CN101450875A - Method for preparing multielement micropore mineral fertilizer from silicate rock through hydrothermal chemical reaction - Google Patents
Method for preparing multielement micropore mineral fertilizer from silicate rock through hydrothermal chemical reaction Download PDFInfo
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Abstract
The invention provides a method for preparing multi-element microporous mineral fertilizer from silicate rocks through a hydrothermal chemical reaction. The method is characterized in that the hydrothermal chemical reaction is carried out in a semi-wet state after the silicate rocks and fine powder of an alkali soil excitant and an activator, thereby wholly converting minerals in the silicate rocks into effective forms which can be absorbed by plant with high efficiency (65 to 85 percent); and the fertilizer has unique microporous structures and becomes the multi-element microporous mineral fertilizer.
Description
Technical field
The invention belongs to the mineral manure production field, specially refer to a kind of method of under half wet condition, utilizing hydrothermal chemical reaction to produce the multielement micropore mineral manure by silicate rock.
Background technology
Plant-growth not only needs nitrogen phosphorus potassium, also needs trace elements such as moderate-elements such as silicon, calcium, magnesium, sulphur and iron, manganese, boron, rare earth, and each essential nutritive element all has its special function, can not be replaced by other element.
Various fertility factors in the soil are not isolated, but connect each other with mutual restriction.According to minimum nutrient law, the supply that the output of farm crop depends primarily on the nutrient of minimum number in the soil (is similar to Law of Barrel, the pondage of wooden barrel depends on the height of shortage), the shortage of element such as potassium silicon magnesium has seriously restricted farm crop absorbing nitrogen phosphorus in the soil.Obviously, for a continuable agricultural tillage system, keeping nutrient balance is a key factor.
The problem of uneven fertilising is very outstanding, excessive applied nitrogen but for a long time,, and mineral substance nutrients such as potassium silicon magnesium ferrimanganic are seldom replenished, secular high yield makes potassium silicon in the soil and other element by mass consumption, and the coordinated balance of soil fertility is broken, and comprehensive fertility constantly descends.
The consequence that soil fertility is unbalance is 1) practical efficiency of nitrogen, phosphate fertilizer is very low, nitrogenous fertilizer less than 30%, this has not only limited the further volume increase of agricultural, and has improved agriculture production cost, causes also that agricultural is three-dimensional to be polluted; 2) shortage of product prime element such as potassium silicon magnesium sulphur does not cause nutritional trouble, and not only pathology easily takes place plant, and the quality of agricultural-food descends, and is fragrant as melon, fruit is sweetless; 3) excessive applied nitrogen causes soil acidification, secondary salinization on the one hand, and harmful organism grows, and also causes residual the exceeding standard of nitrate in the agricultural-food simultaneously easily.
Therefore, press for a kind of effective multi-element mineral fertilizer, this multi-element mineral fertilizer can effectively be absorbed by plant, and replenishes the required various nutrients of plant-growth comprehensively.
We know that soil is transformed by natural geochemistry weathering soil-forming process by rock, and in mass, the about 95% various mineral substance that is come by rock decay of solid phase of soil material is formed.Yet these mineral substance overwhelming majority are to exist with the form that plant can not absorb, and having only a few part (3%-8%) to be converted in the weathering soil-forming process can be by effective nutritive ingredient that plant absorbed.The effective mineral substance nutrient of this sub-fraction makes that soil can growing plant just.
But, natural soil-forming process very long (thousands of-tens thousand of years), and transformation efficiency is very low.Therefore people attempt with the various mineral substance in the silicate rock transforming into effective form that plant can absorb always efficient and vast scale.Have the previous work of certain association can roughly be summarised as following three aspects therewith: the water-insoluble potassium that 1, will contain in the potassium silicate rock (the insoluble potassium that is otherwise known as ore deposit) is converted into soluble potassium and develops potash fertilizer; 2, utilize mineral manures such as exploitation calcium silicate fertilizer such as ironmaking waste residue, yellow phosphorus waste slag; 3, the roasting of carbonate rock being become lime make ca and mg fertilizer uses.Wherein, study at most by containing potassium silicate rock extraction soluble potassium.
Utilize at present to contain the method that the potassium silicate rock is produced potash fertilizer, conclude and get up to mainly contain three kinds, be i.e. calcination method or sintering process, hydrothermal chemistry method, microbial method.Wherein existing hydrothermal chemistry method mainly comprises following method.
GB186199 discloses a kind of method of extracting potassium from feldspar, at first in ball mill or cylinder grinding machine, potassium bearing rock is ground to form fine powder, place the acid proof colloidal mill to grind to form high fineness suspended substance potassium bearing rock fine powder and dilute hydrochloric acid solution mixing then, again the high fineness suspended substance that obtains is transferred in the autoclave, about 225 ℃ (25 normal atmosphere) heat treated, potassium a large amount of in the potassium bearing rock are filtered by in the pass into solution, evaporation concentration can obtain KCl.The potassium bearing rock fine powder also can mix with alkaline solution, is processed into high fineness suspended substance in colloidal mill, and then in autoclave heat treated, more after filtration, evaporation concentration makes the KOH product.
Jumei Yamasaki once carried out under 100 ℃～400 ℃ conditions with Ca (OH)
2The research of the potassium in the slurries high pressure extraction potassium felspar sand, the leaching yield of potassium are 90% (Jumei Yamasaki.J.Chem.Soc.Japan Ind Chem Sect.1951,54 (1): 704).Chemak finds, in the time of 150 ℃～200 ℃, KOH solution and the shale reaction of Switzerland Opalinus area, can generate phillipsite, make on the one hand that potassium obtains activation in the shale, be unlikely leaching again because potassium ion is in the cavity of zeolite and the passage on the other hand, can make a kind of long-acting potash fertilizer (J.A.Chermak.Clays and clayMiner.1993,41 (3): 365-372) by water institute.Brave prompt (the Lan Jixiang of Southeast China University's blue meter perfume (or spice) and East China University of Science's face, Yan Yongjie, [J], hi-tech communication, 1994,8:26-28) studied the compressive reaction condition of slaked lime and potassium felspar sand, reaction is to carry out 0.5 liter of volume in FYX05A type permanent magnetism stirring-type autoclave, 350 ℃ of maximum operating temperatures, operating pressure 200atm, stirring velocity 50～1000rpm, the potassium leaching rate of potassium felspar sand can reach 90% or higher.The shortcoming of this leaching method is to implement dynamic agitation, water and solid material bigger (minimum can not less than 8), and power consumption is big, and its equipment stopping property is tight, the cost height.
