability properties similar to those of humin. Analogous to the properties of natural humin in soil, we regard it as "artificial humin" obtained by modification of self-water coke.
根据本发明的实施方案，所述改性水焦炭的分子量(MW)不低于10万，例如在10万-1000万之间，示例性为10万、20万、50万、80万、100万、200万、300万、400万、500万、600万、800万、1000万或上述点值任意两两组合之间的任一点值。According to an embodiment of the present invention, the molecular weight ( MW ) of the modified water coke is not less than 100,000, for example, between 100,000 and 10,000,000, exemplarily 100,000, 200,000, 500,000, 800,000, 1 million, 2 million, 3 million, 4 million, 5 million, 6 million, 8 million, 10 million or any point value between any combination of the above point values.
根据本发明的实施方案，所述改性水焦炭以水焦炭为原料，对所述水焦炭进行纳米结构的改性，形成具有海绵状结构的碳化合物，即改性水焦炭。According to an embodiment of the present invention, the modified water coke uses water coke as a raw material, and the water coke is modified by nanostructure to form a carbon compound having a sponge-like structure, that is, modified water coke.
根据本发明的实施方案，所述水焦炭由生物质经水热重组(HTR)处理得到。例如，所述水热重组包括水热碳化(HTC)和/或水热腐殖质化(hydrothermal humification，即HTH)。According to an embodiment of the present invention, the water coke is obtained by hydrothermal reforming (HTR) treatment of biomass. For example, the hydrothermal recombination includes hydrothermal carbonization (HTC) and/or hydrothermal humification (HTH).
优选地，所述水焦炭为结构致密的水焦炭。Preferably, the water coke is a water coke with a dense structure.
根据本发明的实施方案，所述生物质包括但不限于下述物质中的一种、两种或更多种：所有的植物、微生物以及以植物、微生物为食物的动物，以及植物、微生物和动物代谢和/或生产产生的废弃物。例如，所述生物质为除粮食、果实以外的秸秆、树木等木质纤维素、农林废弃物、食品废物或城市固体废物(OFMSW)中的有机部分等中的至少一种。更优选地，所述生物质为含水量高的湿生物质，比如含水量高于30wt％的湿生物质，又如含水量高于40wt％、50wt％、60wt％、70wt％的湿生物质，示例性为植物秸秆、谷壳、植被落叶、园林修剪落叶、景观绿化废物、食品废物或城市固体废物的有机部分等中的至少一种。According to embodiments of the present invention, the biomass includes, but is not limited to, one, two or more of the following: all plants, microorganisms, and animals that feed on plants, microorganisms, and plants, microorganisms, and Waste from animal metabolism and/or production. For example, the biomass is at least one of straws other than grains and fruits, lignocelluloses such as trees, agricultural and forestry wastes, food wastes, or organic parts of municipal solid wastes (OFMSW). More preferably, the biomass is wet biomass with high water content, such as wet biomass with water content higher than 30wt%, or wet biomass with water content higher than 40wt%, 50wt%, 60wt%, 70wt% , exemplified by at least one of plant straw, chaff, fallen leaves of vegetation, fallen leaves of garden trimming, landscaping waste, food waste or organic parts of municipal solid waste, and the like.
本发明还提供所述改性水焦炭的制备方法，包括以水焦炭为原料，对所述水焦炭进行纳米结构的改性，形成具有海绵状结构的碳化合物，即改性水焦炭。The present invention also provides a method for preparing the modified water coke, comprising using the water coke as a raw material, and modifying the nanostructure of the water coke to form a carbon compound with a sponge-like structure, that is, a modified water coke.
根据本发明的实施方案，所述水焦炭由生物质经水热重组(HTR)处理得到。例如，所述水热重组包括水热碳化(HTC)或经过水热腐殖质化(hydrothermal humification，即HTH和水热碳化的混合过程)。优选地，所述生物质具有如上文所述的含义。According to an embodiment of the present invention, the water coke is obtained by hydrothermal reforming (HTR) treatment of biomass. For example, the hydrothermal recombination includes hydrothermal carbonization (HTC) or undergoes hydrothermal humification (ie, a hybrid process of HTH and hydrothermal carbonization). Preferably, the biomass has the meaning as described above.
根据本发明的实施方案，改性纳米结构的方法可以为无氧热解法。According to an embodiment of the present invention, the method of modifying the nanostructures may be an oxygen-free pyrolysis method.
根据本发明的实施方案，形成水焦炭HTC工序的处理温度为200-280℃，例如220-270℃，示例性为200℃、210℃、220℃、230℃、240℃、250℃、260℃、267℃、270℃、280℃。According to embodiments of the present invention, the treatment temperature of the water coke forming HTC process is 200-280°C, such as 220-270°C, exemplarily 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C , 267℃, 270℃, 280℃.
根据本发明的实施方案，本发明对HTC工序或HTC与HTH混合工序的操作顺序不做特别限定，比如HTH工序位于HTC工序之前。According to the embodiments of the present invention, the present invention does not specifically limit the operation sequence of the HTC process or the HTC and HTH mixing process, for example, the HTH process is located before the HTC process.
根据本发明的实施方案，HTH工序的处理温度不低于150℃且小于200℃，例如为160-190℃，示例性为150℃、160℃、170℃、180℃、190℃、191℃、195℃。According to an embodiment of the present invention, the processing temperature of the HTH process is not lower than 150°C and less than 200°C, such as 160-190°C, exemplarily 150°C, 160°C, 170°C, 180°C, 190°C, 191°C, 195°C.
根据本发明的实施方案，所述无氧热解法处理的温度为350-700℃，例如400-650℃，示例性为350℃、400℃、450℃、500℃、550℃、600℃、650℃、700℃。According to an embodiment of the present invention, the temperature of the anaerobic pyrolysis treatment is 350-700°C, such as 400-650°C, exemplarily 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650℃, 700℃.
根据本发明的实施方案，所述无氧热解法处理在惰性气氛下进行。例如，所述惰性气氛可以由氮气和/或氦气提供，优选由氮气提供。进一步地，所述氮气的流量为0.5-3L/min，例如为1-2L/min。According to an embodiment of the present invention, the oxygen-free pyrolysis treatment is carried out under an inert atmosphere. For example, the inert atmosphere may be provided by nitrogen and/or helium, preferably by nitrogen. Further, the flow rate of the nitrogen gas is 0.5-3L/min, for example, 1-2L/min.
根据本发明的实施方案，所述无氧热解法处理的时间为1-5h，例如2-4h，示例性为1h、2h、3h、4h、5h。According to an embodiment of the present invention, the time of the anaerobic pyrolysis treatment is 1-5h, such as 2-4h, exemplarily 1h, 2h, 3h, 4h, 5h.
根据本发明的实施方案，所述无氧热解法处理可以在催化剂存在或不存在条件下进行。例如，所述催化剂为KOH。According to embodiments of the present invention, the anaerobic pyrolysis treatment may be performed in the presence or absence of a catalyst. For example, the catalyst is KOH.
根据本发明的实施方案，所述改性水焦炭的制备方法包括如下步骤：对生物质进行水热重组处理，得到水焦炭；所述水焦炭经无氧热解法处理，得到所述改性水焦炭。According to an embodiment of the present invention, the preparation method of the modified water coke includes the following steps: performing hydrothermal recombination treatment on biomass to obtain water coke; and treating the water coke by anoxic pyrolysis to obtain the modified water coke Water coke.
本发明还提供所述改性水焦炭在土壤、种植业等领域中的应用。例如，用作土壤肥料、促进土壤微生物和土壤动物生态平衡、促进土壤中有毒物质的降解或失活、土壤pH改良、植物肥料、促进植物生长、植物灌溉等。The invention also provides the application of the modified water coke in the fields of soil, planting and the like. For example, it is used as soil fertilizer, promoting the ecological balance of soil microorganisms and soil animals, promoting the degradation or inactivation of toxic substances in soil, soil pH improvement, plant fertilizer, promoting plant growth, plant irrigation, etc.
本发明还提供一种肥料，所述肥料含有上述改性水焦炭或以上述改性水焦炭为原料制备得到的肥料。其中，所述肥料可以为固液混合肥料或固态肥料。优选地，所述肥料用作土壤肥料和/或植物肥料。The present invention also provides a fertilizer, which contains the above-mentioned modified water coke or a fertilizer prepared by using the above-mentioned modified water coke as a raw material. Wherein, the fertilizer may be a solid-liquid mixed fertilizer or a solid fertilizer. Preferably, the fertilizer is used as soil fertilizer and/or plant fertilizer.
根据本发明的实施方案，所述肥料中还添加腐殖酸(胡敏酸或/和富里酸)。优选地，所述腐殖酸可以为天然腐殖酸或人工腐殖酸(也称“人造腐殖酸”)。According to an embodiment of the present invention, humic acid (humic acid or/and fulvic acid) is also added to the fertilizer. Preferably, the humic acid may be natural humic acid or artificial humic acid (also referred to as "artificial humic acid").
根据本发明的实施方案，所述人工腐殖酸含有较多的芳烃和长链脂肪烃结构。例如，所述芳烃的含量为7.30-7.50％，长链脂肪烃的含量为7.10-7.20％。示例性地，所述芳烃的含量为7.43％，长链脂肪烃的含量为7.15％。According to an embodiment of the present invention, the artificial humic acid contains more aromatic hydrocarbons and long-chain aliphatic hydrocarbon structures. For example, the content of aromatic hydrocarbons is 7.30-7.50%, and the content of long-chain aliphatic hydrocarbons is 7.10-7.20%. Exemplarily, the content of aromatic hydrocarbons is 7.43%, and the content of long-chain aliphatic hydrocarbons is 7.15%.
