CN111393668B - Preparation method of nano hollow shell fertilizer slow release agent - Google Patents
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- CN111393668B CN111393668B CN202010258531.6A CN202010258531A CN111393668B CN 111393668 B CN111393668 B CN 111393668B CN 202010258531 A CN202010258531 A CN 202010258531A CN 111393668 B CN111393668 B CN 111393668B
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 28
- 239000011591 potassium Substances 0.000 claims abstract description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000003245 coal Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000006228 supernatant Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000005485 electric heating Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 4
- 238000007605 air drying Methods 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 2
- 238000000227 grinding Methods 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 238000005303 weighing Methods 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 15
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical group C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000005119 centrifugation Methods 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000002689 soil Substances 0.000 description 3
- 239000004021 humic acid Substances 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
- C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- 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
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
本发明涉及纳米材料的制备领域，具体是一种纳米中空壳化肥缓释剂的制备方法。将煤样磨成粉末，然后将煤样粉末、氢氧化钾混合并加入蒸馏水，之后在50℃条件下，搅拌并加热回流8‑10 h，然后将反应液冷却至室温，离心收集上清液；将上清液烘干至恒重，获得纳米中空壳的腐植酸钾化肥缓释剂。制备获得的腐植酸钾中的腐植酸功能团有芳环和酯环，且环上连有的羧基、羟基、羰基、甲氧基等官能团能够通过氢键吸附化肥中的元素，从而作为一种化肥缓释剂。本发明所述化肥缓释剂独有的中空壳能够增大吸附表面积且利用空心球内部空间可作为化肥载体。
The invention relates to the field of preparation of nanometer materials, in particular to a preparation method of a nanometer hollow shell chemical fertilizer slow-release agent. Grind the coal sample into powder, then mix the coal sample powder and potassium hydroxide and add distilled water, then at 50°C, stir and heat under reflux for 8-10 h, then cool the reaction solution to room temperature, and collect the supernatant by centrifugation ; Drying the supernatant to constant weight to obtain the potassium humate chemical fertilizer slow-release agent with nano hollow shell. The humic acid functional groups in the prepared potassium humate have aromatic rings and ester rings, and the carboxyl, hydroxyl, carbonyl, methoxy and other functional groups connected to the ring can adsorb the elements in the fertilizer through hydrogen bonds, thus serving as a kind of Fertilizer release agent. The unique hollow shell of the fertilizer slow-release agent of the present invention can increase the adsorption surface area, and the inner space of the hollow sphere can be used as a fertilizer carrier.
Description
技术领域technical field
本发明涉及纳米材料的制备领域，具体是一种纳米中空壳化肥缓释剂的制备方法。The invention relates to the field of preparation of nanometer materials, in particular to a preparation method of a nanometer hollow shell chemical fertilizer slow-release agent.
背景技术Background technique
腐植酸是一种天然有机大分子混合物，腐植酸及其盐在农业领域有着极其广泛的应用。腐植酸钾中的腐植酸功能团可以吸收贮存钾离子，防止在沙土及淋溶性土壤中随水流失，又可防止粘性土壤对钾的固定。除此之外，腐植酸钾中的腐植酸功能团有芳环和酯环，且环上连有的羧基、羟基、羰基、甲氧基等官能团能够通过氢键吸附化肥中的元素，从而作为一种化肥缓释剂。目前，现有技术根据腐植酸钾的尺寸将其定义为纳米材料且将腐植酸钾单独或者其他腐植酸盐混合作为化肥缓释剂使用。但是现有技术并没有制备和表征出纳米尺寸的中空壳的腐植酸钾。本发明通过煤为原料首次制备出纳米尺寸的中空壳的腐植酸钾。Humic acid is a mixture of natural organic macromolecules, and humic acid and its salts are widely used in agriculture. The humic acid functional group in potassium humate can absorb and store potassium ions, prevent the loss with water in sandy soil and leaching soil, and prevent the fixation of potassium in cohesive soil. In addition, the humic acid functional groups in potassium humate have aromatic rings and ester rings, and the carboxyl, hydroxyl, carbonyl, methoxy and other functional groups connected to the ring can adsorb the elements in the fertilizer through hydrogen bonds, thus serving as a A fertilizer slow-release agent. At present, the prior art defines potassium humate as a nanomaterial according to its size and uses potassium humate alone or mixed with other humates as a fertilizer slow-release agent. However, the prior art does not prepare and characterize nano-sized hollow shell potassium humate. The present invention prepares nanometer-sized hollow shell potassium humate for the first time by using coal as a raw material.