People such as the Zhao Heng of Central South University duty (Zhao Hengqin, Hu Chongjie, Ma Hualong etc., [J] Chinese manganese industry, 2003,20 (1): 27-29) feldspar in powder is placed 300 ℃ of high pressure base aqueous systems, ore is dissociated obtain Al (OH)
3With KOH solution.
The inventor has since nineteen ninety-six also carried out the research of extracting potassium from contain potassium silicate rock (insoluble potassium ore deposit), has successively obtained three patents of invention (patent No. ZL01100474.6, ZL01100475.4 and ZL02156824.3).Carry both at home and abroad on the empirical basis of potassium in reference, created a kind of hydrothermal chemical reaction method and put forward the potassium novel process, can obtain KOH, K
2CO
3And K
2SO
4Goods.That wherein adopts contains the special rock of a class that the potassium silicate rock mainly is made up of spontaneous silicate minerals.In this rocks, potassium-bearing mineral is mainly potassium felspar sand, illite, glaukonine, mica mineral etc., K in the chemical ingredients
2O content is higher, generally more than 10%.Though these patented technologies can be transformed into original insoluble potassium in the rock potassium in the water soluble, also stay a large amount of solid residues simultaneously.These solid residues do not find the suitable applications field as yet, if long-term the stacking very easily caused environmental pressure, and need be taken a large amount of soils.
As fully visible, producing in the technology of potash fertilizer by containing the potassium silicate rock in existing hydrothermal chemical reaction method, all is that one or more elements in the rock are converted into plant nutrient ingredient, as potash fertilizer, phosphate fertilizer, ca and mg fertilizer, calcium silicate fertilizer etc. usually.And the potassium silicate rock that contains that uses in the prior art mainly is by K
2The special rock that the higher spontaneous silicate minerals of O content is formed does not also have a kind of method of utilizing common silicate rock to produce mineral manure.The more important thing is up to now, also do not have a kind ofly can to simulate geochemistry weathering soil-forming process, the various mineral substance in the silicate rock are integrally transformed into the available nutrient of plant-growth and make it have the technology of unique microvoid structure.
Summary of the invention
The objective of the invention is: provide a kind of can integrally change into can be by the hydrothermal chemical reaction method of the novel mineral manure of multielement of plant absorbing with the principal element in the silicate rock and trace element.
The present invention solves one of scheme that its technical problem adopts: utilize hydrothermal chemical reaction to produce the multielement micropore mineral manure by silicate rock, its characteristics comprise the following steps:
(1) with silicate rock and alkaline earth exciting agent separated pulverizing and be finely ground to pulverulent material;
(2) according to the silicate rock of 1:0.5～1: alkaline earth exciting agent ratio, above-mentioned pulverulent material is dropped in the water, make that the ratio of water and pulverulent material gross weight is 1～3:1, and mix;
(3) material that mixes is carried out hydro-thermal reaction in 130 ℃～250 ℃ in closed reaction vessel, the reaction times is 5～24 hours;
(4) with reaction product drying, crushing screening, can obtain the multielement micropore mineral manure,
Wherein said alkaline earth exciting agent comprises lime, light calcined magnesia and calcined dolomite in powder.
The present invention solves two of scheme that its technical problem adopts: utilize hydrothermal chemical reaction to produce the multielement micropore mineral manure by silicate rock, its characteristics comprise the following steps:
(1) with silicate rock, alkaline earth exciting agent and activator separated pulverizing and be finely ground to pulverulent material;
(2) according to silicate rock: the alkaline earth exciting agent: the ratio of 1:0.5～1:0.01 between the activator～0.25, above-mentioned pulverulent material is dropped in the water, make that the ratio of water and pulverulent material gross weight is 1～3:1, and mix;
(3) material that mixes is carried out hydro-thermal reaction in 130 ℃～250 ℃ in closed reaction vessel, the reaction times is 5～24 hours;
(4) with reaction product drying, crushing screening, can obtain the multielement micropore mineral manure,
Wherein said alkaline earth exciting agent comprises lime, light calcined magnesia and calcined dolomite in powder, and described activator comprises gypsum and magnesium borate.
By containing the multielement micropore mineral manure that the potassium silicate rock is prepared, comprise 15%～30% solubility in citric acid silicon, 30%～40% solubility in citric acid calcium magnesium, 4%～6% water-soluble and solubility in citric acid K according to method provided by the present invention
2O, 1%～5% solubility in citric acid iron, not chloride, mainly by holder shellfish mullite [Ca
5Si
6O
16(OH)
2.4H
2O] and hydration ca aluminosilicate [Ca
3Al
2(SiO
4) (OH)
8] the micro-crystal of two kinds of synthetic minerals is formed, and wherein the hydration ca aluminosilicate is the spherulitic of 1-5 micron dimension, holder shellfish mullite is the laminar of tens of～hundreds of nano thickness.
The present invention integrally changes into principal element in the silicate rock and trace element and can have been reformed the notion of traditional single-element chemical fertilizer or simple several elements compounding fertilizer by the multi-element mineral fertilizer of plant absorbing.And the method for preparing multi-element mineral fertilizer of the present invention can be fast, efficient and vast scale ground transforms into effective form that plant can absorb with the various mineral substance in the silicate rock at low cost, thereby might fundamentally finish to depend on since the dawn of human civilization the state that natural wind changes into the effective mineral substance nutrient of native process acquisition soil always.
