CN103086778A - Method for producing alkaline fertilizer from insoluble potassium-containing rock by kiln process - Google Patents
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Abstract
The invention discloses a method for producing an alkaline fertilizer from insoluble potassium-containing rock by a kiln process, belonging to the technical field of chemical production. The method comprises the following steps: mixing phosphate rock tailings or low-grade phosphate rock with the insoluble potassium-containing rock according to the weight ratio of 1:(0.4-0.9), further adding anthracite accounting for 3-8% of the total mixed weight, drying, grinding and further preparing a material block; and then placing into a kiln, roasting at the temperature of 1000-1200 DEG C for 30-150 minutes to prepare sintered clinker, finally performing water quenching, reducing the temperature of the sintered clinker to 400-700 DEG C, and draining, drying, crushing and grinding the sintered clinker after water quenching to prepare the alkaline fertilizer. According to the method disclosed by the invention, the roasting temperature is only 1000-1200 DEG C, the energy consumption is low, and the process is simple; and phosphogypsum is not used, SO2 gas causing serious pollution of air is not contained in tail gas, and the special treatment of the tail gas is not required.
Description
Technical field:
The present invention relates to a kind of method with phosphorite tailings or low-grade phosphate ore and insoluble potassium bearing rock kiln method production alkaline fertilizer, belong to chemical production technical field.
Background technology:
Producing the required phosphorus ore of high dense phosphate fertilizer can also be by obtaining mid low grade phosphate rock and high-magnesium-phosphorus ore flotation except the rich phosphorus ore of direct use, the mine tailing that floatation process produces (account for flotation ore deposit total amount 25～35%) is often stacked with the form of Tailings Slurry, fast development along with the dense phosphate fertilizer industry of domestic and international height, the accumulation of phosphorite tailings not only takies a large amount of land resources, and environment is caused more and more serious pollution.At present, enterprise's mining ubiquity is adopted richness and is abandoned poor behavior, causes low-grade phosphate ore to be wasted in a large number, causes the waste of phosphate rock resource, therefore faces the day by day present situation of scarcity of current phosphor resource, how to expand phosphor resource and utilizes scope to be significant.Chinese patent literature CN101747090(application number 200910218353.8) a kind of method of utilizing phosphate rock floating mine tailing blast furnace process to prepare fused(calcium magnesium)phosphate is disclosed, Chinese patent literature CN101747091(application number 200910218354.2) disclose a kind of take the phosphate rock floating mine tailing as raw material cyclone furnace legal system the method for standby fused(calcium magnesium)phosphate, these two pieces of patent documentations all are mixed phosphorite tailings and primary phosphorus ore, obtain butt P
2O
5Weight ratio is 〉=13% phosphorus ore raw material, then prepares fused(calcium magnesium)phosphate with silica, serpentine and coke (or coal dust) roasting.1), temperature higher (1350～1450 ℃) during roasting its advantage is to have the phosphorite tailings of pollution to recycle to environment, wherein phosphorus magnesium resource is converted into effective constituent in fused(calcium magnesium)phosphate, but all has the following disadvantages:, energy consumption is larger.2), desired raw material is more, also needs adapted silica, serpentine and coke (or coal dust), and all needs to carry out grinding, increased the complexity of technique.
China's water-soluble potassium resource is less, the liquid salt lake resources is less than 5% of world's Potash Resources, most of potassium resource all exists with insoluble potassium felspar sand and potassium bearing rock forms such as containing potassium silicic acid rock, and this has caused China's potash fertilizer production to be difficult to satisfy the needs of domestic agriculture production.In fact China is that potash fertilizer consumption and import rely on one of maximum country, if with insoluble potassium bearing rock as raw material production potash fertilizer, will greatly alleviate the demand of China's agricultural to potash fertilizer, reduce import, save capital.Chinese patent literature CN101428769(application number 200810069029.X), disclose the insoluble potassium bearing rock of a kind of use and phosphogypsum and produced the method for potash-lime fertilizer co-producing sulfuric acid, obtained better result take insoluble potassium bearing rock as the raw material production potash-lime fertilizer, this patent documentation is with insoluble potassium rock, after phosphogypsum and hard coal ball processed or clamp dog, roasting prepares potash-lime fertilizer, its advantage is that the existing production technique maturing temperature (1150～1350 ℃) of its maturing temperature in production technique (1000～1200 ℃) is lower, simultaneously with discarded phosphogypsum recycling, with the calcium resource be transformed into can be absorbed by crops potash-lime fertilizer in, the transformation efficiency of potassium is up to 98% simultaneously.Shortcoming is the SO that discharges in production process
2Concentration is low, makes the technical process that generates sulfuric acid complicated, and cost is high.
