CN116730771B - Slow-release nitrogen fertilizer and preparation method thereof - Google Patents
Slow-release nitrogen fertilizer and preparation method thereof Download PDFInfo
- Publication number
- CN116730771B CN116730771B CN202310557101.8A CN202310557101A CN116730771B CN 116730771 B CN116730771 B CN 116730771B CN 202310557101 A CN202310557101 A CN 202310557101A CN 116730771 B CN116730771 B CN 116730771B
- Authority
- CN
- China
- Prior art keywords
- slow
- mof
- nitrogen fertilizer
- release nitrogen
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000618 nitrogen fertilizer Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 36
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 32
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 26
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 26
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 26
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000661 sodium alginate Substances 0.000 claims abstract description 24
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 24
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000741 silica gel Substances 0.000 claims abstract description 8
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 238000010168 coupling process Methods 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 20
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 10
- 229960001553 phloroglucinol Drugs 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 229910007926 ZrCl Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000003337 fertilizer Substances 0.000 abstract description 31
- 239000002689 soil Substances 0.000 abstract description 14
- 230000009471 action Effects 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000004964 aerogel Substances 0.000 abstract description 3
- 239000007822 coupling agent Substances 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 235000016709 nutrition Nutrition 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000007788 liquid Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 235000015097 nutrients Nutrition 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 206010016807 Fluid retention Diseases 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000012272 crop production Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- 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
-
- 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
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
-
- 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
- C05G3/80—Soil conditioners
-
- 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)
- Pest Control & Pesticides (AREA)
- Soil Sciences (AREA)
- Fertilizers (AREA)
Abstract
The invention provides a slow-release nitrogen fertilizer and a preparation method thereof, wherein the slow-release nitrogen fertilizer comprises the following raw materials: MOF-COF composite material, sodium carboxymethylcellulose, sodium alginate, ammonium chloride and water; the preparation method comprises the following steps: s1, nanometer Fe 3 O 4 As raw material, fe is prepared by silica gel coupling method under the action of coupling agent 3 O 4 @SiO 2 Nanoparticle, and Fe preparation 3 O 4 @MOF; s2, fe obtained in the step S1 3 O 4 Introducing COF into the MOF to obtain a MOF-COF composite material; compared with the conventional MOF (Cu) @ biochar hybrid aerogel structure slow-release nitrogen fertilizer, the slow-release nitrogen fertilizer provided by the invention has the advantages of MOF and COF, greatly improves the stability in aqueous solution, has a good slow-release effect, can adsorb soil heavy metal ions, provides nutritional ingredients, and has good water and fertilizer retention performance.
Description
Technical Field
The invention relates to the technical field of fertilizers, in particular to a slow-release nitrogen fertilizer and a preparation method thereof.
Background
The fertilizer is grain of crops, and as the demands of farmers on high quality, special use, capability of improving stress resistance, immunity and the like of crops are becoming stronger, the development of comprehensive and multifunctional fertilizers is becoming more urgent. The nitrogenous fertilizer is taken as one of fertilizers with the largest yield and demand, and is an important helper for improving the grain yield in China. At the same time, nitrogen element is also an important element required by each stage of crop growth, and the utilization rate of the nitrogen element is also closely related to the crop yield.
However, compared with the traditional nitrogen fertilizer, the nitrogen fertilizer has single nutrient, poor stress resistance, low yield, high loss rate and environment pollution and water source, and is easy to volatilize, ablate and denitrify when being applied to soil. The slow release fertilizer can improve the utilization rate of nitrogen element, prolong the fertilizer efficiency period and reduce the environmental problems caused by nutrient loss. Therefore, the improvement of the existing nitrogen fertilizer and the enhancement of the slow release function and the fertilizer efficiency are technical problems which need to be solved in the industry.