根据本发明的实施方案，所述人工腐殖酸可以根据Fan Yang.et al,Ahydrothermal process to turn waste biomass into artificial fulvic and humicacids for soil remediation,Science of the Total Environment,686(2019),1140-1151中公开的方法制备得到。According to an embodiment of the present invention, the artificial humic acid can be based on Fan Yang. et al, Ahydrothermal process to turn waste biomass into artificial fulvic and humic acids for soil remediation, Science of the Total Environment, 686 (2019), 1140-1151 prepared by the method disclosed in .
根据本发明的实施方案，所述肥料中还含有有机碳介质营养素。According to an embodiment of the present invention, the fertilizer also contains organic carbon medium nutrients.
根据本发明的实施方案，所述有机碳介质营养素的来源包括：上述HTC和/或HTH等水热工序制备过程中得到的液相工作介质；或对所述液相工作介质进一步浓缩循环处理得到。According to an embodiment of the present invention, the sources of nutrients for the organic carbon medium include: the liquid-phase working medium obtained during the preparation of the above-mentioned hydrothermal processes such as HTC and/or HTH; or the liquid-phase working medium is further concentrated and recycled. .
根据本发明的实施方案，所述液相工作介质中含有无机元素，例如钾、磷、氮等中的至少一种。优选地，所述无机元素还可以以其盐的形式存在，比如钾盐、磷酸盐、硝酸盐等形式。优选地，所述无机元素的浓度可调，例如根据改性水焦炭产品的应用进行调整，比如含有设计浓度的无机元素。According to an embodiment of the present invention, the liquid-phase working medium contains inorganic elements, such as at least one of potassium, phosphorus, nitrogen, and the like. Preferably, the inorganic elements may also exist in the form of their salts, such as potassium salts, phosphates, nitrates and the like. Preferably, the concentration of the inorganic element is adjustable, for example, it is adjusted according to the application of the modified water coke product, for example, the inorganic element at the designed concentration is contained.
根据本发明的实施方案，所述液相工作介质中含有不同形式的有机碳。According to an embodiment of the present invention, the liquid phase working medium contains various forms of organic carbon.
根据本发明的实施方案，所述液相工作介质中含有有机物。例如所述有机物为羧酸、糠醛，优选为短链羧酸(意指碳链上的碳原子数小于6的脂肪酸)、羟甲基糠醛(HMF)，示例性为甲酸、乙酸、丙酸、乙酰丙酸、氨基酸等。优选地，所述有机物的浓度可调，例如根据液相工作介质的应用进行调整，比如含有设计浓度的有机物。According to an embodiment of the present invention, the liquid phase working medium contains organic matter. For example, the organic substances are carboxylic acids, furfural, preferably short-chain carboxylic acids (meaning fatty acids with less than 6 carbon atoms on the carbon chain), hydroxymethylfurfural (HMF), exemplified by formic acid, acetic acid, propionic acid, levulinic acid, amino acids, etc. Preferably, the concentration of the organic matter is adjustable, for example, it is adjusted according to the application of the liquid-phase working medium, such as containing a designed concentration of organic matter.
根据本发明的实施方案，所述液相工作介质中还可以含有植物基胺、木质素酚、呋喃、黄腐酸、腐殖酸等中的一种、两种或更多种。优选地，这些物质的浓度可调，例如根据液相工作介质的应用进行调整，比如含有设计浓度。According to an embodiment of the present invention, the liquid phase working medium may further contain one, two or more of plant-based amines, lignin phenols, furans, fulvic acids, humic acids, and the like. Preferably, the concentrations of these substances are adjustable, for example, according to the application of the liquid-phase working medium, such as containing a design concentration.
根据本发明的实施方案，所述液相工作介质不含有或者几乎不含有对植物(优选农作物)、动物、土壤等有害的物质。例如，有害物质包括但不限于有害有机物、有害无机物、重金属元素等中的至少一种。其中，所述几乎不含有意指有害物质的含量低于0.05％，例如低于0.02％，又如低于0.01％或其他的设计含量。According to an embodiment of the present invention, the liquid-phase working medium contains no or almost no substances harmful to plants (preferably crops), animals, soil and the like. For example, the harmful substances include, but are not limited to, at least one of harmful organic substances, harmful inorganic substances, heavy metal elements, and the like. Wherein, the almost free of intentionally means that the content of harmful substances is lower than 0.05%, for example, lower than 0.02%, or lower than 0.01% or other designed contents.
根据本发明的实施方案，浓缩循环的次数至少为一次、两次、三次或更多次。优选至浓缩循环后的液相工作介质中元素的浓度符合农业用产品中所需营养素含量。According to embodiments of the present invention, the number of concentration cycles is at least one, two, three or more. Preferably, the concentration of the elements in the liquid-phase working medium after the concentration cycle corresponds to the desired nutrient content in the agricultural product.
根据本发明的实施方案，在浓缩循环处理过程中，可以包括但不限于调节pH，调节水热碳化进料，调节水热碳化液相工作介质的组分、组分输出量，任选加入或不加入其他反应物、添加剂(例如重金属沉降剂等)等中的一种、两种或更多种处理方式。According to an embodiment of the present invention, in the concentration cycle treatment process, it may include but not limited to adjusting pH, adjusting the hydrothermal carbonization feed, adjusting the components and component output of the hydrothermal carbonization liquid phase working medium, optionally adding or One, two or more treatment methods of other reactants, additives (such as heavy metal sedimentation agents, etc.) are not added.
根据本发明的实施方案，在浓缩循环处理过程中，还可以包括对水热碳化处理得到的水焦炭中含有的有毒物质和/或可能形成有毒物质的元素、离子、基团和/或物质分子从介质水中分离(例如吸附分离)、或者抑制有毒物质的形成。According to an embodiment of the present invention, during the concentration cycle treatment process, the toxic substances contained in the water coke obtained by the hydrothermal carbonization treatment and/or the elements, ions, groups and/or substance molecules that may form toxic substances may also be included. Separation from medium water (eg adsorption separation), or inhibition of the formation of toxic substances.
例如，所述可能形成有毒物质的元素包括但不限于S、Cl、重金属等中的至少一种。For example, the elements that may form toxic substances include, but are not limited to, at least one of S, Cl, heavy metals, and the like.
例如，所述可能形成有毒物质的离子包括但不限于重金属离子等。For example, the ions that may form toxic substances include but are not limited to heavy metal ions and the like.
优选地，所述分离可以通过向水热碳化介质水中加入催化剂和/或通过改变和/或添加介质水的干扰回路等手段实现分离和/或抑制有毒物质(例如氯酚族化合物)的形成。Preferably, the separation can be achieved by adding a catalyst to the hydrothermal carbonization medium water and/or by changing and/or adding interference loops of the medium water and/or inhibiting the formation of toxic substances (eg chlorophenolic compounds).
根据本发明的实施方案，所述肥料含有所述改性水焦炭、腐殖酸和有机碳介质营养素。According to an embodiment of the present invention, the fertilizer contains the modified water coke, humic acid and organic carbon medium nutrients.
本发明还提供上述肥料的制备方法，包括由含有上述改性水焦炭的原料制备得到所述肥料。The present invention also provides a method for preparing the above-mentioned fertilizer, which comprises preparing the above-mentioned fertilizer from a raw material containing the above-mentioned modified water coke.
根据本发明的实施方案，所述肥料的制备方法包括含有所述改性水焦炭、腐殖酸和有机碳介质营养素的原料制备得到。According to an embodiment of the present invention, the preparation method of the fertilizer comprises the preparation of raw materials containing the modified water coke, humic acid and organic carbon medium nutrients.
本发明还提供一种有机碳介质营养素，所述有机碳介质营养素具有如上文所述的含义。The present invention also provides an organic carbon mediator nutrient having the meaning as described above.
本发明还提供上述有机碳介质营养素的制备方法，包括由上述HTC和/或HTH等水热工序制备过程中得到的液相工作介质；或对所述液相工作介质进一步浓缩处理得到。The present invention also provides a method for preparing the above-mentioned organic carbon medium nutrients, including the liquid-phase working medium obtained during the preparation of the above-mentioned hydrothermal processes such as HTC and/or HTH; or obtained by further concentrating the liquid-phase working medium.
本发明还提供一种土壤肥料，所述土壤肥料含有上述改性水焦炭或以含有上述改性水焦炭的原料制备。其中，所述土壤肥料可以为液固混合肥料或固体肥料。The present invention also provides a soil fertilizer, which contains the above-mentioned modified water coke or is prepared from a raw material containing the above-mentioned modified water coke. Wherein, the soil fertilizer can be liquid-solid mixed fertilizer or solid fertilizer.
本发明还提供上述土壤肥料的制备方法，包括由含有上述改性水焦炭的原料制备得到。The present invention also provides a method for preparing the above-mentioned soil fertilizer, which comprises preparing from the raw material containing the above-mentioned modified water coke.
本发明还提供一种土壤调理剂，所述土壤调节剂含有上述改性水焦炭或以含有上述改性水焦炭的原料制备。其中，所述土壤调节剂可以为液固混合调节剂或固体调理剂。The present invention also provides a soil conditioner, which contains the above-mentioned modified water coke or is prepared from a raw material containing the above-mentioned modified water coke. Wherein, the soil conditioner may be a liquid-solid mixed conditioner or a solid conditioner.
