CN102659454B - Method for preparing diammonium phosphate and slow release fertilizer by using high-impurity phosphorite - Google Patents
Method for preparing diammonium phosphate and slow release fertilizer by using high-impurity phosphorite Download PDFInfo
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- CN102659454B CN102659454B CN201210120131.4A CN201210120131A CN102659454B CN 102659454 B CN102659454 B CN 102659454B CN 201210120131 A CN201210120131 A CN 201210120131A CN 102659454 B CN102659454 B CN 102659454B
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- diammonium phosphate
- neutralization
- release fertilizer
- phosphate
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Abstract
The invention discloses a method for preparing diammonium phosphate and a slow release fertilizer by using high-impurity phosphorite, which is characterized in that the method comprises the following steps: extracting the high-impurity phosphorite by adopting a wet-method phosphate process, directly neutralizing extracted high-impurity phosphate with a basic compound and controlling the neutralization degree of a system to be 0.05-0.7, the temperature to be 60-130 DEG C and the reaction time to be 10-120 minutes; filtering after reaction, producing filter residues into a raw material or a wrapping material of the slow release fertilizer or a blending fertilizer or other slow release fertilizers, concentrating a filtrate and controlling the P2O5 concentration of concentrated solution to be 36-45 percent; and continuously neutralizing the concentrated solution with a basic compound, controlling the neutralization degree of the solution to be 1.3-1.6 and producing neutralized slurry into the diammonium phosphate by adopting a traditional method. The method has the beneficial effects that the prophase flotation process of the high-impurity phosphorite is saved, and the utilization rate of phosphorus resources is improved; the applicability to the phosphorite is strong, and a diammonium phosphate product with excellent quality can be produced as long as the neutralization is properly adjusted.
Description
Technical field
The present invention relates to a kind of method that high impurity phosphorus ore prepares diammonium phosphate and slow-release fertilizer, belong to the preparation field of ammophos.
Background technology
China's high-quality phosphorus ore proportion is low, and it is only 6.4% that the data of take 2005 are calculated, and high impurity low-grade phosphate ore accounts for 66.2%.Along with the fast development of China's Eleventh Five-Year Plan sulphur dioxide of phosphor chemical industry, the high-quality phosphorus ore remains little at present, and high impurity phosphorus ore can only adopt the method for flotation to improve quality, otherwise 1,100 ten thousand tons of diammonium phosphate product quality of China can't reach the standard of 18-46-0.The yield of flotation of phosphate rock is generally 80～90%, and the phosphorus loss is serious, and the mine tailing amount is also large, is unfavorable for the comprehensive utilization of resource.Also do not have at present a kind of effective technology directly to utilize high impurity phosphorus ore, especially utilize high impurity phosphorus ore to produce to meet the diammonium phosphate technology of Traditional Method diammonium phosphate premium grads index in GB10205-2009.Chinese patent ZL200610021182.6 discloses " adopting method and the secondary ammoniation reactor of the concentrated production diammonium phosphate (DAP) of acid slime ".This patent adopts twice ammonification to produce DAP, and the degree of neutralization of an ammonification is 0.5～1.0, and this acid slime is concentrated to moisture 13～20%; Secondary ammoniation and preparation DAP adopt traditional DAP technique to be produced.Its objective is and adopt slip to concentrate steam saving, but deficiency on the implementation is:
1, the impurity that an ammonification of phosphoric acid generates is all in slip, while using raw material for high impurity phosphorus ore, when water content is 13～30%, can form thick material, the heat transfer coefficient of concentration heat exchanger sharply descends, and thickening efficiency reduces, and slip can't be carried simultaneously;
While 2, using high impurity phosphorus ore to produce DAP, this technique can't solve the underproof problem of product.For example work as the P in phosphorus ore
2o
5/ MgO (weight ratio) was lower than 20 o'clock, and the DAP quality does not reach the index of Traditional Method diammonium phosphate premium grads in GB10205-2009.
The patent that application number is 200810048758.7 discloses a kind of " technique of slurry concentrated process co-producing diammonium phosphate and monoammonium phosphate ".This technology is the same with ZL 200610021182.6 also adopts twice ammonification.One time the ammonification degree of neutralization is 1.0～1.15, settlement separate after ammonification, the thick slurry in bottom with in be used for producing monoammonium phosphate after concentrated together with slip; Secondary ammoniation production diammonium phosphate after clear liquid is concentrated.This technology has following shortcoming:
1, for high impurity phosphorus ore, the monoammonium phosphate quality that this technology is produced will meet the requirement of slurry concentration process monoammonium phosphate salable product in GB10205-2009, must have in a large amount of phosphoric acid and prepare burden with slip, that is to say, the output of monoammonium phosphate will be far longer than diammonium phosphate product, when its major product is monoammonium phosphate, production equipment could normal operation.