发明内容SUMMARY OF THE INVENTION
本发明为了解决现有技术缺乏纳米尺寸的中空壳的腐植酸钾技术的问题，提供了一种纳米中空壳化肥缓释剂的制备方法。In order to solve the problem that the prior art lacks the potassium humate technology of nano-sized hollow shells, the present invention provides a preparation method of a nanometer hollow shell chemical fertilizer slow-release agent.
本发明是通过以下技术方案实现的：一种纳米中空壳化肥缓释剂的制备方法，包括以下步骤：The present invention is achieved through the following technical solutions: a preparation method of nano hollow shell chemical fertilizer slow-release agent, comprising the following steps:
首先将煤样磨成粉末，然后将煤样粉末、氢氧化钾混合并加入蒸馏水，之后在50℃条件下，搅拌并加热回流8-10 h，然后将反应液冷却至室温，离心收集上清液；将上清液烘干至恒重，获得纳米中空壳的腐植酸钾化肥缓释剂。First grind the coal sample into powder, then mix the coal sample powder and potassium hydroxide and add distilled water, then at 50 °C, stir and heat under reflux for 8-10 h, then cool the reaction solution to room temperature, and collect the supernatant by centrifugation liquid; drying the supernatant to constant weight to obtain the potassium humate chemical fertilizer slow-release agent with nano hollow shell.
作为本发明技术方案的进一步改进，所述煤样粉末与氢氧化钾的质量比为10:1。As a further improvement of the technical solution of the present invention, the mass ratio of the coal sample powder to potassium hydroxide is 10:1.
作为本发明技术方案的进一步改进，所述离心的参数为3600 r/min的转速离心20min。As a further improvement of the technical solution of the present invention, the parameters of the centrifugation are centrifugation at a rotational speed of 3600 r/min for 20 minutes.
作为本发明技术方案的进一步改进，所述煤样为风化煤或褐煤。As a further improvement of the technical solution of the present invention, the coal sample is weathered coal or lignite.
作为本发明技术方案的进一步改进，所述煤样粉末的粒径为80-200目。As a further improvement of the technical solution of the present invention, the particle size of the coal sample powder is 80-200 mesh.
作为本发明技术方案的进一步改进，所述上清液烘干的温度为230℃。As a further improvement of the technical solution of the present invention, the drying temperature of the supernatant is 230°C.
本发明进一步提供了通过上述纳米中空壳化肥缓释剂的制备方法制备获得的纳米中空壳的腐植酸钾化肥缓释剂。The present invention further provides a nano-hollow shell potassium humate slow-release fertilizer prepared by the above-mentioned preparation method of the nano-hollow shell chemical fertilizer slow-release agent.
作为腐植酸钾化肥缓释剂技术方案的进一步改进，腐植酸钾化肥缓释剂的颗粒外形尺寸为5-105μm，壁厚为0.5-5μm。As a further improvement of the technical scheme of the potassium humate chemical fertilizer slow-release agent, the particle size of the potassium humate chemical fertilizer slow-release agent is 5-105 μm, and the wall thickness is 0.5-5 μm.
本发明所提供的一种纳米中空壳化肥缓释剂的制备方法，制备获得的腐植酸钾中的腐植酸功能团有芳环和酯环，且环上连有的羧基、羟基、羰基、甲氧基等官能团能够通过氢键吸附化肥中的元素，从而作为一种化肥缓释剂。本发明所述化肥缓释剂独有的中空壳能够增大吸附表面积且利用空心球内部空间可作为化肥载体。In the preparation method of a nano hollow shell chemical fertilizer slow-release agent provided by the present invention, the humic acid functional group in the prepared potassium humate has an aromatic ring and an ester ring, and the rings are connected with carboxyl, hydroxyl, carbonyl, Functional groups such as methoxy can adsorb elements in fertilizers through hydrogen bonds, thus acting as a slow-release agent for fertilizers. The unique hollow shell of the fertilizer slow-release agent of the present invention can increase the adsorption surface area, and the inner space of the hollow sphere can be used as a fertilizer carrier.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained according to these drawings without creative efforts.