本发明还提供上述土壤调理剂的制备方法，包括由含有上改性水焦炭的原料制备得到。The present invention also provides a method for preparing the above-mentioned soil conditioner, which comprises preparing from the raw material containing the upper modified water coke.
本发明还提供一种植物肥料，所述植物肥料含有上述改性水焦炭或以含有上述改性水焦炭的原料制备。其中，所述植物肥料可以为液固混合肥料或固体肥料。The present invention also provides a plant fertilizer, which contains the above-mentioned modified water coke or is prepared from a raw material containing the above-mentioned modified water coke. Wherein, the plant fertilizer can be liquid-solid mixed fertilizer or solid fertilizer.
本发明还提供上述植物肥料的制备方法，包括由含有上述改性水焦炭的原料制备得到所述植物肥料。The present invention also provides a method for preparing the above-mentioned plant fertilizer, comprising preparing the above-mentioned plant fertilizer from a raw material containing the above-mentioned modified water coke.
本发明还提供一种植物生长剂，所述植物生长剂含有上述改性水焦炭或以含有上述改性水焦炭为原料制备。The present invention also provides a plant growth agent, which contains the above-mentioned modified water coke or is prepared by using the above-mentioned modified water coke as a raw material.
本发明还提供上述植物生长剂的制备方法，包括由含有上述改性水焦炭的原料制备得到所述植物生长剂。The present invention also provides a method for preparing the above-mentioned plant growth agent, which comprises preparing the above-mentioned plant growth agent from a raw material containing the above-mentioned modified water coke.
本发明的有益效果：Beneficial effects of the present invention:
(1)发明人意外地发现本发明制得的改性水焦炭与胡敏素的结构和功能相近，能够提供有益土壤生物的良好能源，为土壤微生物和土壤动物提供所需能量和矿物需求。有益的土壤生物缺乏从太阳中获取能量的光合装置，因此必须在土壤上或土壤中含有残余碳物质中生存。碳键内储存的能量可以为这些生物体内的各种代谢反应提供能量。有益的土壤生物(藻类、酵母菌、细菌、真菌线虫、菌根和小动物)具有许多影响土壤肥力和植物健康的有益功能。例如，细菌释放有机酸，有助于土壤中结合的矿物元素的增溶。细菌还释放复杂的多糖(糖基化合物)，帮助创造土壤碎屑(聚集体)。土壤碎屑使土壤具有理想的结构。其他有益的土壤微生物，如放线菌将抗生素释放到土壤中。这些抗生素被植物吸收以防止害虫。抗生素还能在根表面(根际)和根附近的土壤(根际)上创造土壤生物的理想生态平衡。真菌在土壤中也有许多有益的功能。例如，菌根有助于植物根系吸收水分和微量元素。其他真菌分解作物残留物和营养物质为其他生物释放结合养分。真菌释放的许多有机化合物有助于形成腐殖质和土壤碎屑。有益的土壤动物在土壤中形成隧道般的通道。这些通道允许土壤呼吸，而且与大气交换气体。土壤动物还有助于腐殖质的形成，并有助于平衡土壤微生物的浓度。健康的肥沃土壤必须含有足够的含碳化合物，以维持肥沃土壤和健康植物所需的数十亿微观生命是以健康且活性十足的方式形式存在。(1) The inventor unexpectedly found that the modified water coke prepared by the present invention is similar in structure and function to humin, can provide good energy for beneficial soil organisms, and provides required energy and mineral requirements for soil microorganisms and soil animals. Beneficial soil organisms lack the photosynthetic apparatus to harvest energy from the sun and must therefore survive on or in soil containing residual carbon material. The energy stored within the carbon bonds can power various metabolic reactions in these organisms. Beneficial soil organisms (algae, yeast, bacteria, fungal nematodes, mycorrhizae, and small animals) have many beneficial functions that affect soil fertility and plant health. For example, bacteria release organic acids that aid in the solubilization of bound mineral elements in the soil. Bacteria also release complex polysaccharides (glycosylated compounds) that help create soil debris (aggregates). Soil debris gives the soil its ideal structure. Other beneficial soil microbes, such as actinomycetes, release antibiotics into the soil. These antibiotics are absorbed by plants to prevent pests. Antibiotics also create an ideal ecological balance of soil organisms on the root surface (rhizosphere) and the soil near the root (rhizosphere). Fungi also have many beneficial functions in the soil. For example, mycorrhizae help plant roots absorb water and trace elements. Other fungi break down crop residues and nutrients to release bound nutrients for other organisms. Many organic compounds released by fungi contribute to the formation of humus and soil debris. Beneficial soil animals form tunnel-like passages in the soil. These channels allow the soil to respire and exchange gases with the atmosphere. Soil fauna also contributes to the formation of humus and helps to balance the concentration of soil microorganisms. A healthy fertile soil must contain enough carbon-containing compounds to maintain the fertile soil and the billions of microscopic life required for healthy plants to exist in a healthy and fully active form.
(2)本发明制得的改性水焦炭可引导土壤中有毒物质的降解或失活，形成改性水焦炭与土壤腐殖质物质混合体可以更稳定或有效地协助有毒物质(如：尼古丁、黄曲霉毒素、抗生素、香葱和大多数有机农药)的降解。在微生物降解过程中，这些毒素中所含的碳并不是全部释放为CO2。这些有毒分子的一部分，主要是芳香环化合物，被稳定地整合在腐殖质的复杂聚合物中。腐殖质表面有带电的场所，可吸引失活农药和其他有毒的物质。因此，本发明制得的改性水焦结构中的腐殖酸可高效清理土壤中被有毒废物占领累积的场所，许多生物的修复活动主动将含腐殖化合物应用于有毒元素的螯合，结合其他腐殖质物质加速毒物(毒素)的降解清理(破坏各种有毒农药的毒性)。同时改性水焦还协助腐殖酸稳定和灭活土壤中的酶。土壤的酶(复合蛋白)是由土壤中的腐殖质物质通过碳元素的共价键稳定的，从而使得这些酶不太容易被微生物降解。一旦稳定并与腐殖质物质结合，酶活性就会大大降低或停止发挥作用。然而，也有许多共价键在土壤中的pH出现变化时相对较弱，这些酶会被释放。当腐殖质物质的某些成分与土壤酶发生反应时，它们的结合会更加紧密。例如，酚类酶复合物经常附着在粘土上，进一步稳定酶。这些酶稳定过程有助于限制潜在植物病原体的活性。当潜在的植物病原体释放酶来破坏植物的防御，病原体酶就会与腐殖质物质结合，使病原体无法入侵潜在的宿主植物。(2) The modified water coke prepared by the present invention can guide the degradation or deactivation of toxic substances in the soil, and the mixture of modified water coke and soil humic substances can be formed to more stably or effectively assist toxic substances (such as: nicotine, yellow degradation of aspergillus, antibiotics, chives and most organic pesticides). During microbial degradation, not all of the carbon contained in these toxins is released as CO 2 . Some of these toxic molecules, mainly aromatic ring compounds, are stably integrated in the complex polymers of humic substances. There are charged sites on the surface of humus that attract inactivated pesticides and other toxic substances. Therefore, the humic acid in the modified water coke structure prepared by the present invention can efficiently clean up the places occupied and accumulated by toxic wastes in the soil, and many biological restoration activities actively apply humic compounds to the chelation of toxic elements, combined with Other humic substances accelerate the degradation and cleaning of poisons (toxins) (destroying the toxicity of various toxic pesticides). At the same time, the modified water coke also assists the humic acid to stabilize and inactivate the enzymes in the soil. Soil enzymes (complex proteins) are stabilized by the covalent bonds of carbon elements in the humic substances in the soil, making these enzymes less susceptible to microbial degradation. Once stabilized and bound to the humic substance, the enzyme activity is greatly reduced or ceases to function. However, there are also many covalent bonds that are relatively weak when pH changes in the soil, and these enzymes are released. When certain components of humic substances react with soil enzymes, they become more tightly bound. For example, phenolic enzyme complexes are often attached to clays, further stabilizing the enzymes. These enzymatic stabilization processes help limit the activity of potential plant pathogens. When potential plant pathogens release enzymes to disrupt plant defenses, pathogen enzymes bind to humic substances, rendering the pathogen unable to invade potential host plants.