2, the same with patent ZL 200610021182.6, after the degree of neutralization of an ammonification reaches 1.0～1.15, the solubleness of phosphorus ammonium in solution sharply descends, and adds that co-producing diammonium phosphate enters the thick slurry of high impurity in this slip, makes monoammonium phosphate concentrate and is difficult to carry out;
3, after secondary ammoniation (degree of neutralization is 1.4～1.8); adopt whitewashing drying-granulating machine drying to obtain diammonium phosphate product; this technique has a large amount of ammonia and overflows; cause the tail gas recycle difficulty, the product of producing in design library part editor and reuse also is difficult to reach the index of Traditional Method diammonium phosphate premium grads in GB10205-2009 simultaneously.
Summary of the invention
The objective of the invention is provides a kind of high impurity phosphorus ore to prepare the method for diammonium phosphate and slow-release fertilizer for the deficiencies in the prior art.Be characterized in directly utilizing high impurity phosphorus ore to produce, prepare the diammonium phosphate and the slow-release fertilizer that meet Traditional Method diammonium phosphate premium grads index in GB10205-2009.
As everyone knows, Traditional Method features of DAP production technique is that dilute phosphoric acid (P205 is less than 30%) is concentrated to 46～50%, and then, with the ammonia neutralization, controlling degree of neutralization is 1.5 left and right, granulation in ammoniation granulator, and roller drying obtains diammonium phosphate product.Along with the dilution of China's phosphorus ore and wherein foreign matter content rising, the diammonium phosphate produced traditionally is difficult to meet national standard.If contain higher magnesium (P in phosphorus ore
2o
5/ MgO is less than 20), because magnesium is all that form with carbonate is present in phosphorus ore usually, in the Wet-process Phosphoric Acid Production process, almost all enter phosphoric acid by wet process, during by such Wet-process Phosphoric Acid Production diammonium phosphate, product does not reach the index of 18-46-0.
Purpose of the present invention by following technical measures realize, wherein said raw material umber except specified otherwise, be parts by weight.
The method that high impurity phosphorus ore prepares diammonium phosphate and slow-release fertilizer comprises the following steps:
(1) adopt Wet Processes of Phosphoric Acid to extract high impurity phosphorus ore, the high impurity phosphoric acid obtained that extracts directly neutralizes by alkaline substance, and the degree of neutralization of the hierarchy of control is 0.05～0.7, in 60～130 ℃ of reaction 10～120min of temperature;
(2) above-mentioned reactant is filtered, filter cake directly is used as raw material or the lapping of slow-release fertilizer or production Bulk Blending Fertilizer or other slow-release fertilizer through granulation;
(3) above-mentioned reactant is filtered, filtrate is concentrated, controls the P of concentrated solution
2o
5concentration is 36～45%; Concentrated solution continues neutralization by alkaline substance, and the degree of neutralization of controlling solution is 1.3～1.6, and the slip after neutralization is according to Traditional Method production diammonium phosphate.
Wet Processes of Phosphoric Acid is any in two wet technologies, half wet technology, Ban Shui-bis-wet technology or two water-half wet technology.
Alkaline substance is at least one in liquefied ammonia, gas ammonia, ammoniacal liquor, volatile salt, ammonium hydrogencarbonate, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, calcium carbonate and lime.
Filtrate is through further purifying monoammonium phosphate or the diammonium phosphate fertilizer of producing high-grade full water-soluble.
In order to obtain the Secondary ammonium phosphate that meets GB, according to the difference of foreign matter content in phosphorus ore used, during the alkaline substance neutralising phosphoric acid, the degree of neutralization of regulation system is to meet the requirement of quality product;
Performance test
Adopt GB/T 1871.1-1995 test P
2o
5content.
Adopt GB/T 1871.2-1995 test Fe
2o
3content.
Adopt GB/T 1871.3-1995 test Al
2o
3content.
Adopt the content of GB/T 1871.5-1995 test MgO.
Adopt the content of GB/T 10209-2008 test N.