At present, the slow release fertilizers at home and abroad are mainly divided into two major categories of coated fertilizers and non-coated fertilizers, wherein the coated fertilizers are mainly sulfur coated fertilizers, but after the sulfur coated fertilizers are applied for a long time, sulfur coated shells are difficult to degrade in soil, so that the soil is acidified; in addition, the polymer coated slow-release nitrogen fertilizer is also the focus of more scholars, but with the intensive research, it is found that most high-molecular polymers such as polyolefin, resin and the like use a large amount of volatile organic solvents in the coating process, so that on one hand, the manufacturing cost of the nitrogen fertilizer is increased, and on the other hand, the nitrogen fertilizer also causes great harm to the environment; the non-coated fertilizer is mainly urea formaldehyde fertilizer and comprises liquid form and particles, however, the preparation process of the fertilizer involves the use of liquid raw materials, so that the production process is complex and cannot be used for crop production on a large scale; in recent years, various novel matrix slow-release nitrogenous fertilizers are introduced into the field of students, mainly including biochar, sodium alginate, hydrogel, montmorillonite and the like, but are mostly in a research stage and are not in practical application.
The patent with publication number CN111943763A discloses a slow-release liquid nitrogen fertilizer and a preparation method thereof, urea liquid is prepared from compound fertilizer, mixed slurry is prepared, atomized ammonia water is added to be mixed, and then the liquid nitrogen fertilizer is obtained, however, the preparation of liquid raw materials, especially urea liquid, and the process thereof are complicated, complex rare earth is introduced, the preparation cost is increased, and the slow-release liquid nitrogen fertilizer cannot be applied to crops in a large area.
The patent with publication number CN112608190A provides a preparation method of a pH/salt-sensitive porous 3D structure slow-release nitrogen fertilizer based on MOF (Cu) @ biochar, which has good slow-release performance and can improve soil productivity, but the MOF is unstable in aqueous solution, and the structure is easy to collapse, so that the fertilizer efficiency of the slow-release nitrogen fertilizer is affected.
Disclosure of Invention
In view of the above, the invention provides a slow-release nitrogen fertilizer and a preparation method thereof, and solves the technical problems of poor slow-release performance, poor stability in water, difficult degradation, pollution to soil and the like of the existing slow-release nitrogen fertilizer.
The technical scheme of the invention is realized as follows:
a slow-release nitrogen fertilizer, which comprises the following raw materials: MOF-COF composite material, sodium carboxymethyl cellulose, sodium alginate, ammonium chloride and water.
Preferably, the preparation method of the MOF-COF composite material comprises the following steps:
s1, nanometer Fe 3 O 4 Preparation of Fe by silica gel coupling method under tetraethoxysilane effect 3 O 4 @SiO 2 A nanoparticle; adding ZrCl again 4 Dispersing in DMF by ultrasonic wave, heating and stirring at 100-120deg.C for 18-24 hr, cleaning with ethanol, and drying to obtain Fe 3 O 4 @MOF；
S2, fe obtained in the step S1 3 O 4 Adding @ MOF and trialdehyde phloroglucinol into an organic solvent, performing ultrasonic treatment, heating and stirring at 100-120 ℃ for 0.5-1h, cooling, adding benzidine, dissolving in a mixed solvent of trimethylbenzene and dioxane, heating and stirring at 100-120 ℃ for 18-24h, separating a product by using a magnet, washing by using DMF, and performing vacuum drying to obtain the MOF-COF composite material.
Preferably, the nano Fe is as described in step S1 3 O 4 The grain diameter is 9-15nm.
Preferably, the nano Fe is as described in step S1 3 O 4 Tetraethoxysilane, zrCl 4 The molar ratio of (1-1.2): 1: (1.16-1.24).
Preferably, the organic solvent in step S2 is trimethylbenzene, dioxane and acetic acid.
Preferably, the volume ratio of trimethylbenzene, dioxane and acetic acid is 1:1: (0.2-0.3).
Further preferably, fe as described in step S2 3 O 4 The mass ratio of the @ MOF to the trialdehyde phloroglucinol to the benzidine is 1: (0.045-0.052): (0.18-0.25)。
Further preferably, the volume ratio of trimethylbenzene to dioxane described in step S2 is (0.8-1.1): 1.
further preferably, the ultrasonic power is 300-400W for 25-45min.
In another aspect, the present invention also provides a method for preparing the slow-release nitrogen fertilizer according to the first aspect, comprising the following steps:
a1, dissolving sodium carboxymethyl cellulose and sodium alginate in water at 55-60 ℃, stirring to dissolve completely, then adding MOF-COF composite material, and carrying out ultrasonic treatment for 0.5-1h to obtain a mixture;
a2, adding ammonium chloride, cooling to-5-0 ℃, dripping a cross-linking agent, reacting for 30-45min at 50-55 ℃, and freeze-drying to obtain the slow-release nitrogen fertilizer.
