CN85100950A - The production method of mixed fertilizer - Google Patents

The production method of mixed fertilizer Download PDF

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CN85100950A
CN85100950A CN 85100950 CN85100950A CN85100950A CN 85100950 A CN85100950 A CN 85100950A CN 85100950 CN85100950 CN 85100950 CN 85100950 A CN85100950 A CN 85100950A CN 85100950 A CN85100950 A CN 85100950A
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phosphate
slip
neutralization stage
acid
reactor
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CN 85100950
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维沃林伦
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Kemira Oyj
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Kemira Oyj
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Abstract

Disclosed one and be applicable to the technological process of the slip of producing the mixed fertilizer that contains nitrogen and phosphorus from Rock Phosphate (72Min BPL) production, in this technological process with nitric acid leaching Rock Phosphate (72Min BPL) to produce an acid slime, then in two neutralization stage at the same time under the refrigerative situation with ammonia this slip that neutralizes.In two neutralization stage, add ammonium phosphate in acid slime to satisfy the needs of mixed fertilizer to phosphorus, wherein be no more than 40%, the acidity that the above-mentioned ammonium phosphate of a part by weight adds this place's slip of first neutralization stage remains on pH2 to 4, and the acidity that the ammonium phosphate of remaining part then adds second this place of neutralization stage remains on pH5 to 6.