The present invention has following advantage:
The present invention compared with prior art, can directly utilize the production of high impurity low-grade phosphate ore to meet the diammonium phosphate product of GB10205-2009 Traditional Method diammonium phosphate premium grads index; This technology is not only saved flotation in the early stage operation of high impurity phosphorus ore, improves the utilization ratio of phosphor resource, has also reduced the investment of flotation design library part editor and reuse; Simultaneously extremely strong to the suitability of phosphorus ore, according to the difference of foreign matter content in phosphorus ore used, as long as suitably adjust degree of neutralization, just can the outstanding DAP product of the quality of production.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used to further illustrate the present invention; but can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
Take containing P
2o
527.3%, R
2o
3three parts of each 1000g of ground phosphate rock of 3.6%, MgO 2.21%, size mixing with 3000g water for first part, and slowly dripping concentration is 93% sulfuric acid 800g, after completion of the reaction, filters, and according to three countercurrent washings, the bath water amount is 600ml.Washing water all return to extracting system, with second part of ground phosphate rock, size mixing, and slowly drip concentration is 93% sulfuric acid 800g simultaneously, after completion of the reaction, filter, and according to three countercurrent washings, the bath water amount is 600ml.Washing water all return to extracting system, with the 3rd part of ground phosphate rock, size mixing, and slowly drip concentration is 93% sulfuric acid 800g simultaneously, after completion of the reaction, filter, and according to three countercurrent washings, the bath water amount is 600ml.Extract and obtain impure high phosphoric acid for three times.Extraction temperature is controlled at 80 ℃, and each reaction times is 3.0h,, according to the technique of two traditional water law phosphoric acid extractions, extracts containing P
2o
523.0%, MgO1.82%, R
2o
31.56% phosphoric acid solution 3110g.Phosphoric acid is placed in to the neutralizer of 3500 liters of Stainless steel 316 L, under stirring, logical ammonia, controlling degree of neutralization is 0.3, reaction times 30min, temperature is controlled at 95 ℃, vacuum filtration, filter cake is slow-release fertilizer, the filter cake dry weight is: 112.06g, containing P
2o
538.3%, N6.2%; Obtain filtrate 2996.6g, wherein containing P
2o
522.4%, this filtrate is as the raw material of preparation diammonium phosphate; Concentrated above-mentioned filtrate, P in concentrated solution
2o
5be 40%, concentrated solution is placed in reactor, under stirring, with gas ammonia, the degree of neutralization of liquid is adjusted to 1.95, cooling after, with dehydrated alcohol, fully wash, filter, vacuum dehydrating at lower temperature, gained diammonium phosphate product weight: 1416.1g, wherein containing P
2o
547.4%, N17.1%, the water-soluble rate of phosphorus is 90.6%.
Embodiment 2
Take containing P
2o
527.3%, R
2o
3three parts of each 1000g of ground phosphate rock of 3.6%, MgO 2.21%, size mixing with 3000g water for first part, and slowly dripping concentration is 93% sulfuric acid 800g, after completion of the reaction, filters, and according to three countercurrent washings, the bath water amount is 600ml.Washing water all return to extracting system, with second part of ground phosphate rock, size mixing, and slowly drip concentration is 93% sulfuric acid 800g simultaneously, after completion of the reaction, filter, and according to three countercurrent washings, the bath water amount is 600ml.Washing water all return to extracting system, with the 3rd part of ground phosphate rock, size mixing, and slowly drip concentration is 93% sulfuric acid 800g simultaneously, after completion of the reaction, filter, and according to three countercurrent washings, the bath water amount is 600ml.Extract and obtain impure high phosphoric acid for three times.Extraction temperature is controlled at 85 ℃, and each reaction times is 4.5h,, according to the technique of two traditional water law phosphoric acid extractions, extracts containing P
2o
523.6%, MgO1.91%, R
2o
31.66% phosphoric acid solution 3227g.Phosphoric acid is placed in to the neutralizer of 3500 liters of Stainless steel 316 L, under stirring, adds volatile salt, controlling degree of neutralization is 0.7, reaction times 10min, and temperature is controlled at 100 ℃, vacuum filtration, filter cake is slow-release fertilizer, the filter cake dry weight is: 151.9g, containing P
2o
540.1%, N8.9%; Obtain filtrate 3072.1g, wherein containing P
2o
522.81%, this filtrate is as the raw material of preparation diammonium phosphate; Concentrated above-mentioned filtrate, P in concentrated solution
2o
5be 40%, concentrated solution is placed in reactor, under stirring, with gas ammonia, the degree of neutralization of liquid is adjusted to 1.95, cooling after, with dehydrated alcohol, fully wash, filter, vacuum dehydrating at lower temperature, the quality of gained diammonium phosphate product reaches the GB requirement.Experimental data and quality product are in Table 1.