(3)本发明制得的改性水焦炭结合腐殖质物质可以缓冲(中和)土壤pH，释放二氧化碳，起到缓冲土壤氢离子(pH)浓度的作用。实验证据表明在土壤中添加改性水焦有助于中和土壤的pH。酸性和碱性土壤都被中和。一旦土壤被中和，那么由于碱性或酸性条件，许多以前结合在土壤中的、不能用于植物根系的微量元素就会被植物根系利用。改性水焦结合腐殖质的共同作用也从土壤中存在的碳酸钙中释放二氧化碳CO2。释放的二氧化碳被植物吸收，也可能形成碳酸。碳酸将作用于土壤矿物质，释放植物养分，为土壤中的有益生物提供能量、提高土壤持水能力、影响土壤结构、从软矿物中释放植物养分、增加微量矿物的可用性以及总体上提高土壤肥力。土壤温度和水分蒸发速率由改性水焦与腐殖质物质共同作用来稳定。有助于稳定土壤温度，减缓水分蒸发速率。腐殖质物质的绝缘性能有助于保持更均匀的土壤温度，特别是在气候变化迅速的时期，如寒潮或热浪。由于水被束缚在腐殖质中，降低了温度波动，土壤水分不太可能释放到大气中。直接影响的范围，包括植物代谢的变化。促进有机大分子如腐殖酸，黄腐酸化合物进入植物细胞，一旦这些化合物进入植物细胞，植物细胞的膜和各种细胞质成分就会发生几种生化变化，以促进植物代谢的条件改善。(3) The modified water coke prepared by the present invention can buffer (neutralize) soil pH in combination with humic substances, release carbon dioxide, and play the role of buffering soil hydrogen ion (pH) concentration. Experimental evidence suggests that the addition of modified water coke to soils helps to neutralize soil pH. Both acidic and alkaline soils are neutralized. Once the soil is neutralized, many trace elements that were previously bound in the soil and not available to plant roots are made available to plant roots due to alkaline or acidic conditions. The combined action of the modified water coke combined with the humus also releases carbon dioxide CO 2 from the calcium carbonate present in the soil. The carbon dioxide released is absorbed by plants and may also form carbonic acid. Carbonic acid will act on soil minerals, release plant nutrients, provide energy for beneficial organisms in the soil, improve soil water holding capacity, affect soil structure, release plant nutrients from soft minerals, increase the availability of trace minerals, and generally improve soil fertility . Soil temperature and water evaporation rate were stabilized by the combined action of modified water coke and humic substances. Helps stabilize soil temperature and slow the rate of water evaporation. The insulating properties of humic substances help maintain a more uniform soil temperature, especially during periods of rapid climate change, such as cold waves or heat waves. Soil moisture is less likely to be released into the atmosphere because water is trapped in the humus, reducing temperature fluctuations. The range of direct effects includes changes in plant metabolism. Promote the entry of organic macromolecules such as humic acid, fulvic acid compounds into plant cells, once these compounds enter plant cells, several biochemical changes will occur in the membrane and various cytoplasmic components of plant cells to promote the improvement of plant metabolism conditions.
(4)含有本发明所述改性水焦炭、腐殖酸(优选人工腐殖酸)和/或有机碳介质营养素的组合物，能够广泛用于土壤肥料、促进土壤微生物和土壤动物生态平衡、促进土壤中有毒物质的降解或失活、土壤pH改良、植物肥料、促进植物生长、植物灌溉等，且能取得优异的效果。(4) The composition containing the modified water coke of the present invention, humic acid (preferably artificial humic acid) and/or organic carbon medium nutrients can be widely used in soil fertilizers, promoting soil microorganisms and soil animal ecological balance, Promote the degradation or inactivation of toxic substances in the soil, soil pH improvement, plant fertilizer, plant growth promotion, plant irrigation, etc., and can achieve excellent results.
附图说明Description of drawings
图1为本发明改性水焦炭在第1d、3d、6d、10d、17d、21d、26d对土壤pH的影响。Figure 1 shows the effects of the modified water coke of the present invention on soil pH at 1d, 3d, 6d, 10d, 17d, 21d, and 26d.
图2为本发明改性水焦炭在第1d、3d、6d、10d、17d、21d、26d对土壤中有机质含量的影响。Figure 2 shows the effects of the modified water coke of the present invention on the content of organic matter in the soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26d.
图3为本发明改性水焦炭在第1d、3d、6d、10d、17d、21d、26d对土壤中速效磷含量的影响。Figure 3 shows the effects of the modified water coke of the present invention on the content of available phosphorus in soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26d.
图4为本发明改性水焦炭在第1d、3d、6d、10d、17d、21d、26d对土壤中速效氮含量的影响。Figure 4 shows the effects of the modified water coke of the present invention on the content of available nitrogen in soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26d.
图5为本发明改性水焦炭在第1d、3d、6d、10d、17d、21d、26d对土壤中速效钾含量的影响。Figure 5 shows the effects of the modified water coke of the present invention on the content of available potassium in the soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26d.
具体实施方式Detailed ways
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following examples are only for illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the intended protection scope of the present invention.
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。Unless otherwise stated, the starting materials and reagents used in the following examples are commercially available or can be prepared by known methods.
实施例1Example 1
一种改性水焦炭，所述改性水焦炭为具有海绵状结构的碳化合物。A modified water coke, the modified water coke is a carbon compound with a sponge-like structure.
所述改性水焦炭具有持水性能(也称保水性能)。The modified water coke has water-holding properties (also called water-holding properties).
所述改性的水焦炭在任何pH下都不溶于水。The modified water coke is insoluble in water at any pH.
所述改性水焦炭具有耐酸和耐碱的特性，即既不溶于碱(高pH)、也不溶于酸(低pH)。The modified water coke has acid and alkali resistance properties, that is, it is neither soluble in alkali (high pH) nor acid (low pH).
所述改性水焦炭具有与胡敏素类似的碳结构和性能。其中，所述胡敏素可以为天然胡敏素或人工胡敏素。The modified water coke has a carbon structure and properties similar to humin. Wherein, the humin can be natural humin or artificial humin.
所述改性的水焦炭的分子量(MW)不低于10万，例如在10万-1000万之间，示例性为10万、20万、50万、80万、100万、200万、300万、400万、500万、600万、800万、1000万或上述点值任意两两组合之间的任一点值。The molecular weight ( MW ) of the modified water coke is not less than 100,000, for example, between 100,000 and 10,000,000, exemplified by 100,000, 200,000, 500,000, 800,000, 1 million, 2 million, 3 million, 4 million, 5 million, 6 million, 8 million, 10 million or any point value between any combination of the above point values.
所述改性水焦炭以水焦炭为原料，对所述水焦炭进行纳米结构的改性，形成具有海绵状结构的碳化合物，即改性水焦炭。The modified water coke uses water coke as a raw material, and the water coke is modified in nanostructure to form a carbon compound with a sponge-like structure, that is, modified water coke.
在一种实施方式中，所述水焦炭由生物质经水热重组(HTR)处理得到。例如，所述水热重组包括水热碳化(HTC)和/或水热腐殖质化(hydrothermal humification，即HTH)。优选地，所述水焦炭为结构致密的水焦炭。In one embodiment, the water coke is obtained by hydrothermal reforming (HTR) processing of biomass. For example, the hydrothermal recombination includes hydrothermal carbonization (HTC) and/or hydrothermal humification (HTH). Preferably, the water coke is a water coke with a dense structure.
所述生物质包括但不限于下述物质中的一种、两种或更多种：所有的植物、微生物以及以植物、微生物为食物的动物，以及植物、微生物和动物代谢和/或生产产生的废弃物。例如，所述生物质为除粮食、果实以外的秸秆、树木等木质纤维素、农林废弃物、食品废物或城市固体废物(OFMSW)中的有机部分等中的至少一种。更优选地，所述生物质为含水量高的湿生物质，比如含水量高于30wt％的湿生物质，又如含水量高于40wt％、50wt％、60wt％、70wt％的湿生物质，示例性为植物秸秆、谷壳、植被落叶、园林修剪落叶、景观绿化废物、食品废物或城市固体废物的有机部分等中的至少一种。The biomass includes, but is not limited to, one, two or more of the following: all plants, microorganisms, and animals that feed on plants, microorganisms, and plants, microorganisms, and animals that metabolize and/or produce of waste. For example, the biomass is at least one of straws other than grains and fruits, lignocelluloses such as trees, agricultural and forestry wastes, food wastes, or organic parts of municipal solid wastes (OFMSW). More preferably, the biomass is wet biomass with high water content, such as wet biomass with water content higher than 30wt%, or wet biomass with water content higher than 40wt%, 50wt%, 60wt%, 70wt% , exemplified by at least one of plant straw, chaff, fallen leaves of vegetation, fallen leaves of garden trimming, landscaping waste, food waste or organic parts of municipal solid waste, and the like.
在一种实施方式中，所述水热碳化(HTC)工序的处理温度为200-280℃，例如220-270℃，示例性为200℃、210℃、220℃、230℃、240℃、250℃、260℃、267℃、270℃、280℃。In one embodiment, the treatment temperature of the hydrothermal carbonization (HTC) process is 200-280°C, such as 220-270°C, exemplarily 200°C, 210°C, 220°C, 230°C, 240°C, 250°C °C, 260 °C, 267 °C, 270 °C, 280 °C.
在一种实施方式中，HTH工序位于HTC工序之前。In one embodiment, the HTH process precedes the HTC process.
在一种实施方式中，所述HTH工序的处理温度不低于150℃且小于200℃，例如为160-190℃，示例性为150℃、160℃、170℃、180℃、190℃、191℃、195℃。In one embodiment, the processing temperature of the HTH process is not lower than 150°C and less than 200°C, such as 160-190°C, exemplarily 150°C, 160°C, 170°C, 180°C, 190°C, 191°C °C, 195 °C.
实施例2Example 2
实施例1所述改性水焦炭的制备方法，包括以水焦炭为原料，对所述水焦炭进行纳米结构的改性，形成具有海绵状结构的碳化合物，即改性水焦炭。The preparation method of modified water coke described in Embodiment 1 includes using water coke as a raw material, and modifying the water coke with nanostructure to form a carbon compound having a sponge-like structure, that is, modified water coke.
改性纳米结构的方法为无氧热解法。The method for modifying the nanostructures is anaerobic pyrolysis.
所述水焦炭由生物质经水热重组(HTR)处理得到。例如，所述水热重组包括水热碳化(HTC)和/或水热腐殖质化(即HTH)。优选地，所述水焦炭、生物质具有如实施例1中所述的含义。The water coke is obtained by hydrothermal reforming (HTR) treatment of biomass. For example, the hydrothermal recombination includes hydrothermal carbonization (HTC) and/or hydrothermal humification (ie, HTH). Preferably, the water coke and biomass have the meanings as described in Example 1.
