CN111269032A - Method for preparing water-soluble silicon-potassium fertilizer from silicate minerals - Google Patents
Method for preparing water-soluble silicon-potassium fertilizer from silicate minerals Download PDFInfo
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910052604 silicate mineral Inorganic materials 0.000 title claims abstract description 35
- KMNWCNNLFBCDJR-UHFFFAOYSA-N [Si].[K] Chemical compound [Si].[K] KMNWCNNLFBCDJR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 104
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 24
- 230000000694 effects Effects 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000005530 etching Methods 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract 2
- 238000010306 acid treatment Methods 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 37
- 239000010703 silicon Substances 0.000 abstract description 35
- 229910052710 silicon Inorganic materials 0.000 abstract description 35
- 239000002893 slag Substances 0.000 abstract description 11
- 238000003723 Smelting Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 description 13
- 239000002689 soil Substances 0.000 description 13
- 229910001385 heavy metal Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 238000012271 agricultural production Methods 0.000 description 3
- 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 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- -1 leaching Chemical compound 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009335 monocropping Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
- C05D1/04—Fertilisers containing potassium from minerals or volcanic rocks
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention belongs to the technical field of agricultural fertilizer preparation, and discloses a method for preparing water-soluble silicon-potassium fertilizer by using silicate minerals, wherein the silicate minerals are used as raw materials, and the silicate mineral powder is obtained by crushing, grinding and screening the raw materials and is used as subsequent feeding; treating silicate mineral powder with sulfuric acid solution, and preparing high chemical reaction activity silicon oxide powder capable of being rapidly dissolved in potassium hydroxide at normal temperature and normal pressure by using leaching, etching and activating effects of sulfuric acid; reacting the silicon oxide powder with a potassium hydroxide solution at normal temperature and normal pressure to obtain the water-soluble silicon-potassium fertilizer. The invention can strictly control the content of harmful elements in the product, and the obtained product has higher effective silicon content and lower content of harmful elements than the traditional method of taking the smelting slag as the silicon fertilizer, and has simple process technology and easy industrialization.
Description
Technical Field
The invention belongs to the technical field of agricultural fertilizer preparation, and particularly relates to a method for preparing a water-soluble silicon-potassium fertilizer from silicate minerals.
Background
Currently, the closest prior art: "people eat as the day and eat as the root of the day. In recent years, with the rapid development of agriculture in China, the environment of agricultural resources is changing, especially the soil environment is changing: soil hardening and soil-borne diseases caused by continuous cropping of crops are continuously aggravated; the high output and the high input all the year round cause the imbalance of the proportion of various nutrient elements in the soil; unreasonable fertilizer usage causes soil acidification and soil salinization; the heavy metal pollution of soil and the like all threaten the sustainable development of agriculture. The imbalance of the proportion of nutrient elements in soil and acidification are main causes of the soil, and the soil comprises the overall deficiency of medium elements such as calcium, silicon, magnesium and the like. The direct consequence of this is that the yield of crops is reduced, the quality is reduced, the taste is deteriorated, and the toxic and harmful agricultural products are in endless numbers. In this large background, soil conditioning is a major problem that needs to be solved urgently.
The silicon fertilizer is a good quality fertilizer, a health-care fertilizer and a plant regulating fertilizer, and is a novel multifunctional fertilizer which is incomparable with other chemical fertilizers. The silicon fertilizer can be used as a fertilizer for providing nutrients, and can also be used as a soil conditioner for improving soil. In addition, the composition also has the effects of preventing diseases, preventing insects, reducing toxicity and relieving heavy metal pollution. The yield increasing effect of silicon fertilizer on rice is better than that of phosphate fertilizer and potash fertilizer. The silicon fertilizer is confirmed by the international soil academy as a fourth growth element fertilizer following nitrogen, phosphorus and potassium fertilizers. Therefore, the method has great significance for the research and production of the silicon fertilizer.
At present, the soluble silicon fertilizer applied to agricultural production is mainly prepared by adding alkali into various industrial solid wastes (such as blast furnace slag, coal gangue, yellow phosphorus slag, phosphogypsum and the like) and mineral (such as wollastonite, medical stone, potassium feldspar and the like) for roasting and modifying, the preparation technology of the silicon fertilizer is rough, and the quality of the produced silicon fertilizer product is poor.
