CN111393668B - Preparation method of nano hollow shell fertilizer slow release agent - Google Patents
Preparation method of nano hollow shell fertilizer slow release agent Download PDFInfo
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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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- hollow shell
- release agent
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- nano hollow
- coal sample
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 15
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 5
- 238000005485 electric heating Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims 1
- 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 8
- 239000002086 nanomaterial Substances 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
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 239000004021 humic acid Substances 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
Images
Classifications
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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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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
The invention relates to the field of preparation of nano materials, in particular to a preparation method of a nano hollow shell fertilizer slow-release agent. Grinding a coal sample into powder, mixing the coal sample powder with potassium hydroxide, adding distilled water, stirring and heating to reflux for 8-10 h at 50 ℃, cooling a reaction liquid to room temperature, centrifuging and collecting a supernatant; and drying the supernatant to constant weight to obtain the nano hollow shell potassium humate fertilizer slow release agent. The humic acid functional groups in the prepared potassium humate have aromatic rings and ester rings, and carboxyl, hydroxyl, carbonyl, methoxyl and other functional groups connected on the rings can adsorb elements in the fertilizer through hydrogen bonds, so that the humic acid functional groups are used as a fertilizer slow release agent. The unique hollow shell of the fertilizer slow-release agent can increase the adsorption surface area, and the internal space of the hollow sphere can be used as a fertilizer carrier.
Description
Technical Field
The invention relates to the field of preparation of nano materials, in particular to a preparation method of a nano hollow shell fertilizer slow-release agent.
Background
Humic acid is a natural organic macromolecular mixture, and the humic acid and the salt thereof have extremely wide application in the field of agriculture. The humic acid functional group in the potassium humate can absorb and store potassium ions, prevent the potassium ions from losing along with water in sandy soil and leaching soil and prevent the potassium ions from being fixed by viscous soil. Besides, humic acid functional groups in the potassium humate comprise aromatic rings and ester rings, and carboxyl, hydroxyl, carbonyl, methoxyl and other functional groups connected on the rings can adsorb elements in the fertilizer through hydrogen bonds, so that the humic acid functional groups are used as a fertilizer slow release agent. At present, the prior art defines potassium humate as a nano material according to the size of the potassium humate, and the potassium humate alone or other humates are mixed to be used as a fertilizer slow release agent. However, the potassium humate of the hollow shell with the nanometer size is not prepared and characterized in the prior art. The invention prepares the potassium humate with the nano-size hollow shell for the first time by using coal as a raw material.
Disclosure of Invention
The invention provides a preparation method of a nano hollow shell fertilizer slow-release agent, aiming at solving the problem that the prior art lacks a nano-sized hollow shell potassium humate technology.
The invention is realized by the following technical scheme: a preparation method of a nano hollow shell fertilizer slow release agent comprises the following steps:
firstly, grinding a coal sample into powder, then mixing the coal sample powder with potassium hydroxide, adding distilled water, stirring and heating and refluxing for 8-10 h at 50 ℃, then cooling a reaction solution to room temperature, centrifuging and collecting a supernatant; and drying the supernatant to constant weight to obtain the potassium humate fertilizer slow release agent with the nano hollow shell.
As a further improvement of the technical scheme of the invention, the mass ratio of the coal sample powder to the potassium hydroxide is 10: 1.
As a further improvement of the technical scheme of the invention, the centrifugation parameter is rotation speed centrifugation of 3600r/min for 20 min.
As a further improvement of the technical scheme of the invention, the coal sample is weathered coal or lignite.
As a further improvement of the technical scheme of the invention, the particle size of the coal sample powder is 80-200 meshes.
As a further improvement of the technical scheme of the invention, the temperature for drying the supernatant is 230 ℃.
The invention further provides the potassium humate fertilizer slow-release agent with the nano hollow shell, which is prepared by the preparation method of the fertilizer slow-release agent with the nano hollow shell.
As a further improvement of the technical scheme of the slow release agent of the potassium humate fertilizer, the particle size of the slow release agent of the potassium humate fertilizer is 5-105 mu m, and the wall thickness is 0.5-5 mu m.
According to the preparation method of the nano hollow shell fertilizer slow release agent provided by the invention, humic acid functional groups in the prepared potassium humate have aromatic rings and ester rings, and carboxyl, hydroxyl, carbonyl, methoxyl and other functional groups connected to the rings can adsorb elements in the fertilizer through hydrogen bonds, so that the nano hollow shell fertilizer slow release agent is used as a fertilizer slow release agent. The hollow shell of the fertilizer slow-release agent can increase the adsorption surface area, and the internal space of the hollow sphere can be used as a fertilizer carrier.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an XRD spectrum of the potassium humate fertilizer slow-release agent with nano hollow shell prepared in example 1 of the present invention.
FIGS. 2 to 4 are Scanning Electron Microscope (SEM) photographs of the nano-hollow potassium humate fertilizer sustained-release agent prepared in example 1 of the present invention at different magnifications.
FIGS. 5 to 6 are Transmission Electron Microscope (TEM) images obtained by the preparation of example 1 of the present invention.