在一种实施方式中，所述无氧热解法处理的温度为350-700℃，例如400-650℃，示例性为350℃、400℃、450℃、500℃、550℃、600℃、650℃、700℃。In one embodiment, the temperature of the anaerobic pyrolysis treatment is 350-700°C, such as 400-650°C, exemplarily 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650℃, 700℃.
所述无氧热解法处理在惰性气氛下进行。例如，所述惰性气氛可以由氮气和/或氦气提供，优选由氮气提供。进一步地，所述氮气的流量为0.5-3L/min，例如为1-2L/min。The oxygen-free pyrolysis treatment is carried out under an inert atmosphere. For example, the inert atmosphere may be provided by nitrogen and/or helium, preferably by nitrogen. Further, the flow rate of the nitrogen gas is 0.5-3L/min, for example, 1-2L/min.
所述无氧热解法处理的时间为1-5h，例如2-4h，示例性为1h、2h、3h、4h、5h。The time of the anaerobic pyrolysis treatment is 1-5h, for example, 2-4h, exemplarily 1h, 2h, 3h, 4h, 5h.
所述无氧热解法处理可以在催化剂存在或不存在条件下进行。例如，所述催化剂为KOH。The anaerobic pyrolysis treatment can be carried out in the presence or absence of a catalyst. For example, the catalyst is KOH.
在一种实施方式中，所述改性水焦炭的制备方法包括如下步骤：对生物质进行水热重组处理，得到水焦炭；所述水焦炭经无氧热解法处理，得到所述改性水焦炭。In one embodiment, the preparation method of the modified water coke includes the following steps: performing hydrothermal recombination treatment on biomass to obtain water coke; and processing the water coke by anaerobic pyrolysis to obtain the modified water coke Water coke.
所述改性水焦炭在土壤、种植业等领域中的应用。例如，用作土壤肥料、促进土壤微生物和土壤动物生态平衡、促进土壤中有毒物质的降解或失活、土壤pH改良、植物肥料、促进植物生长、植物灌溉等。The application of the modified water coke in the fields of soil, planting and the like. For example, it is used as soil fertilizer, promoting the ecological balance of soil microorganisms and soil animals, promoting the degradation or inactivation of toxic substances in soil, soil pH improvement, plant fertilizer, promoting plant growth, plant irrigation, etc.
实施例3Example 3
一种肥料，所述肥料含有实施例1所述改性水焦炭或实施例2所述制备方法制得的改性水焦炭或以上述改性水焦炭为原料制备得到的肥料。其中，所述肥料可以为固液混合肥料或固态肥料。优选地，所述肥料用作土壤肥料和/或植物肥料。A fertilizer containing the modified water coke described in Example 1 or the modified water coke prepared by the preparation method described in Example 2 or a fertilizer prepared by using the above modified water coke as a raw material. Wherein, the fertilizer may be a solid-liquid mixed fertilizer or a solid fertilizer. Preferably, the fertilizer is used as soil fertilizer and/or plant fertilizer.
在一种实施方式中，所述肥料中还含有腐殖酸。优选地，所述腐殖酸可以为天然腐殖酸或人工腐殖酸(也称“人造腐殖酸”)。In one embodiment, the fertilizer also contains humic acid. Preferably, the humic acid may be natural humic acid or artificial humic acid (also referred to as "artificial humic acid").
所述人工腐殖酸含有较多的芳烃和长链脂肪烃结构。例如，所述芳烃的含量为7.30-7.50％，长链脂肪烃的含量为7.10-7.20％。示例性地，所述芳烃的含量为7.43％，长链脂肪烃的含量为7.15％。The artificial humic acid contains more aromatic hydrocarbons and long-chain aliphatic hydrocarbon structures. For example, the content of aromatic hydrocarbons is 7.30-7.50%, and the content of long-chain aliphatic hydrocarbons is 7.10-7.20%. Exemplarily, the content of aromatic hydrocarbons is 7.43%, and the content of long-chain aliphatic hydrocarbons is 7.15%.
所述人工腐殖酸可以根据Fan Yang.et al,A hydrothermal process to turnwaste biomass into artificial fulvic and humic acids for soil remediation,Science of the Total Environment,686(2019),1140-1151中公开的方法制备得到。The artificial humic acid can be prepared according to the method disclosed in Fan Yang.et al, A hydrothermal process to turnwaste biomass into artificial fulvic and humic acids for soil remediation, Science of the Total Environment, 686 (2019), 1140-1151 .
在一种实施方式中，所述肥料中还含有有机碳介质营养素。In one embodiment, the fertilizer also contains organic carbon medium nutrients.
所述有机碳介质营养素的来源包括：实施例2所述HTC和/或HTH等水热工序制备过程中得到的液相工作介质；或对所述液相工作介质进一步浓缩循环处理得到。The sources of the organic carbon medium nutrients include: the liquid-phase working medium obtained during the preparation of the hydrothermal process such as HTC and/or HTH described in Example 2; or the liquid-phase working medium is further concentrated and recycled.
所述液相工作介质中含有无机元素，例如钾、磷、氮等中的至少一种。优选地，所述无机元素还可以以其盐的形式存在，比如钾盐、磷酸盐、硝酸盐等形式。优选地，所述无机元素的浓度可调，例如根据改性水焦炭产品的应用进行调整，比如含有设计浓度的无机元素。The liquid-phase working medium contains inorganic elements, such as at least one of potassium, phosphorus, nitrogen and the like. Preferably, the inorganic elements may also exist in the form of their salts, such as potassium salts, phosphates, nitrates and the like. Preferably, the concentration of the inorganic element is adjustable, for example, it is adjusted according to the application of the modified water coke product, for example, the inorganic element at the designed concentration is contained.
所述液相工作介质中含有不同形式的有机碳。The liquid phase working medium contains various forms of organic carbon.
所述液相工作介质中含有有机物。例如所述有机物为羧酸、糠醛，优选为短链羧酸(意指碳链上的碳原子数小于6的脂肪酸)、羟甲基糠醛(HMF)，示例性为甲酸、乙酸、丙酸、乙酰丙酸、氨基酸等。优选地，所述有机物的浓度可调，例如根据液相工作介质的应用进行调整，比如含有设计浓度的有机物。The liquid phase working medium contains organic matter. For example, the organic substances are carboxylic acids, furfural, preferably short-chain carboxylic acids (meaning fatty acids with less than 6 carbon atoms on the carbon chain), hydroxymethylfurfural (HMF), exemplified by formic acid, acetic acid, propionic acid, levulinic acid, amino acids, etc. Preferably, the concentration of the organic matter is adjustable, for example, it is adjusted according to the application of the liquid-phase working medium, such as containing a designed concentration of the organic matter.
在一种实施方式中，所述液相工作介质中还可以含有植物基胺、木质素酚、呋喃、黄腐酸、腐殖酸等中的一种、两种或更多种。优选地，这些物质的浓度可调，例如根据液相工作介质的应用进行调整，比如含有设计浓度。In one embodiment, the liquid-phase working medium may further contain one, two or more of plant-based amines, lignin phenols, furans, fulvic acids, humic acids, and the like. Preferably, the concentrations of these substances are adjustable, for example, according to the application of the liquid-phase working medium, such as containing a design concentration.
在一种实施方式中，所述液相工作介质不含有或者几乎不含有对植物(优选农作物)、动物、土壤等有害的物质。例如，有害物质包括但不限于有害有机物、有害无机物、重金属元素等中的至少一种。其中，所述几乎不含有意指有害物质的含量低于0.05％，例如低于0.02％，又如低于0.01％或其他的设计含量。In one embodiment, the liquid-phase working medium contains no or almost no substances harmful to plants (preferably crops), animals, soil and the like. For example, the harmful substances include, but are not limited to, at least one of harmful organic substances, harmful inorganic substances, heavy metal elements, and the like. Wherein, the almost free of intentionally means that the content of harmful substances is lower than 0.05%, for example, lower than 0.02%, or lower than 0.01% or other designed contents.
其中，浓缩循环的次数至少为一次、两次、三次或更多次。优选至浓缩循环后的液相工作介质中元素的浓度符合农业用产品中所需营养素含量。Wherein, the number of concentration cycles is at least one, two, three or more times. Preferably, the concentration of the elements in the liquid-phase working medium after the concentration cycle corresponds to the desired nutrient content in the agricultural product.
在一种实施方式中，在浓缩循环处理过程中，可以包括但不限于调节pH，调节水热碳化进料，调节水热碳化液相工作介质的组分、组分输出量，任选加入或不加入其他反应物、添加剂(例如重金属沉降剂等)等中的一种、两种或更多种处理方式。In one embodiment, during the concentration cycle treatment process, it may include, but is not limited to, adjusting pH, adjusting the hydrothermal carbonization feed, adjusting the components and component output of the hydrothermal carbonization liquid phase working medium, optionally adding or One, two or more treatment methods of other reactants, additives (such as heavy metal sedimentation agents, etc.) are not added.
在一种实施方式中，在浓缩循环处理过程中，还可以包括对水热碳化处理得到的水焦炭中含有的有毒物质和/或可能形成有毒物质的元素、离子、基团和/或物质分子从介质水中分离(例如吸附分离)、或者抑制有毒物质的形成。In one embodiment, during the concentration cycle treatment process, the toxic substances contained in the water coke obtained by the hydrothermal carbonization treatment and/or the elements, ions, groups and/or substance molecules that may form toxic substances may also be included. Separation from medium water (eg adsorption separation), or inhibition of the formation of toxic substances.