Description of drawings
Fig. 1 is the X-ray powder crystal diffraction phase analysis figure of hydro-thermal reaction product;
Fig. 2 is the scanning electron microscope Photomicrograph of hydro-thermal reaction product.
Embodiment
Among the present invention to the silicate rock that is used to produce mineral manure without any special restriction, and need not carry out ore dressing, roasting etc. and handle complicated early stage.
The alkaline earth exciting agent that is adopted among the present invention both can be purer commercial lime, also can be industrial light calcined magnesia, can also use the calcined dolomite in powder that is obtained by dolomite calcination, and wherein CaO-MgO can be arbitrary proportion.
The activator that is adopted among the present invention is gypsum both, also magnesium borate.In the present invention, the existence of gypsum has excited Ca (OH) greatly
2Or/and Mg (OH)
2Activity, make transformation efficiency higher.And magnesium borate can promote the disintegration of silicon-oxy tetrahedron and aluminum-oxygen tetrahedron structure in the silicate minerals to destroy, thereby reaches the raising transformation efficiency, increases the purpose of active constituent content in the product.
The granular size that solid materials grinds among the present invention is chosen in 200 orders following (being that 0.074mm is following).The excessive speed of response that influences of particle causes active constituent content reduction in the product.Particle is also unsuitable meticulous, otherwise current consumption increases in grinding, and causes production cost to rise.
In preparation method of the present invention, the consumption of water is of crucial importance.The very few result of extraction that can not guarantee various components of the water yield, hypervolia then make the treatment capacity of material reduce, thereby reduce productivity.The consumption of water is to select according to the amount of solid materials among the present invention, so that solid materials is in half wet condition.In the present invention, the amount ratio of water and solid materials, promptly solid-to-liquid ratio is 1: 1～3, preferred 1: 1.2～1.5.
In addition, the pressure in the reaction system is also very important for hydro-thermal reaction.In suitability for industrialized production, can in reaction system, feed steam to keep constant reaction pressure.Generally speaking, pressure is big more, helps the carrying out of hydro-thermal reaction more.But, consider existing evaporation of water in equipment cost and the reaction system, the pressure of the steam of feeding is preferably 0.2～5Mpa, and more preferably 0.5～2Mpa most preferably is about 1.2～1.3Mpa.
Temperature of reaction and time are the important factors of decision hydro-thermal reaction effect.Generally speaking, higher temperature helps containing in the hydrothermal chemical reaction structural collapse destruction of potassium silicate, thereby reaches the purpose that improves transformation efficiency, increases active constituent content in the product, also can shorten the reaction times simultaneously, boosts productivity.But it is higher, tighter that too high temperature of reaction requires heat-resisting, the withstand voltage properties of reactor, causes facility investment to strengthen, and is unfavorable for reducing production costs.On the other hand, lower temperature causes transformation efficiency to descend, and active constituent content reduces in the product, and makes the reaction times long, increases production cost.When temperature is lower than 100 ℃, when promptly being lower than the boiling point of water, hydro-thermal reaction is carried out extremely slowly, and can not get multielement micropore mineral manure of the present invention basically.Therefore, from obtaining the ideal multi-element mineral fertilizer and the consideration that reduces cost, range of reaction temperature of the present invention is preferably 100～300 ℃, more preferably 130～250 ℃, most preferably be 170～200 ℃, and the reaction times is preferably 5～24 hours, more preferably 7～14 hours.
Hydro-thermal reaction of the present invention is carried out under static conditions, both can reduce energy consumption greatly, makes technology simple again, be easy in the technical process realize, and workman's easy handling is implemented.And do not have the discharging of waste water, waste gas and solid waste in the whole process of production, belong to the environmental type Technology.
The result that the hydrothermal reaction product is carried out solubility test according to Ministry of Agriculture's regulated procedure shows, the 65%-85% that its solid matter is formed can both be dissolved among 0.5 mole the hydrochloric acid soln, and belonging to can be by the water-soluble or solubility in citric acid component that plant absorbed.Wherein water-soluble and solubility in citric acid K
2The content of O is about 4%-6% (potash-lime fertilizer that is equivalent to sell in the market), is a kind of chlorideless potassic fertilizer.Also contain 20% simultaneously ± solubility in citric acid silicon (having reached the siliceous fertilizer standard of Ministry of Agriculture's promulgation), 〉=other solubility in citric acid component (comprising various trace elements and rare earth element in the silicate rock) of 30% solubility in citric acid calcium magnesium, the solubility in citric acid iron of 1%-5% and larger proportion.Therefore this product is multiple-element long active slowly-releasing mineral manures such as a kind of good potassium, silicon, calcium, magnesium, iron, manganese, boron.
The X-ray powder crystal diffraction phase analysis result of the hydrothermal reaction product that shows by Fig. 1 as seen, multi-element mineral fertilizer of the present invention mainly is made up of the micro crystal of following two kinds of synthetic minerals: hold in the palm shellfish mullite [Ca
5Si
6O
16(OH)
2.4H
2O] and hydration ca aluminosilicate [Ca
3Al
2(SiO
4) (OH)
8].
Fig. 2 has shown the scanning electron microscope analysis result of multi-element mineral fertilizer of the present invention.According to the observation and the microstructural analysis of particle form size, the particle of forming this novel mineral manure is very fine, is nanometer-submicron level; Wherein the hydration ca aluminosilicate is micron-sized spherulitic (a particle diameter 1-5 micron), and holder shellfish mullite then is nano level laminar (thickness of thin slice is tens of-hundreds of nanometers).And this mineral manure also shows very flourishing microvoid structure under scanning electronic microscope, so this mineral manure quality is loose, unit weight has only 0.70-0.80g/cm
3, therefore also be called the micropore mineral manure.Because the subparticle and the microvoid structure of this mineral manure uniqueness, it has very high activity, has improved its ability that is absorbed by roots of plants acid dissolving greatly.And the distinctive microvoid structure of this product also makes it have preserve moisture and fertility, improved soil nodule structure, the ventilated function of promotion plant root.