In summary, the problems of the prior art are as follows: the soluble silicon fertilizer applied to agricultural production at present is mainly modified by adding alkali into various industrial solid wastes and mineral raw materials and roasting, the preparation technology of the silicon fertilizer is rough, the effective silicon content of the produced silicon fertilizer product is low, harmful elements such as aluminum and heavy metal in smelting slag are not beneficial to the growth of plants, and polluted agricultural products threaten the health of human bodies.
The difficulty of solving the technical problems is as follows: the existing silicon fertilizer production technology is rough, smelting slag is generally used as a raw material and is simply treated to be applied as the silicon fertilizer, elements in ores, such as aluminum, are harmful elements in the plant production process and are not beneficial to plant growth, and agricultural products polluted by heavy metal are not beneficial to human health after being eaten by human beings. However, the separation of harmful elements in the smelting slag is difficult, because the ore is vitrified under high temperature conditions in the smelting process, and the separation of the elements in the ore is more difficult than the separation of the raw ore, so the separation and removal of the harmful elements in the smelting slag are difficult, the effective separation is difficult to realize by the common 'gravity', 'magnetic' and 'floating' ore dressing methods, the cost is high usually by adopting chemical methods, and the effect is difficult to achieve.
The significance of solving the technical problems is as follows: at present, the problems of soil silicon deficiency and heavy metal pollution in China are serious, the popularization of the production and application of the silicon fertilizer has very obvious social benefit and economic benefit, and the future development prospect is very wide. However, the smelting slag is adopted as a production raw material of the silicon fertilizer, so that pollution is easily caused, and meanwhile, the content of available silicon in the smelting slag is low, so that the production of the silicon fertilizer is not paid enough attention at present. According to the invention, the silicate minerals are treated by sulfuric acid, so that harmful elements such as aluminum, heavy metals and the like in the minerals can be removed efficiently, the obtained silicon oxide powder is dissolved in potassium hydroxide under normal temperature and pressure to obtain the silicon potash fertilizer, the effective silicon content of the product is high, and no harmful elements can be contained.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing a water-soluble silicon-potassium fertilizer by using silicate minerals.
The invention is realized in such a way that the method for preparing the water-soluble silicon-potassium fertilizer by using the silicate minerals comprises the following steps:
(1) various silicate minerals widely existing in nature are used as raw materials, silicon in the ore mainly exists in the form of silicate, and the ore containing no or less elements harmful to crops and human bodies such as heavy metals, aluminum and the like is preferred. The silicate mineral is crushed, ground and screened to obtain mineral powder with the granularity of less than 0.2mm as subsequent feeding.
(2) The silicate mineral powder is treated by sulfuric acid solution, and the high chemical reaction activity silicon oxide is prepared by using the functions of sulfuric acid such as leaching, etching, activation (chemical bond destruction) and the like.
The leaching effect is that harmful elements such as heavy metal, aluminum and the like in the ore are dissolved into solution under the leaching effect of sulfuric acid, and the main effect is to remove the harmful elements in the ore; the etching effect is that metal elements in the silicate minerals are dissolved and hollowed, and the specific surface area of the residual silicon framework is obviously increased compared with that of the raw ore; the activation is that under the action of sulfuric acid, cations playing a role in connecting or balancing electrovalence are transferred into the solution, chemical bonds of almost all metal elements and oxygen atoms in the ore, hydrogen bonds and partial silica bonds in the ore are broken, the original stable structure of the ore is destroyed, the chemical reaction activity is enhanced, and the obtained silicon oxide is white or grey white powder with high chemical reaction activity. The sulfuric acid treatment is 1-3 stages of countercurrent sulfuric acid treatment under the normal pressure condition, and the technological conditions of the sulfuric acid treatment are as follows: concentration of sulfuric acid: 10-18 mol/L, liquid-solid ratio: 2: 1-4: 1, reaction time: 1 to 3 hours. The selection of the concentration of the sulfuric acid and the reaction time depends on the removal difficulty of aluminum, heavy metal and the like in the ore reaction process, the sulfuric acid treatment aims at removing harmful impurities in the ore and activating silicon in the ore, the ore after the sulfuric acid treatment does not contain harmful elements such as aluminum, heavy metal and the like, and the selection of parameters such as the concentration of the sulfuric acid, the leaching time and the like is also the basis for selecting the high-chemical-reaction-activity silicon dioxide, which is favorable for reducing the energy consumption in the alkali dissolution process, and the low impurity content is favorable for preparing the high-quality silicon potash fertilizer.
