CN102557834A - Method for producing composite fertilizer fillers by using phosphorite tailings - Google Patents
Method for producing composite fertilizer fillers by using phosphorite tailings Download PDFInfo
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- CN102557834A CN102557834A CN2012100511614A CN201210051161A CN102557834A CN 102557834 A CN102557834 A CN 102557834A CN 2012100511614 A CN2012100511614 A CN 2012100511614A CN 201210051161 A CN201210051161 A CN 201210051161A CN 102557834 A CN102557834 A CN 102557834A
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- composite fertilizer
- phosphorite tailings
- acid
- product
- waste water
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Abstract
The invention discloses a method for producing composite fertilizer fillers by using phosphorite tailings. The method comprises the following steps: (1) drying and crushing phosphorite tailings, and then performing hybrid reaction on the phosphorite tailings and acidic waste water in sulfuric acid and phosphoric acid factories into a reactor; (2) drying the obtained product at the temperature of 80 to 100 DEG C, stacking until the temperature reaches normal temperature, and crushing and processing the product into powdered composite fertilizer fillers; and (3) mixing the powdered product, urea, monoammonium phosphate, potassium sulfate or potassium chloride, then conveying the mixture into a disc granulating machine, adding water, pelleting, drying and sieving to obtain the granular composite fertilizer. According to the method, phosphorus in the acidic waste water in the sulfuric acid and phosphoric acid factories is utilized, so that phosphorus consumption during production of the composite fertilizer is reduced; and the fillers consumed during the production of the composite fertilizer is replaced by the product, so the production cost of the composite fertilizer is reduced, the pressure of land for stacking the phosphorite tailings is relieved, damage to the environment caused by the phosphorite tailings and the waste water is reduced, the maintenance cost of a tailings storage and the treatment cost of the acidic waste water in the phosphoric acid factory are reduced, and remarkable environmental and economic significance is achieved.
Description
Technical field
The present invention relates to chemical field, relating in particular to a kind of is the method for raw material production composite fertilizer stopping composition with the mid low grade phosphate rock mine tailing.
Background technology
Phosphorus ore is a kind of important chemical raw mineral materials.Can produce phosphate fertilizer with it, also can be used for making yellow phosphorus, phosphoric acid, phosphide and other phosphoric acid salts, to be used for industrial sectors such as medicine, food, match, dyestuff, sugaring, pottery, national defence.The history in existing more than 100 year of the application of phosphorus ore in industry.Along with the exploitation and the utilization of phosphorus ore, phosphate rock resource is dilution day by day, can not satisfy one of 20 kinds of mineral of national economic development demand after having been listed in 2010 by Ministry of Land and Resources, classifies non-renewable strategic resource as.The phosphorus ore of China 80% is a mid low grade phosphate rock; In order to satisfy the specification of quality of phosphoric acid by wet process to raw ore; China mainly obtains to be fit to produce the phosphorus concentrate of phosphoric acid through various technique of preparings at present; 1 ton of phosphorus concentrate of every production, with the mine tailing that produces 0.44 ton, will produce the phosphorite tailings more than 7,000,000 tons every year.The phosphorus mine tailing is because P
2O
5Content is low, and detrimental impurity content is high, can not satisfy the requirement to ore grade and quality of phosphoric acid by wet process and acid system phosphate fertilizer far away, though there was the technology of some phosphorus comprehensive utilization of tailing to occur in recent years, does not fundamentally solve the problem of utilizing of flotation of phosphate rock mine tailing.The comprehensive utilization ratio of China's phosphorite tailings is merely about 7%, because the bulk deposition of phosphorite tailings not only can take large-area soil and farmland resource, expends more stockyard construction and maintenance cost; And outdoor storage, receiving wind, Exposure to Sunlight for a long time, drench with rain, objectionable constituent can be passed through dielectric breakdown ecotopes such as atmosphere, the soil face of land or underground water, reduce crop yield and quality, directly or indirectly influence local resident's health; The dust that the mining tailing wasteland surface produces can worsen the sanitary condition of peripheral region; Relevant composition in the mine tailing and residual dressing agent also cause serious harm to ecotope.At present, the contaminated area that China causes because of mine tailing reaches 1,000,000 mu, more than 1,000 ten thousand mu of indirect pollution land areas.
