CN112778538B - Humic acid complex and preparation method and application thereof - Google Patents
Humic acid complex and preparation method and application thereof Download PDFInfo
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a humic acid complex and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding humic acid and urea into water, and heating to 80-180 ℃ for reaction to obtain the humic acid complex. The preparation method has simple process, does not need to additionally add any activating agent or complexing agent, effectively reduces the preparation cost and is suitable for large-scale industrial production and application; the prepared humic acid complex can be applied to a sodium ion battery as an electrode material after high-temperature pyrolysis, so that the sodium ion battery has good rate capability.
Description
Technical Field
The invention belongs to the technical field of organic complex materials, and particularly relates to a humic acid complex and a preparation method and application thereof.
Background
Humic acid is a natural organic polymer mixture with complex components formed and accumulated by microbial decomposition and transformation of animal and plant residues, microbial cells and the like and a series of geochemical processes, and has wide sources and distribution in nature. The basic structure of humic acid molecule is aromatic ring and alicyclic ring, and the ring is connected with carboxyl, hydroxyl and other functional groups; humic acid can be adsorbed and complexed with a plurality of heavy metal ions due to the large specific surface area and strong adsorbability, and the complex product can be suitable for the fields of agriculture, animal husbandry and the like.
The humic acid urea is used as a humic acid complex formed by the reaction of humic acid and urea, and the preparation method thereof is multiple; the method commonly used at present is to use organic solvent or add reaction auxiliary agent to prepare. CN102503732A discloses a method for preparing an active humic acid urea slow-release compound fertilizer: the method comprises the steps of taking a low-activity humic acid raw material as a raw material, taking urea and ammonium sulfate as activating agents, converting and activating humic acid in the humic acid raw material by utilizing molten ammonium sulfate-urea liquid in an activation reaction tank to form active humic urea liquid, spraying the active humic urea liquid onto compound fertilizer materials in a granulation cylinder, and carrying out spheronization granulation, drying and screening to obtain humic urea slow release fertilizer products with different content ratios. CN103086808A discloses a method for preparing an active humic acid urea slow-release compound fertilizer special for potatoes, which comprises the following steps: the method takes low-activity humic acid raw materials as raw materials, combines compound fertilizer production equipment, takes urea and ammonium sulfate as activating agents, utilizes molten ammonium sulfate-urea liquid to convert and activate humic acid in the humic acid raw materials in an activation reaction tank to form active humic acid urea liquid, combines the compound fertilizer production, sprays the active humic acid urea liquid onto compound fertilizer materials in a granulation cylinder to carry out spheronization granulation, and then carries out drying and screening to prepare the special humic acid urea slow release fertilizer product for potatoes. CN105489908A discloses a preparation method of humic acid composite biochar, which comprises the following steps: (1) dissolving humic acid in water, adjusting the pH to 10-11 by using a NaOH solution, and stirring to fully dissolve the humic acid; (2) adding iron salt into the humic acid solution, stirring, adjusting the pH to 8-9 by using NaOH solution, stirring, fully reacting, and freeze-drying to obtain solid powder; (3) the preparation method comprises the steps of pyrolyzing solid powder under the protection of inert gas, mixing the solid powder with KOH after cooling, carrying out pyrolysis reaction for 2 hours at the temperature of 900 ℃, washing the solid powder with hydrochloric acid solution, carrying out suction filtration and washing to be neutral, and drying the solid powder at the temperature of 60-100 ℃ to obtain the humic acid composite biochar. However, the three methods for preparing the humic acid complex are complex, the process is complicated, additives are required, the preparation cost is increased, and the method is not suitable for industrial mass production and limits the application.
Therefore, the development of the preparation method of the humic acid complex which is simple without adding any auxiliary agent has important research significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a humic acid complex and a preparation method and application thereof, wherein in the preparation method, humic acid and urea are reacted at the temperature of 80-180 ℃, and the humic acid complex can be obtained only by one step; the reaction process is simple, an activating agent and a complexing agent are not required to be added, the obtained humic acid complex is in a micro-nano porous structure, can be applied to an ion battery or a super capacitor as an electrode material, and has important research value.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a humic acid complex, the method comprising: adding humic acid and urea into water, heating to 80-180 ℃ (such as 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃ or 170 ℃ and the like) for reaction, and obtaining the humic acid complex.