(3) In the 1-3 stage countercurrent sulfuric acid treatment process under the normal pressure condition, external heating or self-heat release through a reaction system without external heating can be adopted to reach the temperature required by the reaction.
(4) Reacting the silicon oxide powder with high chemical reaction activity with a potassium hydroxide solution with a certain concentration at normal temperature and normal pressure to obtain the water-soluble silicon-potassium fertilizer. The reaction of the silicon oxide powder and the potassium hydroxide is carried out at normal temperature and normal pressure, and the reaction conditions are as follows: temperature: 15-30 ℃, potassium hydroxide concentration: 1 mol/L-10 mol/L, liquid-solid ratio: 2: 1-4: 1, reaction time: 0.5-2 h. The chemical reaction conditions under normal temperature and normal pressure do not need additional heating to bring cost, the requirement on equipment in the process is low, and the method is beneficial to reducing production investment and industrialization.
Specifically, the sulfuric acid leaching in the step (2) is to leach heavy metals, aluminum and iron in the ore and other associated metal elements into a solution under the action of a sulfuric acid solution, and obtain a pregnant leach solution and silicon oxide powder without harmful elements through filtering and overnight separation;
specifically, the sulfuric acid etching in the step (2) is to etch and hollow metal elements included between the surface of the ore and the internal silicon skeleton under the action of sulfuric acid to obtain the silicon skeleton with high specific surface area;
specifically, the sulfuric acid activation in the step (2) is that under the action of the sulfuric acid solution, cations playing a role in connecting or balancing electrovalence in the ore are transferred into the solution, chemical bonds between almost all metal elements and oxygen atoms in the ore, hydrogen bonds and partial silicon-oxygen bonds in the ore are broken, an original stable structure in the ore is destroyed, and the chemical reaction activity is enhanced;
specifically, the fineness of the silicon oxide powder in the step (2) is 0-5 um, the silicon oxide powder has high chemical reaction activity, and can react with potassium hydroxide at normal temperature and normal pressure;
the invention also aims to provide the water-soluble silicon-potassium fertilizer prepared by the method for preparing the water-soluble silicon-potassium fertilizer by using the silicate minerals.
In summary, the advantages and positive effects of the invention are:
(1) the method can thoroughly remove harmful elements in the ore through the leaching, etching and activating action of sulfuric acid, so that the content of the harmful elements in the final product can be strictly controlled, the obtained product can hardly contain harmful elements such as aluminum and heavy metal elements, and the product produced by the method has higher quality than the traditional silicon fertilizer taking smelting slag as silicon fertilizer;
(2) the invention is derived from the discovery that the silicate mineral can be treated by sulfuric acid to obtain the silicon oxide powder which can be quickly dissolved in potassium hydroxide at normal temperature and normal pressure, and the obtained silicon oxide powder can be quickly dissolved in potassium hydroxide at normal temperature and normal pressure, which means lower production cost and lower equipment requirement;
(2) the content of available effective silicon for plants in the product produced by the invention is higher than that of the product which takes the smelting slag as the silicon fertilizer;
(3) the process technology of the invention is simple and easy to realize industrialization.
Drawings
FIG. 1 is a flow chart of a method for preparing a water-soluble silicon-potassium fertilizer by using silicate minerals.
FIG. 2 is SEM and TEM images of a highly chemically reactive silica powder provided in an embodiment of the present invention.
FIG. 3 is a graph showing the dissolution efficiency of the silica powder in the potassium hydroxide solution at normal temperature and pressure according to the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The soluble silicon fertilizer applied to agricultural production at present is mainly modified by adding alkali into various industrial solid wastes and mineral raw materials for roasting, the preparation technology of the silicon fertilizer is rough, and the quality of the produced silicon fertilizer product is poor.
To solve the above problems, the present invention will be described in detail with reference to the accompanying drawings.