Another of Guizhou Xiyang Fertilizer Industry Co., Ltd. piece patent documentation " a kind of method of producing potash-lime fertilizer with potassium felspar sand, Wingdale and phosphogypsum " (application number 200910102556.0) has been announced the method for preparing potash-lime fertilizer with roasting after insoluble potassium felspar sand, Wingdale and phosphogypsum ball processed or clamp dog, its advantage is maturing temperature lower (1000～1150 ℃) in more above-mentioned patent documentation (application number 200810069029.X) production potash-lime fertilizer technique, time shorter (30～60 minutes), equally also phosphogypsum has been carried out resource reutilization, the transformation efficiency of potassium is the highest by 98%.This patent technique no opparent defect, but compare Chemical Mixed Fertilizer, in potash-lime fertilizer, nutrient is too single, only has potassium element to exist.
Have not yet to see with phosphorite tailings or low-grade phosphate ore and the patent of insoluble potassium bearing rock kiln method production alkaline fertilizer and the report of correlation technique.
Summary of the invention:
For the deficiencies in the prior art, the invention provides a kind of energy consumption low, technique is simple, effective constituent more comprehensively, the production method of the alkaline fertilizer that nutrient is abundant, the method is that a new approach is opened up in the comprehensive utilization of resources of phosphorite tailings and low-grade phosphate ore, produces alkaline fertilizer take phosphorite tailings or low-grade phosphate ore and insoluble potassium bearing rock as raw material, except containing the effective constituents such as magnesium, silicon, calcium, also contain simultaneously nutrient phosphorus and potassium.
The term explanation
Phosphorite tailings: the phosphorus ore raw ore is through grinding, adopt different technique of preparings to carry out residual material after enrichment to phosphorus, except containing a certain amount of P
2O
5Also contain calcium, magnesium, silicon, iron, aluminium and organic impurity outward; Due to the difference of technique of preparing, P in phosphorite tailings
2O
5Content is generally 8%～15%.
Low-grade phosphate ore: P in phosphorus ore
2O
5Content is lower than 20% the low-grade phosphate ore that is called, main component: P in raw ore
2O
5Content is lower than 20%, MgO content, 2%～5% left and right, and silicate content is more than 20%.
Insoluble potassium bearing rock: contain potassium silicate class potassium ore resources take potassium felspar sand as representative.
Technical scheme of the present invention is as follows:
The insoluble potassium bearing rock kiln of a kind of use method is produced the method for alkaline fertilizer, comprises the steps:
(1) phosphorite tailings or low-grade phosphate ore are mixed 1:0.4 ~ 0.9 in mass ratio with insoluble potassium bearing rock, then add the hard coal of above-mentioned mixing total mass 3～8%, get mixture;
(2) step (1) gained mixture is dry, grinding gets pulverulent material;
(3) finish mix of the pulverulent material that step (2) is made;
(4) the material piece that step (3) is made is put into kiln, and 1000～1200 ℃ of roasting temperatures 30～150 minutes make sintered clinker;
(5) sintered clinker that makes of above-mentioned steps (4) carries out shrend, and sintered clinker temperature in 1～10 minute is down to 400～700 ℃, and the sintered clinker after shrend makes alkaline fertilizer through draining, drying, fragmentation and grinding.
Preferred according to the present invention, in described step (1), the mass ratio of phosphorite tailings or low-grade phosphate ore and insoluble potassium bearing rock is 1:0.55～0.77, and anthracitic add-on accounts for 4～7% of phosphorite tailings or low-grade phosphate ore and insoluble potassium bearing rock total amount.
Preferred according to the present invention, mixture properties of powder performace to 60 in described step (2)～150 orders, preferred, 80～120 orders, screen over-size＜5wt%.
Preferred according to the present invention, in described step (3), pulverulent material adds finish mix of water, and the mass ratio of pulverulent material and water is 1:0.08～0.15.
Preferred according to the present invention, the material piece in described step (3) is that diameter is that spherical material piece or the volume of 5～15mm is 0.1～2.2dm
3Square material piece.
Preferred according to the present invention, in described step (4), maturing temperature is 1100～1200 ℃, and roasting time is 30～50 minutes.