According to the preparation method of the humic acid complex, urea and humic acid are selected to react in a hydrothermal environment, and the humic acid complex can be obtained. Urea is an amide compound with a high nitrogen content; under the temperature of 80-180 ℃, humic acid and urea can react in water to form a complex, and the coordination and complexation between the humic acid and the urea enables anions such as carboxyl and phenolic hydroxyl in the nano-structure humic acid and unpaired electrons of N in amide groups of the urea to form a ligand, so that the nano-porous humic acid complex is formed. The whole reaction process is simple, an activating agent and a complexing agent are not required to be added, the cost is saved, and the industrial mass production and application are facilitated.
Preferably, the humic acid is added in an amount of 0.35 to 3.5g, such as 0.4g, 0.8g, 1.2g, 1.6g, 2.0g, 2.4g, 2.8g or 3.2g, based on 1L of water, and specific values therebetween, which are not exhaustive for the invention and for the sake of brevity.
Preferably, the mass ratio of the humic acid to the urea is 1 (0.01-0.35), such as 1:0.05, 1:0.09, 1:0.12, 1:0.15, 1:0.18, 1:0.21, 1:0.24, 1:0.27, 1:0.3 or 1: 0.33.
As a preferred technical scheme, when the mass ratio of the humic acid to the urea is 1 (0.01-0.35), a nano-porous humic acid complex can be obtained better, and if the content of the humic acid is too high, a humic acid complex with a porous structure cannot be formed; if the content of humic acid is too low, the yield of humic acid complex is too low, and urea reagent is wasted.
Preferably, the particle size of the humic acid is 40 to 90nm, such as 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm or 85nm, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction time is 2 to 24 hours, such as 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours or 22 hours, and specific values therebetween, for reasons of space and brevity, the invention is not exhaustive, and further preferably 2 to 8 hours.
Preferably, the method further comprises the steps of suction filtration, cleaning and drying after the reaction is finished.
Preferably, the washing comprises washing with absolute ethyl alcohol and deionized water.
As a preferable technical scheme, the preparation method comprises the following steps: adding humic acid and urea with the mass ratio of 1 (0.01-0.35) into water, heating to 80-180 ℃, reacting for 2-24 h, performing suction filtration, cleaning with absolute ethyl alcohol and deionized water, and drying to obtain a humic acid complex; and the addition amount of the humic acid is 0.35-3.5 g by taking the water as 1L.
In a second aspect, the present invention provides a humic acid complex prepared by the preparation method according to the first aspect.
Preferably, the humic acid complex has a particle size of 50 to 100nm, such as 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm or 95nm, and specific values therebetween, not exhaustive of the ranges included herein for brevity and conciseness.
Preferably, the humic acid complex has a specific surface area of greater than 130m2In terms of/g, e.g. 200m2/g、250m2/g、300m2/g、350m2/g、400m2/g、500m2/g、600m2/g、700m2/g、800m2G or 900m2The present invention is not intended to be exhaustive of the specific point values included in the ranges, limited to space and for the sake of brevity, as well as the specific point values between the point values recited above.
In a third aspect, the present invention provides a humic acid complex pyrolyzate material obtained by pyrolyzing the humic acid complex as described in the second aspect.
Preferably, the pyrolysis temperature is 500-1000 ℃, such as 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or 950 ℃, and the specific values therebetween are not exhaustive, and the specific values included in the range are not limited by the disclosure and for the sake of brevity.
Preferably, the pyrolysis time is 1 to 5 hours, such as 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, or 4.5 hours, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity and conciseness.
In a fourth aspect, the invention provides a humic acid complex pyrolysis material as described in the third aspect, which is used as an electrode material in an ion battery or a super capacitor.
The ion battery may be, for example, a sodium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method of the humic acid complex, urea and humic acid are selected to react at 80-180 ℃, and the humic acid complex can be obtained in one step; the preparation method has simple process, does not need to additionally add any activating agent or complexing agent, effectively reduces the preparation cost and is suitable for large-scale industrial production and application.
(2) The humic acid complex prepared by the preparation method can be used as an electrode material to be applied to a sodium ion battery after being pyrolyzed at high temperature, and the capacity of a sodium ion half battery prepared by the humic acid complex pyrolysis material is 82.7-175 mAh/g under the current density of 0.5A/g, which can be equivalent to that of the existing electrode material, so that the humic acid complex pyrolysis material has important application value.