The subparticle of this mineral manure uniqueness and microvoid structure are because adopted the application of exclusive alkaline earth exciting agent and the technology of half wet condition in its preparation process, and have controlled temperature, pressure and the time of hydrothermal chemical reaction rightly.And the calcium silicate fertilizer that the slag that uses the potassium calcium silicate fertilizer of sinter process production, the yellow phosphorus slag that uses phosphatization factory and iron and steel enterprise is produced, under scanning electronic microscope, do not possess this microvoid structure, and X-ray powder crystal diffraction phase analysis shows that it is non-crystalline state or cryptocrystalline texture.
Multielement micropore mineral manure of the present invention does not add any objectionable impurities, the crude substance composition characteristics that has kept silicate rock self, the same with the soil of naturally weathered formation, after using, the farmland can not produce especially murder by poisoning and pollution, be suitable for producing natural green food.And multielement micropore mineral manure product of the present invention can not cause widespread pollution from the overuse of fertilizers and pesticides in rural area as solubility in citric acid long-acting slow-release fertilizer.
2006 and 2007 in Beijing, ground such as Hebei, Jilin, Inner Mongol, Sichuan, Guizhou, Fujian, Jiangxi, Xinjiang, Shandong, Liaoning carried out preliminary field fertilizer efficiency to farm crop such as corn, paddy rice, wheat, Glutinous Semen Maydis, apple, honey peach, grape, winter jujube, tealeaves, Sunflower Receptacle, capsicum, Chinese cabbage, rape, celery, broad bean, pachyrhizuses, obtained effect preferably.The output increase of various agricultural-food can reach 2%-20% (referring to annex 1) respectively.Detect according to grain quality supervision and inspection center of the Ministry of Agriculture, the quality of paddy rice also increases, compare with the paddy rice of not executing this mineral manure, nine (except the chalk rice rates) in ten quality parameter of its detection (moisture, crude protein, amylose starch, brown rice rate, glutinous rice rate, whole glutinous rice rate, glue denseness, alkali disappear value (level)/gelatinization point, chalk rice rate, the white size of chalk, hard whiteness) all have raising (referring to annex 2) in various degree.
Describe the present invention in more detail below in conjunction with specific embodiment, but these embodiment only are used for illustration purpose, and the scope that does not limit the present invention in any way.
Embodiment 1
1) choose raw material, comprise potassium bearing rock and lime:
Contain the potassium silicate rock: pick up from Miyun County South Mountain, Beijing, (%) is as follows for its chemical constitution
| SiO 2 | TiO 2 | AlO 3 | Fe 2O 3+FeO | MnO | CaO | MgO | K 2O | Na 2O | P 2O 5 | Loss on ignition | Add up to |
| 63.09 | 0.71 | 15.69 | 4.41 | 0.02 | 0.15 | 0.37 | 12.79 | 0.22 | 0.04 | 1.93 | 99.42 |
X ray powder crystal diffraction analysis points out that this potassium bearing rock is based on potassium felspar sand, and other is a quartz etc.
Lime: contain CaO 97% (chemical pure, China Drug Co.'s Beijing purchasing and supply station).
2) production process:
(1) with potassium bearing rock, below lime separated pulverizing to 200 order, in plastic ware, add earlier 30ml water, in ware, add 5.000 gram potassium bearing rock breezes, 5.000 gram lime powders successively then, stir with stirring rod;
(2) plastic ware that will fill sample was inserted in the autoclave, 197 ℃ of reactions 7 hours;
(3) plastic ware is taken out in autoclave cooling back, and reaction product is transferred on the glass table ware, and is levigate at 105 ℃ of baking oven inner heating dryings, promptly obtains the mineral manure product.
3) in order to measure the solubility rate of potassium in the potassium-bearing mineral, the product that obtains is moved into strainer, go out soluble potassium with water extraction.Obtain 100ml in the test and contain the potassium filtered liquid, record the concentration of potassium in the liquid sample after the dilution with flame photometer, measurement result is converted into K
2O concentration is 4540mg/l.5.000 gram potassium bearing rock breeze contains K
2O 639.5mg, and leaching liquid is amounted to K
2O concentration is 4540mg/l, and then the 100ml filtered liquid contains K
2O 454.0mg, therefore, the solubility rate of potassium is 70.99% in the potassium-bearing mineral.
Embodiment 2
1) choose raw material, comprise potassium bearing rock, lime and gypsum:
Contain the potassium silicate rock: pick up from Miyun County South Mountain, Beijing, (%) is as follows for its chemical constitution
| SiO 2 | TiO 2 | AlO 3 | Fe 2O 3+FeO | MnO | CaO | MgO | K 2O | Na 2O | P 2O 5 | Loss on ignition | Add up to |
| 63.09 | 0.71 | 15.69 | 4.41 | 0.02 | 0.15 | 0.37 | 12.79 | 0.22 | 0.04 | 1.93 | 99.42 |
X ray powder crystal diffraction analysis points out that this potassium bearing rock is based on potassium felspar sand, and other is a quartz etc.
Lime: contain CaO 97% (chemical pure is available from supply station, China Drug Co. Beijing).
Gypsum: pick up from Xinjiang and Bu Kesaier county summer son lid wilkinite mining area, be the selenitum of complete crystallization, 120 ℃ were heated 1 hour in the lab oven at, obtained semi-hydrated gypsum (CaSO
41/2H
2O).
2) production process:
(1) with potassium bearing rock, lime, below semi-hydrated gypsum separated pulverizing to 200 order, in plastic ware, add 30ml water earlier, in ware, add 1.000 gram semi-hydrated gypsum powders, 5.000 gram potassium bearing rock breezes, 4.000 gram lime powders successively then, stir with stirring rod;
(2) plastic ware that will fill sample was inserted in the autoclave, 197 ℃ of reactions 7 hours;
(3) plastic ware is taken out in autoclave cooling back, and reaction product is transferred on the glass table ware, and is levigate at 105 ℃ of baking oven inner heating dryings, promptly obtains the mineral manure product.