Further preferably, the mass ratio of sodium carboxymethylcellulose, sodium alginate and MOF-COF composite material in step A1 is (0.8-1): (1.6-2.2): (0.7-1).
Further preferably, the cross-linking agent is glutaraldehyde.
It is further preferred that the mass ratio of crosslinker, ammonium chloride to the mixture of step A1 in step A2 is (0.02-0.03): 1: (0.2-0.3).
Further preferably, the freeze-drying conditions in step A2 are temperature ranging from-30 ℃ to-25 ℃ and pressure ranging from 1.3MPa to 1.8MPa.
Compared with the prior art, the slow-release nitrogen fertilizer and the preparation method thereof have the following beneficial effects:
(1) The slow-release nitrogen fertilizer of the invention introduces a MOF-COF composite material, which has a MOF-COF framework structure, compared with the prior hybrid aerogel structure of MOF (Cu) @ biochar, the stability of the slow-release nitrogen fertilizer in aqueous solution is greatly improved, and the slow-release nitrogen fertilizer has the advantages of MOF and COF respectively, by the method of nano Fe 3 O 4 An outer layer is formed of SiO 2 Layer, surface negative charge increases, when Fe is formed 3 O 4 After @ MOF, its surface is covered with amine groups, the surface charge is changed from negative to positive, fe 3 O 4 The @ MOF in combination with COF provides better porosity, increasing adsorption capacity; and the MOF-COF composite material contains high-density nitrogen-containing groups and oxygen-containing groups, and lone pair electrons on nitrogenIs beneficial to improving the adsorption performance;
(2) The MOF-COF composite material not only can protect nitrogen fertilizer, but also can adsorb other heavy metal pollutants in soil, further enhances the absorption of crops to the fertilizer, and enhances the stability of slow-release nitrogen fertilizer;
(3) According to the invention, sodium carboxymethylcellulose and sodium alginate are simultaneously introduced, and the sodium carboxymethylcellulose and the MOF-COF composite material form a slow-release nitrogen fertilizer with a porous structure, so that the slow-release performance is improved, meanwhile, the water and fertilizer retaining capacity is better, the crop productivity is effectively improved, and the environment is not polluted.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the Cu ion content of soil heavy metal ions in example 1 and comparative example 2 of the slow-release nitrogen fertilizer of the invention 2+ Adsorption conditions of (2);
figure 2 shows the water retention of the slow-release nitrogen fertilizer of the invention in example 1 and comparative examples 1-3 at different times.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Example 1
A slow-release nitrogen fertilizer, which comprises the following raw materials: MOF-COF composite material, sodium carboxymethylcellulose, sodium alginate, ammonium chloride and water;
the preparation method of the MOF-COF composite material comprises the following steps:
s1, nanometer Fe with the grain diameter of 9nm 3 O 4 Preparing Fe by coupling reaction under the action of tetraethoxysilane as raw material 3 O 4 @SiO 2 Nanoparticle, and ZrCl is added 4 Ultrasonic dispersing in DMF for 45min with ultrasonic power of 300W, wherein nanometer Fe 3 O 4 Tetraethoxysilane, zrCl 4 The mass ratio of (2) is 1:1:1.16, heating and stirring at 100deg.C for 24 hr, cleaning with ethanol, and drying to obtain Fe 3 O 4 @MOF；
S2, fe obtained in the step S1 3 O 4 The @ MOF and the trialdehyde phloroglucinol are added into 3ml of mixed solution of trimethylbenzene, dioxane and acetic acid, and the volume ratio of the trimethylbenzene, the dioxane and the acetic acid is 1:1:0.2; ultrasonic for 45min with ultrasonic power of 300W, heating and stirring at 100deg.C for 1 hr, cooling to 50deg.C, and adding benzidine, wherein Fe 3 O 4 The mass ratio of the @ MOF to the trialdehyde phloroglucinol to the benzidine is 1:0.045:0.18, in a mixed solvent of 3ml of trimethylbenzene and dioxane, the volume ratio of the trimethylbenzene to the dioxane is 0.8:1, heating and stirring for 24 hours at 100 ℃, separating a product by using a magnet, washing by using DMF, and carrying out vacuum drying at 50 ℃ to obtain the MOF-COF composite material.