Embodiment 3
Take containing P
2o
527.3%, R
2o
3three parts of each 1000g of ground phosphate rock of 3.6%, MgO 2.21%, size mixing with 3000g water for first part, and slowly dripping concentration is 93% sulfuric acid 800g, after completion of the reaction, filters, and according to three countercurrent washings, the bath water amount is 600ml.Washing water all return to extracting system, with second part of ground phosphate rock, size mixing, and slowly drip concentration is 93% sulfuric acid 800g simultaneously, after completion of the reaction, filter, and according to three countercurrent washings, the bath water amount is 600ml.Washing water all return to extracting system, with the 3rd part of ground phosphate rock, size mixing, and slowly drip concentration is 93% sulfuric acid 800g simultaneously, after completion of the reaction, filter, and according to three countercurrent washings, the bath water amount is 600ml.Extract and obtain impure high phosphoric acid for three times.Extraction temperature is controlled at 82 ℃, and each reaction times is 4.0h,, according to the technique of two traditional water law phosphoric acid extractions, extracts containing P
2o
522.3%, MgO 1.62%, R
2o
31.61% phosphoric acid solution 3265g.Phosphoric acid is placed in to the neutralizer of 3500 liters of Stainless steel 316 L, under stirring, ventilation ammonia, controlling degree of neutralization is 0.5, reaction times 60min, temperature is controlled at 90 ℃, vacuum filtration, filter cake is slow-release fertilizer, the filter cake dry weight is: 129.7g, containing P
2o
539.3%, N8.1%; Obtain filtrate 3130.0g, wherein containing P
2o
521.63%, this filtrate is as the raw material of preparation diammonium phosphate; Concentrated above-mentioned filtrate, P in concentrated solution
2o
5be 40%, concentrated solution is placed in reactor, under stirring, with gas ammonia, the degree of neutralization of liquid is adjusted to 1.95, cooling after, with dehydrated alcohol, fully wash, filter, vacuum dehydrating at lower temperature, the quality of gained diammonium phosphate product reaches the GB requirement.Experimental data and quality product are in Table 2.
Embodiment 4
Adopt half water law Wet Processes of Phosphoric Acid to extract high impurity phosphorus ore, the high impurity phosphoric acid extracted is directly with the lime neutralization, and the degree of neutralization of the hierarchy of control is 0.05, and temperature is 60 ℃, reaction times 120min; After reaction, filter, filter residue is used for producing slow-release fertilizer or Bulk Blending Fertilizer, and filtrate is concentrated, controls the P of concentrated solution
2o
5concentration is 36～45%; Adopt liquefied ammonia to continue neutralization, the degree of neutralization of controlling solution is 1.3, and the slip after neutralization is according to Traditional Method diammonium phosphate explained hereafter Secondary ammonium phosphate, and the quality of product reaches the GB requirement.
Embodiment 5
Adopt half water-wet phosphoric acid by dihydrate technique to extract high impurity phosphorus ore, the high impurity phosphoric acid extracted does not need to concentrate directly and neutralizes with potassium hydroxide, and the degree of neutralization of the hierarchy of control is 0.7, and temperature is 130 ℃, 10 minutes reaction times; After reaction, filter, filter residue is used for producing slow-release fertilizer or Bulk Blending Fertilizer, and filtrate is concentrated, controls the P of concentrated solution
2o
5concentration is 45%; Concentrated solution adopts ammoniacal liquor to continue neutralization, and the degree of neutralization of controlling solution is 1.6, and the slip after neutralization is according to Traditional Method diammonium phosphate explained hereafter Secondary ammonium phosphate, and the quality of product reaches the GB requirement.
Embodiment 6
Adopt two water-half water law Wet Processes of Phosphoric Acid to extract high impurity phosphorus ore, the high impurity phosphoric acid extracted does not need to concentrate directly and neutralizes with sodium carbonate, and the degree of neutralization of the hierarchy of control is 0.35, and temperature is 90 ℃, 70 minutes reaction times; After reaction, filter, filter residue is used for producing slow-release fertilizer or Bulk Blending Fertilizer, and filtrate is concentrated, controls the P of concentrated solution
2o
5concentration is 40%; Concentrated solution adopts gas ammonia to continue neutralization, and the degree of neutralization of controlling solution is 1.4, and the slip after neutralization is according to Traditional Method diammonium phosphate explained hereafter Secondary ammonium phosphate, and the quality of product reaches the GB requirement.