As shown in fig. 1, the method for preparing water-soluble silicon-potassium fertilizer from silicate minerals provided by the embodiment of the invention comprises the following steps:
s101: silicate minerals are used as raw materials, and are crushed, ground and screened to obtain silicate mineral powder which is used as subsequent feeding materials.
S102: the silicate mineral powder is treated by sulfuric acid solution, and the silicon oxide powder with high chemical reaction activity is prepared by using the leaching, etching and activating effects of sulfuric acid.
S103: and (3) reacting the silicon oxide powder with high chemical reaction activity with a potassium hydroxide solution to obtain the water-soluble silicon-potassium fertilizer.
The present invention will be described in further detail with reference to examples.
Example 1
The specific implementation and the obtained technical indexes of the method for preparing the water glass by using the silicate minerals are as follows:
takes some kaolinite in Yunnan as mineral raw material, and the main chemical component in the ore is SiO245.31％，Al2O332.07％，Fe2O3And 5.08 percent. 5kg of kaolin is washed and crushed to-0.1 mm.
The kaolin after crushing and grinding is subjected to three-stage countercurrent heating sulfuric acid treatment, the specific operation is that the solid phase after the first-stage sulfuric acid treatment is used as the second-stage feeding material, the solid phase after the second-stage treatment is used as the third-stage feeding material, the liquid phase after the third-stage treatment enters the second stage, the liquid phase after the second-stage treatment enters the first stage, and the concentration of sulfuric acid is adjusted in the process by means of concentration and new acid supplementation. The technological conditions of the three-stage countercurrent heating sulfuric acid treatment are respectively as follows: a first stage: leaching temperature: 140 ℃ and sulfuric acid concentration: 10mol/L, liquid-solid ratio: 4:1, reaction time: 2 h; and (2) second stage: temperature: 170 ℃ and sulfuric acid concentration: 15mol/L, liquid-solid ratio: 4:1, reaction time: 2 h; and (3) three stages: temperature: 200 ℃, sulfuric acid concentration: 18mol/L, liquid-solid ratio: 2:1, reaction time: 1 h; after being treated by sulfuric acid, the gray silicon oxide powder is obtained, and the content of silicon dioxide in the obtained powder is up to 95 percent.
Taking 20g of the obtained silicon oxide powder to react with a potassium hydroxide solution at normal temperature and normal pressure, wherein the reaction process conditions are as follows: temperature 25 ℃, potassium hydroxide concentration: 4mol/L, liquid-solid ratio: 6:1, reaction time: 1 h; after reacting for 1h, the dissolution rate of the silicon dioxide in the powder reaches 90 percent, and the liquid silicon-potassium fertilizer is obtained by filtering.
Example 2
The specific implementation and the obtained technical indexes of the method for preparing the water glass by using the silicate minerals are as follows:
taking montmorillonite of Sichuan as mineral raw material, and washing and grinding 5kg of montmorillonite to-0.074 mm. The crushed and ground kaolin is subjected to two-counter-current sulfuric acid treatment, the specific operation is similar to that of the example 1, and the technological conditions of the sulfuric acid treatment are as follows: a first stage: concentration of sulfuric acid: 10mol/L, liquid-solid ratio: 4:1, reaction time: 2h, heating is not carried out in the first-stage sulfuric acid treatment process, the self-heat release of the reaction system is applied, and the temperature reached after the self-heat release of the system is measured as follows: 140 ℃; and (2) second stage: the reaction temperature was controlled by external heating: 200 ℃, sulfuric acid concentration: 17mol/L, liquid-solid ratio: 4:1, reaction time: 2 h; white silicon oxide powder is obtained after sulfuric acid treatment, and the content of silicon dioxide in the obtained powder is as high as 80%.
Taking 20g of the obtained silicon oxide powder to react with a potassium hydroxide solution at normal temperature and normal pressure, wherein the reaction process conditions are as follows: temperature 30 ℃, potassium hydroxide concentration: 3mol/L, liquid-solid ratio: 8:1, reaction time: 1 h; after reacting for 1h, the dissolution rate of the silicon dioxide in the powder reaches 91 percent, and the liquid silicon-potassium fertilizer is obtained by filtering.