3) in order to measure the solubility rate of potassium in the potassium-bearing mineral, the product that obtains is moved into strainer, go out soluble potassium with water extraction.Obtain 100ml in the test and contain the potassium filtered liquid, record the concentration of potassium in the liquid sample after the dilution with flame photometer, measurement result is converted into K
2O concentration is 5080mg/l.5.000 gram potassium bearing rock breeze contains K
2O 639.5mg, and leaching liquid is amounted to K
2O concentration is 5080mg/l, and then the 100ml filtered liquid contains K
2O 508.0mg, therefore, the solubility rate of potassium is 79.44% in the potassium-bearing mineral.
Comparing embodiment 1 and example 2 add a certain amount of gypsum (this place is a semi-hydrated gypsum) as can be seen in the prescription, excited the activity of lime, make that the solubility rate of potassium has improved 8.45% in the potassium bearing rock.
Embodiment 3
1) choose raw material, comprise potassium bearing rock and lime:
Contain the potassium silicate rock: pick up from Miyun County South Mountain, Beijing, (%) is as follows for its chemical constitution:
| SiO 2 | TiO 2 | AlO 3 | Fe 2O 3+FeO | MnO | CaO | MgO | K 2O | Na 2O | P 2O 5 | Loss on ignition | Add up to |
| 63.09 | 0.71 | 15.69 | 4.41 | 0.02 | 0.15 | 0.37 | 12.79 | 0.22 | 0.04 | 1.93 | 99.42 |
X ray powder crystal diffraction analysis points out that this silicate rock mineral composition is based on potassium felspar sand, and other is a quartz etc.
Lime: contain CaO 97% (chemical pure, China Drug Co.'s Beijing purchasing and supply station).
2) production process:
(1) silicate rock, lime is levigate respectively to 200 orders, obtain the silicate rock stone flour, lime powder; In plastic ware, add 15ml water, then 5.700g silicate rock stone flour, 4.300g lime powder are joined in the vessel successively, and stir, make mixing of materials even;
(2) plastic ware that will fill sample was inserted in the autoclave, 191 ℃ of reactions 8 hours;
(3) after the autoclave cooling, take out plastic ware, reaction product is transferred in the glass table ware, at 105 ℃ of baking oven inner heating dryings;
(4) dried reaction product is levigate, promptly obtain multi-element mineral fertilizer.
3) active constituent content (dissolution time is 30 minutes, induction stirring for the stripping quantity of 1.000g multi-element mineral fertilizer sample in 100ml0.5mol/l hydrochloric acid, room temperature) of the multi-element mineral fertilizer of measurement acquisition, the result is as shown in table 1.
Table 1 embodiment 3 multi-element mineral fertilizer active constituent contents (%)
| SiO 2 | K 2O | Na 2O | Fe 2O 3 | TiO 2 | CaO | MgO | Al 2O 3 | MnO | P 2O 5 |
| 19.15 | 3.95 | 0.08 | 3.14 | 0.05 | 31.86 | 0.18 | 5.98 | 0.03 | 0.01 |
Used instrument: compose the direct-reading plasma emission spectrometer entirely, IRIS Advantage type, U.S. power ﹠ light company produces
Embodiment 4
1) choose raw material, comprise containing potassium silicate rock, lime and light-burned boron magnesium stone ore:
Contain the potassium silicate rock: pick up from Miyun County South Mountain, Beijing, (%) is as follows for its chemical constitution:
| SiO 2 | TiO 2 | AlO 3 | Fe 2O 3+FeO | MnO | CaO | MgO | K 2O | Na 2O | P 2O 5 | Loss on ignition | Add up to |
| 63.09 | 0.71 | 15.69 | 4.41 | 0.02 | 0.15 | 0.37 | 12.79 | 0.22 | 0.04 | 1.93 | 99.42 |
X ray powder crystal diffraction analysis points out that this potassium bearing rock mineral composition is based on potassium felspar sand, and other is a quartz etc.
Lime: CaO content 97%, (chemical pure, China Drug Co.'s Beijing purchasing and supply station).
Light-burned boron magnesium stone ore: primary sample holds the chemical plant available from sky, Liaoning, and raw ore coarse crushing sample is placed in the retort furnace, 700 ℃ of heated constant temperature 0.5 hour, takes out, and obtains the light-burned boron magnesium stone ore of thing based on vitreous state.
2) production process:
(1) with potassium bearing rock, lime, below light-burned boron magnesium stone ore separated pulverizing to 200 order, in plastic ware, add 15ml water earlier, in ware, add the light-burned szaibelyite breeze of 100mg, 5.700g potassium bearing rock breeze, 4.200g lime powder successively then, stir with stirring rod.
(2) plastic ware that will fill sample placed autoclave, 190 ℃ of reactions 8 hours;
(3) plastic ware is taken out in autoclave cooling back, reaction product is moved on the glass surface ware, at 105 ℃ of baking oven inner heating dryings;
(4) dried reaction product is levigate, promptly obtain the multielement micropore mineral manure.
3) active constituent content (dissolution time is 30 minutes, induction stirring for the stripping quantity of 1.000g mineral manure sample in 100ml 0.5mol/l hydrochloric acid, room temperature) of the multi-element mineral fertilizer of measurement acquisition, the result is as shown in table 2.
Table 2 embodiment 4 multielement micropore mineral manure active constituent contents (%)
| SiO 2 | K 2O | Na 2O | Fe 2O 3 | TiO 2 | CaO | MgO | Al 2O 3 | MnO | P 2O 5 | B |
| 21.31 | 4.32 | 0.05 | 3.26 | 0.07 | 31.82 | 0.47 | 6.19 | 0.03 | 0.02 | 0.83 |
Used instrument: compose the direct-reading plasma emission spectrometer entirely, IRIS Advantage type, U.S. power ﹠ light company produces
Comparative example 3 and example 4, can find, owing to added an amount of light-burned szaibelyite breeze in the prescription, further excited the activity of lime, can promote the disintegration of silicon-oxy tetrahedron and aluminum-oxygen tetrahedron structure in the silicate minerals to destroy, thereby reach the raising transformation efficiency, increase the purpose of active constituent content in the product.