The discharging of phosphorus-containing wastewater not only can cause such as environmental problems such as body eutrophications, the phosphor resource that also can greatly waste.Discharge a large amount of acid waste waters when for example certain phosphoric acid factory produces phosphoric acid, per hour reach 600m
3, solubility P wherein
2O
5Mass percent is 2%～3%, calculates like this, annual solubility P by carry-over loss in the sewage
2O
5Above 20,000 tons.
In China; Composite fertilizer's output is up to more than 5,000 ten thousand tons; Need during composite fertilizer produces to consume a large amount of packing materials, play the effect of adjustment nutrient content or change rerum natura, at present common stopping composition such as attapulgite, wilkinite etc. all need exploitation, transportation, broken, ball milling; These process need great amount of manpower and material resources make composite fertilizer's production cost uprise.
Summary of the invention
The objective of the invention is to above-mentioned phosphor resource waste, environmental pollution is serious, existing issues such as composite fertilizer's production cost height; A kind of method of utilizing phosphorite tailings production composite fertilizer stopping composition is provided,, the phosphorus in phosphorite tailings and the phosphoric acid factory acid waste water is recycled to realize phosphorite tailings and phosphoric acid factory acid waste water recycling; Product is as composite fertilizer's stopping composition simultaneously; Improve the compound fertilizer granulating granulating rate, improve composite fertilizer's rerum natura, reduce composite fertilizer's production cost.
The method of utilizing phosphorite tailings production composite fertilizer stopping composition provided by the invention comprises the steps:
(1) with phosphorite tailings oven dry, pulverizing back and mass concentration 93%-98% sulfuric acid and the phosphoric acid factory acid waste water hybrid reaction in reactor drum that contains P2O5 mass concentration 2%-5%; Phosphorite tailings wherein: sulfuric acid: the mass ratio of phosphoric acid factory acid waste water is 100:50-90:100; Control stir speed (S.S.) 200-500r/min; Reaction times 10-30min, temperature of reaction is at 30-60 ℃;
(2) product that obtains is dried water cut 1-3% under 80-100 ℃, stack to room temperature, the powdered composite fertilizer of grinding and processing stopping composition,
(3) with powdery product with send into granulating disc after urea, phosphorus ammonium, vitriolate of tartar or Repone K mix and add the water granulation, through dry, screening make its particle be 1-4mm >=90%, granulating rate >=70% granule strength >=25N makes granular compound fertilizer.
The above-mentioned method of utilizing phosphorite tailings production composite fertilizer stopping composition, wherein: P in the powdery product after oven dry is pulverized
2O
5Content is 4%-12%, granularity>=100 orders.
The above-mentioned method of utilizing phosphorite tailings production composite fertilizer stopping composition, wherein: the insoluble phosphorus in the phosphorite tailings is converted into the available phosphorus that can supply plant absorbing to utilize more than 50%.
The above-mentioned method of utilizing phosphorite tailings production composite fertilizer stopping composition, wherein sulfuric acid both can be used industrial sulphuric acid, also can be with the sulfuric acid of spent acid or recovery.