Preferred according to the present invention, in described step (4), use fuel to be bituminous coal during roasting.
Preferred according to the present invention, in described step (4), kiln is down-draft kiln, tunnel furnace or rotary kiln.
Preferred according to the present invention, in described step (5) during the sintered clinker shrend in 1～5 minute temperature be down to 400～600 ℃.
In step of the present invention (5), draining, drying, fragmentation and grinding are prior art, get final product according to existing operational condition operation.
Method of the present invention can change into the insoluble phosphorus in phosphorite tailings or low-grade phosphate ore and can by the molten phosphorus of the Chinese holly that farm crop absorb, the potassium in insoluble potassium bearing rock can also be changed into effective potassium that farm crop can absorb simultaneously.The product of producing not only contains the nutrients such as silicon, calcium, magnesium, phosphorus, also contains nutrient potassium, and in the products such as fused(calcium magnesium)phosphate, silicon-calcium-magnesium-phosphorus fertilizer, potash-lime fertilizer, silico-calcium potash fertilizer, alkali divides and increases more on the market, so we claim that this product is alkaline fertilizer.
Main component in phosphorite tailings or low-grade phosphate ore is CaMg (CO
3)
2And Ca
5F (PO
4)
3, insoluble potassium bearing rock is with potassium felspar sand (K
2OAl
2O
36SiO
2) being representative, the at high temperature calcium in phosphorite tailings or low-grade phosphate ore and potassium felspar sand reaction makes the insoluble potassium in insoluble potassium bearing rock change water-soluble potassium into, can be absorbed by crops.Its principal reaction is as follows:
CaMg(CO
3)
2→CaO+MgO+2CO
2↑
K
2O·Al
2O
3·6SiO
2+6CaO→6（CaO·SiO
2）+K
2O·Al
2O
3
Ca in while phosphorite tailings or low-grade phosphate ore
5F (PO
4)
3With the SiO in potassium felspar sand
2Form a kind of silicate glass network under the heat that fuel provides, make the PO in melt
4 3-Be frozen in process of cooling in silicate network, can by the slow stripping of weak acid, be absorbed by farm crop.
The present invention has the following advantages and beneficial effect:
1, the method for production alkaline fertilizer of the present invention, maturing temperature are only 1000～1200 ℃, produce 1350～1450 ℃ of the maturing temperatures of fused(calcium magnesium)phosphate lower than prior art, and temperature is low, and energy consumption is little, and technique is simple.
2, at high temperature calcium and the potassium felspar sand reaction in phosphorite tailings or low-grade phosphate ore of method of the present invention makes the insoluble potassium in insoluble potassium bearing rock change water-soluble potassium into, and water-soluble potassium can be absorbed by crops, simultaneously Ca in phosphorite tailings or low-grade phosphate ore
5F (PO
4)
3With the SiO in potassium felspar sand
2Form a kind of silicate glass network under the heat that fuel provides, make the PO in melt
4 3-Be frozen in process of cooling in silicate network, can by the slow stripping of weak acid, be absorbed by farm crop.Both phosphorite tailings and the little low-grade phosphate ore of economic worth that causes environmental pollution utilized, also made contribution for environmental protection, improved economic benefit.
3, the pulverulent material of the present invention after with grinding adds finish mix of water, makes the material contact tightr, is conducive to the roasting of product, can reduce dust pollution simultaneously.
4, the raw material of the present invention's use is few, also has insoluble potassium bearing rock and coal except phosphorus ore mine tailing or low-grade phosphate ore, and the existing production fused(calcium magnesium)phosphate of the purchasing of raw materials and grinding process is simple.
5, the alkaline fertilizer that goes out of kiln method sintering of the present invention is except containing the effective constituents such as phosphorus, silicon, calcium, magnesium, also contain nutrient potassium, effective constituent more comprehensively, nutrient is abundanter, with insoluble potassium bearing rock as raw material production potash fertilizer, greatly alleviate China's agricultural to the demand of potash fertilizer, reduce import, save capital.
6, the present invention does not use phosphogypsum, and adopting insoluble potassium bearing rock is raw material and phosphorite tailings or the reaction of low-grade phosphate fertilizer, does not contain the SO that air is caused severe contamination in tail gas
2Therefore gas do not need tail gas is carried out special processing.
Embodiment:
The present invention will be further described below by specific embodiment, but be not limited to this.