Description

The production method of mixed fertilizer
The invention relates to and manufacture the required slip of mixed fertilizer, particularly contain the fertilizer of nitrogen and phosphorus.
The present invention is more special causes in nitric acid decomposing phosphate rock stone to produce acid slime, with ammonia it is neutralized then, the method that also can add some other acids is simultaneously produced the slip that is suitable for making nitrogenous and phosphorus and also may contains the mixed fertilizer of potassium.
Be generally used for making nitrogenous, the mixed fertilizer of phosphorus and potassium, that is the raw material of the phosphorus of so-called NPK fertilizer is a Rock Phosphate (72Min BPL).Purpose is the phosphorus in the ore will be changed into plant is had the form that causes.When this occurred in nitric acid and Rock Phosphate (72Min BPL) reaction, the phosphorus in the ore can disengage with the form of phosphoric acid.In the stage in succession with ammonia with the acidic mixture that makes and the phosphoric acid of interpolation, even also have sulfuric acid, be neutralized to desired degree.
Rock Phosphate (72Min BPL) often contains the phosphatic rock as band phosphorus ore material, for every L P 2O 5It on average contains 3.35 CaO molecules molecule, wherein 3 and P 2O 5Combine, 0.35 combines with fluorine and other negatively charged ion.Molecule of such compound formation, its phosphorus is invalid to plant.In this law, this molecular breakdown is obtained the phosphorus of soluble or free form with nitric acid.
In the reaction of phosphatic rock and nitric acid, use slightly excessive nitric acid, thereby reach short reaction times and high efficient.Adopt the nitric acid of 6.8 molecules for each molecular phosphorus lime stone.
When the mixture ammonification, obtain ammonium nitrate, P 2O 5Through mono-calcium phosphate (P 2O 5, CaO) become phosphoric acid=calcium (P 2O 52CaO), and part calcium still is nitrocalcite C a(NO 3) 2
Reaction between phosphatic rock and nitric acid:
Neutralization reaction:
Nitrocalcite Ca(NO 3) 2Must remove, because its height water absorbability can cause the difficulty that is difficult to overcome in fertilizer.
In Odda method (Farm Chemicals magazine 1967 May the 29th page), removing part is to be nitrocalcite four hydrates with its crystallization by the method for the calcium of decomposing phosphate rock stone gained.But this method has shortcoming, i.e. Ang Gui crystallisation process and be difficult to the byproduct of pin life in a large number.
In other method, in the PEC method (Farm Chemicals magazine 1967 May the 28th page), calcium is through some acid, and for example phosphoric acid precipitates in many ammonification grooves.A shortcoming of this method is to need a large amount of ammonification grooves progressively to improve the pH value of nitre phosphoric acid salt slip to the manufacturing that is suitable for mixed fertilizer.
In also known each method for distinguishing phosphoric acid is added to the Rock Phosphate (72Min BPL) catabolic phase with nitric acid, phosphoric acid is to replace the part phosphorus in the Rock Phosphate (72Min BPL) by this.Phosphoric acid that nitric acid is generated with Rock Phosphate (72Min BPL) reaction and nitric acid and other compounds neutralize with ammonia with the phosphoric acid of interpolation again.Because slip has very big retrogradation tendency, these methods comprise several neutralization stage usually or will finish the neutralization of part in drawing machines.
Have now found that above-mentioned shortcoming can eliminate, simultaneously, neutralization stage also can be reduced to secondary.Connect method of the present invention, Rock Phosphate (72Min BPL), for example the phosphorus in the phosphatic rock can change into the effective form of plant.The present invention sprinkles and is suitable for making the production method of the slip of gas phosphorus mixed fertilizer.This method comprises: with the nitric acid decomposing phosphate rock made of stones acid slime, and two neutralization stage with add ammonia this acid slime that neutralizes.
Adding nitric acid makes its phosphorus become phosphoric acid in Rock Phosphate (72Min BPL) to disengage.When pH when neutralization stage increases, the reaction of phosphoric acid and calcium, the overwhelming majority generates the Lin Suanergais that dissolve in ammonium citrate, water-soluble mono-calcium phosphate only accounts for small portion.For making phosphorus contained in the mixed fertilizer meet the water miscible requirement of tool, the charging of a part of phosphorus should be water-soluble form in some cases, promptly as ammonium phosphate type or phosphoric acid.
In this method, add the ammonium phosphate (diammonium phosphate or an ammonium) that is no more than 40% total requiremants in first neutralization stage, the acidity of slip remains on pH2 to 4.Ammonium phosphate adds to its pH of second neutralization stage 5 to 6 under the Yu.In neutralization stage, preferably slip is cooled to 110 to 150 ℃ temperature range in case of necessity.
It is to eliminate with above-mentioned method that the amount owing to the phosphorus that adds to neutralization stage known causes the situation of slip retrogradation, promptly replace the part Rock Phosphate (72Min BPL) with ammonium phosphate, at least 60% ammonium phosphate will be added in second neutralization stage, herein pH high to slip can retrogradation.Can make having good stability in the reactor in addition.
The present invention is described in detail in detail in following with reference to accompanying drawing, accompanying drawing has described to intend using the device of the inventive method.
A is first decomposition reactor among the figure, and B is second decomposition reactor, and C is first neutralization reactor, and D is second kind of neutralization reactor, and E is a washing system.
Rock phosphate in powder through manage 1 and nitric acid add the first decomposition reactor A that does the machine of mixing be housed through managing 2. Produce an acid slime with phosphoric acid when nitric acid and rock phosphate in powder reaction, its temperature is adjusted to about 60-90 ℃ according to the ratio in acid and ore deposit. If think when another decomposition reactor is essential, make acid slime flow into to be equipped with and do the second decomposition reactor B that mixes through managing 3 by the first decomposition reactor A. Add respectively more rock phosphate in powder and nitric acid to reactor B through managing 4 and 5 in case of necessity. According to the grade of intend producing fertilizer, sulfuric acid is added to reactor B rock phosphate in powder is further decomposed through managing 6. When adopting sulfuric acid, the temperature of reactor B can raise, owing to distributing of NOX gas can increase along with temperature raises, so do not permit it above 90 ℃.