Embodiment 5
1) choose raw material, comprise containing potassium silicate rock and lime:
Contain the potassium silicate rock: pick up from Miyun County South Mountain, Beijing, (%) is as follows for its chemical constitution:
| SiO 2 | TiO 2 | AlO 3 | Fe 2O 3+FeO | MnO | CaO | MgO | K 2O | Na 2O | P 2O 5 | Loss on ignition | Add up to |
| 63.09 | 0.71 | 15.69 | 4.41 | 0.02 | 0.15 | 0.37 | 12.79 | 0.22 | 0.04 | 1.93 | 99.42 |
X ray powder crystal diffraction analysis points out that this potassium bearing rock mineral composition is based on potassium felspar sand, and other is a quartz etc.
Lime: CaO content 97%, (chemical pure, China Drug Co.'s Beijing purchasing and supply station).
2) production process:
(1) with potassium bearing rock and lime separated pulverizing to 200 order, in plastic ware, add 15ml water earlier, in ware, add 5.700g potassium bearing rock breeze, 4.300g lime powder successively then, stir with stirring rod.
(2) plastic ware that will fill sample placed autoclave, 130 ℃ of reactions 24 hours;
(3) plastic ware is taken out in autoclave cooling back, reaction product is moved on the glass surface ware, at 105 ℃ of baking oven inner heating dryings;
(4) dried reaction product is levigate, promptly obtain the multielement micropore mineral manure.
3) active constituent content (dissolution time is 30 minutes, induction stirring for the stripping quantity of 1.000g mineral manure sample in 100ml 0.5mol/l hydrochloric acid, room temperature) of the multi-element mineral fertilizer of measurement acquisition, the result is as shown in table 3.
Table 3 embodiment 5 multielement micropore mineral manure active constituent contents (%)
| SiO 2 | K 2O | Na 2O | Fe 2O 3 | CaO | MgO | Al 2O 3 | MnO | P 2O 5 |
| 7.30 | 1.57 | 0.49 | 0.43 | 33.94 | 0.31 | 1.97 | 0.02 | 0.01 |
Used instrument: compose the direct-reading plasma emission spectrometer entirely, IRIS Advantage type, U.S. power ﹠ light company produces
Embodiment 6
1) choose raw material, comprise containing potassium silicate rock and lime:
Contain the potassium silicate rock: pick up from Miyun County South Mountain, Beijing, (%) is as follows for its chemical constitution:
| SiO 2 | TiO 2 | AlO 3 | Fe 2O 3+FeO | MnO | CaO | MgO | K 2O | Na 2O | P 2O 5 | Loss on ignition | Add up to |
| 63.09 | 0.71 | 15.69 | 4.41 | 0.02 | 0.15 | 0.37 | 12.79 | 0.22 | 0.04 | 1.93 | 99.42 |
X ray powder crystal diffraction analysis points out that this potassium bearing rock mineral composition is based on potassium felspar sand, and other is a quartz etc.
Lime: CaO content 97%, (chemical pure, China Drug Co.'s Beijing purchasing and supply station).
2) production process:
(1) with potassium bearing rock and lime separated pulverizing to 200 order, in plastic ware, add 15ml water earlier, in ware, add 5.700g potassium bearing rock breeze, 4.300g lime powder successively then, stir with stirring rod.
(2) plastic ware that will fill sample placed autoclave, 250 ℃ of reactions 5 hours;
(3) plastic ware is taken out in autoclave cooling back, reaction product is moved on the glass surface ware, at 105 ℃ of baking oven inner heating dryings;
(4) dried reaction product is levigate, promptly obtain the multielement micropore mineral manure.
3) active constituent content (dissolution time is 30 minutes, induction stirring for the stripping quantity of 1.000g mineral manure sample in 100ml 0.5mol/l hydrochloric acid, room temperature) of the multi-element mineral fertilizer of measurement acquisition, the result is as shown in table 4.
Table 4 embodiment 6 multielement micropore mineral manure active constituent contents (%)
| SiO 2 | K 2O | Na 2O | Fe 2O 3 | CaO | MgO | Al 2O 3 | MnO | P 2O 5 |
| 25.98 | 5.47 | 0.51 | 2.66 | 35.46 | 0.43 | 6.95 | 0.03 | 0.01 |
Used instrument: compose the direct-reading plasma emission spectrometer entirely, IRIS Advantage type, U.S. power ﹠ light company produces
Comparative example 5 and example 6 can find that high temperature helps containing in the hydrothermal chemical reaction structural collapse destruction of potassium silicate, thereby reach the purpose that improves transformation efficiency, increases active constituent content in the product.
Embodiment 7:(5 tonne of industrialness preparation test)
1) choose raw material, comprise containing potassium silicate rock, lime and gypsum:
Contain the potassium silicate rock: pick up from Zhangjiakou City Xuanhua, Hebei province, (%) is as follows for its chemical constitution:
| SiO 2 | TiO 2 | AlO 3 | Fe 2O 3+FeO | MnO | CaO | MgO | K 2O | Na 2O | P 2O 5 | Loss on ignition | Add up to |
| 59.09 | 0.58 | 16.62 | 7.57 | 0.03 | 0.22 | 0.83 | 11.69 | 0.37 | 0.10 | 3.65 | 100.75 |
X ray powder crystal diffraction analysis points out that its mineral composition is based on potassium felspar sand and illite, and other is a quartz etc.
Lime: contain CaO 84%, contain MgO 3%, the positive calcium ash of Xuanhua Iron ﹠ Steel Co. dragon factory produces.
Gypsum: dihydrate gypsum, available from building materials shop, Xuanhua.