As shown in figure 1, the potassium humate nano material has a wider absorption band at 20-35 degrees, and the potassium humate is an amorphous substance. The low magnification SEM images from figures 2 and 3 show that potassium humate has the morphology of nano-hollow shells of micro-size. The nanometer hollow shells of the potassium humate have different particle diameters, the particle external dimension is 5-105 μm, and the wall thickness is 0.5-5 μm. And some of the larger spherical particles have broken. From the high magnification SEM image in fig. 4, it is seen that the surface of the nano hollow shell is rough and many nanoparticles are aggregated together. As can be seen from fig. 5 and 6, the nano-hollow shell of potassium humate has three morphologies, including cubic shell nanoparticles having a length of about 35-60nm and a width of about 25-40 nm; shuttle-shaped nanoparticles having a width, a length of about 80-105nm, and a width of about 25-35 nm; approximately spherical nanoparticles of about 35-60nm in diameter.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The technical solution of the present invention will be described in detail by the following specific examples.
Example 1
A preparation method of a nano hollow shell fertilizer slow release agent comprises the following steps:
firstly, grinding a Shanxi weathered coal sample into powder with the particle size of 80 meshes, then weighing 100.00g of the coal sample and 10.00g of potassium hydroxide in a three-neck flask, adding 1000mL of distilled water into the three-neck flask, stirring the mixture by using an electromagnetic stirrer at the temperature of 50 ℃, heating and refluxing the mixture for 9 hours by using an electric heating sleeve, then cooling a reaction liquid to the room temperature, centrifuging the reaction liquid at the rotating speed of 3600r/min for 20min, and collecting supernatant; and (3) putting the supernatant into a forced air drying oven, and drying at constant temperature of 230 ℃ to obtain the nano hollow shell potassium humate solid powder.
Example 2
A preparation method of a nano hollow shell fertilizer slow release agent comprises the following steps:
firstly, grinding a Shanxi weathered coal sample into powder with the particle size of 150 meshes, then weighing 100.00g of the coal sample and 10.00g of potassium hydroxide in a three-neck flask, adding 1000mL of distilled water into the three-neck flask, stirring the mixture by using an electromagnetic stirrer at the temperature of 50 ℃, heating and refluxing the mixture for 9 hours by using an electric heating sleeve, then cooling a reaction liquid to the room temperature, centrifuging the reaction liquid at the rotating speed of 3600r/min for 20min, and collecting supernatant; and (3) putting the supernatant into a forced air drying oven, and drying at constant temperature of 230 ℃ to obtain the nano hollow shell potassium humate solid powder.
Example 3
A preparation method of a nano hollow shell fertilizer slow release agent comprises the following steps:
firstly, grinding a Yunnan lignite coal sample into powder with the particle size of 200 meshes, then weighing 100.00g of the coal sample and 10.00g of potassium hydroxide in a three-neck flask, adding 1000mL of distilled water into the three-neck flask, stirring the mixture by using an electromagnetic stirrer at the temperature of 50 ℃, heating and refluxing the mixture for 10 hours by using an electric heating sleeve, then cooling a reaction liquid to the room temperature, and centrifuging the reaction liquid for 20 minutes at the rotating speed of 3600r/min to collect supernatant; and (3) putting the supernatant into a forced air drying oven, and drying at constant temperature of 230 ℃ to obtain the nano hollow shell potassium humate solid powder.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (2)
1. A preparation method of a nano hollow shell fertilizer slow release agent is characterized by comprising the following steps:
firstly, grinding a Shanxi weathered coal sample into powder with the particle size of 80 meshes, then weighing 100.00g of the coal sample and 10.00g of potassium hydroxide in a three-neck flask, adding 1000mL of distilled water into the three-neck flask, stirring the mixture by using an electromagnetic stirrer at the temperature of 50 ℃, heating and refluxing the mixture for 9 hours by using an electric heating sleeve, then cooling a reaction liquid to the room temperature, centrifuging the reaction liquid at the rotating speed of 3600r/min for 20min, and collecting supernatant; putting the supernatant into a forced air drying oven, and drying at constant temperature of 230 ℃ to obtain the solid powder of the potassium humate with the nano hollow shell;
or,
firstly, grinding a Shanxi weathered coal sample into powder with the particle size of 150 meshes, then weighing 100.00g of the coal sample and 10.00g of potassium hydroxide in a three-neck flask, adding 1000mL of distilled water into the three-neck flask, stirring the mixture by using an electromagnetic stirrer at the temperature of 50 ℃, heating and refluxing the mixture for 9 hours by using an electric heating sleeve, then cooling a reaction liquid to the room temperature, centrifuging the reaction liquid at the rotating speed of 3600r/min for 20min, and collecting supernatant; and (3) putting the supernatant into a forced air drying oven, and drying at constant temperature of 230 ℃ to obtain the nano hollow shell potassium humate solid powder.
2. The method for preparing the nano hollow shell fertilizer slow release agent as claimed in claim 1, wherein the potassium humate of the nano hollow shell is cubic shell nano particles with the length of 35-60nm and the width of 25-40 nm; or shuttle-shaped nanoparticles with length of 80-105nm and width of 25-35 nm; or approximately spherical nanoparticles with a diameter of 35-60 nm.
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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
- 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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| CN111393668A (en) | 2020-07-10 |
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