The preparation method of the slow-release nitrogen fertilizer comprises the following steps:
a1, dissolving sodium carboxymethyl cellulose and sodium alginate in water at 55 ℃, stirring until the sodium carboxymethyl cellulose and the sodium alginate are completely dissolved, and then adding an MOF-COF composite material, wherein the mass ratio of the sodium carboxymethyl cellulose to the sodium alginate to the MOF-COF composite material is 0.8:1.6:0.7, carrying out ultrasonic treatment for 0.5h, wherein the ultrasonic power is 300W, so as to obtain a mixture;
a2, adding ammonium chloride, cooling to-5 ℃, and dropwise adding a cross-linking agent, wherein the mass ratio of the cross-linking agent to the mixture of the ammonium chloride and the step A1 is 0.02:1:0.2, reacting at 50 ℃ for 45min, and freeze-drying at-30 ℃ and 1.3Mpa to obtain the slow-release nitrogen fertilizer.
Example 2
A slow-release nitrogen fertilizer, which comprises the following raw materials: MOF-COF composite material, sodium carboxymethylcellulose, sodium alginate, ammonium chloride and water;
the preparation method of the MOF-COF composite material comprises the following steps:
s1, nanometer Fe with particle size of 15nm 3 O 4 As raw material, under the action of tetraethoxysilane, preparing Fe by using a silica gel coupling method 3 O 4 @SiO 2 A nanoparticle; adding ZrCl again 4 Ultrasonic dispersing in DMF for 25min with ultrasonic power of 400W, wherein nanometer Fe 3 O 4 Tetraethoxysilane, zrCl 4 The mass ratio of (2) is 1.2:1:1.24, heating and stirring at 120 ℃ for 18h, cleaning with ethanol, and drying to obtain Fe 3 O 4 @MOF；
S2, fe obtained in the step S1 3 O 4 The @ MOF and the trialdehyde phloroglucinol are added into 3ml of mixed solution of trimethylbenzene, dioxane and acetic acid, and the volume ratio of the trimethylbenzene, the dioxane and the acetic acid is 1:1:0.3; ultrasonic for 25min with ultrasonic power of 400W, heating and stirring at 120deg.C for 0.5 hr, cooling to 50deg.C, and adding benzidine, wherein Fe 3 O 4 The mass ratio of the @ MOF to the trialdehyde phloroglucinol to the benzidine is 1:0.052:0.25, in a mixed solvent of 3ml of trimethylbenzene and dioxane, wherein the volume ratio of the trimethylbenzene to the dioxane is 1.1:1, heating and stirring for 18h at 120 ℃, separating the product by using a magnet, washing by using DMF, and drying in vacuum at 50 ℃ to obtain the MOF-COF composite material.
The preparation method of the slow-release nitrogen fertilizer comprises the following steps:
a1, dissolving sodium carboxymethyl cellulose and sodium alginate in water at 60 ℃, stirring until the sodium carboxymethyl cellulose and the sodium alginate are completely dissolved, and then adding the MOF-COF composite material, wherein the mass ratio of the sodium carboxymethyl cellulose to the sodium alginate to the MOF-COF composite material is 1:2.2:1, carrying out ultrasonic treatment for 1h, wherein the ultrasonic power is 400W, so as to obtain a mixture;
a2, adding ammonium chloride, cooling to 0 ℃, and dropwise adding a cross-linking agent, wherein the mass ratio of the cross-linking agent to the mixture of the ammonium chloride and the step A1 is 0.03:1:0.3, reacting for 30min at 55 ℃, and freeze-drying at-25 ℃ and 1.8MPa to obtain the slow-release nitrogen fertilizer.