Embodiment 7
Adopt wet phosphoric acid by dihydrate technique to extract high impurity phosphorus ore, the high impurity phosphoric acid extracted does not need to concentrate directly and neutralizes with calcium carbonate, and the degree of neutralization of the hierarchy of control is 0.15, and temperature is 90 ℃, 80 minutes reaction times; After reaction, filter, filter residue is used for producing slow-release fertilizer or Bulk Blending Fertilizer, and filtrate is concentrated, controls the P of concentrated solution
2o
5concentration 36%; Concentrated solution adopts gas ammonia to continue neutralization, and the degree of neutralization of controlling solution is 1.4, and the slip after neutralization is according to Traditional Method diammonium phosphate explained hereafter Secondary ammonium phosphate, and the quality of product reaches the GB requirement.
Embodiment 8
Adopt wet phosphoric acid by dihydrate technique to extract high impurity phosphorus ore, the high impurity phosphoric acid extracted does not need to concentrate directly and neutralizes with saleratus, and the degree of neutralization of the hierarchy of control is 0.15, and temperature is 90 ℃, 80 minutes reaction times; After reaction, filter, filter residue is used for producing slow-release fertilizer or Bulk Blending Fertilizer, and filtrate is concentrated, controls the P of concentrated solution
2o
5concentration is 40%; Concentrated solution adopts gas ammonia to continue neutralization, and the degree of neutralization of controlling solution is 1.4, and the slip after neutralization is according to Traditional Method diammonium phosphate explained hereafter Secondary ammonium phosphate, and the quality of product reaches the GB requirement.
Table 1
Table 2
Claims (4)
1. one kind high impurity phosphorus ore prepares the method for diammonium phosphate and slow-release fertilizer, it is characterized in that the method comprises the following steps:
(1) adopt Wet Processes of Phosphoric Acid to extract high impurity phosphorus ore, the high impurity phosphoric acid obtained that extracts directly neutralizes by alkaline substance, and the degree of neutralization of the hierarchy of control is 0.05～0.7, in 60～130 ℃ of reaction 10～120min of temperature;
(2) above-mentioned reactant is filtered, filter cake directly is used as raw material or the lapping of slow-release fertilizer or production Bulk Blending Fertilizer or other slow-release fertilizer through granulation;
(3) above-mentioned reactant is filtered, filtrate is concentrated, controls the P of concentrated solution
2o
5concentration is 36～45%; Concentrated solution continues neutralization by alkaline substance, and the degree of neutralization of controlling solution is 1.3～1.6, and the slip after neutralization is according to Traditional Method production diammonium phosphate.
2. high impurity phosphorus ore prepares the method for diammonium phosphate and slow-release fertilizer as claimed in claim 1, it is characterized in that Wet Processes of Phosphoric Acid is any in two wet technologies, half wet technology, Ban Shui-bis-wet technology or two water-half wet technology.
3. the method for high impurity phosphorus ore production diammonium phosphate and slow-release fertilizer as claimed in claim 1, is characterized in that alkaline substance is at least one in liquefied ammonia, gas ammonia, ammoniacal liquor, volatile salt, ammonium hydrogencarbonate, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, calcium carbonate and lime.
4. the method for high impurity phosphorus ore production diammonium phosphate and slow-release fertilizer as claimed in claim 1, is characterized in that filtrate is through further purifying monoammonium phosphate or the diammonium phosphate fertilizer of producing high-grade full water-soluble.
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| CN103435376A (en) * | 2013-07-29 | 2013-12-11 | 山东明瑞化工集团有限公司 | Method and apparatus used for preparing ammonium phosphate fertilizer from phosphoric acid sediment |
| CN104261371B (en) * | 2014-09-01 | 2016-04-20 | 云南云天化国际化工有限公司 | A kind of method by high impurity phosphorus ore production diammonium phosphate |
| CN105036816B (en) * | 2015-07-28 | 2019-02-22 | 中化云龙有限公司 | A method of the super nutrient of monoammonium phosphate is adjusted using phosphate ore flotation tailings |
| CN106904586B (en) * | 2017-01-19 | 2019-02-19 | 赵常然 | A kind of co-production of active charcoal bag membrane material and crystal phosphoric acid monoammonium, diammonium |
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