图1为本发明实施例1制备获得的纳米中空壳的腐植酸钾化肥缓释剂的XRD图谱。Fig. 1 is the XRD pattern of the potassium humate chemical fertilizer slow-release agent with nano hollow shell prepared in Example 1 of the present invention.
图2-4为不同放大倍数的本发明实施例1制备获得的纳米中空壳的腐植酸钾化肥缓释剂的扫描电镜（SEM）照片。2-4 are scanning electron microscope (SEM) photographs of the nano-hollow shell potassium humate slow-release fertilizer prepared in Example 1 of the present invention at different magnifications.
图5-6为本发明实施例1制备获得的透射电镜（TEM）图片。5-6 are transmission electron microscope (TEM) pictures prepared in Example 1 of the present invention.
从图1看出，腐植酸钾纳米材料在20-35°出现较宽的吸收带，腐植酸钾为非晶态物质。从图2和3中的低放大倍数SEM图像显示了腐植酸钾具有微小尺寸的纳米中空壳的形态。腐植酸钾的纳米中空壳的粒径不同，颗粒外形尺寸为5-105μm，壁厚为0.5-5μm。而且一些较大的球形颗粒已经破裂。从图4中高倍数SEM图像看出，纳米中空壳的表面很粗糙，许多纳米颗粒聚集在一起。从图5和图6中看出，腐植酸钾的纳米中空壳具有三种形态，包括长约35-60 nm，宽约25-40 nm的立方壳纳米颗粒；宽、长约80-105 nm，宽约25-35 nm的梭型纳米颗粒；直径约35-60 nm的近球形纳米颗粒。It can be seen from Figure 1 that potassium humate nanomaterials have a wide absorption band at 20-35°, and potassium humate is an amorphous substance. The low-magnification SEM images from Figures 2 and 3 show the morphology of potassium humate with nanoscale hollow shells. The particle size of the nano hollow shell of potassium humate is different, the particle size is 5-105 μm, and the wall thickness is 0.5-5 μm. And some of the larger spherical particles have broken up. From the high-magnification SEM image in Figure 4, it can be seen that the surface of the nano-hollow shell is very rough, and many nanoparticles are aggregated together. It can be seen from Figure 5 and Figure 6 that the nano-hollow shell of potassium humate has three morphologies, including cubic shell nanoparticles with a length of about 35-60 nm and a width of about 25-40 nm; width and length of about 80-105 nm, shuttle-shaped nanoparticles with a width of about 25-35 nm; nearly spherical nanoparticles with a diameter of about 35-60 nm.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚，下面将对本发明的技术方案进行详细的描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所得到的所有其它实施方式，都属于本发明所保护的范围。In order to make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be described in detail below. Obviously, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other implementations obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.
下面通过具体实施例对本发明的技术方案进行详细的说明。The technical solutions of the present invention will be described in detail below through specific embodiments.
实施例1Example 1
一种纳米中空壳化肥缓释剂的制备方法，包括以下步骤：A preparation method of nano hollow shell chemical fertilizer slow-release agent, comprising the following steps:
首先将山西风化煤煤样磨成粒径为80目的粉末，然后称取100.00g煤样、10.00g氢氧化钾于三颈烧瓶中，并向其中加入1000 mL蒸馏水，之后在50℃条件下，用电磁搅拌器搅拌，电热套加热回流9h，然后将反应液冷却至室温，以3600r/min的转速离心20 min收集上层清液；将上层清液放入鼓风干燥箱中，230℃温度下恒温烘干，得到纳米中空壳的腐植酸钾固体粉末。First, the Shanxi weathered coal sample was ground into powder with a particle size of 80 mesh, and then 100.00 g of coal sample and 10.00 g of potassium hydroxide were weighed into a three-necked flask, and 1000 mL of distilled water was added to it. Stir with an electromagnetic stirrer, heat under reflux for 9 h with an electric heating mantle, then cool the reaction solution to room temperature, and centrifuge at 3600 r/min for 20 min to collect the supernatant; put the supernatant in a blast drying oven, at a temperature of 230 °C Drying at constant temperature to obtain potassium humate solid powder with nano hollow shell.
