CN101585547B - Method for preparing ammonium sulfate as fertilizer by phosphogypsum through ball milling - Google Patents

Method for preparing ammonium sulfate as fertilizer by phosphogypsum through ball milling Download PDF

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CN101585547B
CN101585547B CN 200910059716 CN200910059716A CN101585547B CN 101585547 B CN101585547 B CN 101585547B CN 200910059716 CN200910059716 CN 200910059716 CN 200910059716 A CN200910059716 A CN 200910059716A CN 101585547 B CN101585547 B CN 101585547B
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phosphogypsum
ball
bicarbonate
ammonium sulfate
ammonia
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CN101585547A (en
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邓跃全
董发勤
许春凤
解忠雷
杨瑞
李佳峻
罗蓉
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Southwest University of Science and Technology
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Abstract

A method for preparing ammonium sulfate as fertilizer by phosphogypsum through ball milling, comprising the steps of taking the phosphogypsum, ammonium bicarbonate and water as raw materials, adding Ca2SO4*2H2O with the dosage 1-20% by weight percentage more than the stoichiometric ratio in the reaction of Ca2SO4*2H2O and NH4HCO3, converting the content of the Ca2SO4*2H2O in the phosphogypsum to the dosage of the needed phosphogypsum and ammonium bicarbonate, adding water in a weight ratio of water and sum of the phosphogypsum and the ammonium bicarbonate, which is 0.05-0.25, adding the raw materials in a ball mill, adding the grinding balls in a ball-material ratio of 3-5, performing ball milling and reaction at normal temperature for 20-60min, and drying to prepare the ammonium sulfate product as fertilizer. The invention uses a ball milling converting technique, performs reaction quickly at normal temperature, and has low energy consumption, high efficiency and strong practicality.