Embodiment 1:
Raw material 1: phosphorite tailings, collecting location: Guizhou gold moral mining industry
In the present embodiment, the main chemical constitution of phosphorite tailings sees Table 1:
Table 1
Raw material 2: potassium felspar sand, collecting location: Feicheng, Shandong
In the present embodiment, the main chemical constitution of potassium felspar sand sees Table 2:
Table 2
Raw material 3: hard coal, the place of production: Zhengzhou, henan
Production method:
Phosphorite tailings and potassium felspar sand are prepared burden for 1:0.55 in mass ratio, add again the hard coal that accounts for phosphorite tailings and potassium felspar sand total amount 4.5wt%, after mixture drying machine oven dry with ball mill grinding to 100 order (tail over≤5wt%), pulverulent material adds water and makes square material piece, and the volume of material piece is at 1.6 ~ 2.2dm
3Between, water content is at 10wt%, and the material piece is sent roasting in rotary kiln back to after preliminary oven dry, control 1100 ℃ of roastings of temperature 50 minutes, sintered clinker is cooled to 600 ℃ through shrend in 5 minutes, and solid is through draining, with ball mill grinding to 80 order, tail over≤be the alkaline fertilizer finished product after the 5wt% packing after dry.
Result of implementation:
The alkaline fertilizer effective constituent that detects preparation through sweep type indutively coupled plasma emission spectrometer ICPS-7500 sees Table 3:
Table 3
As seen from the above table, each effective constituent index of alkaline fertilizer by preparation of industrialization meets company standard.K in potassium ore
2The O transformation efficiency reaches 97%, P in phosphorite tailings
2O
5Transformation efficiency reaches 98%, and phosphorus potassium resultant is more than 11%, simultaneously SiO
2, CaO, MgO all become the effective constituent that can be absorbed by farm crop, conversion efficiency is also more than 90%.
Embodiment 2:
Raw material 1: phosphorite tailings, collecting location: Guizhou gold moral mining industry
In the present embodiment, the main chemical constitution of phosphorite tailings sees Table 4:
Table 4
Raw material 2: potassium felspar sand, collecting location: gas level ground, Guizhou
In the present embodiment, the main chemical constitution of potassium felspar sand sees Table 5:
Table 5
Raw material 3: hard coal, the place of production: Zhengzhou, henan
Production method:
phosphorite tailings and potassium felspar sand are prepared burden for 1:0.6 in mass ratio, add again the hard coal that accounts for phosphorite tailings and potassium felspar sand total amount 5wt%, after mixture drying machine oven dry with ball mill grinding to 120 order (tail over≤5%), pulverulent material adds water and makes spherical material piece, material piece diameter is 10 ~ 15mm, water content 12wt%, the material piece send roasting in tunnel furnace after preliminary oven dry, control 1150 ℃ of roasting time of temperature 40 minutes, sintered clinker is cooled to 500 ℃ through shrend in 5 minutes, solid is through draining, dry rear with ball mill grinding to 80 order, tail over≤5% the packing after be the alkaline fertilizer finished product.
Result of implementation:
The alkaline fertilizer effective constituent that detects preparation through sweep type indutively coupled plasma emission spectrometer ICPS-7500 sees Table 6:
Table 6
As seen from the above table, each effective constituent index of alkaline fertilizer by preparation of industrialization meets company standard.K in potassium ore
2The O transformation efficiency reaches 98%, P in phosphorite tailings
2O
5Transformation efficiency reaches 99%, and phosphorus potassium resultant is more than 12%, simultaneously SiO
2, CaO, MgO all become the effective constituent that can be absorbed by farm crop, conversion efficiency is also more than 90%.
Embodiment 3:
Raw material 1: low-grade phosphate ore, collecting location: From Fuquan, Guizhou
The main chemical constitution of the present embodiment mid low grade phosphate rock sees Table 7:
Table 7
Raw material 2: potassium felspar sand, collecting location: gas level ground, Guizhou
In the present embodiment, the main chemical constitution of potassium felspar sand sees Table 8:
Table 8
Raw material 3: hard coal, the place of production: Zhengzhou, henan
Production method:
Low-grade phosphate ore and potassium felspar sand are prepared burden for 1:0.65 in mass ratio, add again the hard coal that accounts for phosphorite tailings and potassium felspar sand total amount 7wt%, after mixture drying machine oven dry with ball mill grinding to 110 order (tail over≤5%), pulverulent material adds water and makes square material piece, and the volume of material piece is at 1.0 ~ 2.0dm
3Between, water content is 13wt%, the material piece send roasting in down-draft kiln after preliminary oven dry, control 1200 ℃ of roasting time of high temperature 30 minutes, sintered clinker is cooled to 550 ℃ through shrend in 5 minutes, solid is through draining, dry after with ball mill grinding to 80 order, tail over≤be the alkaline fertilizer finished product after 5% packing.