Drawings
FIG. 1 is a scanning electron micrograph of a humic acid complex obtained in example 1;
FIG. 2 is a scanning electron microscope image of a humic acid complex pyrolysis material obtained in application example 1;
FIG. 3 is a scanning electron micrograph of the humic acid complex obtained in example 4;
FIG. 4 is a scanning electron micrograph of the humic acid complex obtained in example 5;
FIG. 5 is a scanning electron micrograph of the humic acid complex obtained in example 6;
FIG. 6 is an infrared spectrum of a humic acid complex obtained in example 1, wherein 1-humic acid complex, 2-humic acid and urea are mixed;
FIG. 7 is a nitrogen adsorption/desorption graph of the humic acid complex obtained in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A method for preparing a humic acid complex, the method comprising: adding 0.375g humic acid (crushed to a particle size of 70nm by a high-speed crusher in Tianjin City photo-repairing fine chemical research institute), 0.07g urea (national drug group chemical reagent Co., Ltd., analytical purity) and 150mL deionized water into a hydrothermal kettle, placing the hydrothermal kettle in an oven at 150 ℃ for reaction for 4h, performing suction filtration, cleaning with anhydrous ethanol and deionized water, and drying at 40 ℃ to obtain the humic acid complex.
Example 2
A method for preparing a humic acid complex, the method comprising: adding 0.075g of humic acid (the particle size of which is 40nm by adopting a high-speed pulverizer, manufactured by Tianjin City photo-chemical research institute), 0.026g of urea and 150mL of deionized water into a hydrothermal kettle, placing the hydrothermal kettle in an oven at 80 ℃ for reaction for 24h, performing suction filtration, cleaning with absolute ethyl alcohol and deionized water, and drying at 40 ℃ to obtain the humic acid complex.
Example 3
A method for preparing a humic acid complex, the method comprising: adding 0.75g of humic acid (the particle size of which is 90nm by adopting a high-speed pulverizer, manufactured by Tianjin City photo-chemical research institute), 0.0075g of urea and 150mL of deionized water into a hydrothermal kettle, placing the hydrothermal kettle in an oven at 180 ℃ for reaction for 2h, performing suction filtration, cleaning with absolute ethyl alcohol and deionized water, and drying at 40 ℃ to obtain the humic acid complex.
Example 4
A humic acid complex preparation method which is different from the preparation method of the embodiment 1 only in that the reaction time is 3 hours, and other conditions and steps are the same as the embodiment 1.
Example 5
A humic acid complex preparation method which is different from the preparation method of the embodiment 1 only in that the reaction time is 5 hours, and other conditions and steps are the same as the embodiment 1.
Example 6
A humic acid complex preparation method which is different from the preparation method of the embodiment 1 only in that the reaction time is 6 hours, and other conditions and steps are the same as the embodiment 1.
Example 7
A humic acid complex preparation method which differs from the method of example 1 only in that the amount of urea is 0.0375g, and other conditions and steps are the same as those of example 1.
Example 8
A humic acid complex preparation method which differs from example 1 only in that the amount of urea used is 0.1125g, and the other conditions and procedures are the same as those of example 1.
Example 9
A humic acid complex preparation method which differs from example 1 only in that the amount of urea used is 0.00375g, and the other conditions and steps are the same as those of example 1.
Example 10
A humic acid complex preparation method which differs from example 1 only in that the amount of urea used is 0.13125g, and the other conditions and steps are the same as those of example 1.
Application examples 1 to 10
A humic acid complex pyrolysis material is prepared by the following steps: and (3) pyrolyzing the humic acid complex obtained in the embodiment 1-10 at 700 ℃ for 2h to obtain the humic acid complex pyrolysis material.
Application examples 11 to 20
A button half cell: respectively comprising the humic acid complex pyrolysis materials obtained in application examples 1-10;
the preparation method comprises the following steps:
(1) mixing conductive agent carbon black, binder polyvinylidene fluoride and humic acid complex pyrolysis material obtained by the application examples 1-10 in a solvent N-methyl pyrrolidone according to a mass ratio of 1:1:8, sealing, and stirring for about 2 hours on a magnetic stirrer; coating the slurry uniformly stirred on a copper foil with a smooth and clean surface, and then volatilizing the solvent on a heating plate at the temperature of about 50 ℃; the mixture is put in a vacuum oven at 100 ℃, taken out for 12 hours, rolled and put in a glove box to be used when a battery is to be filled.