例如，所述可能形成有毒物质的元素包括但不限于S、Cl、重金属等中的至少一种。For example, the elements that may form toxic substances include, but are not limited to, at least one of S, Cl, heavy metals, and the like.
例如，所述可能形成有毒物质的离子包括但不限于重金属离子等。For example, the ions that may form toxic substances include but are not limited to heavy metal ions and the like.
优选地，所述分离可以通过向水热碳化介质水中加入催化剂和/或通过改变和/或添加介质水的干扰回路等手段实现分离和/或抑制有毒物质(例如氯酚族化合物)的形成。Preferably, the separation can be achieved by adding a catalyst to the hydrothermal carbonization medium water and/or by changing and/or adding interference loops of the medium water and/or inhibiting the formation of toxic substances (eg chlorophenolic compounds).
在一种实施方式中，所述肥料含有所述改性水焦炭、腐殖酸和有机碳介质营养素。In one embodiment, the fertilizer contains the modified water coke, humic acid and organic carbon medium nutrients.
上述肥料的制备方法，包括由含有实施例1所述改性水焦炭和/或实施例2所述制备方法制得的改性水焦炭的原料制备得到所述肥料。The preparation method of the above fertilizer includes preparing the fertilizer from the raw material containing the modified water coke described in Embodiment 1 and/or the modified water coke obtained by the preparation method described in Embodiment 2.
在一种实施方式中，所述肥料的制备方法包括含有实施例1所述改性水焦炭和/或实施例2所述制备方法制得的改性水焦炭、腐殖酸和有机碳介质营养素的原料制备得到。In one embodiment, the preparation method of the fertilizer comprises the modified water coke containing the modified water coke described in Example 1 and/or the modified water coke obtained by the preparation method described in Example 2, humic acid and organic carbon medium nutrients raw materials were prepared.
实施例4Example 4
一种有机碳介质营养素，所述有机碳介质营养素具有如实施例3所述的含义。An organic carbon mediator nutrient having the meaning as described in Example 3.
上述有机碳介质营养素的制备方法，包括由实施例2所述HTC和/或HTH等水热工序制备过程中得到的液相工作介质；或对所述液相工作介质进一步浓缩处理得到。The preparation method of the above-mentioned organic carbon medium nutrients includes the liquid phase working medium obtained during the preparation of the hydrothermal process such as HTC and/or HTH described in Example 2; or obtained by further concentrating the liquid phase working medium.
实施例5Example 5
一种土壤肥料，所述土壤肥料含有实施例1所述改性水焦炭和/或实施例2所述制备方法制得的改性水焦炭或以含有上述改性水焦炭的原料制备。其中，所述土壤肥料可以为液固混合肥料或固体肥料。A soil fertilizer, the soil fertilizer containing the modified water coke described in Example 1 and/or the modified water coke prepared by the preparation method described in Example 2 or prepared from the raw material containing the above modified water coke. Wherein, the soil fertilizer can be liquid-solid mixed fertilizer or solid fertilizer.
上述土壤肥料的制备方法，包括由含有实施例1所述改性水焦炭和/或实施例2所述制备方法制得的改性水焦炭的原料制备得到。The above-mentioned preparation method of soil fertilizer includes preparation from raw materials containing the modified water coke described in Embodiment 1 and/or the modified water coke obtained by the preparation method described in Embodiment 2.
实施例6Example 6
一种土壤调理剂，所述土壤调节剂含有实施例1所述改性水焦炭和/或实施例2所述制备方法制得的改性水焦炭或以含有上述改性水焦炭的原料制备。其中，所述土壤调节剂可以为液固混合调节剂或固体调理剂。A soil conditioner, the soil conditioner contains the modified water coke described in Example 1 and/or the modified water coke prepared by the preparation method described in Example 2, or is prepared from the raw material containing the above modified water coke. Wherein, the soil conditioner may be a liquid-solid mixed conditioner or a solid conditioner.
上述土壤调理剂的制备方法，包括由含有实施例1所述改性水焦炭和/或实施例2所述制备方法制得的改性水焦炭的原料制备得到。The preparation method of the above soil conditioner includes preparing from the raw material containing the modified water coke described in Example 1 and/or the modified water coke prepared by the preparation method described in Embodiment 2.
实施例7Example 7
一种植物肥料，所述植物肥料含有实施例1所述改性水焦炭和/或实施例2所述制备方法制得的改性水焦炭或以含有上述改性水焦炭的原料制备。其中，所述植物肥料可以为液固混合肥料或固体肥料。A plant fertilizer, the plant fertilizer contains the modified water coke described in Example 1 and/or the modified water coke prepared by the preparation method described in Example 2, or is prepared from the raw material containing the above-mentioned modified water coke. Wherein, the plant fertilizer can be liquid-solid mixed fertilizer or solid fertilizer.
上述植物肥料的制备方法，包括由含有实施例1所述改性水焦炭和/或实施例2所述制备方法制得的改性水焦炭的原料制备得到所述植物肥料。The preparation method of the above-mentioned plant fertilizer includes preparing the plant fertilizer from raw materials containing the modified water coke described in Embodiment 1 and/or the modified water coke obtained by the preparation method described in Embodiment 2.
实施例8Example 8
一种植物生长剂，所述植物生长剂含有实施例1所述改性水焦炭和/或实施例2所述制备方法制得的改性水焦炭或以含有上述改性水焦炭为原料制备。A plant growth agent, the plant growth agent contains the modified water coke described in Example 1 and/or the modified water coke prepared by the preparation method described in Example 2, or is prepared from the modified water coke containing the above-mentioned modified water coke.
上述植物生长剂的制备方法，包括由含有实施例1所述改性水焦炭和/或实施例2所述制备方法制得的改性水焦炭改性水焦炭的原料制备得到所述植物生长剂。The preparation method of the above-mentioned plant growth agent includes preparing the plant growth agent from raw materials containing the modified water coke described in Example 1 and/or the modified water coke obtained by the preparation method described in Example 2. .
实施例9：样品的制备Example 9: Preparation of samples
原料：选用城市污泥的干污泥为原料，其中城市污泥的来源为污水处理厂的剩余污泥，其含水率为90.4％，经105℃烘干至恒重即得到干污泥。将上述原料5g，使用如下方法分别处理：Raw material: The dry sludge of municipal sludge is selected as the raw material. The source of municipal sludge is the excess sludge of sewage treatment plant, and its moisture content is 90.4%. Dry sludge is obtained by drying at 105°C to constant weight. With above-mentioned raw material 5g, use the following method to handle respectively:
(1)热解：气氛炉真空条件下，700℃下无氧热解法处理1h，得到样品1。(1) Pyrolysis: Under the vacuum condition of the atmosphere furnace, the sample 1 was obtained by anaerobic pyrolysis treatment at 700°C for 1 hour.
(2)水热碳化：向5g干污泥中加入145mL水，然后于200℃，自有压力(无外加压力)下，水热碳化1h，得到样品2。(2) Hydrothermal carbonization: Add 145 mL of water to 5 g of dry sludge, and then perform hydrothermal carbonization at 200° C. under its own pressure (no external pressure) for 1 h to obtain sample 2.
(3)水热碳化热解：向5g干污泥中加入145mL水，然后于200℃，自有压力(无外加压力)下，水热碳化1h，固液分离，固体105℃烘干至恒重，在气氛炉真空条件下，700℃下无氧热解法处理1h，得到改性水焦炭样品3，为具有海绵状结构的碳材料。(3) Hydrothermal carbonization and pyrolysis: add 145mL of water to 5g of dry sludge, then at 200℃, under its own pressure (no external pressure), hydrothermally carbonize for 1h, separate solid from liquid, and dry the solid at 105℃ to constant The modified water coke sample 3 was obtained by anaerobic pyrolysis treatment at 700 °C for 1 h under the vacuum condition of the atmosphere furnace, which is a carbon material with a sponge-like structure.
(4)水热碳化热解活化：200℃，自有压力(无外加压力)下，水热碳化1h，固液分离，固体105℃烘干至恒重，在气氛炉真空条件下，700℃下无氧热解法处理1h，再用浓度为3mol/L的氢氧化钾溶液作为活化剂，按照固液比为1:45，浸泡8h，使用超纯水清洗至清洗液pH值为中性，150℃烘干至恒重，得到改性水焦炭样品4。(4) Hydrothermal carbonization and pyrolysis activation: 200 °C, under its own pressure (no external pressure), hydrothermal carbonization for 1 hour, solid-liquid separation, solid-liquid drying at 105 °C to constant weight, under vacuum conditions in an atmosphere furnace, 700 °C Under the anaerobic pyrolysis method for 1h, then use potassium hydroxide solution with a concentration of 3mol/L as an activator, according to the solid-liquid ratio of 1:45, soak for 8h, and use ultrapure water to wash until the pH value of the cleaning solution is neutral , and dried at 150°C to constant weight to obtain modified water coke sample 4.
(5)重复方法(4)，不同之处在于使用浓度为6mol/L的硝酸水溶液作为活化剂，得到改性水焦炭样品5。(5) Method (4) was repeated, except that an aqueous solution of nitric acid with a concentration of 6 mol/L was used as the activator to obtain modified
(6)重复方法(4)，不同之处在于使用浓度为3mol/L的氢氧化钠溶液作为活化剂，得到改性水焦炭样品6。(6) Method (4) was repeated, except that a sodium hydroxide solution with a concentration of 3 mol/L was used as the activator to obtain modified water coke sample 6.
测试例1：比表面积测定Test Example 1: Measurement of Specific Surface Area
将实施例9中的样品1-4分别磨碎后，过200目筛，然后采用物理吸附仪测定其比表面积，结果如下表1所示。The samples 1-4 in Example 9 were respectively ground, passed through a 200-mesh sieve, and then the specific surface area was measured by a physical adsorption instrument. The results are shown in Table 1 below.
表1Table 1
表1结果表明，生物质原料先经过水热碳化处理，再经过无氧热解法处理后得到的改性水焦炭，比单纯经过无氧热解法处理后的样品能够显著提高样品的比表面积；而经过活性改性处理后能够进一步提高改性水焦炭的比表面积(可提高约两倍)。因此，本发明通过采用水热碳化和无氧热解法相结合的方式，通过二者协同作用能够显著提高改性水焦炭的比表面积。The results in Table 1 show that the modified water coke obtained after the biomass raw material is first treated by hydrothermal carbonization and then treated by anaerobic pyrolysis method can significantly improve the specific surface area of the sample compared with the sample treated by anaerobic pyrolysis method. ; And the specific surface area of modified water coke can be further increased after active modification treatment (can be increased by about two times). Therefore, the present invention can significantly increase the specific surface area of the modified water coke through the combination of the hydrothermal carbonization and the anaerobic pyrolysis method through the synergistic effect of the two.
测试例2：碘吸附值测定Test Example 2: Determination of Iodine Adsorption Value
按照《木质活性炭试验方法碘吸附值的测定(GB/T 12496.8-1999)》测定改性水焦炭样品4、样品5、样品6的碘吸附值，结果如下表2所示。The iodine adsorption values of modified
表2Table 2
测试例3：有效磷和钾的含量测定Test Example 3: Determination of Available Phosphorus and Potassium Content
按照复混肥料中有效磷含量的测定方法，测定干污泥原料和改性水焦炭样品3的有效磷含量；并按照王水提取-电感耦合等离子体质谱法测定改性水焦炭样品3的钾含量。结果如下表3所示。According to the method for measuring available phosphorus content in compound fertilizer, the available phosphorus content of dry sludge raw material and modified water coke sample 3 was determined; and the potassium content of modified water coke sample 3 was determined according to aqua regia extraction-inductively coupled plasma mass spectrometry content. The results are shown in Table 3 below.
表3table 3
注：“-”指未测定。Note: "-" means not determined.
由上表结果可知：干污泥经过水热碳化及无氧热解法处理改性后，有效磷的含量得到显著的提升。It can be seen from the results in the above table that the content of available phosphorus was significantly increased after the dry sludge was treated and modified by hydrothermal carbonization and anaerobic pyrolysis.
测试例3：吸附能力测试Test Example 3: Adsorption Capacity Test
将实施例9制备的样品5、样品6和椰壳活性炭样品(样品Y，其碘值为997mg/g)分别与水热处理液(吸附前液体)混合，其中样品的用量均为水热处理液质量的10％，常温震荡过夜后，检测溶液中COD、氨氮含量。其中：COD含量按照重铬酸盐法测定；氨氮含量按纳氏试剂分光光度法测定，结果如下表4所示。
表4Table 4
由上表结果可知：与市售的椰壳活性炭相比，本发明制得的改性水焦炭与市售椰壳活性炭在COD方面吸附能力相当，但氨氮吸附能力显著高于椰壳活性炭。As can be seen from the results in the above table: compared with the commercially available coconut shell activated carbon, the modified water coke prepared by the present invention is comparable to the commercially available coconut shell activated carbon in terms of COD adsorption capacity, but the ammonia nitrogen adsorption capacity is significantly higher than that of the coconut shell activated carbon.
测试例4：缓释作用测试Test Example 4: Sustained Release Test
(1)分别将测试例3中样品5和样品6吸附水热处理液后得到的样品在105℃条件下干燥至恒重后，加入超纯水，其中干燥后的样品与水的质量比为1:10。常温震荡浸泡过夜后(计为浸泡第1次)，检测水溶液中的COD和氨氮含量。(1) The samples obtained after the adsorption of the hydrothermal treatment solution in
(2)将步骤(1)混合物中的固体分离，以相同的干燥条件再次干燥，再加入与步骤(1)相同质量的水，如此重复共3次(分别计为浸泡第2次、第3次和第4次)，分别测定溶液中COD、氨氮含量，汇总于下表中。(2) Separate the solid in the mixture in step (1), dry it again under the same drying conditions, and then add water of the same quality as in step (1), repeat this for a total of 3 times (respectively counted as the second soaking, the third soaking The second and fourth times), the COD and ammonia nitrogen contents in the solution were measured respectively, which are summarized in the following table.
表5table 5
由上表结果可知：本发明制得的改性水焦炭具有缓释作用。It can be seen from the results in the above table that the modified water coke prepared by the present invention has a slow-release effect.
测试例5：改善土壤营养的作用Test Example 5: Effect of improving soil nutrition
取过2mm筛的风干土，按占总土量1％的量混入测试例3中吸附后的改性水焦炭样品5，混合均匀后分别置于20个相同的塑料容器中培养，每个容器装土量为200g，未混入改性水焦炭的风干土同样装入另外20个塑料容器中培养作为对照组处理。实验过程中，用称量法控制盆中土壤水分在28％左右(相当于75％田间持水量)。Take the air-dried soil that has passed through a 2mm sieve, and mix it into the adsorbed modified
土壤培养初期分别在第1d、3d、6d、10d、17d、21d、26d取土样进行理化分析，共历时26d。土壤样品风干后，四分法把部分土样过20目和100目土筛后用于土壤质量指标的测定。In the early stage of soil culture, soil samples were taken on the 1st, 3rd, 6th, 10th, 17th, 21d, and 26d for physical and chemical analysis, which lasted for 26d. After the soil samples were air-dried, part of the soil samples were passed through 20-mesh and 100-mesh soil sieves for the determination of soil quality indicators.
其中，土壤理化性质均按鲍士旦的方法测定。Among them, soil physical and chemical properties were determined according to Bao Shidan's method.
有机质含量采用重铬酸钾容量法——外加热法测定；pH值采用pH计法(水土比5：1)；速效氮含量采用碱解扩散法测定；速效磷含量采用0.5mol/L碳酸氢钠浸提——钼锑抗比色法测定；速效钾含量采用1mol/L醋酸铵提取——ICP-OES法测定。The content of organic matter was determined by potassium dichromate volumetric method-external heating method; the pH value was determined by pH meter method (water-soil ratio 5:1); the content of available nitrogen was determined by alkaline hydrolysis diffusion method; the content of available phosphorus was determined by 0.5mol/L hydrogen carbonate Sodium leaching—determined by molybdenum antimony anti-colorimetric method; the content of available potassium was determined by 1mol/L ammonium acetate extraction—ICP-OES method.
图1为本发明改性水焦炭在第1d、3d、6d、10d、17d、21d、26d对土壤pH的影响。图2为本发明改性水焦炭在第1d、3d、6d、10d、17d、21d、26d对土壤中有机质含量的影响。图3为本发明改性水焦炭在第1d、3d、6d、10d、17d、21d、26d对土壤中速效磷含量的影响。图4为本发明改性水焦炭在第1d、3d、6d、10d、17d、21d、26d对土壤中速效氮含量的影响。图5为本发明改性水焦炭在第1d、3d、6d、10d、17d、21d、26d对土壤中速效钾含量的影响。从图中可以看出：添加了改性水焦炭的土壤pH值更稳定，并显著提高了土壤有机质、速效氮和速效钾的含量，尤其是对提高土壤中速效钾含量效果显著(孵育20d后，添加改性水焦炭的土壤中速效钾含量比未添加改性水焦炭的土壤中速效钾含量提高近一倍)。由此表明改性水焦炭可显著提高土壤中有效营养物质的含量，从而改善土壤营养结构，并为植物提供更好的生长环境，以促进植物生长。Figure 1 shows the effects of the modified water coke of the present invention on soil pH at 1d, 3d, 6d, 10d, 17d, 21d, and 26d. Figure 2 shows the effects of the modified water coke of the present invention on the content of organic matter in the soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26d. Figure 3 shows the effects of the modified water coke of the present invention on the content of available phosphorus in soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26d. Figure 4 shows the effects of the modified water coke of the present invention on the content of available nitrogen in soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26d. Figure 5 shows the effects of the modified water coke of the present invention on the content of available potassium in the soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26d. It can be seen from the figure that the soil pH value added with modified water coke is more stable, and the content of soil organic matter, available nitrogen and available potassium is significantly increased, especially the effect of increasing the content of available potassium in the soil is significant (after 20d incubation , the content of available potassium in the soil with modified water coke was nearly doubled compared with that in the soil without modified water coke). This shows that the modified water coke can significantly increase the content of available nutrients in the soil, thereby improving the nutrient structure of the soil, and providing a better growth environment for plants to promote plant growth.