Example 3
A slow-release nitrogen fertilizer, which comprises the following raw materials: MOF-COF composite material, sodium carboxymethylcellulose, sodium alginate, ammonium chloride and water;
the preparation method of the MOF-COF composite material comprises the following steps:
s1, nanometer Fe with the particle size of 10nm 3 O 4 As raw material, under the action of tetraethoxysilane, preparing Fe by using a silica gel coupling method 3 O 4 @SiO 2 Nanoparticle, and ZrCl is added 4 Ultrasonic power of 350W is obtained after ultrasonic dispersion in DMF for 30min, wherein nano Fe 3 O 4 Tetraethoxysilane, zrCl 4 The mass ratio of (2) is 1.1:1:1.18, heating and stirring for 20h at 110 ℃, cleaning with ethanol, and drying to obtain Fe 3 O 4 @MOF；
S2, fe obtained in the step S1 3 O 4 The @ MOF and the trialdehyde phloroglucinol are added into 3ml of mixed solution of trimethylbenzene, dioxane and acetic acid, and the volume ratio of the trimethylbenzene, the dioxane and the acetic acid is 1:1:0.25; ultrasonic for 30min with ultrasonic power of 350W, heating and stirring at 110deg.C for 0.6 hr, cooling, and adding benzidine, wherein Fe 3 O 4 The mass ratio of the @ MOF to the trialdehyde phloroglucinol to the benzidine is 1:0.05:0.2, in a mixed solvent of 3ml of trimethylbenzene and dioxane, the volume ratio of the trimethylbenzene to the dioxane is 0.9:1, heating and stirring for 20h at 110 ℃, separating the product by using a magnet, washing by using DMF, and drying in vacuum to obtain the MOF-COF composite material.
The preparation method of the slow-release nitrogen fertilizer comprises the following steps:
a1, dissolving sodium carboxymethyl cellulose and sodium alginate in water at 58 ℃, stirring to dissolve completely, and then adding the MOF-COF composite material, wherein the mass ratio of the sodium carboxymethyl cellulose to the sodium alginate to the MOF-COF composite material is 0.9:1.8:0.9, ultrasonic treatment is carried out for 0.6h, the ultrasonic power is 350W, and a mixture is obtained;
a2, adding ammonium chloride, cooling to-2 ℃, and dropwise adding a cross-linking agent, wherein the mass ratio of the cross-linking agent to the mixture of the ammonium chloride and the step A1 is 0.025:1:0.25, reacting for 35min at 52 ℃, and freeze-drying at-28 ℃ and 1.5MPa to obtain the slow-release nitrogen fertilizer.
Comparative example 1
A slow-release nitrogen fertilizer differs from example 1 in that no MOF-COF composite material is introduced, and the missing part is filled with sodium carboxymethylcellulose.
Comparative example 2
A slow-release nitrogen fertilizer is different from example 2 in that a MOF-COF structure is formed without introducing COF, and the preparation method is referred to in the patent with publication number CN 112608190A.
Comparative example 3
A slow-release nitrogen fertilizer is distinguished from example 3 in that sodium carboxymethylcellulose and sodium alginate are not added.
Comparative example 4
A slow-release nitrogen fertilizer is different from example 1 in that nano Fe 3 O 4 The particle size was 25nm.
Comparative example 5
A slow-release nitrogen fertilizer is different from example 1 in that nano Fe 3 O 4 The mole ratio of the silica gel is 0.5:1.
comparative example 6
A slow-release nitrogen fertilizer is different from example 1 in that the mass ratio of the sodium carboxymethyl cellulose, the sodium alginate and the MOF-COF composite material is 1.5:1.6:1.
comparative example 7
A slow-release nitrogen fertilizer is different from the slow-release nitrogen fertilizer in example 1 in that the freeze-drying condition in the step A2 is that the temperature is-10 ℃ and the pressure is 0.9MPa.
Comparative example 8
A biochar-based slow-release nitrogen fertilizer is prepared by a preparation method of the biochar-based slow-release nitrogen fertilizer, and the preparation method is referenced in a patent with the publication number of CN 107226765A.
Comparative example 9
A slow-release nitrogen fertilizer is prepared by referring to a patent with publication number CN 115010545A.
Slow release performance test of slow release nitrogen fertilizer
Referring to the evaluation standard of the European standards committee on the slow release fertilizer, the release amount of the fertilizer nutrient in 24 hours is detected under the culture condition of 25 ℃, and then the release amount of the fertilizer nutrient in 28 days is detected, and the release mechanism and the calculation method refer to a Korsmeyer-Peppas model.