Result of implementation:
Detect the alkaline fertilizer effective constituent of preparation sees through sweep type indutively coupled plasma emission spectrometer ICPS-7500
Table 9:
Table 9
As seen from the above table, each effective constituent index of alkaline fertilizer by preparation of industrialization meets company standard.K in potassium ore
2The O transformation efficiency reaches 90%, P in phosphorite tailings
2O
5Transformation efficiency reaches 98%, and phosphorus potassium resultant is more than 17%, simultaneously SiO
2, CaO, MgO all become the effective constituent that can be absorbed by farm crop, conversion efficiency is also more than 90%.
Embodiment 4:
Raw material 1: low-grade phosphate ore, collecting location: From Fuquan, Guizhou
The main chemical constitution of the present embodiment mid low grade phosphate rock sees Table 10:
Table 10
Raw material 2: potassium felspar sand, collecting location: Feicheng, Shandong
In the present embodiment, the main chemical constitution of potassium felspar sand sees Table 11:
Table 11
Raw material 3: hard coal, the place of production: Zhengzhou, henan
Production method:
low-grade phosphate ore and potassium felspar sand are prepared burden for 1:0.7 in mass ratio, add again the hard coal that accounts for phosphorite tailings and potassium felspar sand total amount 10wt%, after mixture drying machine oven dry with ball mill grinding to 120 order (tail over≤5%), pulverulent material adds water and makes spherical material piece, material piece diameter is 5 ~ 10mm, water content is 15wt%, the material piece is sent roasting in rotary kiln back to after preliminary oven dry, control 1200 ℃ of roasting time of temperature 30 minutes, sintered clinker is cooled to 450 ℃ through shrend in 8 minutes, solid is through draining, dry rear with ball mill grinding to 80 order, tail over≤5% the packing after be the alkaline fertilizer finished product.
Result of implementation:
The alkaline fertilizer effective constituent that detects preparation through sweep type indutively coupled plasma emission spectrometer ICPS-7500 sees Table 12:
Table 12
As seen from the above table, each effective constituent index of alkaline fertilizer by preparation of industrialization meets company standard.K in potassium ore
2The O transformation efficiency reaches 90%, P in phosphorite tailings
2O
5Transformation efficiency reaches 99%, and phosphorus potassium resultant is more than 16%, simultaneously SiO
2, CaO, MgO all become the effective constituent that can be absorbed by farm crop, conversion efficiency is also more than 85%.
Claims (10)
1. a method of producing alkaline fertilizer with insoluble potassium bearing rock kiln method, comprise the steps:
(1) phosphorite tailings or low-grade phosphate ore are mixed 1:0.4 ~ 0.9 in mass ratio with insoluble potassium bearing rock, then add the hard coal of above-mentioned mixing total mass 3～8%, get mixture;
(2) step (1) gained mixture is dry, grinding gets pulverulent material;
(3) finish mix of the pulverulent material that step (2) is made;
(4) the material piece that step (3) is made is put into kiln, and 1000～1200 ℃ of roasting temperatures 30～150 minutes make sintered clinker;
(5) sintered clinker that makes of above-mentioned steps (4) carries out shrend, and sintered clinker temperature in 1～10 minute is down to 400～700 ℃, and the sintered clinker after shrend makes alkaline fertilizer through draining, drying, fragmentation and grinding.
2. method according to claim 1, it is characterized in that: in described step (1), the mass ratio of phosphorite tailings or low-grade phosphate ore and insoluble potassium bearing rock is 1:0.55～0.77, and anthracitic add-on accounts for 4～7% of phosphorite tailings or low-grade phosphate ore and insoluble potassium bearing rock total mass.
3. method according to claim 1, is characterized in that: mixture properties of powder performace to 60 in described step (2)～150 orders, screen over-size＜5wt%.
4. according to claim 1 or 3 described methods, is characterized in that: mixture properties of powder performace to 80 in described step (2)～120 orders, screen over-size＜5wt%.
5. method according to claim 1 is characterized in that: in described step (3), pulverulent material adds finish mix of water, and the mass ratio of pulverulent material and water is 1:0.08～0.15.