2) preparation process:
(1) it is levigate respectively to 200 orders to contain potassium silicate rock, lime, gypsum, obtains containing potassium silicate rock powder, lime powder and gypsum breeze; Three kinds of raw material according to the form below ratio proportionings:
The proportioning raw materials of table 5 embodiment 7 multielement micropore mineral manures
| Raw material | Rich potassium silicate rock powder | Lime powder | Gypsum |
| Ratio (%) | 50 | 40 | 10 |
(2) at first in material-storage jar, put into the 1270L tap water, then 100Kg terra alba, 500Kg are contained potassium silicate rock powder, the 400Kg lime powder is added to the water successively, and stir, make mixing of materials even, prepare 5 tons of materials (promptly preparing 5 jars of materials) altogether.
(3) material is transferred in the autoclave, and the feeding high compressed steam (0.95～1.05MPa), 183 ℃ of reactions 10 hours.
(4) reactor was opened in the step-down cooling after hydrothermal chemical reaction was finished, and took out reaction product, and natural air drying promptly gets the multielement micropore mineral manure after the pulverizing.
3) to above-mentioned reaction product sampling analysis after air-dry, its active constituent content is listed in table 4 (dissolution time is 30 minutes, induction stirring for the stripping quantity of 1.000g mineral manure sample in 100ml 0.5mol/l hydrochloric acid, room temperature).
The active constituent content (%) of table 6 embodiment 7 multielement micropore mineral manures
| Component | SiO 2 | K 2O | Na 2O | Fe 2O 3 | TiO 2 | CaO | Al 2O 3 | MgO | MnO | P 2O 5 |
| Content | 17.76 | 3.67 | 0.50 | 2.11 | 0.07 | 32.06 | 5.08 | 1.74 | 0.04 | 0.04 |
Used instrument: compose the direct-reading plasma emission spectrometer entirely, IRIS Advantage type, U.S. power ﹠ light company produces
The loss on ignition of this mineral manure sample is 16.20%, and block proportion is 0.755g/cm
3
Embodiment 8:(40 tonne type approval test)
1) choose raw material, comprising:
Contain the potassium silicate rock: pick up from Zhangjiakou City Xuanhua, Hebei province, (%) is as follows for chemical constitution:
| SiO 2 | TiO 2 | AlO 3 | Fe 2O 3+FeO | MnO | CaO | MgO | K 2O | Na 2O | P 2O 5 | Loss on ignition | Add up to |
| 57.22 | 0.57 | 18.34 | 6.09 | 0.06 | 0.33 | 1.12 | 12.01 | 0.07 | 0.11 | 3.60 | 99.52 |
X ray powder crystal diffraction analysis points out that its mineral composition is based on potassium felspar sand and illite, and other is a quartz etc.
Lime: contain CaO 84%, contain MgO 3%, the positive calcium ash of Xuanhua Iron ﹠ Steel Co. dragon factory produces.
Light-burned szaibelyite: primary sample holds the chemical plant available from sky, Liaoning, and raw ore coarse crushing sample is placed in the retort furnace, 700 ℃ of heated constant temperature 0.5 hour, takes out, and obtains the light-burned boron magnesium stone ore of thing based on vitreous state.
2) production process:
(1) will contain potassium silicate rock, lime, light-burned szaibelyite is levigate respectively to 200 orders, obtains containing potassium silicate rock powder, lime powder and light-burned szaibelyite breeze; Three kinds of raw material according to the form below ratio proportionings:
The proportioning raw materials of table 7 embodiment 8 multielement micropore mineral manures
| Raw material | Contain potassium silicate rock powder | Lime powder | Light-burned szaibelyite breeze |
| Ratio (%) | 57 | 42 | 1 |
(2) at first in material-storage jar, put into the 1400L tap water, then the light-burned szaibelyite powder of 10Kg, 570Kg are contained potassium silicate rock powder, the 420Kg lime powder is added to the water successively, and stir, make mixing of materials even, prepare 40 tons of materials (promptly preparing 40 jars of materials) altogether.
(3) material is transferred in the autoclave, and the feeding high compressed steam (0.95～1.05MPa), carry out hydrothermal chemical reaction at 180 ℃, reacted 14 hours.
(4) reactor was opened in step-down cooling cooling after hydrothermal chemical reaction was finished, and took out reaction product, and natural air drying promptly gets the multielement micropore mineral manure after the pulverizing.
40 tons of products that above-mentioned air-dry back obtains are gathered fertilizer sample with sampling thief from up to a hundred points, combine, thorough mixing to about 2kg, and carries out the material composition and the microstructure analysis of system with diagonal lines quartering reduced sample.Its detected result is as follows:
A. micropore mineral manure chemical analysis data:
The main secondary element content (wt%) of the multielement micropore mineral manure of table 8 embodiment 8
| Component | SiO 2 | TiO 2 | Al 2O 3 | Fe 2O 3 | MnO | MgO | CaO | Na 2O | K 2O | P 2O 5 | Los | Total amount |
| Content | 28.25 | 0.34 | 9.25 | 4.37 | 0.09 | 2.09 | 31.61 | 0.17 | 5.45 | 0.10 | 17.63 | 99.35 |
The micronutrient levels of the multielement micropore mineral manure of table 9 embodiment 8 (mg/kg, i.e. ppm)
| Component | B | Ba | Cd | Co | Cr | Cu | Mo | Ni | Pb | Sr | V | Zn |
| Content | 559.0 | 262.4 | 3.85 | 10.15 | 58.65 | 5.85 | 10.15 | 53.95 | 10.15 | 216.85 | 141.75 | 81.5 |
Used instrument: the sequential Xray fluorescence spectrometer, the XRF-1500 type, Shimadzu Corp makes
B. thing phase composite
Through X-ray powder crystal diffraction analysis (seeing accompanying drawing 1), this micropore mineral manure is by holder shellfish mullite [Ca
5Si
6O
16(OH)
2.4H
2O], hydration ca aluminosilicate [Ca
3Al
2(SiO
4) (OH)
8] and thing phase composite such as lime carbonate (used instrument: x-ray diffractometer, the D/MAX-2400 type, Japanese Rigaku Denki Co., Ltd makes).