If make acid slime then flow out to enter the first neutralization reactor C that does the machine of mixing is housed through managing 7 from reactor A during without reactor B from the second decomposition reactor B(. A part of MAP or two ammoniums are added reactor C simultaneously through managing 8, when adopting sulfuric acid then with one section or all add through managing 9. Acid slime and the last acid of adding are neutralized to PH2.0-4.0 then ammonia adds reactor C through the pipe 10 that is connected several spouts. According to the grade of intending producing, a part of nitric acid may be managed 11 adding reactor C and is added on decomposition reactor A and B with replacement. According to the composition of the salt that generates and the moisture of slip, the temperature of conditioned reaction device C is to about 110-150 ℃.
Slip enters from the first neutralization reactor C the second neutralization reactor D that does the machine of mixing is housed through managing 12. If MAP under the Yu or two ammoniums when reaching the sulfuric acid that adopts under the Yu, can add reactor D through managing 13 and 14 respectively, and ammonia adds reactor D through the pipe 15 that is being connected several spouts slip is neutralized to pH5.0-6.0. According to the composition of generation salt and the moisture of slip, the temperature of conditioned reaction device D is to about 110-150 ℃. Last slip is discharged from reactor D through overflow pipe 16. At this moment, depend on the composition of institute's saliferous in the slip, moisture is about 10-16% in the slip that has neutralized, and this slip is delivered to the system of further processing, for example granulation and dry by the fire in.
Total P at neutralization reactor2O 5In the charging, the part that adds to the first neutralization reactor C should be in the scope of 0-40%. P under the Yu2O 5To add to reactor D.
By the collected dust of the gas-cleaning installation of fertilizer processing oven dry workshop section and sylvite and trace element (as employing time) usually through managing 17 addings, the second neutralization reactor D.Ammonium nitrate (can in order to replace part ammonia and nitric acid) adds to reactor C or reactor D or adds to the two simultaneously through managing 18 and 19 respectively.
Gas by decomposition reactor A and B and neutralization reactor C and D generation imports washing system E along tubing system 20 and 21 respectively.Washing water add washing system E through managing 22, are directed at neutralization reactor C or D by the washing water of washing system E discharge along tubing system 23.Sulfuric acid or phosphoric acid can add the pH of washing system E in order to the control washings through managing 24 as washing composition.
If when washing, the sulfuric acid that directly adds reactor must corresponding minimizing with sulfuric acid.If use phosphoric acid when washing, the ammonium phosphate charging should reduce and the charging increase of ammonia, the ammonium phosphate amount that the amount that makes the phosphoric acid that adds to washing system E add the ammonia that increases like this can be equivalent to reduce.Gas through washing E cleaning is discharged by pipe 25.
In following example, narrate the present invention in more detail.
Example 1
Raw material:
Rock Phosphate (72Min BPL) 32.4% P 2O 5
Nitric acid 60% HNO 3
Monoammonium phosphate 11% N
55% P 2O 5
Ammonia 100% NH 3
Potassium nitride 60% K 2O
When producing 15-15-15(N-P with 63 tons productive rate per hour 2O 5-K 2O) during fertilizer, technological process and shell to such an extent that the inlet amount of fertilizer desired raw material per ton is as follows:
With Rock Phosphate (72Min BPL) 190Kg with add decomposition reactor A in the nitric acid 315Kg of 100% acid.Temperature in the reactor A is 75 ℃.
After this acid slime is directly imported the first neutralization reactor C, ammonia can be sent into through several spouts of reactor bottom and make the pH of slip rise to 3.0 then.Mat adds from the temperature in the washing water of washing system E and the transpiring moisture maintenance reactor C in 12.5 ℃.
Slip flows into the second neutralization reactor D by reactor C.With whole expense 170Kg of monoammonium phosphate, add reactor D.Do not use sulfuric acid.The Repone K amount that adds reactor D is 254Kg.Ammonia goes into to make the pH of slip to rise to 5.8 through several spout roads of reactor bottom.The total flow of ammonia is 82Kg in neutralization reactor C and D.Temperature among the reactor D is at 120 ℃.
The product that is obtained by reactor D is moisture 15% NPK slip.This slip is suitable for doing further processing with common granulating method.
Example 2
Raw material:
Rock Phosphate (72Min BPL) 34% P 2O 5
Nitric acid 60% HNO 3
Ammonium nitrate (solution) 90% NH 4NO 3
Monoammonium phosphate 11% N
55% P 2O 5
Sulfuric acid 93 % H 2SO 4
Ammonia 100% NH 3
Repone K 60% K 2O
Sal epsom
Borate fertilizer
Making 20-10-10 N-P with 50 tons productive rate per hour 2O 5-K 2O) its technological process and to produce the inlet amount of fertilizer desired raw material per ton as follows during fertilizer:
65Kg Rock Phosphate (72Min BPL) and 300Kg nitric acid (in 100% acid) are added the first decomposition reactor A.Temperature in the reactor A is 65 ℃.
After this acid slime is imported the second decomposition reactor B ， And and add the sulfuric acid of 60Kg in 100% acid.The temperature of the second decomposition reactor B rises to 80 ℃.
Slip flows into the first neutralization reactor C from the second decomposition reactor B, adds 20% of the monoammonium phosphate amount used as raw material.Gaseous ammonia is sent into through several spouts of reactor bottom and is made the pH of slip rise to 3.3 simultaneously.Washing water and transpiring moisture that mat adds from washing system E make the temperature among the reactor C remain on 140 ℃.
Slip flows into the second neutralization reactor D with reactor C, adds with 100%NH 4NO 3The ammonium nitrate solution 95Kg of meter and 80% total monoammonium phosphate consumption of ammonium phosphate expense are 144Kg.The Repone K that adds reactor D is 165Kg.Trace element (35Kg sal epsom and 4Kg borate fertilizer) also adds in the reactor D.Ammonia makes the pH of slip rise to 5.6 through several spouts feedings of reactor bottom.The total flow of ammonia is 110Kg in neutralization reactor C and D.Temperature among the reactor D remains on 140 ℃.
The product that is obtained by reactor D is moisture 10% NPK slip.This slip is suitable for obtaining high-quality granulation 20-10-10 fertilizer with the further Jia Gong of common granulating method And.
Figure 85100950_IMG1