Example 3
The specific implementation and the obtained technical indexes of the method for preparing the water glass by using the silicate minerals are as follows:
taking certain vermiculite in Yunnan as a mineral raw material, taking 5kg of montmorillonite, washing the ore, and grinding to-0.074 mm. The crushed and ground kaolin is subjected to secondary countercurrent heating sulfuric acid treatment, the specific operation is similar to that of the example 1, and the technological conditions of the sulfuric acid treatment are as follows: a first stage: leaching temperature: 150 ℃, sulfuric acid concentration: 10mol/L, liquid-solid ratio: 4:1, reaction time: 2 h; and (2) second stage: temperature: 220 ℃ and sulfuric acid concentration: 18mol/L, liquid-solid ratio: 4:1, reaction time: 2 h; white silicon oxide powder is obtained after sulfuric acid treatment, and the content of silicon dioxide in the obtained powder is up to 90%.
Taking 20g of the obtained silicon oxide powder to react with a potassium hydroxide solution at normal temperature and normal pressure, wherein the reaction process conditions are as follows: temperature 30 ℃, potassium hydroxide concentration: 4mol/L, liquid-solid ratio: 8:1, reaction time: 1 h; after reacting for 1h, the dissolution rate of the silicon dioxide in the powder is up to 86 percent, and the liquid silicon-potassium fertilizer is obtained by filtering.
FIG. 2 is SEM and TEM images of a highly chemically reactive silica powder provided in an embodiment of the present invention.
FIG. 3 is a graph showing the dissolution efficiency of the silica powder in the potassium hydroxide solution at normal temperature and pressure according to the embodiment of the present invention.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. The method for preparing the water-soluble silicon-potassium fertilizer from the silicate minerals is characterized by comprising the following steps of:
(1) taking silicate minerals as raw materials, and crushing, grinding and screening to obtain silicate mineral powder serving as subsequent feeding;
(2) treating silicate mineral powder with sulfuric acid solution, and preparing silicon oxide powder with high chemical reaction activity by using the leaching, etching and activating effects of sulfuric acid;
(3) and (3) reacting the silicon oxide powder with high chemical reaction activity with a potassium hydroxide solution to obtain the water-soluble silicon-potassium fertilizer.
2. The method for preparing water-soluble silicon-potassium fertilizer by using silicate mineral as claimed in claim 1, wherein in the step (1), the obtained mineral powder has a particle size of less than 0.2 mm.
3. The method for preparing the water-soluble silicon-potassium fertilizer by using the silicate minerals as claimed in claim 1, wherein in the step (2), the sulfuric acid treatment is 1-3 stages of countercurrent sulfuric acid treatment under normal pressure conditions, and the process conditions of the sulfuric acid treatment are as follows: concentration of sulfuric acid: 10-18 mol/L, liquid-solid ratio: 2: 1-4: 1, reaction time: 1 to 3 hours.
4. The method for preparing water-soluble silicon-potassium fertilizer from silicate mineral according to claim 1, wherein in the step (2), the reaction temperature is reached by external heating or directly by self-heat release of the reaction system during the treatment of the silicate mineral powder with the sulfuric acid solution.
5. The method for preparing the water-soluble silicon-potassium fertilizer by using the silicate minerals as claimed in claim 1, wherein the fineness of the silicon oxide powder in the step (2) is 0-5 um.
6. The method for preparing the water-soluble silicon-potassium fertilizer by using the silicate minerals as claimed in claim 1, wherein in the step (3), the reaction between the silicon oxide powder and the potassium hydroxide is carried out at normal temperature and normal pressure, and the reaction conditions are as follows: temperature: 15-30 ℃, potassium hydroxide concentration: 1 mol/L-10 mol/L, liquid-solid ratio: 2: 1-4: 1, reaction time: 0.5-2 h.
7. A water-soluble silicon-potassium fertilizer prepared by the method for preparing the water-soluble silicon-potassium fertilizer by using the silicate mineral as claimed in any one of claims 1 to 6.
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| CN111886994A (en) * | 2020-07-08 | 2020-11-06 | 北京大学 | Method for promoting crop growth and reducing insect pests |
| CN115093290A (en) * | 2022-07-27 | 2022-09-23 | 甘肃巨源达生物科技有限公司 | Method for preparing oil shale semicoke silicon potash fertilizer by hydrothermal method |
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