实施例2Example 2
一种纳米中空壳化肥缓释剂的制备方法，包括以下步骤：A preparation method of nano hollow shell chemical fertilizer slow-release agent, comprising the following steps:
首先将山西风化煤煤样磨成粒径为150目的粉末，然后称取100.00g煤样、10.00g氢氧化钾于三颈烧瓶中，并向其中加入1000 mL蒸馏水，之后在50℃条件下，用电磁搅拌器搅拌，电热套加热回流9h，然后将反应液冷却至室温，以3600r/min的转速离心20 min收集上层清液；将上层清液放入鼓风干燥箱中，230℃温度下恒温烘干，得到纳米中空壳的腐植酸钾固体粉末。First, the Shanxi weathered coal sample was ground into powder with a particle size of 150 mesh, and then 100.00 g of coal sample and 10.00 g of potassium hydroxide were weighed into a three-necked flask, and 1000 mL of distilled water was added to it. Stir with an electromagnetic stirrer, heat under reflux for 9 h with an electric heating mantle, then cool the reaction solution to room temperature, and centrifuge at 3600 r/min for 20 min to collect the supernatant; put the supernatant in a blast drying oven, at a temperature of 230 °C Drying at constant temperature to obtain potassium humate solid powder with nano hollow shell.
实施例3Example 3
一种纳米中空壳化肥缓释剂的制备方法，包括以下步骤：A preparation method of nano hollow shell chemical fertilizer slow-release agent, comprising the following steps:
首先将云南褐煤煤样磨成粒径为200目的粉末，然后称取100.00g煤样、10.00g氢氧化钾于三颈烧瓶中，并向其中加入1000 mL蒸馏水，之后在50℃条件下，用电磁搅拌器搅拌，电热套加热回流10h，然后将反应液冷却至室温，以3600r/min的转速离心20 min收集上层清液；将上层清液放入鼓风干燥箱中，230℃温度下恒温烘干，得到纳米中空壳的腐植酸钾固体粉末。First, the Yunnan lignite coal sample was ground into powder with a particle size of 200 mesh, and then 100.00 g of coal sample and 10.00 g of potassium hydroxide were weighed into a three-necked flask, and 1000 mL of distilled water was added to it. Stir with an electromagnetic stirrer, heat under reflux for 10 h with an electric heating mantle, then cool the reaction solution to room temperature, and centrifuge the supernatant at 3600 r/min for 20 min to collect the supernatant; put the supernatant in a blast drying oven, and keep it at a constant temperature of 230 °C. Drying to obtain potassium humate solid powder with nano hollow shell.
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention. should be included within the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010258531.6A CN111393668B (en) | 2020-04-03 | 2020-04-03 | Preparation method of nano hollow shell fertilizer slow release agent |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2624735A1 (en) * | 2007-03-07 | 2008-09-07 | Timac Agro Espana, S.A. | Heteromolecular metal-humic (chelate) complexes |
| CN104403112A (en) * | 2014-12-04 | 2015-03-11 | 太原师范学院 | Method for quickly extracting humic acid |
| CN107266690A (en) * | 2017-06-08 | 2017-10-20 | 申建立 | A kind of nanometer humic acid potassium and its production method |
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- 2020-04-03 CN CN202010258531.6A patent/CN111393668B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2624735A1 (en) * | 2007-03-07 | 2008-09-07 | Timac Agro Espana, S.A. | Heteromolecular metal-humic (chelate) complexes |
| CN104403112A (en) * | 2014-12-04 | 2015-03-11 | 太原师范学院 | Method for quickly extracting humic acid |
| CN107266690A (en) * | 2017-06-08 | 2017-10-20 | 申建立 | A kind of nanometer humic acid potassium and its production method |
Non-Patent Citations (1)
| Title |
|---|
| "宝清褐煤提取腐植酸钾实验研究";李晓峰等;《神华科技》;20191213;第17卷(第8期);第69-71、81页 * |
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