Claims (10)

1, a production method that is suitable for making the slip of the mixed fertilizer that contains nitrogen and phosphorus, its phosphorus comes the white phosphorus ore, this method comprise with the nitric acid decomposing phosphate rock made of stones get acid slime and can select acid slime is neutralized two neutralization stage with ammonia under the refrigerative condition simultaneously, and add in the ammonium phosphate acid slime in the stage in above-mentioned two to satisfy the phosphorus requirement of mixed fertilizer, wherein being no more than 40% the above-mentioned ammonium phosphate of part by weight is to add to first neutralization stage, the acidity of this place's slip remains on pH2 to 4, ammonium phosphate under the Yu adds to second neutralization stage, and the acidity of this place's slip remains on pH5 to 6.
2, according to the method for prescription 1,20% adding, first neutralization stage of total ammonium phosphate amount will be no more than by weight wherein.
3, according to the method for prescription 1 or 2, wherein remain between 110 and 150 ℃ in the 1st and second neutralization stage temperature.
4, according to the method for prescription 1,2 or 3, diammonium phosphate is added to above-mentioned neutralization stage.
5, according to the method for prescription 1,2,3 or 4, wherein except that ammonium phosphate, sulfuric acid is added at least one neutralization stage.
6, according to the method for any above-mentioned requirements right, wherein decomposing phosphate rock stone is to carry out two stages, comprises also sulfuric acid being added second catabolic phase except that nitric acid and Rock Phosphate (72Min BPL).
7, according to any method that public prescription, comprise that also adding sylvite goes into second neutralization stage, slip additionally contains potassium herein.
8, according to the method for any above-mentioned requirements right, in second neutralization stage finally, it is 10 to 16% moisture by weight that slip contains.
9, according to the method for any above-mentioned requirements right, the Rock Phosphate (72Min BPL) of wherein mentioning contains phosphatic rock.
10, according to the method for any above-mentioned requirements right, ammonium nitrate is added to a wherein minimum neutralization stage.
CN 85100950 1985-04-01 1985-04-01 The production method of mixed fertilizer Pending CN85100950A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1328224C (en) * 2000-03-10 2007-07-25 四川大学 Process for preparing compound phosphorus nitrate fertilizer by spray, freeze, crystallization and decorbonizing and decalcifying hydrazidine
CN102126739A (en) * 2011-01-20 2011-07-20 山东金正大生态工程股份有限公司 Method for producing nitre-chlorine-based compound fertilizer with byproduct of plaster by decomposing phosphorite with nitric acid
CN102211956A (en) * 2010-11-24 2011-10-12 贵州省冶金化工研究所 Utilization method of middle-low grade phosphate ore containing rare earth
CN102227392A (en) * 2008-11-28 2011-10-26 伍德肥料技术有限责任公司 Urea granulation process with acidic scrubbing system and subsequent integration of ammonium salt into urea granules
CN102584401A (en) * 2012-02-28 2012-07-18 朱绍禄 Compound fertilizer and preparation method thereof
CN104803367A (en) * 2015-05-06 2015-07-29 贵州省化工研究院 Process for preparing phosphate concentrate as well as byproducts magnesium ammonium sulfate and calcium ammonium nitrate by use of medium and low grade phosphorus ores

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1328224C (en) * 2000-03-10 2007-07-25 四川大学 Process for preparing compound phosphorus nitrate fertilizer by spray, freeze, crystallization and decorbonizing and decalcifying hydrazidine
CN102227392A (en) * 2008-11-28 2011-10-26 伍德肥料技术有限责任公司 Urea granulation process with acidic scrubbing system and subsequent integration of ammonium salt into urea granules
CN102211956A (en) * 2010-11-24 2011-10-12 贵州省冶金化工研究所 Utilization method of middle-low grade phosphate ore containing rare earth
CN102211956B (en) * 2010-11-24 2013-06-19 贵州省冶金化工研究所 Utilization method of middle-low grade phosphate ore containing rare earth
CN102126739A (en) * 2011-01-20 2011-07-20 山东金正大生态工程股份有限公司 Method for producing nitre-chlorine-based compound fertilizer with byproduct of plaster by decomposing phosphorite with nitric acid
CN102126739B (en) * 2011-01-20 2013-01-30 山东金正大生态工程股份有限公司 Method for producing nitre-chlorine-based compound fertilizer with byproduct of plaster by decomposing phosphorite with nitric acid
CN102584401A (en) * 2012-02-28 2012-07-18 朱绍禄 Compound fertilizer and preparation method thereof
CN102584401B (en) * 2012-02-28 2014-06-25 朱绍禄 Compound fertilizer and preparation method thereof
CN104803367A (en) * 2015-05-06 2015-07-29 贵州省化工研究院 Process for preparing phosphate concentrate as well as byproducts magnesium ammonium sulfate and calcium ammonium nitrate by use of medium and low grade phosphorus ores
CN104803367B (en) * 2015-05-06 2017-03-15 贵州省化工研究院 A kind of technique that phosphorus concentrate producing ammonium sulfate byproduct magnesium, calcium ammonium nitrate are prepared by mid low grade phosphate rock

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