Water retention capacity: mixing 4g of fertilizer of each example with 100g of 20 mesh soil uniformly in a beaker, addingWater until the aqueous phase was visible in the soil gap, put in a constant temperature oven at 25 ℃, record beaker weight every other day, water retention = m 1 -m n /100，m 1 M is the total weight after adding water n The weight recorded for every other day.
In addition, the fertilizer of each example was prepared into blocks of 3cm×3cm×0.3mm, buried in soil at the same time at a depth of 10cm, watered once every 4-5d, taken out every 15d, carefully washed with water to remove the surface soil, dried at 50 ℃, weighed, and repeated 4 times. The mass of each fertilizer is weighed by a precision balance, and the degradation rate is calculated according to the mass change, wherein the degradation rate (%) =m Initially, the method comprises —M Taking out /M Initially, the method comprises 。
Table 1 the release rate (%)
| Examples | 1d | 28d | 60d | 120d |
| Example 1 | 6.51 | 20.14 | 31.22 | 80.45 |
| Example 2 | 6.60 | 20.19 | 31.45 | 80.53 |
| Example 3 | 6.63 | 20.26 | 31.51 | 80.65 |
| Comparative example 1 | 7.44 | 24.51 | 38.42 | 83.62 |
| Comparative example 2 | 7.39 | 23.26 | 35.06 | 82.27 |
| Comparative example 3 | 7.07 | 22.55 | 34.57 | 81.59 |
| Comparative example 4 | 6.94 | 21.03 | 32.41 | 81.36 |
| Comparative example 5 | 7.16 | 22.98 | 34.84 | 81.90 |
| Comparative example 6 | 7.00 | 22.21 | 34.29 | 81.47 |
| Comparative example 7 | 6.86 | 20.77 | 32.03 | 81.15 |
| Comparative example 8 | 6.69 | 20.28 | 31.91 | 80.68 |
| Comparative example 9 | 10.22 | 44.06 | 61.43 | 94.20 |
TABLE 2 degradation rates of slow-release nitrogenous fertilizers at different times (%)
As can be seen from the data in tables 1-2, example 1 was compared with comparative examples 1 and 2, and MOF-COF was not incorporatedWhen the composite material or the MOF structure is only introduced, fe 3 O 4 The @ MOF does not bind to the COF to provide good porosity, and therefore has limited adsorption capacity, reduced stability in aqueous solution, and unstable structure; and Fe (Fe) 3 O 4 Negative charge of @ MOF @ COF surface layer and NH 4 + The slow release rate of the example 1 is obviously better than that of the comparative examples 1 and 2 because of a certain static effect so as to slow down the release rate of the nutrient substances in the soil and effectively improve the slow release performance of the nitrogenous fertilizer.
Comparing example 1 with comparative example 3, it can be seen that sodium carboxymethylcellulose and sodium alginate are not added to form a unique porous grid structure, and the slow release capability and degradation capability of the porous grid structure are also reduced due to the influence; example 1 compared with comparative example 6, it can be seen that the different proportions of sodium carboxymethylcellulose, sodium alginate and MOF-COF composite material, especially when sodium carboxymethylcellulose is excessive, have a certain influence on the stability of the porous grid structure.
Example 1 compared with comparative examples 4 and 5, the composition was prepared with nano Fe 3 O 4 Particle size of (2) and nano Fe 3 O 4 After the mole ratio of the nano Fe to the silica gel is changed, the slow release capacity and the degradation level of the nano Fe are reduced, and the nano Fe is supposed to be nano Fe 3 O 4 The too large particle size and the higher proportion of the silica gel affect Fe 3 O 4 Formation of the @ MOF Structure, thus for Fe 3 O 4 The structural stability of @ MOF @ COF is affected.
Example 1 compared with comparative example 7 shows that the temperature and pressure of freeze-drying affect Fe 3 O 4 Molding of @ MOF @ COF.
Compared with the comparative examples 8 and 9, the slow-release nitrogen fertilizer provided by the invention has better slow-release capability and better water retention performance under the condition of insignificant degradation level difference compared with the existing coated fertilizer and non-coated fertilizer.