Description

Phosphogypsum ball grinds the standby method of making the ammonium sulfate of fertilizer
Technical field
The invention belongs to the preparation method of the vitriol of ammonium, relate to a kind of phosphogypsum ball and grind the standby method of making the ammonium sulfate of fertilizer.Be particularly suitable for preparing the high-quality binary chemical fertilizer that contain solubility sulphur and nitrogen of agricultural as fertilizer; Also be suitable for the preparation of ammonium sulfate product, product is as food catalyzer, buffer reagent, leather deliming agent, and the raw material of dyeing and weaving, medicinal industry etc.
Background technology
Phosphogypsum is the by product in the Wet-process Phosphoric Acid Production process, and its main component is CaSO 42H 2O.Along with the development of phosphoric acid industry, the quantity discharged of phosphogypsum also increases day by day, and every production 1t phosphoric acid (is pressed 100%P 2O 5Meter) will produce the phosphogypsum of 4.5～5.0t.The quantity discharged of the annual phosphogypsum of China is above 2,000 ten thousand tons, its utilization ratio is very low, phosphogypsum is mainly used in the preparation of building materials, agricultural and Chemicals at present, quite a few enterprise takes the method for landfill and stacking to handle this waste residue, not only take a large amount of soils, and surrounding environment caused detrimentally affect, bring very big burden to manufacturing enterprise.Therefore, the disposal of phosphogypsum and utilization more and more obtain people's attention, become the key that phosphoric acid industry realizes Sustainable development.
In the prior art, the technology that is prepared ammonium sulfate by phosphogypsum is generally the wet method conversion method, that is: in the stirred reactor of sealing, add bicarbonate of ammonia and water, make the bicarbonate of ammonia dissolving, and add proper ammonia, then add an amount of phosphogypsum powder, at a certain temperature, stir and make the following chemical reaction of its generation:
CaSO 4·2H 2O+2NH 4HCO 3＝(NH 4) 2SO 4+CaCO 3+CO 2+3H 2O
Behind reaction 2.0～3.0h, stopped reaction takes out feed liquid, and suction filtration separates, and washes precipitation with water, and filtrate is concentrated to supersaturation, and cooling, crystallization, drying make ammonium sulfate product.These processing condition are: 60～70 ℃ of temperature of reaction, reaction times 2.0～3.0h, material proportioning (n Phosphogypsum: n NH4HCO3)=1.01～1.20, liquid-solid ratio 2.4～15 (weight ratio).
Adopt this method to produce ammonium sulfate and have following deficiency:
(1) reaction requires to carry out under comparatively high temps, and not only equipment complexity, and energy expenditure is big, and production cost is higher;
(2) reaction times longer, the processing efficiency of material is low;
(3) liquid-solid ratio is excessive, and amount of water is too much, and not only the concentrating of later stage, crystallization, drying will consume lot of energy, and phosphogypsum and the bicarbonate of ammonia inventory handled are little, and efficient is low.
Summary of the invention
Purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, with phosphogypsum and bicarbonate of ammonia is raw material, by adopting the mode of ball milling, provide the phosphogypsum ball that a kind of speed is fast, productive rate is high, energy consumption is low, efficient is high to grind the standby method of making the ammonium sulfate of fertilizer.
Content of the present invention is: a kind of phosphogypsum ball grinds the standby method of making the ammonium sulfate of fertilizer, and its feature part is to comprise the following steps:
A, batching: getting phosphogypsum, bicarbonate of ammonia and water is raw material; According to CaSO 4.2H 2O and NH 4HCO 3The stoichiometric ratio of reaction is with CaSO 4.2H 2The consumption of O is excessive by weight percentage 1%～20% (that is: presses CaSO 4.2H 2The theory of O is got CaSO with 101%～120% of weight 4.2H 2The O batching); Press the CaSO in the phosphogypsum 4.2H 2O content is converted to the consumption of required phosphogypsum and bicarbonate of ammonia, and by water: the part by weight of (phosphogypsum+bicarbonate of ammonia)=0.05～0.25 adds water;
B, ball-milling reaction: phosphogypsum, bicarbonate of ammonia and water are dropped in the ball mill, are 3～5 input abrading-balls by ratio of grinding media to material (weight ratio), at normal temperatures, behind ball-milling reaction 20min～60min, are dried the ammonium sulfate product that promptly makes as fertilizer.The ammonium sulfate productive rate reaches 99.99% in the material that obtains.
Below the chemical equation of the present invention:
CaSO 4·2H 2O+2NH 4HCO 3＝(NH 4) 2SO 4+CaCO 3+CO 2+3H 2O
In the content of the present invention: the calculating of described raw material phosphogypsum and bicarbonate of ammonia proportioning, for example: if CaSO in the raw material phosphogypsum 4.2H 2O content is 86.285%, and the consumption of phosphogypsum is excessive 15%, then:
Figure GSB00000324164000031
In the formula: m PhosphogypsumBe the consumption (weight, back are together) of raw material phosphogypsum, m CaSO42H2OBe CaSO 4.2H 2The consumption of O, m Bicarbonate of ammoniaAnd m NH4HCO3Be NH 4HCO 3Consumption, M CaSO42H2OBe CaSO 4.2H 2The molar mass of O, M NH4HCO3Be NH 4HCO 3Molar mass.
Content of the present invention can also comprise the following steps:
C, preparation ammonium sulfate: get the material behind the ball-milling reaction, by the material behind the ball-milling reaction: the part by weight of water=1: 1 adds water, stirring, ammonium sulfate is fully dissolved, filtering separation is pressed the material behind the ball-milling reaction: the part by weight water intaking of water=1: 0.3～0.5, divide and 2～3 times filter residue cleaned merging filtrate again, filtrate is concentrated, crystallization, rough ammonium sulfate can be made, with rough ammonium sulfate recrystallization 1 time, industrial first grade ammonium sulfate product can be made after the drying again.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) contain abundant sulphur in the phosphogypsum, and element sulphur is called as the essential the fourth-largest element of plant-growth, sulfur fertilizer amount and phosphate fertilizer that common crop needs are suitable, and ammonium sulfate is optimal sulfur fertilizer.The present invention utilizes phosphogypsum to transform system ammonium sulfate and does not consume sulfuric acid, required SO 4 2-Provide by phosphogypsum, so both utilized the sulphur in the phosphorus ore, phosphor resource, protected environment again, also made the high-quality binary chemical fertilizer that contains solubility sulphur and nitrogen; This binary chemical fertilizer is applicable to general soil and crop, can make shoot and leaf growth vigorous, strengthens the resistivity of crop, improves fruit quality and output, and is more remarkable to happiness sulphur crop yields such as soybean, rape, peanut, tobacco, garlics; Ammonium sulfate product also can be used as food catalyzer, buffer reagent, the raw material of leather deliming agent and dyeing and weaving, medicinal industry;