Compared with prior art; The insoluble phosphorus major part was transformed into the reasonable process route of water-soluble phosphorus and citric acid soluble phosphorus during its outstanding feature was under guide of theory, to have found phosphorite tailings; This process reaction is complete, and flow process is simple, and is with low cost; Used raw material is phosphorite tailings, sulfur waste acid and phosphoric acid factory acid waste water, for product has increased phosphorus, magnesium, sulphur and various trace elements.Reaction does not produce spent acid, waste liquid and waste material after accomplishing, and has avoided secondary pollution.Because the raw material that utilizes is the phosphorite tailings and the phosphoric acid factory acid waste water of the enterprise development of restriction phosphorous chemical industry, when having practiced thrift phosphor resource, has also reduced the pollution of environment and the expense and the soil of processing of waste.Realized the resource circulation utilization, turned waste into wealth, opened up a new way for handling the phosphorite tailings that pile up like a mountain.Reacted product can be used as composite fertilizer's stopping composition, and the available phosphorus that contains in the product can reduce phosphorus consumption of raw materials in composite fertilizer's production, and its granulation effect in composite fertilizer is better, can effectively improve composite fertilizer's rerum natura, improves granulating rate and granule strength.Reduced exploitation, and, can effectively reduce composite fertilizer's production cost expenses such as the fragmentation of mineral such as attapulgite, ball milling, transportations to mineral such as attapulgite, wilkinites.This technology has good environment and economic benefit.
Embodiment
Embodiment 1
Raw material:
(1) sulfuric acid: industrial sulphuric acid, w (H
2SO
4) 98%
(2) phosphoric acid factory acid waste water: w (P
2O
5) 2.0%
(3) phosphorite tailings: w (P
2O
5) 12.0%
100kg phosphorus mine tailing, 100kg phosphoric acid factory acid waste water, 70kg sulfuric acid add in the reactive tank that has whisking appliance and carry out hybrid reaction; Temperature of reaction is 30 ℃, and the reaction times is 10min, stir speed (S.S.) 200r/min; Reacting rear material is 80 ℃ of oven dry down; Stack to room temperature, with material grinding and processing powdering composite fertilizer stopping composition product, powder-like product is crossed 100 mesh sieves.Get the 8.66kg powder and urea 15.88kg monoammonium phosphate 46.5kg, 21.67kg Repone K potassium and the little fertilizer of 7.388kg etc. add water granulation in composite fertilizer; Dry, cooling is sieved and is the granular complex fertilizer product that nutrient content is 12-23-13, and granulating rate is 76% in the granulation process.Granule strength 29N.The product quality analysis result is following:
Embodiment 2
Raw material:
(4) sulfuric acid: industrial sulphuric acid, w (H
2SO
4) 96%
(5) phosphoric acid factory acid waste water: w (P
2O
5) 2.5%
(6) phosphorite tailings: w (P
2O
5) 8.1%
100kg phosphorus mine tailing, 100kg phosphoric acid factory acid waste water, 60kg sulfuric acid add in the reactive tank that has whisking appliance and carry out hybrid reaction; Temperature of reaction is 40 ℃, and the reaction times is 20min, stir speed (S.S.) 300r/min; Reacting rear material is 80 ℃ of oven dry down; Stack to room temperature, with material grinding and processing powdering composite fertilizer stopping composition product, powder-like product is crossed 100 mesh sieves.Get the 7.5kg powder and urea 26.0kg monoammonium phosphate 30.5 kg, 30.0kg vitriolate of tartar and the little fertilizer of 6.0 kg etc. add water granulation in composite fertilizer; Dry, cooling is sieved and is the granular complex fertilizer product that nutrient content is 15-15-15, and granulating rate is 78% in the granulation process.Granule strength 29N.The product quality analysis result is following:
Embodiment 3
Raw material:
(7) sulfuric acid: industrial sulphuric acid, w (H
2SO
4) 96%
(8) phosphoric acid factory acid waste water: w (P
2O
5) 3.2%
(9) phosphorite tailings: w (P
2O
5) 7.2%
100kg phosphorus mine tailing, 100kg phosphoric acid factory acid waste water, 50kg sulfuric acid add in the reactive tank that has whisking appliance and carry out hybrid reaction; Temperature of reaction is 60 ℃, and the reaction times is 20min, stir speed (S.S.) 400r/min; Reacting rear material is 90 ℃ of oven dry down; Stack to room temperature, with material grinding and processing powdering composite fertilizer stopping composition product, powder-like product is crossed 100 mesh sieves.Get the 11.8kg powder and urea 26.2kg monoammonium phosphate 29.5 kg, 26.5kg Repone K and the little fertilizer of 6.0 kg etc. add water granulation in composite fertilizer; Dry, cooling is sieved and is the granular complex fertilizer product that nutrient content is 15-15-15, and granulating rate is 80% in the granulation process.Granule strength 29N.The product quality analysis result is following:
Embodiment 4
Raw material:
(10) sulfuric acid: industrial sulphuric acid, w (H
2SO
4) 93%
(11) phosphoric acid factory acid waste water: w (P
2O
5) 5.0%
(12) phosphorite tailings: w (P
2O
5) 4.0%
100kg phosphorus mine tailing, 100kg phosphoric acid factory acid waste water, 90kg sulfuric acid add in the reactive tank that has whisking appliance and carry out hybrid reaction; Temperature of reaction is 50 ℃, and the reaction times is 30min, stir speed (S.S.) 500r/min; Reacting rear material is 100 ℃ of oven dry down; Stack to room temperature, with material grinding and processing powdering composite fertilizer stopping composition product, powder-like product is crossed 100 mesh sieves.Get the 9.0kg powder and urea 18.1kg monoammonium phosphate 36.9 kg, 30.0kg vitriolate of tartar and the little fertilizer of 6.0 kg etc. add water granulation in composite fertilizer; Dry, cooling is sieved and is the granular complex fertilizer product that nutrient content is 12-18-15, and granulating rate is 85% in the granulation process.Granule strength 32N.The product quality analysis result is following:
Claims (3)
1. a method of utilizing phosphorite tailings production composite fertilizer stopping composition comprises the steps:
(1) with phosphorite tailings oven dry, pulverizing back and mass concentration 93%-98% sulfuric acid and the phosphoric acid factory acid waste water hybrid reaction in reactor drum that contains P2O5 mass concentration 2%-5%; Phosphorite tailings wherein: sulfuric acid: the mass ratio of phosphoric acid factory acid waste water is 100:50-90:100; Control stir speed (S.S.) 200-500r/min; Reaction times 10-30min, temperature of reaction is at 30-60 ℃;
(2) product that obtains is dried water cut 1-3% under 80-100 ℃, stack to room temperature, the powdered composite fertilizer of grinding and processing stopping composition,
(3) with powdery product with send into granulating disc after urea, phosphorus ammonium, vitriolate of tartar or Repone K mix and add the water granulation, through dry, screening make its particle be 1-4mm >=90%, granulating rate >=70% granule strength >=25N makes granular compound fertilizer.
2. the method for utilizing phosphorite tailings production composite fertilizer stopping composition as claimed in claim 1 is characterized in that: P in the powdery product after oven dry is pulverized
2O
5Content is 4%-12%, granularity>=100 orders.
3. the method for utilizing phosphorite tailings production composite fertilizer stopping composition as claimed in claim 1, it is characterized in that: sulfuric acid both can be used industrial sulphuric acid, also can be with the sulfuric acid of spent acid or recovery.