As can be seen from FIG. 1, compared with the existing MOF hybrid aerogel nitrogen fertilizer, the slow-release nitrogen fertilizer provided by the invention can adsorb heavy metal ions Cu in soil 2+ Thereby providing nutrient components for crops more effectively; as can be seen from FIG. 2, compared with the existing slow-release nitrogen fertilizer and possessing MOF hybridizationThe invention introduces the composite material, fe 3 O 4 The structural stability of the @ MOF @ COF is good, and the water retention capacity of the slow-release nitrogen fertilizer is improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. The slow-release nitrogen fertilizer is characterized by comprising the following raw materials: MOF-COF composite material, sodium carboxymethyl cellulose, sodium alginate, ammonium chloride and water,
the preparation method of the MOF-COF composite material comprises the following steps:
s1, nanometer Fe 3 O 4 Preparation of Fe by silica gel coupling method under tetraethoxysilane effect 3 O 4 @SiO 2 A nanoparticle; adding ZrCl again 4 Dispersing in DMF by ultrasonic wave, heating and stirring at 100-120deg.C for 18-24 hr, cleaning with ethanol, and drying to obtain Fe 3 O 4 @MOF；
S2, fe obtained in the step S1 3 O 4 Adding @ MOF and trialdehyde phloroglucinol into an organic solvent, performing ultrasonic treatment, heating and stirring at 100-120 ℃ for 0.5-1h, cooling, adding benzidine, dissolving in a mixed solvent of trimethylbenzene and dioxane, heating and stirring at 100-120 ℃ for 18-24h, separating a product by using a magnet, washing by using DMF (dimethyl formamide), and performing vacuum drying to obtain the MOF-COF composite material;
nano Fe described in step S1 3 O 4 Tetraethoxysilane, zrCl 4 The mass ratio of (1-1.2): 1: (1.16-1.24), fe as described in step S2 3 O 4 The mass ratio of the @ MOF to the trialdehyde phloroglucinol to the benzidine is 1: (0.045-0.052): (0.18-0.25).
2. The slow release nitrogen fertilizer of claim 1, wherein the nano Fe of step S1 3 O 4 The grain diameter is 9-15nm.
3. The slow-release nitrogen fertilizer according to claim 1, wherein the volume ratio of trimethylbenzene to dioxane in step S2 is (0.8-1.1): 1.
4. a method for preparing a slow release nitrogen fertilizer according to any one of claims 1-3, comprising the steps of:
a1, dissolving sodium carboxymethyl cellulose and sodium alginate in water at 55-60 ℃, stirring to dissolve completely, then adding MOF-COF composite material, and carrying out ultrasonic treatment for 0.5-1h to obtain a mixture;
a2, adding ammonium chloride, cooling to-5-0 ℃, dripping a cross-linking agent, reacting for 30-45min at 50-55 ℃, and freeze-drying to obtain the slow-release nitrogen fertilizer.
5. The method for preparing a slow-release nitrogen fertilizer according to claim 4, wherein the mass ratio of the sodium carboxymethyl cellulose, the sodium alginate and the MOF-COF composite material in the step A1 is (0.8-1): (1.6-2.2): (0.7-1).
6. The method for preparing a slow-release nitrogen fertilizer according to claim 4, wherein the mass ratio of the cross-linking agent, ammonium chloride and the mixture of step A1 in step A2 is (0.02-0.03): 1: (0.2-0.3).
