WO2023130816A1 - 一种纳米三氧化二铁催化合成人工腐殖酸的水稻促生方法 - Google Patents

一种纳米三氧化二铁催化合成人工腐殖酸的水稻促生方法 Download PDF

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WO2023130816A1
WO2023130816A1 PCT/CN2022/128275 CN2022128275W WO2023130816A1 WO 2023130816 A1 WO2023130816 A1 WO 2023130816A1 CN 2022128275 W CN2022128275 W CN 2022128275W WO 2023130816 A1 WO2023130816 A1 WO 2023130816A1
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humic acid
artificial humic
artificial
rice
transition metal
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French (fr)
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王震宇
李晓娜
廉菲
王传洗
乐乐
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江南大学
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01C—PLANTING; SOWING; FERTILISING
    • A01C1/00—Apparatus, or methods of use thereof, for testing or treating seed, roots, or the like, prior to sowing or planting
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G31/00—Soilless cultivation, e.g. hydroponics
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P21/00—Plant growth regulators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the invention relates to a rice growth-promoting method for synthesizing artificial humic acid catalyzed by nanometer ferric oxide, which belongs to the field of nanometer agriculture.
  • Carbon is a macroelement necessary for plant growth. It is estimated that the carbon content in the terrestrial carbon pool is about 10 16 tons, which is 1.15 ⁇ 10 4 times that of the atmospheric carbon pool, and plays an important role in the global carbon supply and balance.
  • the active carbon pool in the terrestrial carbon pool is mainly organic carbon, about 1.50 ⁇ 10 12 tons, which plays an important role in maintaining soil structure, improving soil fertility, and supporting crop growth.
  • Humic acid is the most active and most abundant part of the organic carbon pool. Humic acid promotes crop growth by providing nutrients, improving photosynthesis and disease resistance, and can increase soil water holding capacity and microbial activity, improve nitrogen mineralization and soil texture, and increase nutrient availability, thereby benefiting the growth of plant roots. grow. In addition, humic acid can also slow down the decomposition of fertilizers and improve the nutrient use efficiency of crops.
  • the natural humus layer in the soil is generally formed by the slow metabolism of litter or plant residues by microorganisms.
  • the formation of natural humic acid takes hundreds of thousands of years, and because the humification of biomass requires anaerobic or extreme temperature environments, the distribution of humus-rich soil in my country is extremely uneven, and most soils show Insufficient humic acid content.
  • extracting natural humic acid from nature requires a lot of material and financial resources. The above factors have greatly limited the role of humic acid in agricultural production. It is understood that more than 220 billion tons of carbon enter plants through photosynthesis every year, most of which will be wasted with waste biomass, and only a small part can be returned to the soil. In addition, improper disposal of waste biomass can cause economic losses and environmental burdens. Therefore, how to reuse these waste biomass containing a large amount of available carbon is a research hotspot.
  • Hydrothermal humification of carbon in biomass to generate artificial humic acid is one of the effective methods.
  • artificial humic acid synthesized by hydrothermal method has similar surface morphology and structural properties to natural humic acid, and has certain application potential in promoting plant nutrient absorption.
  • the traditional hydrothermal method for the synthesis of humic acid requires an extreme environment of strong acid and strong alkali, and has the disadvantages of low yield and violent reaction.
  • the present invention uses waste biomass as raw material and transition metals as catalysts to synthesize artificial humic acid; the composition and synthesis process of artificial humic acid substances are identified by UPLC-MS/MS, and then the artificial humic acid Acids are used in plant growth tests for their growth-promoting effects.
  • the method for synthesizing artificial humic acid described in the invention is green and simple, convenient and easy to operate in agricultural application and has good effect.
  • the first object of the present invention is to provide a method for utilizing transition metal catalyzed waste biomass to synthesize artificial humic acid, comprising the steps of:
  • the biomass includes bulk farmland waste biomass and greening waste biomass, wherein the bulk farmland waste biomass includes straw, rice husk and peanut shell, etc., and the Green waste biomass includes branches and leaves etc.
  • the alkali includes potassium hydroxide and sodium hydroxide.
  • the transition metal catalyst is nanometer ferric oxide; the particle size of the transition metal catalyst is nanoscale ( ⁇ 100nm).