C. the observation of scanning electron microscope microscopic morphology and structure and analysis
With scanning electronic microscope (LE01450VP type, company difficult to understand produces in the Germany) mineral manure has been carried out displaing microstructure observing and analysis, find that two kinds of main synthetic minerals of micropore mineral manure all are the subparticle of nanometer-submicron level, one is spherical (hydration ca aluminosilicate), another mineral and is laminar (holder shellfish mullite) on the form, and a large amount of micropores that distribute (seeing accompanying drawing 2) therefore are called the micropore mineral manure.
D. bulk density
Measure the bulk density of novel microporous mineral manure with conventional volumetric flask method, measurement result is 659g/l or 0.659 gram/cubic centimetre.Obviously, unusual little of its proportion, this with the observation of scanning electron microscope microscopic morphology in a large amount of micropores of seeing to distribute be consistent.
E.0.5mol/l stripping component (that is effective constituent) Determination on content in the hydrochloric acid soln
The micropore mineral manure is ground to below 200 orders, gets 1.000 gram samples, place triangular flask, add 100ml 0.5mol/l hydrochloric acid soln, under room temperature environment (21 ℃), on magnetic stirrer, stirred 30 minutes, filter, measure the composition of stripping in the filtrate, the result is shown in table 8 and table 9:
The effective constituent (%) of the multielement micropore mineral manure of table 10 embodiment 8
| Component | SiO 2 | K 2O | Na 2O | Fe 2O 3 | TiO 2 | CaO | Al 2O 3 | MgO | MnO | P 2O 5 |
| Content | 19.62 | 4.15 | 0.14 | 3.44 | 0.18 | 31.19 | 7.31 | 1.03 | 0.07 | 0.05 |
The effective trace elements content of the multielement micropore mineral manure of table 11 embodiment 8 (mg/kg, i.e. ppm)
| Component | B | Ba | Cd | Co | Cr | Mo | Ni | Pb | Sr | V | Zn | Cu |
| Content | 458.70 | 78.70 | 0.20 | 2.90 | 23.10 | 2.90 | 30.30 | 2.90 | 211.89 | 94.30 | 18.20 | 0.00 |
Used instrument: compose the direct-reading plasma emission spectrometer entirely, IRIS Advantage type, U.S. power ﹠ light company produces
From the foregoing description, as can be known, adopt hydrothermal chemical reaction of the present invention to contain the water-soluble of the 4%-6% that has an appointment and solubility in citric acid K by the multielement micropore mineral manure of silicate rock preparation
2O (being equivalent to a kind of chlorideless potassic fertilizer), 15%～30% solubility in citric acid silicon, 30%～40% solubility in citric acid calcium magnesium, 1%～5% solubility in citric acid iron and other solubility in citric acid component (comprising various trace elements and rare earth element in the silicate rock) of larger proportion.Therefore this product is multielement slow release long-acting mineral manures such as a kind of good potassium, silicon, calcium, magnesium, iron, manganese, boron.
Claims (9)
1, a kind of hydrothermal chemical reaction that utilizes is produced the method for multielement micropore mineral manure by silicate rock, and this method comprises the following steps:
(1) with silicate rock and alkaline earth exciting agent separated pulverizing and be finely ground to pulverulent material;
(2) according to the silicate rock of 1:0.5～1: alkaline earth exciting agent ratio, above-mentioned pulverulent material is dropped in the water, make that the ratio of water and pulverulent material gross weight is 1～3:1, and mix;
(3) material that mixes is carried out hydro-thermal reaction in 130 ℃～250 ℃ in closed reactor, the reaction times is 5～24 hours;
(4) with reaction product drying, crushing screening, can obtain the multielement micropore mineral manure,
Wherein said alkaline earth exciting agent comprises lime, light calcined magnesia and calcined dolomite in powder.
2, method according to claim 1, wherein the granular size of the pulverulent material in the step (1) is below 200 orders.
3, method according to claim 1, wherein the weight ratio of water in the step (2) and pulverulent material is 1.2～1.5:1.
4, method according to claim 1, wherein the hydro-thermal reaction in the step (3) is to carry out 7～14 hours under 170 ℃～200 ℃.
5, a kind of hydrothermal chemical reaction that utilizes is produced the method for multielement micropore mineral manure by silicate rock, and this method comprises the following steps:
(1) with silicate rock, alkaline earth exciting agent and activator separated pulverizing and be finely ground to pulverulent material;
(2) according to silicate rock: the alkaline earth exciting agent: the ratio of 1:0.5～1:0.01 between the activator～0.25, above-mentioned pulverulent material is dropped in the water, make that the ratio of water and pulverulent material gross weight is 1～3:1, and mix;
(3) material that mixes is carried out hydro-thermal reaction in 130 ℃～250 ℃ in closed reactor, the reaction times is 5～24 hours;
(4) with reaction product drying, crushing screening, can obtain the multielement micropore mineral manure,
Wherein said alkaline earth exciting agent comprises lime, light calcined magnesia and calcined dolomite in powder, and described activator comprises gypsum and magnesium borate.
6, method according to claim 5, wherein said magnesium borate comprise szaibelyite raw ore and light-burned szaibelyite.
7, method according to claim 5, wherein the granular size of the pulverulent material in the step (1) is below 200 orders.
8, method according to claim 5, wherein the weight ratio of water in the step (2) and pulverulent material is 1.2～1.5:1.
9, method according to claim 5, wherein the reaction in the step (3) is to carry out 7～14 hours under 170 ℃～200 ℃.
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| CN 200710178794 CN101450875A (en) | 2007-12-05 | 2007-12-05 | Method for preparing multielement micropore mineral fertilizer from silicate rock through hydrothermal chemical reaction |
| PCT/CN2008/001185 WO2009070953A1 (en) | 2007-12-05 | 2008-06-18 | Method for preparing microporous mineral fertilizer from silicates rock using hydrothermal chemical reaction |
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