7. The method for preparing a slow-release nitrogen fertilizer according to claim 4, wherein the freeze-drying condition in the step A2 is at a temperature ranging from-30 ℃ to-25 ℃ and a pressure ranging from 1.3MPa to 1.8MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310557101.8A CN116730771B (en) | 2023-05-17 | 2023-05-17 | Slow-release nitrogen fertilizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310557101.8A CN116730771B (en) | 2023-05-17 | 2023-05-17 | Slow-release nitrogen fertilizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116730771A CN116730771A (en) | 2023-09-12 |
| CN116730771B true CN116730771B (en) | 2024-03-19 |
Family
ID=87903562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310557101.8A Active CN116730771B (en) | 2023-05-17 | 2023-05-17 | Slow-release nitrogen fertilizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116730771B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608190A (en) * | 2020-12-21 | 2021-04-06 | 湖北民族大学 | Preparation method of pH/salt-sensitive porous 3D structure slow-release nitrogen fertilizer based on MOF (Cu) @ biochar |
| CN115010545A (en) * | 2022-07-15 | 2022-09-06 | 中交上海航道勘察设计研究院有限公司 | Slow-release nitrogen fertilizer and preparation method thereof |
| CN115746393A (en) * | 2022-11-30 | 2023-03-07 | 苏州因安特新材料科技有限公司 | Multi-stage-hole COF-MOF-hydrogel composite material and preparation method thereof |
-
2023
- 2023-05-17 CN CN202310557101.8A patent/CN116730771B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608190A (en) * | 2020-12-21 | 2021-04-06 | 湖北民族大学 | Preparation method of pH/salt-sensitive porous 3D structure slow-release nitrogen fertilizer based on MOF (Cu) @ biochar |
| CN115010545A (en) * | 2022-07-15 | 2022-09-06 | 中交上海航道勘察设计研究院有限公司 | Slow-release nitrogen fertilizer and preparation method thereof |
| CN115746393A (en) * | 2022-11-30 | 2023-03-07 | 苏州因安特新材料科技有限公司 | Multi-stage-hole COF-MOF-hydrogel composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Fe_3O_4@ABc复合材料的制备及其对水中甲基橙的吸附;王向辉;石建军;游诚航;颜慧琼;史载锋;林强;;精细化工(第07期) * |
| 王向辉 ; 石建军 ; 游诚航 ; 颜慧琼 ; 史载锋 ; 林强 ; .Fe_3O_4@ABc复合材料的制备及其对水中甲基橙的吸附.精细化工.(第07期),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116730771A (en) | 2023-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111533613B (en) | Nano-cellulose gel-based water-retaining slow-release fertilizer and preparation method thereof | |
| CN113402325A (en) | Double-coated slow-release water-retention urea fertilizer and preparation method thereof | |
| CN114656033B (en) | Preparation method of slow-release carbon source with corncobs as core groups | |
| CN116730771B (en) | Slow-release nitrogen fertilizer and preparation method thereof | |
| CN116064044B (en) | Soil conditioner and soil conditioning method for repairing acidification hardening and heavy metal pollution | |
| CN110235747B (en) | Soilless culture substrate and preparation method thereof | |
| CN114736064B (en) | Microbial compound fertilizer and preparation method thereof | |
| CN116904201A (en) | Sustained-release soil conditioner and preparation method thereof | |
| CN110627563A (en) | Novel naturally degradable fertilizer coating agent, preparation method and use method thereof | |
| CN116286018A (en) | Soil conditioner based on biomass charcoal and preparation method and application thereof | |
| CN114634388B (en) | Controlled release fertilizer and preparation method thereof | |
| CN108558529A (en) | A kind of charcoal/urea-acetate starch composite membrane and its preparation and the application in slow-release fertilizer | |
| CN110183690B (en) | Polyvinyl alcohol/modified nano-cellulose supramolecular hydrogel and preparation method and application thereof | |
| CN113185363A (en) | Cellulose-attapulgite modified polyacrylic acid coated controlled release fertilizer and preparation method thereof | |
| CN112266292A (en) | Slow-release compound fertilizer and preparation method thereof | |
| CN112250513A (en) | Universal type slow-release fertilizer for green plants cultivated in a pot | |
| CHEN et al. | Preparation and characteristics of urea coated with water-based copolymer-biochar composite film material | |
| CN115340427B (en) | Hematite-carboxymethyl cellulose-nutrient salt compound and preparation method and application thereof | |
| CN113845395B (en) | Photosensitive water-retention slow-release fertilizer with nuclear membrane structure and preparation method thereof | |
| CN113198432B (en) | Preparation method of biomass activated carbon | |
| CN114773123B (en) | Environment-friendly slow-release coated urea fertilizer and preparation method thereof | |
| CN112961008B (en) | Preparation method of low-water-solubility nitrogen-containing coating material and prepared nitrogen-containing coating material | |
| CN117625204A (en) | Composite soil restoration agent for farmland and preparation method thereof | |
| CN114031468A (en) | Humic acid fertilizer for preventing soil hardening and preparation method thereof | |
| CN114560733A (en) | Preparation method of nitrogen-fixing, phosphorus-protecting and carbon-storing sludge-kitchen-based soil slow-release fertilizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |