CN1171948C - Production technology of nano-clay-polyester mixed polymer fertilizer coating cementing agent - Google Patents
Production technology of nano-clay-polyester mixed polymer fertilizer coating cementing agent Download PDFInfo
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- CN1171948C CN1171948C CNB021260095A CN02126009A CN1171948C CN 1171948 C CN1171948 C CN 1171948C CN B021260095 A CNB021260095 A CN B021260095A CN 02126009 A CN02126009 A CN 02126009A CN 1171948 C CN1171948 C CN 1171948C
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Abstract
The present invention relates to a preparation method of nanometer clay-polyester mixed polymer of kaolin and montmorillonite clay, and the nanometer clay-polyester mixed polymer is obtained by taking typical clay minerals, such as kaoline and montmorillonite clay as raw materials and adopting aquated ion expansion method, a micro emulsification technology and a high shearing technology. The nanometer clay-polyester mixed polymer of kaolin and montmorillonite clay is applied to slow release and controlled release fertilizer coating cementing agents, organic-inorganic compound fertilizer binding agents, dryland soil water retention agents, and liquid mulching film and sandy soil structure modifying agents.
Description
The invention belongs to agricultural, ecotope field.
Clay mineral is maximum is applied to pottery, cement and refractory materials.On agricultural, past attempts is used for the adhesive for granulating and the stopping composition of inorganic composite mixed fertilizer as " soil moved in to improve the original " improvement sand soil after nineteen nineties.The clay mineral distribution is very wide on earth, and most representative is kaolin and polynite.
Kaolin is that potash feldspar passes through kaolinization and generates kaolinite (Al
2O
32SiO
22H
2O), generate kaolin after the weathering.Mineral crystal is by one deck (tetrahedral) silica sheet and one deck (octahedral) water aluminium flake alternate composition, so be called 1: 1 type mineral.Two-layer in the single kaolin crystal is to be connected by the common Sauerstoffatom with the aluminium atom by separately Siliciumatom in every layer, by the hydrogen chain each crystal unit coupled together again, and its lattice is a fixed.Compare with montmorillonite, its radius is bigger, and 0.1～5 μ m is most between 0.2～2 μ m.Compare with the silicate of other type, kaolinic plasticity-, cohesiveness, shrinkability and swelling property are all lower.
Polynite, its mineral crystal is clipped between two silica sheets (tetrahedron) by a water aluminium flake (octahedron), so be called 2: 1 type mineral.Loosely connected by very weak hydrogen chain between the crystal unit, moisture and positively charged ion are easy to be attracted to two gaps between the crystal unit, cause lattice dilatation.Crystalline thickness is between 0.01～1 μ m, and is more much smaller than kaolinite glue nuclear.Compare with kaolinite, the montmorillonite crystal is easy to be divided into artificially the particulate near single crystallographic dimension.Montmorillonite has very high plasticity-and force of cohesion, will take place when dry sharply to shrink.
Beijing University of Chemical Technology utilizes in-situ polymerization intercalated technology to make clay/nylon 6 nano-composite and attapulgite/nylon 6 nano-composite; Use the macromole graft process and made nano composite materials such as clay/polystyrene, clay/polymethyl acrylic acid, clay/polyoxyethylene, clay/styrene-butadiene rubber(SBR), clay/paracril, clay/polyvinyl alcohol.Its operational path is: clay (polynite, kaolin) is through interlayer modified, make hydrophilic become between oleophilic layer → addition polymerization monomer adduct → polymer monomer enter interlayer, again after polymerization, with clay mineral crystal layer " spreading ", small bits of clay is scattered in superpolymer and connects in the liquid → clay polymer nanocomposites (N.C.Brady:The Nature and Properties of Soil, Macmillan, New York, 1974; Wang Yizhong, Dong Hua, Yu Dingsheng, nylon 6/ attapulgite clay nano level composite material synthetic, synthetic resins and plastics, 14 (2), 16 (1997); Yu Dingsheng, Wang Yizhong, " the synthetic and sign that nylon 6/ clay is intercalation compound ", polymer material science and engineering, 14 (2), 26～29, (1998).
The problem that the agricultural existence of clay class mineral is following: when (1) is used for the inorganic composite mixed fertilizer granulation, since bad dispersibility, skewness, and each compound fertilizer granule nutrient content is different.During (2) with clay class mineral coated urea, coating is too thick, reduces nutrient content.After the drying, fertiliser granulates top layer clay powdering easily comes off, and influences the coating quality.(3) the clay nanocomposites cost is too high, and only is confined to laboratory stage, and not pilot scale is agricultural very difficult.
The objective of the invention is the problem that in fertilizer application, exists at clay class mineral, adopt hydrated ion expanding method and micro-emulsion technology, high-shear technology, clay (kaolin, polynite) and unsaturated polyester are prepared into nano level clay-polyester mixed polymer aqueous solution, be used for the slowly/controlled releasing fertilizer coating cementing agent, organic-inorganic complex fertilizer adhesive for granulating, dryland soil water-holding agent and liquid ground film, sand texture modifier etc.
Detailed description of the present invention
The principle of the present invention's utilization is that potassium, sodium hydrated ion " support pine " with kaolin crystal layer oxygen-hydroxide ion key, " cutter by the waist " again, crystal layer becomes the monomer aspect, and by high-shear, the fragmentation of monomer aspect becomes the nano-scale part.Oxygen between the polynite crystal unit-oxonium ion key magnetism is faint, and easier is manual breakage.
The main technique route
The preparation of 1 nanoclay mineral suspensions
1.1 the dispersion of clay particle is dried levigate mistake 300 mesh sieve holes with kaolin or polynite, sieve diameter is equivalent to 0.053～0.044mm, take by weighing 1000g, add water 1000ml, add dispersion agent sodium dodecyl benzene sulfonate aqueous solution (20%) 200～500ml, fully stir, become slurry.Add 0.5N NaOH (use in southern acid soil area) or KOH solution (use in northern calcareous soil area) 100～150ml, 3000～5000r/min stirred 1 hour, placed to become clay breeze alkaline suspension liquid in 24 hours.
1.2 the preparation of nano level clay mineral suspension solution with above-mentioned clay breeze alkaline suspension liquid, adds HCI or H under agitation condition
2SO
4The aqueous solution (1: 1) adjust pH about 7, pour High shear device (seeing 02123522.8 application for a patent for invention that the inventor submitted on July 2nd, 2002) then into, 30,000 r/min high-shears, 5～10min, the easy manual breakage of polynite mineral crystal layer, time can lack, and is nano level clay mineral suspension liquid.
The preparation of 2 nano level unsaturated polyester aqueous solution of ester
2.1 unsaturated polyester emulsion prepares unsaturated polyester and is called for short polyester, we adopt unsaturated polyester resins for general purpose (Unsaturated polyester rosins of general purpose types abridge UP), basal component is dibasic alcohol, MALEIC ANHYDRIDE and Tetra hydro Phthalic anhydride, selects for use Tianjin synthetic materials factory to produce 306 and 307.
Under stirring condition, in 306 resins, add 20% Sodium dodecylbenzene sulfonate solution, add-on is 25%～30% of 306 resins.306 become white milk sap by light yellow.
2.2 the preparation of nano level unsaturated polyester aqueous solution of ester is poured above-mentioned 306 emulsions into High shear device (seeing 02123522.8 application for a patent for invention that the inventor submitted on July 2nd, 2002), add isopyknic water, 30,000 r/min shear about 10min, promptly become nano level unsaturated polyester aqueous solution of ester.
The 3 nano levels clay-polyester aqueous solution
With nano level clay mineral suspension liquid and nano level unsaturated polyester aqueous solution, its ratio is 5～10: 1, decides according to different crops, and the special-purpose fertile unsaturated polyester ratio of rice crop is the highest, secondly be wheat, corn, the leaf vegetables ratio in the vegetables is minimum.Two kinds of solution stir about 20min in emulsify at a high speed decollator (30,000 r/min), become heterogeneous nano level clay-polyester and mix polywater solution, and color is an oyster white.
The application of 4 nano level clay-polyester mixed polymers
4.1 the slowly/controlled releasing fertilizer coating cementing agent under agitation condition, mixes the polywater solution dilution with nano level clay-polyester, is benchmark with the clay, is diluted to argillaceous 0.1%～1%, it is different and decide to regard thing as.With garden particulate state N, P, K compound fertilizer, organic-inorganic compound mixed fertilizer or urea granules coating, garden dish or rotary drum limit rotate on garden dish tablets press or rotary drum granulator, on one side high-pressure fog (greater than 0.3MPa) parcel.Consumption: the 1000kg granulated fertilizer uses the clay-polyester mixed polymer aqueous solution 50～70kg after the dilution, then with talcum powder face powder, warm air drying.
4.2 the inorganic or organic-inorganic compound mixed fertilizer adhesive for granulating clay-polyester mixed polymer aqueous solution after with above-mentioned dilution is sprayed in mineral manure blend composition or organic and the mineral manure blend composition; even blend in mixer, granulation on garden dish tablets press or rotary drum granulator.Mix the polymers amount of aqueous solution used: 10%～15% of weight of material (butt).
Accompanying drawing 1 is seen in technical process of the present invention.
Description of drawings:
Fig. 1 nano-clay-polyester mixed polymer fertilizer coating jointing compound technological process of production figure
Advantage of the present invention:
Feed kaolin and imvite aboundresources, cost is low, the cost of 1000kg coated fertilizer and grade N, P, K nutrient Chemical Mixed Fertilizer is compared, and cost only increases 50-100 unit. Nanoscale clay-polyester mixed polymer is water-soluble, and coating is even, uses Amount is economized, and intensity is higher, and anti-crushing power can reach more than the 15N. Pollution-free to soil and ecological environment. This coating cementing agent also can Be used for compound fertilizer pelletizing adhesive, dryland soil water-loss reducer and liquid ground film, sand texture modifier, " potion " is many With.
Claims (2)
1. the production method of a nano-clay-polyester mixed polymer fertilizer coating jointing compound, its feature is made up of preparation, the preparation of nano level unsaturated polyester aqueous solution of ester, the nano level clay-polyester aqueous solution preparation of nano level clay mineral suspension liquid, its product is used for the slowly/controlled releasing fertilizer coating cementing agent, organic-inorganic complex fertilizer adhesive for granulating, dryland soil water-holding agent and liquid ground film, sand texture modifier, that is:
1) preparation of nano level clay mineral suspension liquid---kaolin or polynite are dried levigate mistake 300 mesh sieve holes, sieve diameter is equivalent to 0.053～0.044mm, take by weighing 1000g, add water 1000ml, add 20% sodium dodecyl benzene sulfonate aqueous solution, 200～500ml, fully stir, become slurry, add 0.5N NaOH or KOH solution 100～150ml again, 3000～5000r/min stirred 1 hour, placed to form in 24 hours;
With above-mentioned clay breeze suspension, the adding volumetric ratio is 1: 1 HCI or H under agitation condition
2SO
4About aqueous solution adjust pH to 7, pour in the High shear device 30,000 r/min high-shears, 5～10min then into;
2) preparation of nano level unsaturated polyester aqueous solution of ester---under stirring condition, 20% Sodium dodecylbenzene sulfonate solution is added in the universal unsaturated polyester, its add-on is 25%～30% of a unsaturated polyester amount, unsaturated polyester becomes white milk sap by light yellow, be poured into High shear device then, add isopyknic water, about 30,000 r/min shearing 10min;
3) nano level clay-polyester mixes the preparation of polywater solution---with nano level clay mineral suspension liquid and nano level unsaturated polyester aqueous solution, its ratio is 5～10: 1, two kinds of solution stir about 20min with 30,000 r/min rotating speeds in the emulsify at a high speed decollator, become the heterogeneous nano level clay-polyester of oyster white and mix polywater solution, decide according to different crops, the special-purpose fertile unsaturated polyester ratio of rice crop is the highest, is wheat, corn secondly, and the leaf vegetables ratio in the vegetables is minimum.
2. according to the production method of the described nano-clay-polyester mixed polymer fertilizer coating jointing compound of claim 1, it is characterized in that in the preparation process of nano level clay mineral suspension liquid, use NaOH when its finished product is used for southern acid soil area, use KOH solution when using for northern calcareous soil area.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021260095A CN1171948C (en) | 2002-08-09 | 2002-08-09 | Production technology of nano-clay-polyester mixed polymer fertilizer coating cementing agent |
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| CNB021260095A CN1171948C (en) | 2002-08-09 | 2002-08-09 | Production technology of nano-clay-polyester mixed polymer fertilizer coating cementing agent |
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| CN1414033A CN1414033A (en) | 2003-04-30 |
| CN1171948C true CN1171948C (en) | 2004-10-20 |
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| CN100554329C (en) * | 2004-11-22 | 2009-10-28 | 中国农业科学院土壤肥料研究所 | The nanometer-submicron level PVA mixed polymer as fertilizer cementing coating agent preparation method |
| CN101367688B (en) * | 2008-09-25 | 2011-10-19 | 中国农业大学 | Controlled release water holding raise seedling culture medium for cucumber and method of preparing the same |
| CN102180731B (en) * | 2011-02-16 | 2013-07-17 | 成都正光投资集团有限公司 | Polymer emulsion coated slow release fertilizer taking nanomaterial as carrier and preparation method thereof |
| CN102612956B (en) * | 2012-03-28 | 2013-12-11 | 太仓市临江农场专业合作社 | Method for facilitating lettuce production by adopting nano compound fertilizer |
| CN102617233A (en) * | 2012-03-28 | 2012-08-01 | 常熟市南洋化肥有限公司 | Nanometer smectite clay compound fertilizer |
| CN102603409A (en) * | 2012-03-28 | 2012-07-25 | 常熟市南洋化肥有限公司 | Compound fertilizer for promoting increase production of leaf lettuce |
| CN102603408B (en) * | 2012-03-28 | 2013-12-25 | 太仓市临江农场专业合作社 | Nanometer smectite clay organic compound fertilizer |
| CN103168640B (en) * | 2012-04-27 | 2015-09-16 | 北京仁创科技集团有限公司 | A kind of nutrient planting sand and sand pattern of farming |
| CN103773378B (en) * | 2014-01-21 | 2016-03-30 | 中国农业科学院农业资源与农业区划研究所 | A kind of suspended state soil conditioner and preparation method thereof |
| CN103951508A (en) * | 2014-04-26 | 2014-07-30 | 上高县泽达生态科技有机农业开发有限公司 | Molecular network type nano-coating efficient slow release organic fertilizer and production process thereof |
| CN104291933A (en) * | 2014-09-15 | 2015-01-21 | 武汉中农国际贸易有限公司 | Special fertilizer for solanaceous vegetables |
| US10053611B2 (en) * | 2016-03-22 | 2018-08-21 | Saudi Arabian Oil Company | In situ generation of nano-clay drilling fluid |
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