(2) And assembling the button cell in a glove box filled with high-purity argon, wherein the content of the water oxygen value in the glove box is less than 0.5ppm when the cell is assembled. The button cell consists of a positive electrode shell, a negative electrode shell, a glass fiber diaphragm, electrolyte, an electrode plate, an elastic sheet, a gasket and a counter electrode sodium sheet/potassium sheet. The assembly sequence of the button cell is as follows: firstly, pressing a sodium block into a sodium sheet with the diameter of 14mm by a rod, and placing the sodium sheet in the middle of a negative electrode shell; adding a certain amount of sodium electrolyte; a diaphragm with a diameter of 16mm is placed in the middle; putting the weighed intact electrode plates with certain mass; sequentially placing a gasket, an elastic sheet and a positive electrode shell; and packaging by a sealing machine to obtain the button half cell.
And (3) performance testing:
(1) and (3) observing the appearance:
the humic acid complexes obtained in examples 1, 4 to 6 and the humic acid complex pyrolysis material obtained in example 1 were tested by a scanning electron microscope (ZEISS SUPRATM55 Germany ZEISS) to observe the surface morphology and particle size of the prepared humic acid complex.
Wherein, the scanning electron micrographs of the humic acid complex prepared in the example 1 and the examples 4 to 6 are respectively shown in fig. 1 and fig. 3 to 5, and the scanning electron micrographs of the humic acid complex pyrolysis material obtained in the application example 1 are shown in fig. 2; as can be seen from FIGS. 1 and 3 to 5, the humic acid complexes prepared in examples 1 and 4 to 6 have a uniform particle size of about 60 nm; as can be seen from FIG. 2, the humic acid complex obtained in example 1 can maintain uniform nano-particle size after pyrolysis treatment, the particle size is about 50nm, and the particle size is reduced, which is caused by the overflow of unstable micromolecules in the complex during pyrolysis and the contraction of carbon skeleton.
(2) Structural characterization:
the humic acid complex obtained in example 1 was tested by an infrared spectrometer (Nicolet iS50 U.S. Thermo Nicolet) and a nitrogen desorption apparatus (ASAP2020 U.S. mike corporation), and it was confirmed that the humic acid complex was successfully prepared by the preparation method provided by the present invention.
Wherein, the infrared spectrogram of the humic acid complex obtained in example 1 is shown in FIG. 6, and as can be seen from FIG. 6, the humic acid complex obtained in example 1 is 3465cm-1、1645cm-1、1380cm-1The peak of the infrared spectrum of the covalent bond is compared with the infrared spectrum of the mixture of humic acid and urea to generate displacement, which indicates the generation of the humic acid complex.
The nitrogen adsorption/desorption curve of example 1 is shown in fig. 7, and it can be seen from fig. 7 that the humic acid complex obtained in example 1 has a porous structure and a specific surface area of 183.4cm2/g。
(3) Rate capability:
the button half-cells obtained in examples 11 to 20 were subjected to performance testing using a blue tester (CT2001A), and the test results are shown in table 1:
TABLE 1
| Capacity of 0.5A/g Current Density (mAh/g) | |
| Application example 11 | 175.0 |
| Application example 12 | 170.6 |
| Application example 13 | 103.7 |
| Application example 14 | 134.8 |
| Application example 15 | 162.4 |
| Application example 16 | 141.3 |
| Application example 17 | 114.3 |
| Application example 18 | 173.8 |
| Application example 19 | 82.7 |
| Application example 20 | 174.6 |
As can be seen from the data in table 1:
The half-cell prepared from the humic acid complex pyrolysis material obtained in the application examples 1-10 has very high cell capacity, and the capacity of 0.5A/g current density is 82.7-175 mAh/g, which is equivalent to the capacity of the existing electrode material; the invention can be proved that the humic acid complex prepared by the simple preparation method can be used as an electrode material of a battery, and the pyrolysis material can be used as the electrode material of the battery, and has great application value.
The applicant states that the present invention is illustrated by the above examples, but the present invention is not limited to the above process steps, i.e. it is not meant to be dependent on the above process steps to carry out the present invention. It will be apparent to those skilled in the art that any modifications to the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific forms, etc., are within the scope and disclosure of the present invention.
Claims (14)
1. A preparation method of a porous humic acid complex used for preparing an electrode material is characterized by comprising the following steps: adding humic acid and urea into water, and heating to 80-180 ℃ for reaction to obtain the humic acid complex;
The mass ratio of the humic acid to the urea is 1 (0.01-0.35);
the reaction time is 2-24 h.
2. The preparation method according to claim 1, wherein the humic acid is added in an amount of 0.35 to 3.5g based on 1L of the water.