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|---|---|---|---|
| CN2012100511614A CN102557834A (en) | 2012-03-01 | 2012-03-01 | Method for producing composite fertilizer fillers by using phosphorite tailings |
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|---|---|---|---|
| CN2012100511614A CN102557834A (en) | 2012-03-01 | 2012-03-01 | Method for producing composite fertilizer fillers by using phosphorite tailings |
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| CN102557834A true CN102557834A (en) | 2012-07-11 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058738A (en) * | 2013-01-05 | 2013-04-24 | 中国地质科学院矿产综合利用研究所 | Method for preparing phosphate fertilizer soil conditioner by using phosphate tailings and acidic wastewater |
| CN103360145A (en) * | 2013-07-28 | 2013-10-23 | 瓮福（集团）有限责任公司 | Technology of producing ammonium sulfate phosphate product from tailing slag |
| CN106365747A (en) * | 2016-09-08 | 2017-02-01 | 郑州大学 | Method for directly producing compound fertilizer by using phosphate tailings |
| CN109020467A (en) * | 2018-09-25 | 2018-12-18 | 宜都兴发化工有限公司 | A kind of mould material of active phosphorus tailing |
| CN110483125A (en) * | 2019-08-02 | 2019-11-22 | 史丹利化肥当阳有限公司 | Utilize the method for waste phosphoric acid production S-based compound fertilizer raw material |
| CN113387744A (en) * | 2021-05-26 | 2021-09-14 | 龙蟒大地农业有限公司 | Granular medium element fertilizer based on phosphorite flotation tailings and preparation method thereof |
Citations (4)
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|---|---|---|---|---|
| JPS5645880A (en) * | 1979-09-21 | 1981-04-25 | Taki Chemical | Manufacture of phosphatic magnesia fertilizer |
| CN101367673A (en) * | 2008-10-30 | 2009-02-18 | 云南省化工研究院 | Method for directly preparing phosphor magnesium fertilizer with by-product mine tailing of phosphorus ore floatation |
| CN101367674A (en) * | 2008-09-27 | 2009-02-18 | 瓮福（集团）有限责任公司 | Method for manufacturing sulphur magnesium fertilizer with high-magnesium phosphor tail slag |
| CN101618981A (en) * | 2009-07-28 | 2010-01-06 | 瓮福（集团）有限责任公司 | Method for producing phosphorus-magnesium compound fertilizer by using phosphate spoil-reclaiming byproduct high-magnesia tailing slag |
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2012
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Patent Citations (4)
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| JPS5645880A (en) * | 1979-09-21 | 1981-04-25 | Taki Chemical | Manufacture of phosphatic magnesia fertilizer |
| CN101367674A (en) * | 2008-09-27 | 2009-02-18 | 瓮福（集团）有限责任公司 | Method for manufacturing sulphur magnesium fertilizer with high-magnesium phosphor tail slag |
| CN101367673A (en) * | 2008-10-30 | 2009-02-18 | 云南省化工研究院 | Method for directly preparing phosphor magnesium fertilizer with by-product mine tailing of phosphorus ore floatation |
| CN101618981A (en) * | 2009-07-28 | 2010-01-06 | 瓮福（集团）有限责任公司 | Method for producing phosphorus-magnesium compound fertilizer by using phosphate spoil-reclaiming byproduct high-magnesia tailing slag |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058738A (en) * | 2013-01-05 | 2013-04-24 | 中国地质科学院矿产综合利用研究所 | Method for preparing phosphate fertilizer soil conditioner by using phosphate tailings and acidic wastewater |
| CN103058738B (en) * | 2013-01-05 | 2015-05-13 | 中国地质科学院矿产综合利用研究所 | Method for preparing phosphate fertilizer soil conditioner by using phosphate tailings and acidic wastewater |
| CN103360145A (en) * | 2013-07-28 | 2013-10-23 | 瓮福（集团）有限责任公司 | Technology of producing ammonium sulfate phosphate product from tailing slag |
| CN106365747A (en) * | 2016-09-08 | 2017-02-01 | 郑州大学 | Method for directly producing compound fertilizer by using phosphate tailings |
| CN109020467A (en) * | 2018-09-25 | 2018-12-18 | 宜都兴发化工有限公司 | A kind of mould material of active phosphorus tailing |
| CN110483125A (en) * | 2019-08-02 | 2019-11-22 | 史丹利化肥当阳有限公司 | Utilize the method for waste phosphoric acid production S-based compound fertilizer raw material |
| CN110483125B (en) * | 2019-08-02 | 2022-03-04 | 史丹利化肥当阳有限公司 | Method for producing raw material for sulfur-based compound fertilizer by using waste phosphoric acid |
| CN113387744A (en) * | 2021-05-26 | 2021-09-14 | 龙蟒大地农业有限公司 | Granular medium element fertilizer based on phosphorite flotation tailings and preparation method thereof |
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Application publication date: 20120711 |