  • the amount ratio of the biomass raw material to the transition metal catalyst is 2.5-3.5:1, more preferably 3:1.
  • the mass ratio of the biomass raw material to water is 1 g: 15-25 mL, more preferably 1: 20 mL.
  • the concentration of the alkali in water is not higher than 0.01 g/mL.
  • the filtration is filtration using a ⁇ 0.45um filter membrane.
  • the second object of the present invention is the artificial humic acid prepared by the method of the present invention.
  • the artificial humic acid contains plant hormones such as coumaric acid and isocitric acid.
  • the third object of the present invention is to provide a method for promoting plant growth using the artificial humic acid of the present invention, said method is to add artificial humic acid to cultivate during the process of plant seed germination or plant growth.
  • the adding of artificial humic acid during seed germination specifically includes: first cultivating plant seeds in a solution added with artificial humic acid at room temperature until germination.
  • the plant seeds need to be sterilized before germination; wherein 5% (v:v) H 2 O 2 solution is used for sterilizing.
  • adding artificial humic acid in the process of plant growth is specifically: taking rice seeds with uniform germination and cultivating them in an environment containing soil and artificial humic acid;
  • the ratio of humic acid to soil is 1/30 (mL/g).
  • the plant seeds include rice seeds; the plants include rice plants.
  • the raw materials used in the preparation of artificial humic acid in the present invention have a wide range of sources, mainly biomass waste, and the preparation method is simple, easy to implement, and has the characteristics of low carbon and environmental protection.
  • the artificial humic acid prepared by the present invention has a similar morphological structure to the natural humic acid.
  • the present invention accelerates the hydrothermal humification process of biomass macromolecules by adopting nano-transition metal catalysis, improves the degradation rate of biomass (reaching more than 14%), and promotes growth hormone analogs (such as isocitric acid) in artificial humic acid , coumaric acid, etc.) synthesis.
  • growth hormone analogs such as isocitric acid
  • the artificial humic acid synthesized by nano-transition metal catalysis in the present invention can promote earlier and faster germination of rice, the germination rate can be increased by 15%, and the growth of rice can be effectively promoted, the root activity can be increased by 166.76%, and the net photosynthetic rate can be increased by 72.08% %, and can improve the absorption of water and nutrients by rice roots and the transport of nutrients, and improve the ability of rice to resist oxidative stress and salt stress.
  • the preparation is simple, the operation is convenient, and it is easy to popularize and apply.
  • Figure 1 is a scanning electron microscope photograph of artificial humic acid; where (a) is natural humic acid extracted from black soil; (b) is KOH; (c) is KOH+FeCl 3 ; (d) is KOH +Fe 2 O 3 .
  • Figure 2 is a picture of the surface functional groups of artificial humic acid.
  • Figure 3 is a schematic diagram of the synthetic process of artificial humic acid.
  • Fig. 4 is the common partial substance of the artificial humic acid in embodiment 1, comparative example 1 and comparative example 2; Wherein A is L-lyxose; B is methionine sulfoxide; C is 3-hydroxypropyl-di Methoxyphenol.
  • Fig. 5 is the specific substance of artificial humic acid in embodiment 1; Wherein A is 4-coumaric acid; B is isocitric acid; C is 4-addylene-L-glutamic acid.
  • Fig. 6 is the specific substance of the artificial humic acid in Comparative Example 1; wherein A is DL-lactic acid; B is pyridine carboxylic acid; C is 3-(2-hydroxyethyl)indole.
  • Figure 7 shows the specific substances of artificial humic acid in Comparative Example 2; wherein A is choline; B is 4E-3-hydroxy-2,4-dimethyl-4-heptanamide; C is 2-anisidine.
  • Fig. 8 is a physical picture of adding artificial humic acid to rice germination.
  • Fig. 9 is a physical picture of the effect of adding artificial humic acid on plant growth.
  • the rice seeds used in Examples and Comparative Examples were purchased from Yueyou 9113 rice hybrid in Wuxi, Jiangsu.
  • Determination of TOC content in artificially synthesized humic acid the liquid product after hydrothermal reaction is filtered through a 0.25um water filter membrane, diluted 300 times with deionized water, and then measured by a TOC analyzer (varioTOC cube/selet, elementar, Germany) content.