测试例6：水热处理液中的营养成分含量及重金属浓度测定Test Example 6: Determination of nutrient content and heavy metal concentration in hydrothermal treatment solution
将污水处理厂的剩余污泥(含水率为90.4％，新鲜污泥)60g，第一次加水90mL，200℃停留时间1h，搅拌速度为300rpm，记为循环0次水热处理液；结束后过滤，取滤液90mL再加入60g新鲜污泥，200℃停留时间1h，搅拌速度为300rpm，记为循环1次水热处理液；结束后过滤，取滤液90mL再加入60g新鲜污泥，200℃停留时间1h，搅拌速度为300rpm，记为循环2次水热处理液。Add 60g of excess sludge (water content 90.4%, fresh sludge) from the sewage treatment plant, add 90mL of water for the first time, stay at 200°C for 1h, stir at 300rpm, and record it as a hydrothermal treatment solution for 0 cycles; filter after the end , take 90mL of the filtrate and add 60g of fresh sludge, the residence time at 200°C is 1h, the stirring speed is 300rpm, and it is recorded as 1 cycle of hydrothermal treatment solution; after filtering, take 90mL of the filtrate and add 60g of fresh sludge, and the residence time at 200°C is 1h. , the stirring speed is 300rpm, and it is recorded as the hydrothermal treatment liquid circulating twice.
在ICP-MS中测定循环2次后，过滤得到的最终滤液中的重金属含量(mg/L)。测试结果如表6所示。The heavy metal content (mg/L) in the final filtrate obtained by filtration was measured in ICP-MS for 2 cycles. The test results are shown in Table 6.
在每次循环过程中分别取水热处理液5mL测定其中的COD、氨氮、总氮、总磷含量。During each cycle, 5 mL of the hydrothermal treatment solution was taken to measure the contents of COD, ammonia nitrogen, total nitrogen and total phosphorus.
其中：COD含量按照重铬酸盐法测定；总氮含量的测试方法为碱性过硫酸钾消解紫外分光光度法；总磷含量的测试方法为中性过硫酸钾消解分光光度法；氨氮含量按纳氏试剂分光光度法测定。测试结果如表7所示。Among them: COD content is determined by dichromate method; the test method of total nitrogen content is alkaline potassium persulfate digestion UV spectrophotometry; the test method of total phosphorus content is neutral potassium persulfate digestion spectrophotometry; ammonia nitrogen content is determined by Nessler's reagent spectrophotometric determination. The test results are shown in Table 7.
表6Table 6
表7Table 7
如表7所示，水热处理液的循环利用，有利于富集水热处理液中的营养成分，以提高营养物质浓度，进而减少水的用量。As shown in Table 7, the recycling of the hydrothermal treatment liquid is conducive to enriching the nutrients in the hydrothermal treatment liquid, so as to increase the concentration of nutrients and reduce the amount of water.
测试例7：污泥水热碳化后得到的水热处理液和水焦炭中腐殖酸的含量测定Test Example 7: Determination of the content of humic acid in the hydrothermal treatment solution and water coke obtained after the hydrothermal carbonization of sludge
将新鲜污泥50g，加水100mL，于密封的水热碳化反应釜中发生水热碳化反应，搅拌速度300rpm，升温至200℃，保温1h。反应结束后，反应物料冷却至室温后，进行固液分离。向分离出来的水热处理液中加入盐酸，将pH值调至2，静置30min，离心，除去上清液，用1mol/L氨水溶解沉淀物，并定容至100ml，然后用容量法测定腐殖酸的含量(即为水热处理液中腐殖酸的含量)；Add 50 g of fresh sludge, add 100 mL of water, and conduct a hydrothermal carbonization reaction in a sealed hydrothermal carbonization reaction kettle. The stirring speed is 300 rpm, the temperature is raised to 200 °C, and the temperature is kept for 1 h. After the reaction, the reaction mass was cooled to room temperature, and then solid-liquid separation was performed. Add hydrochloric acid to the separated hydrothermal treatment solution, adjust the pH value to 2, stand for 30min, centrifuge, remove the supernatant, dissolve the precipitate with 1mol/L ammonia water, and set the volume to 100ml, and then use the volumetric method to determine the rot. The content of humic acid (that is, the content of humic acid in the hydrothermal treatment solution);
另将上述剩余的沉淀物(水焦炭)105℃烘干至恒重后，称取约0.2g样品，加入100mL 0.03mol/L焦磷酸钠溶液，80℃水浴1.5h，抽滤，弃掉滤渣，向滤液中加入盐酸，将pH值调至2，静置30min，离心，除去上清液，用1mol/L氨水溶解沉淀物，并定容至100ml，然后用容量法测定腐殖酸的含量(即为水焦炭中腐殖酸的含量)。In addition, after drying the remaining precipitate (water coke) at 105°C to constant weight, weigh about 0.2g of the sample, add 100mL of 0.03mol/L sodium pyrophosphate solution, bathe at 80°C for 1.5h, filter with suction, and discard the filter residue , add hydrochloric acid to the filtrate, adjust the pH value to 2, stand for 30min, centrifuge, remove the supernatant, dissolve the precipitate with 1mol/L ammonia water, and dilute to 100ml, and then determine the content of humic acid by volumetric method (that is, the content of humic acid in water coke).
其中：容量法测定腐殖酸含量的方法，步骤如下：Wherein: the method for volumetric determination of humic acid content, the steps are as follows:
依次准确吸取10.0mL上述两种待测液于250mL锥形瓶中，分别加入5.0mL0.8mol/L重铬酸钾溶液，缓慢加入20mL浓硫酸，于沸水浴中加热氧化30min。将氧化后的溶液从沸水浴中取下，冷却至室温，加入70mL水，5～6滴邻菲罗啉-亚铁混合指示剂，用硫酸亚铁标准滴定液(0.2mol/L)滴定，溶液由橙色转为亮绿色，最后变为暗红色为终点。记录硫酸亚铁标准滴定液消耗的体积(V)。除不加试样外，按照以上步骤进行空白实验。两次空白实验的滴定数绝对差值不大于0.05mL时，V0值为两次算数平均值。Accurately draw 10.0 mL of the above two solutions to be tested in a 250 mL conical flask, respectively, add 5.0 mL of 0.8 mol/L potassium dichromate solution, slowly add 20 mL of concentrated sulfuric acid, and heat and oxidize in a boiling water bath for 30 min. Remove the oxidized solution from the boiling water bath, cool it to room temperature, add 70 mL of water, 5-6 drops of phenanthroline-ferrous mixed indicator, and titrate with ferrous sulfate standard titration solution (0.2mol/L), The solution turned from orange to bright green and finally to dark red as the end point. Record the volume (V) of the ferrous sulfate standard titrant consumed. The blank experiment was carried out according to the above steps except that no sample was added. When the absolute difference of the titration numbers of the two blank experiments is not more than 0.05mL, the V 0 value is the arithmetic mean of the two times.
水溶性腐植酸含量ω以质量分数(％)表示，按下式计算：The water-soluble humic acid content ω is expressed in mass fraction (%) and calculated as follows:
式中：where:
c——滴定试样及空白实验时使用的硫酸亚铁标准滴定液的浓度，单位为摩尔每升(mol/L)；c——the concentration of ferrous sulfate standard titration solution used in the titration sample and blank experiment, the unit is mole per liter (mol/L);
V0——空白实验时，消耗硫酸亚铁标准滴定液的浓度，单位为摩尔每升(mol/L)；V 0 ——During the blank experiment, the concentration of the standard titration solution of ferrous sulfate consumed, the unit is mole per liter (mol/L);
V——测定试样时，硫酸亚铁标准滴定液的浓度，单位为摩尔每升(mol/L)；V——The concentration of ferrous sulfate standard titration solution when measuring the sample, the unit is mole per liter (mol/L);
0.003——与1.00硫酸亚铁标准滴定液相当的碳含量的数值；0.003——the value of carbon content equivalent to 1.00 ferrous sulfate standard titration solution;
1.724——有机碳换算成有机质的系数；1.724——the coefficient of converting organic carbon into organic matter;
1.43——氧化校正系数1.3与腐植酸沉淀系数1.1之乘积；1.43——The product of oxidation correction coefficient 1.3 and humic acid precipitation coefficient 1.1;
m——试样的质量，单位为(g)。m——the mass of the sample, the unit is (g).
取平行测定结果的算数平均值为测定结果(结果保留三位有效数字)。污泥水热碳化后得到的水热处理液、水焦炭中的腐殖酸含量的测定结果如表8所示。Take the arithmetic mean of the parallel determination results as the determination result (retain three significant figures for the result). Table 8 shows the measurement results of the humic acid content in the hydrothermal treatment solution and water coke obtained after the hydrothermal carbonization of the sludge.
表8Table 8
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101056968A (en) * | 2004-11-10 | 2007-10-17 | 环境能量技术股份有限公司 | Method of slurry dewatering and conversion of biosolids to a renewable fuel |
| AU2014280837A1 (en) * | 2013-06-11 | 2015-12-24 | Licella Pty Ltd | Biorefining method |
| CN106315578A (en) * | 2016-08-19 | 2017-01-11 | 华中科技大学 | System and method for co-producing super active carbon and liquid product |
| CN110520510A (en) * | 2016-10-07 | 2019-11-29 | 马克·费尔德曼 | Method and system for improving the greenhouse gas emission reduction performance of biofuels, heating media and combustion materials and/or for enriching agricultural areas with carbonaceous humus |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101056968A (en) * | 2004-11-10 | 2007-10-17 | 环境能量技术股份有限公司 | Method of slurry dewatering and conversion of biosolids to a renewable fuel |
| AU2014280837A1 (en) * | 2013-06-11 | 2015-12-24 | Licella Pty Ltd | Biorefining method |
| CN106315578A (en) * | 2016-08-19 | 2017-01-11 | 华中科技大学 | System and method for co-producing super active carbon and liquid product |
| CN110520510A (en) * | 2016-10-07 | 2019-11-29 | 马克·费尔德曼 | Method and system for improving the greenhouse gas emission reduction performance of biofuels, heating media and combustion materials and/or for enriching agricultural areas with carbonaceous humus |
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