3. The preparation method according to claim 1, wherein the particle size of the humic acid is 40-90 nm.
4. The preparation method according to claim 1, wherein the reaction time is 2-8 h.
5. The preparation method according to claim 1, characterized by further comprising the steps of suction filtration, washing and drying after the reaction is finished.
6. The method of claim 5, wherein the washing comprises washing with absolute ethanol and deionized water.
7. The method of manufacturing according to claim 1, comprising: adding humic acid and urea with the mass ratio of 1 (0.01-0.35) into water, heating to 80-180 ℃, reacting for 2-24 h, performing suction filtration, cleaning with absolute ethyl alcohol and deionized water, and drying to obtain the humic acid complex; the addition amount of the humic acid is 0.35-3.5 g by taking 1L of water.
8. Humic acid complex, which is prepared by the preparation method according to any one of claims 1 to 7.
9. The humic acid complex according to claim 8, wherein the particle size of the humic acid complex is 50 to 100 nm.
10. Humic acid complex according to claim 8, characterized in that it has a specific surface area of more than 130m2/g。
11. A humic acid complex pyrolysis material, which is obtained by pyrolyzing the humic acid complex according to any one of claims 8 to 10.
12. The humic acid complex pyrolytic material according to claim 11, wherein the temperature of the pyrolysis is 500-1000 ℃.
13. The humic acid complex pyrolytic material according to claim 11, wherein the time for pyrolysis is 1-5 h.
14. Use of the humic acid complex pyrolysate material according to any one of claims 11 to 13 as an electrode material in an ion battery or a supercapacitor.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260111A (en) * | 2011-05-17 | 2011-11-30 | 谭钧 | Method for preparing humic acid-urea complex in aqueous medium |
| CN103408356A (en) * | 2013-07-17 | 2013-11-27 | 安徽瑞然生物药肥科技有限公司 | Nanometer carbon active water-containing humic acid water-soluble fertilizer and preparation method thereof |
| CN103755478A (en) * | 2014-01-23 | 2014-04-30 | 贵州特力达纳米碳素科技有限公司 | Nano-carbon organic compound fertilizer |
| CN105489908A (en) * | 2016-01-13 | 2016-04-13 | 中国科学院广州能源研究所 | Application of humic acid composite biochar in microbial fuel cell and preparation method of humic acid composite biochar |
| CN108439618A (en) * | 2018-03-14 | 2018-08-24 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | A kind of coal gasification buck scale preventative and preparation method thereof |
| CN110354828A (en) * | 2019-06-11 | 2019-10-22 | 兰州大学 | A kind of preparation method and adsorbent of adsorbent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641117A (en) * | 2013-12-17 | 2014-03-19 | 中国科学院新疆理化技术研究所 | Method for preparing activated carbon material with humic acid as raw material and application of activated carbon material |
-
2020
- 2020-12-10 CN CN202011458075.6A patent/CN112778538B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260111A (en) * | 2011-05-17 | 2011-11-30 | 谭钧 | Method for preparing humic acid-urea complex in aqueous medium |
| CN103408356A (en) * | 2013-07-17 | 2013-11-27 | 安徽瑞然生物药肥科技有限公司 | Nanometer carbon active water-containing humic acid water-soluble fertilizer and preparation method thereof |
| CN103755478A (en) * | 2014-01-23 | 2014-04-30 | 贵州特力达纳米碳素科技有限公司 | Nano-carbon organic compound fertilizer |
| CN105489908A (en) * | 2016-01-13 | 2016-04-13 | 中国科学院广州能源研究所 | Application of humic acid composite biochar in microbial fuel cell and preparation method of humic acid composite biochar |
| CN108439618A (en) * | 2018-03-14 | 2018-08-24 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | A kind of coal gasification buck scale preventative and preparation method thereof |
| CN110354828A (en) * | 2019-06-11 | 2019-10-22 | 兰州大学 | A kind of preparation method and adsorbent of adsorbent |
Non-Patent Citations (4)
| Title |
|---|
| "低温条件下纳米腐殖酸-尿素配合物的制备及表征";程亮 等;《化工学报》;20150731;第66卷(第7期);第2725-2736页 * |
| 三种腐植酸对铅酸电池负极板电化学性能的影响;赵婧等;《蓄电池》;20160420(第02期);第55-58页 * |
| 腐植酸尿素新型生产工艺及田间应用效果研究;林海涛等;《腐植酸》;20100820(第04期);第9-16页 * |
| 腐植酸――脲络合物的工艺开发;成绍鑫等;《腐植酸》;19940430(第04期);第29-32页 * |
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