  • Test of germination rate Take rice seeds with uniform conditions and sterilize them with 5% (v:v) H 2 O 2 solution for 10 minutes, put them into a seedling tray equipped with vermiculite medium, add artificial humic acid 0.5mL, Each treatment was repeated 3 times, and 10 rice seeds were placed in each square. The number of rice seeds germinated in each square was recorded every day during the 7 days of culture, and the germination rate was calculated.
  • Tests of plant height, dry weight, fresh weight, nutrient content, photosynthetic rate, soluble sugar and soluble protein content Take rice seedlings with uniform germination conditions for cultivation experiments, and measure the photosynthetic rate with a photosynthetic instrument.
  • Determination of nutrient content by ICP-MS cut the dry samples of aerial parts and roots into small pieces, weigh 25 mg of dry samples and place them in a digestion tube, add 3 mL of HNO 3 and 3 mL of H 2 O, and place them in a microwave digestion instrument (MARS 6, CEM, USA) digestion. After cooling, transfer to a 50mL centrifuge tube to volume. Then use inductively coupled plasma mass spectrometry (iCAP-TQ, Thermo Fisher, Germany) to measure the content of P and K elements in the shoots and roots of plants;
  • iCAP-TQ inductively coupled plasma mass spectrometry
  • M molar concentration of standard acid
  • W sample weight (g)
  • V 0 consumption of standard acid for titration of blank sample (mL)
  • V consumption of standard acid for titration of sample (mL).
  • the content of soluble sugar was determined by anthrone method: Weigh 20mg (W) dry sample into a 1.5mL centrifuge tube, add 80% alcohol in water bath for 30 minutes, centrifuge to take the supernatant, add a little activated carbon in water bath for decolorization, and take 1mL decolorized supernatant Add 5 mL of anthrone reagent to the supernatant, and measure the absorbance at a wavelength of 625 nm.
  • the calculation formula of soluble sugar content is as formula (2)
  • Soluble sugar content (%) [(C*V/a)/W]*10 -4 (2)
  • Soluble protein (mg/Gfw) (C ⁇ V/Va)/W (3)
  • a kind of method utilizing nano ferric oxide to synthesize artificial humic acid comprises the steps:
  • Example 1 Adjusts the nano-ferric oxide in Example 1 to be ferric chloride, and keep the others the same as in Example 1 to obtain artificial humic acid (KOH+FeCl 3 ).
  • Example 1 the artificial humic acid obtained in Example 1 and Comparative Examples 1 and 2 is similar in structure to the natural humic acid extracted from black soil.
  • Fig . 2 compared with the comparative example 2 without catalyst, the addition of ferric chloride as the artificial humic acid prepared as a catalyst has more -CH and -CH groups, indicating that in comparative example 1 Contain more lipids in the artificial humic acid;
  • Fig. 3 is a schematic diagram of the synthesis process of artificial humic acid; it can be seen from Fig. 3 that: artificially synthesized humic acid contains substances such as methionine sulfoxide, which can promote the germination of plant seeds (Fig. 4). At the same time, compared with the comparative example 2 without catalyst, there are substances such as coumaric acid and isocitric acid in the KOH+Fe 2 O 3 group ( FIG. 5 ), which can promote plant growth.
  • the KOH+FeCl 3 group contained substances such as lactic acid and hexahydropyridinecarboxylic acid ( Figure 6). It is difficult to extract such substances in the extraction of natural humic acid.
  • Embodiment 2 germination
  • a method utilizing artificial humic acid to promote rice seed germination comprising the steps of:
  • Embodiment 2 and comparative example 3 are in seed germination process, record germination rate, test result is as table 1:
  • Embodiment 3 rice growth
  • a method for utilizing artificial humic acid to promote rice growth comprising the steps of:
  • Rice seeds were germinated in vermiculite medium, and the seeds with uniform germination were selected and placed in a 100mL PVC test tube, 60g of soil was added, and 2mL of artificial humic acid (KOH, KOH+FeCl 3 , KOH+Fe 2 O 3 ) was cultivated for 30 days ;
  • the culture conditions are: light for 12 hours, day and night temperature are 25°C and 20°C respectively;
  • Example 3 The addition of artificial humic acid was omitted, and the others were consistent with Example 3, and rice was planted, which was recorded as a blank group (CK).
  • the plant height, dry weight, fresh weight, nutrient content, photosynthetic rate, soluble sugar and soluble protein content of rice were measured.
  • Table 2 Rice plant height, root length, biomass and water content
  • Example 1 The KOH in Example 1, Comparative Examples 1 and 2 was replaced by HCl, and other conditions were consistent with Example 1 to obtain artificial humic acid.
  • the present invention catalyzes the synthesis of artificial humic acid by adding nano-ferric oxide, and the biomass degradation rate in the hydrothermal process is increased by more than 14%. Acids and other plant hormones. This not only improves the preparation efficiency of the artificial humic acid and the content of beneficial components in the product, but also significantly promotes the germination and growth of rice.
  • This technology of using nano-ferric oxide to catalyze the synthesis of artificial humic acid to promote rice growth can effectively avoid the accumulation of waste biomass and environmental hazards, and realize the reflux and neutralization of soil carbon pools, which is very important for the development of green agriculture and the alleviation of the global climate crisis. are all significant.

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Abstract

本发明公开了一种纳米三氧化二铁催化合成人工腐殖酸的水稻促生方法，属于纳米农业领域。本发明所述的利用过渡金属催化废弃生物质合成人工腐殖酸的方法，包括如下步骤：在生物质原料中加入碱、过渡金属催化剂、水的混合溶液，在160～250℃催化反应6～48小时；反应结束后，将反应产物进行固液分离，之后将得到的液体进行过滤，得到人工腐殖酸。本发明采用纳米过渡金属催化合成的人工腐殖酸可促进水稻更早更快萌发，发芽率提高15％，还能有效促进水稻的生长，根系活力提高166.76％，净光合速率提高72.08％，且能提高水稻根系对水分和养分的吸收以及养分的转运，提高水稻抵御氧化胁迫和盐胁迫的能力。制备简单，操作便捷，易于推广应用。

Description

一种纳米三氧化二铁催化合成人工腐殖酸的水稻促生方法 技术领域
本发明涉及一种纳米三氧化二铁催化合成人工腐殖酸的水稻促生方法，属于纳米农业领域。
背景技术
碳是植物生长所必需的一种大量元素。据估计，陆地碳库中的碳含量约为10 16吨，是大气碳库的1.15×10 4倍，在全球碳供应和平衡中发挥着重要作用。而陆地碳库中的活性碳库主要以有机碳为主，约为1.50×10 12吨，对维持土壤结构、提高土壤肥力、支持作物生长具有重要作用。腐殖酸是有机碳库中最活跃且含量最多的部分。腐殖酸通过提供养分、提高光合作用和抗病性来促进作物生长，并能提高土壤持水能力和微生物活性，改善氮素矿化和土壤质地，提高养分有效性，从而有利于植物根系的生长。此外，腐植酸还可以减缓肥料的分解，提高作物的养分利用效率。
土壤中天然腐殖质层一般是由枯枝落叶或植物残体经微生物代谢缓慢形成的。然而，天然腐殖酸的形成需要成百上千年的时间，且由于生物质腐殖化需要厌氧或极端温度环境，因此，我国富含腐殖质土壤的分布是极不均匀的，大部分土壤呈现腐殖酸含量不足现象。通常，从自然中提取天然腐殖酸需要耗费大量的物力财力。以上因素都极大限制了腐殖酸在农业生产中的作用。据了解，每年有2200多亿吨的碳通过光合作用进入植物，这些碳大部分会跟随废弃生物质被浪费掉，只有很少的部分能返回土壤。此外，废弃生物质的不当处理还会带来经济损失和环境负担。因此，如何再利用这些含有大量有效碳的废弃生物质是研究的热点。
通过化学方法将生物质中的碳经水热腐殖化生成人工腐殖酸是有效方法之一。已有研究表明水热法合成的人工腐殖酸与天然腐殖酸具有相似表面形态和结构性质，在促进植物养分吸收方面具有一定应用潜力。然而，传统的水热法合成腐殖酸方法需要强酸强碱的极端环境，且具有收率低和反应剧烈等缺点。此外，目前对人工合成腐殖酸的物质组成还未有报道，其促进植物生长的关键物质还不明确。
发明内容
[技术问题]
传统的水热法合成人工腐殖酸过程反应过于剧烈，产物回收率低且促进植物生长的活性成分较少，人工腐殖酸中物质组成不明确。
[技术方案]
为了解决上述问题，本发明以废弃生物质为原料，采用过渡金属作为催化剂合成人工腐 殖酸；通过UPLC-MS/MS对人工腐殖酸物质的组成和合成过程进行鉴定，之后将人工腐殖酸用于植物生长检验其促生作用。本发明所述的合成人工腐殖酸的方法绿色简单，而且农业施用方便易操作且效果好。
本发明的第一个目的是提供一种利用过渡金属催化废弃生物质合成人工腐殖酸的方法，包括如下步骤：
在生物质原料中加入碱、过渡金属催化剂、水的混合溶液，在160～250℃催化反应6～48小时；反应结束后，将反应产物进行固液分离，之后将得到的液体进行过滤，得到人工腐殖酸。
在本发明的一种实施方式中，所述的生物质包括大宗农田废弃生物质、绿化废弃生物质，其中，所述的大宗农田废弃生物质包括秸秆、稻壳和花生壳等，所述的绿化废弃生物质包括树枝和树叶等。
在本发明的一种实施方式中，所述的碱包括氢氧化钾、氢氧化钠。
在本发明的一种实施方式中，所述的过渡金属催化剂为纳米三氧化二铁；所述的过渡金属催化剂的粒径为纳米级别(<100nm)。
在本发明的一种实施方式中，所述的生物质原料和过渡金属催化剂用量比为2.5～3.5:1，进一步优选为3：1。
在本发明的一种实施方式中，所述的生物质原料和水的质量比为1g：15～25mL，进一步优选为1：20mL。
在本发明的一种实施方式中，所述的碱在水中的浓度不高于0.01g/mL。
在本发明的一种实施方式中，所述的过滤是采用<0.45um的滤膜过滤。
本发明的第二个目的是本发明所述的方法制备得到的人工腐殖酸。
在本发明的一种实施方式中，所述的人工腐殖酸中含有香豆酸、异柠檬酸等植物激素类物质。
本发明的第三个目的是提供一种利用本发明的人工腐殖酸促进植物生长的方法，所述的方法是在植物种子萌发或者植株生长的过程中添加人工腐殖酸进行培养。
在本发明的一种实施方式中，所述的在种子萌发过程中添加人工腐殖酸具体是：先将植物种子在添加人工腐殖酸的溶液中室温培养至发芽。
在本发明的一种实施方式中，所述的植物种子在萌发之前需要杀菌；其中杀菌是采用5％(v:v)H 2O 2溶液。
在本发明的一种实施方式中，所述的植株生长的过程中添加人工腐殖酸具体是：取发芽情况均一的水稻种子在含有土壤和人工腐殖酸的环境中进行培养；其中，人工腐殖酸与土壤 比为1/30(mL/g)。
在本发明的一种实施方式中，所述的植物种子包括水稻种子；所述的植株包括水稻植株。
[有益效果]
(1)本发明制备人工腐殖酸所用的原料来源广泛，主要为生物质废弃物，且制备方法简单、易于实施，具有低碳环保的特点。
(2)本发明制备人工腐殖酸与天然腐殖酸具有相似的形态结构。
(3)本发明采用纳米过渡金属催化加速了生物质大分子水热腐殖质化过程，提高生物质降解率(达到14％以上)，促进人工腐殖酸中生长激素类似物(如，异柠檬酸、香豆酸等)的合成。
(4)本发明采用纳米过渡金属催化合成的人工腐殖酸可促进水稻更早更快萌发，发芽率提高15％，还能有效促进水稻的生长，根系活力提高166.76％，净光合速率提高72.08％，且能提高水稻根系对水分和养分的吸收以及养分的转运，提高水稻抵御氧化胁迫和盐胁迫的能力。制备简单，操作便捷，易于推广应用。
附图说明
图1是人工腐殖酸扫面电镜照片；其中(a)为黑土(black soil)中提取的天然腐殖酸；(b)为KOH；(c)为KOH+FeCl 3；(d)为KOH+Fe 2O 3。
图2是人工腐殖酸表面官能团的图片。
图3是人工腐殖酸合成过程的示意图。
图4为实施例1、对比例1和对比例2中的人工腐殖酸的共有的部分物质；其中A是L-来苏糖；B是蛋氨酸亚砜；C是3-羟丙基-二甲氧基苯酚。
图5为实施例1中的人工腐殖酸特有的物质；其中A是4-香豆酸；B是异柠檬酸；C是4-亚加基-L-谷氨酸。
图6为对比例1中的人工腐殖酸特有的物质；其中A是DL-乳酸；B是吡啶羧酸；C是3-(2-羟乙基)吲哚。
图7为对比例2中的人工腐殖酸特有的物质；其中A是胆碱；B是4E-3-羟基-2，4-二甲基-4-庚酰胺；C是2-茴香胺。
图8是添加人工腐殖酸对水稻萌发的实物图。
图9是添加人工腐殖酸对植物生长影响的实物图。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解实施例是为了更好地解释本发明，不用于限制本发明。
实施例与对比例采用的水稻种子购自江苏无锡的岳优9113水稻杂交种。
测试方法：
人工合成腐殖酸中TOC含量的测定：水热反应后的液体产物经0.25um水系滤膜过滤，用去离子水稀释300倍后用TOC分析仪(varioTOC cube/selet,elementar,Germany)测定TOC含量。
发芽率的测试：取情况均一的水稻种子用5％(v:v)H 2O 2溶液消毒10分钟后放入装有蛭石培养基的育苗盘中，加入人工腐殖酸0.5mL，每个处理重复3次，每个方格中放入10粒水稻种子。在培养的7天内每天记录每个方格内发芽的水稻种子的数目，计算发芽率。
株高、干重、鲜重和养分含量、光合速率、可溶性糖和可溶性蛋白的含量的测试：取发芽情况均一的水稻幼苗进行培养实验，光合速率用光合仪测定。培养30天后收获水稻植株；用清水洗净后用直尺测定水稻的地上部长度(株高)和根长，并称重，记录水稻地上部和根的鲜重后；将这些样品放入纸质信封中在烘箱内105℃杀青半小时后60℃烘至恒重，称量，记录样品干重。
养分含量用ICP-MS测定：将地上部和根部的干样剪成小块，称量25mg的干样置于消解管中，加入3mLHNO 3和3mLH 2O，置于微波消解仪(MARS 6,CEM,USA)消解。冷却后，转移到50mL离心管中定容。随后用电感耦合等离子体质谱仪(iCAP-TQ,Thermo Fisher,Germany)测定植物地上部和根部中P、K元素的含量；
使用凯氏定氮仪仪测定N元素的含量；取0.3～0.5g干样置于大试管中，加入0.2g硫酸铜和3g硫酸钾(国标)(硫酸铜：硫酸钾＝1:15)，加入10mL浓硫酸，在通风橱中置于消化炉上加热消化，消化后的样品放到凯氏定氮仪上蒸馏，用0.05M标准盐酸滴定；具体计算公式如下式(1)：
Figure PCTCN2022128275-appb-000001
式(1)中：M＝标准酸摩尔浓度；W＝样品重量(g)；V 0＝空白样滴定标准酸量消耗量(mL)；V＝样品滴定标准酸消耗量(mL)。
可溶性糖含量采用蒽酮法测定：称取20mg(W)干样放入1.5mL离心管中，加80％酒精水浴30分钟，离心取上清液加少许活性炭水浴脱色，取1mL脱色后的上清液加5mL蒽酮试剂，在波长625nm处测吸光度。可溶性糖含量的计算公式如式(2)
可溶性糖含量(％)＝[(C*V/a)/W]*10 -4     (2)
式(2)中：C＝提取液中可溶性糖浓度，标曲可查；W＝样品重量(g)；V＝提取液总体积(ml)；a＝测定时所用体积。
可溶性蛋白测定：称取0.5g干样放入研钵中，加5mLpH＝7.8的磷酸缓冲液，冰浴研磨，匀浆倒入离心管中，冷冻离心20分钟(10000×g)，上清液(酶液)20微升(V)+3毫升G-250放置2分钟，595nm比色，同时做空白(20微升缓冲液+3毫升G-250)。可溶性蛋白含量的计算公式如式(3)
可溶性蛋白(mg/Gfw)＝(C×V/Va)/W   (3)
式(3)中：C＝提取液中可溶性蛋白浓度，标曲可查；W＝样品重(g)；V＝提取液总体积(ml)；Va＝测定时所用体积。
实施例1
一种利用纳米三氧化二铁合成人工腐殖酸的方法，包括如下步骤：
称取3g玉米秸秆作为反应前提物质放入100mL反应釜中，加入0.62g氢氧化钾(分析纯)、1g纳米三氧化二铁(5nm)、60mL去离子水的混合溶液，放入烘箱中200℃催化反应24小时；反应结束后待冷却至室温，打开反应釜，分离液体和固体残渣；把反应后的液体用0.22um滤膜过滤，得到人工腐殖酸(KOH+Fe 2O 3)。
对比例1
调整实施例1中的纳米三氧化二铁为氯化铁，其他和实施例1保持一致，得到人工腐殖酸(KOH+FeCl 3)。
对比例2
省略实施例1中的纳米三氧化二铁，其他和实施例1保持一致，得到人工腐殖酸(KOH)。
将实施例1和对比例1、2得到的人工腐殖酸进行性能测试，测试结果如下：
从图1可以看出：实施例1和对比例1、2得到的人工腐殖酸与黑土中提取的天然腐殖酸结构相似。
从图2可以看出：与不加催化剂的对比例2相比，加入氯化铁作催化剂制备的人工腐殖酸中-CH 2和–CH 3基团的含量更多，说明对比例1中的人工腐殖酸中含有更多的脂类物质；实施例1中加入纳米三氧化二铁作催化剂制备的人工腐殖酸中含氧官能团的数量减少，说明实施例1的人工腐殖化程度更高，C含量更多。
图3是人工腐殖酸合成过程的示意图；从图3可以看出：人工合成腐殖酸中含有蛋氨酸亚砜等物质，可促进植物种子的萌发(图4)。同时，与不加催化剂的对比例2相比，KOH+Fe 2O 3组中有香豆酸和异柠檬酸等物质(图5)，该类物质可促进植物生长。KOH+FeCl 3组中含有乳酸和六氢吡啶羧酸等物质(图6)。而在天然腐殖酸的提取中很难提取出这类物质。
实施例2发芽
一种利用人工腐殖酸促进水稻种子发芽的方法，包括如下步骤：
将水稻种子用5％H 2O 2杀菌15min；置于9cm培养皿中，室温(25℃)培养7天；
之后在培养皿中分别装入10mL蒸馏水和0.5mL三种人工腐殖酸(KOH、KOH+FeCl 3、KOH+Fe 2O 3)，进行培养7天。
对比例3
省略人工腐殖酸的添加，其他和实施例2一致，进行种子的萌发，记为空白组(CK)。
实施例2和对比例3在种子萌发过程中，记录发芽率，测试结果如表1：
表1添加人工腐殖酸对水稻发芽率的影响
Figure PCTCN2022128275-appb-000002
从图7和表1可以看出：添加纳米三氧化二铁催化合成的人工腐殖酸(KOH+Fe 2O 3)能促进水稻种子更快萌发，可使水稻种子的发芽率提高15％。
实施例3水稻生长
一种利用人工腐殖酸促进水稻生长的方法，包括如下步骤：
水稻种子在蛭石培养基中萌发，选择发芽情况均一的种子放入100mL PVC试管中，加入60g土，2mL人工腐殖酸(KOH、KOH+FeCl 3、KOH+Fe 2O 3)培养30天；其中，培养条件为：光照12h，昼夜温度分别为25℃和20℃；
对比例4
省略人工腐殖酸的添加，其他和实施例3一致，进行水稻的种植，记为空白组(CK)。
在培养结束后，测定了水稻的株高、干重、鲜重和养分含量、光合速率、可溶性糖和可溶性蛋白的含量等。
从图8和表2～表5可以看出：添加纳米三氧化二铁催化合成的人工腐殖酸使水稻株高提高了89.50％，根长增加了50.80％(表2)，根系活力提高166.76％，净光合速率提高72.08％(表3)，水稻对养分的吸收和转运能力都有显著提高(表4、表5)。
表2水稻株高、根长、生物量及含水率
Figure PCTCN2022128275-appb-000003
Figure PCTCN2022128275-appb-000004
注：不同小写字母表示4个处理之间差异显著(P<0.05)。
表3水稻光合及根系活力指标
Figure PCTCN2022128275-appb-000005
注：不同小写字母表示4个处理之间差异显著(P<0.05)。
表4水稻养分含量
Figure PCTCN2022128275-appb-000006
表5水稻养分利用率
Figure PCTCN2022128275-appb-000007
注：不同小写字母表示4个处理之间差异显著(P<0.05)。
对比例5
将实施例1、对比例1和2中的KOH替换成HCl，其他条件与实施例1一致，得到人工腐殖酸。
将实施例1和对比例1、2、5的人工腐殖酸进行对比，结果如表6；
从表6可以看出：在碱性条件下合成的腐殖酸中TOC含量更好，且加入催化剂能提高 TOC的含量。
表6 TOC的测试结果
Figure PCTCN2022128275-appb-000008
注：不同小写字母表示各处理之间差异显著(P<0.05)。
综上所述，本发明通过添加纳米三氧化二铁催化合成人工腐殖酸，水热过程中生物质降解率提高了14％以上，同时合成的人工腐殖酸中含有香豆酸、异柠檬酸等植物激素类物质。这样不仅提高了人工腐殖酸的制备效率和产物中有益组分的含量，且对水稻的萌发和生长有显著的促进效果。这种利用纳米三氧化二铁催化合成人工腐殖酸促进水稻生长的技术，可有效避免废弃生物质的堆积及环境危害，实现土壤碳库的回流中和，对发展绿色农业和缓解全球气候危机都具有重要意义。

Claims (10)

  1. 一种利用过渡金属催化废弃生物质合成人工腐殖酸的方法，其特征在于，包括如下步骤：
    在生物质原料中加入碱、过渡金属催化剂、水的混合溶液，在160～250℃催化反应6～48小时；反应结束后，将反应产物进行固液分离，之后将得到的液体进行过滤，得到人工腐殖酸；
    其中，所述的过渡金属催化剂为纳米三氧化二铁；
    所述的生物质原料和过渡金属催化剂用量比为2.5～3.5:1。
  2. 一种利用过渡金属催化废弃生物质合成人工腐殖酸的方法，其特征在于，包括如下步骤：
    在生物质原料中加入碱、过渡金属催化剂、水的混合溶液，在160～250℃催化反应6～48小时；反应结束后，将反应产物进行固液分离，之后将得到的液体进行过滤，得到人工腐殖酸。
  3. 根据权利要求2所述的方法，其特征在于，所述的生物质包括大宗农田废弃生物质、绿化废弃生物质，其中，所述的大宗农田废弃生物质包括秸秆、稻壳和花生壳等，所述的绿化废弃生物质包括树枝和树叶等。
  4. 根据权利要求2所述的方法，其特征在于，所述的过渡金属催化剂为纳米三氧化二铁。
  5. 根据权利要求2所述的方法，其特征在于，所述的生物质原料和过渡金属催化剂用量比为2.5～3.5:1。
  6. 根据权利要求2所述的方法，其特征在于，制备得到的人工腐殖酸中含有香豆酸、异柠檬酸。
  7. 一种利用人工腐殖酸促进植物生长的方法，其特征在于，所述的方法是在植物种子萌发或者植株生长的过程中添加人工腐殖酸进行培养；
    其中，人工腐殖酸的制备方法包括如下步骤：
    在生物质原料中加入碱、过渡金属催化剂、水的混合溶液，在160～250℃催化反应6～48小时；反应结束后，将反应产物进行固液分离，之后将得到的液体进行过滤，得到人工腐殖酸。
  8. 根据权利要求7所述的方法，其特征在于，在植物种子萌发过程中添加人工腐殖酸具体是：先将植物种子在添加人工腐殖酸的溶液中室温培养至发芽。
  9. 根据权利要求8所述的方法，其特征在于，植物种子在萌发之前需要杀菌；其中杀菌是采用5％(v:v)H 2O 2溶液。
  10. 根据权利要求7所述的方法，其特征在于，植株生长的过程中添加人工腐殖酸具体 是：取发芽情况均一的水稻种子在含有土壤和人工腐殖酸的环境中进行培养；其中，人工腐殖酸与土壤比为1/30(mL/g)。
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