6. method according to claim 1 is characterized in that: the material piece in described step (3) is that diameter is that spherical material piece or the volume of 5～15mm is 0.1～2.2dm
3Square material piece.
7. method according to claim 1 is characterized in that: in described step (4), maturing temperature is 1100～1200 ℃, and roasting time is 30～50 minutes.
8. method according to claim 1, is characterized in that: in described step (4), use fuel to be bituminous coal during roasting.
9. method according to claim 1, it is characterized in that: in described step (4), kiln is down-draft kiln, tunnel furnace or rotary kiln.
10. method according to claim 1 is characterized in that: in described step (5) during the sintered clinker shrend in 1～5 minute temperature be down to 400～600 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496605A (en) * | 2014-12-24 | 2015-04-08 | 金正大诺泰尔化学有限公司 | Method and device for recycling sulfur dioxide in furnace gas to produce alkali fertilizer |
| CN105217589A (en) * | 2015-09-16 | 2016-01-06 | 黄钰雪 | The power-economizing method of yellow phosphorus coproduction sylvite, sodium carbonate and aluminum oxide |
| CN106477544A (en) * | 2016-10-10 | 2017-03-08 | 云南民族大学 | A kind of method that potassium-bearing shale is comprehensively utilized with low-grade phosphate ore |
| CN109942347A (en) * | 2019-01-31 | 2019-06-28 | 贵州大学 | A method of making microbial manure using coal gangue as raw material |
| CN111302845A (en) * | 2019-07-09 | 2020-06-19 | 深圳前海大地矿物科技有限公司 | Nitrogen phosphorus potassium full slow release fertilizer and its production and application method |
| WO2023044840A1 (en) * | 2021-09-23 | 2023-03-30 | 湖北富邦科技股份有限公司 | Low-energy-consumption method for producing potassium calcium magnesium phosphate fertilizer |
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| CN101525256A (en) * | 2009-04-17 | 2009-09-09 | 中国-阿拉伯化肥有限公司 | Low-chloride phosphorus potassium fertilizer and preparation method thereof |
| CN101747090A (en) * | 2009-12-14 | 2010-06-23 | 云南省化工研究院 | Method for preparing calcium magnesium phosphate fertilizer by utilizing phosphorite flotation tailing blast furnace method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496605A (en) * | 2014-12-24 | 2015-04-08 | 金正大诺泰尔化学有限公司 | Method and device for recycling sulfur dioxide in furnace gas to produce alkali fertilizer |
| CN105217589A (en) * | 2015-09-16 | 2016-01-06 | 黄钰雪 | The power-economizing method of yellow phosphorus coproduction sylvite, sodium carbonate and aluminum oxide |
| CN105217589B (en) * | 2015-09-16 | 2017-08-11 | 黄钰雪 | The power-economizing method of yellow phosphorus coproduction sylvite, sodium carbonate and aluminum oxide |
| CN106477544A (en) * | 2016-10-10 | 2017-03-08 | 云南民族大学 | A kind of method that potassium-bearing shale is comprehensively utilized with low-grade phosphate ore |
| CN109942347A (en) * | 2019-01-31 | 2019-06-28 | 贵州大学 | A method of making microbial manure using coal gangue as raw material |
| CN109942347B (en) * | 2019-01-31 | 2021-06-15 | 贵州大学 | Method for preparing microbial fertilizer by taking coal gangue as raw material |
| CN111302845A (en) * | 2019-07-09 | 2020-06-19 | 深圳前海大地矿物科技有限公司 | Nitrogen phosphorus potassium full slow release fertilizer and its production and application method |
| CN111302845B (en) * | 2019-07-09 | 2022-10-28 | 深圳前海大地矿物科技有限公司 | Nitrogen phosphorus potassium full slow release fertilizer and its production and application method |
| WO2023044840A1 (en) * | 2021-09-23 | 2023-03-30 | 湖北富邦科技股份有限公司 | Low-energy-consumption method for producing potassium calcium magnesium phosphate fertilizer |
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Address after: 550400 Guizhou Province, Qiannan Buyei and Miao Autonomous Prefecture in the Industrial Park Patentee after: KINGENTA NORSTERRA CHEMICAL CO., LTD. Address before: 550401 Guizhou Province, Qiannan Buyei and Miao Autonomous Prefecture Weng'an county economic development zone Patentee before: Guizhou Kingenta Ecological Engineering Co., Ltd. |