(2) adopt the present invention, under ball action, the phosphogypsum powder is disperseed fully, is fully contacted with the bicarbonate of ammonia molecule, and rapid reaction under the effect of mechanical energy, transforms to generate ammonium sulfate and lime carbonate; Reaction can be carried out at normal temperatures, need not warming apparatus, and energy consumption is low; Adopt the energy-conservation method for transformation of ball milling, the reaction times is short, only is about 20% of wet method, has improved the material processing efficiency; Liquid-solid ratio is very little, and water consumption only is 1% of a wet method, can improve phosphogypsum and bicarbonate of ammonia material's proportion greatly, reduces the concentrating of later stage, crystallization and in the water yield in dry stage, can reduce a large amount of energy consumptions;
(3) the present invention adopts ball-milling technology, and facility investment is little, and working condition requires low, and technology is simple, and the material treatment capacity is big, very easily realizes suitability for industrialized production; It is fast to have speed, the productive rate height, and energy consumption is low, and characteristics such as efficient height are practical, for phosphogypsum comprehensive utilization provides a kind of energy-conservation, efficient, cleaning, new way that application prospect is good.
Embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; the person skilled in art to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
Embodiment 1:
A kind of phosphogypsum ball grinds the standby method of making the ammonium sulfate of fertilizer, comprises the following steps:
A, batching: get and contain CaSO 4.2H 2The weight percentage of O is that 86.285% phosphogypsum, bicarbonate of ammonia and water are raw material; According to CaSO 4.2H 2O and NH 4HCO 3The stoichiometric ratio of reaction is with CaSO 4.2H 2The consumption of O excessive by weight percentage 10%; Press the CaSO in the phosphogypsum 4.2H 2O content is converted to the consumption of required phosphogypsum and bicarbonate of ammonia, and by water: the part by weight of (phosphogypsum+bicarbonate of ammonia)=0.05 adds water;
The consumption m of phosphogypsum in the batching PhosphogypsumThe consumption m of (weight, back are together) and bicarbonate of ammonia Bicarbonate of ammoniaPart by weight be as can be known as calculated:
m Phosphogypsum/ m Bicarbonate of ammonia=1.39
B, ball-milling reaction: phosphogypsum, bicarbonate of ammonia and water are dropped in the ball mill, are 3 input abrading-balls by ratio of grinding media to material (weight ratio), at normal temperatures, behind the ball-milling reaction 20min, are dried the ammonium sulfate product that promptly makes as fertilizer.
Embodiment 2-10:
A kind of phosphogypsum ball grinds the standby method of making the ammonium sulfate of fertilizer, and method steps is with embodiment 1, the consumption m of phosphogypsum in the batching PhosphogypsumThe consumption m of (weight, back are together) and bicarbonate of ammonia Bicarbonate of ammoniaPart by weight be the material proportioning, the part by weight of water and solid (the weight sum of phosphogypsum+bicarbonate of ammonia) is a liquid-solid ratio, and other has related parameter to see the following form:
Figure GSB00000324164000051
Annotate: used phosphogypsum is the Chuan Xi product among interior each embodiment of table, contains CaSO 4.2H 2The weight percentage of O is 86.285%.
Other is with embodiment 1, slightly.
Embodiment 11:
A kind of phosphogypsum ball grinds the standby method of making the ammonium sulfate of fertilizer, comprises the following steps:
A, batching;
B, ball-milling reaction;
C, preparation ammonium sulfate: get the material behind the ball-milling reaction, by the material behind the ball-milling reaction: the part by weight of water=1: 1 adds water, stirring, ammonium sulfate is fully dissolved, filtering separation is pressed the material behind the ball-milling reaction: the part by weight water intaking of water=1: 0.3, divide and 2 times filter residue cleaned merging filtrate again, filtrate is concentrated, crystallization, rough ammonium sulfate can be made, with rough ammonium sulfate recrystallization 1 time, industrial first grade ammonium sulfate product can be made after the drying again.
Other is with arbitrary among the embodiment 1-10, slightly.
Embodiment 12:
A kind of phosphogypsum ball grinds the standby method of making the ammonium sulfate of fertilizer, comprises the following steps:
A, batching;
B, ball-milling reaction;
C, preparation ammonium sulfate: get the material behind the ball-milling reaction, by the material behind the ball-milling reaction: the part by weight of water=1: 1 adds water, stirring, ammonium sulfate is fully dissolved, filtering separation is pressed the material behind the ball-milling reaction: the part by weight water intaking of water=1: 0.5, divide and 3 times filter residue cleaned merging filtrate again, filtrate is concentrated, crystallization, rough ammonium sulfate can be made, with rough ammonium sulfate recrystallization 1 time, industrial first grade ammonium sulfate product can be made after the drying again.
Other is with arbitrary among the embodiment 1-10, slightly.
Embodiment 13:
A kind of phosphogypsum ball grinds the standby method of making the ammonium sulfate of fertilizer, comprises the following steps:
A, batching: get and contain CaSO 4.2H 2The weight percentage of O is that 86.285% phosphogypsum, bicarbonate of ammonia and water are raw material; According to CaSO 4.2H 2O and NH 4HCO 3The stoichiometric ratio of reaction is with CaSO 4.2H 2The consumption of O excessive by weight percentage 1%; Press the CaSO in the phosphogypsum 4.2H 2O content is converted to the consumption of required phosphogypsum and bicarbonate of ammonia, and by water: the part by weight of (phosphogypsum+bicarbonate of ammonia)=0.15 adds water;
The consumption m of phosphogypsum in the batching PhosphogypsumConsumption m with bicarbonate of ammonia Bicarbonate of ammoniaPart by weight be as can be known as calculated:
m Phosphogypsum/ m Bicarbonate of ammonia=1.28
B, ball-milling reaction: phosphogypsum, bicarbonate of ammonia and water are dropped in the ball mill, are 4 input abrading-balls by ratio of grinding media to material (weight ratio), at normal temperatures, behind the ball-milling reaction 30min, are dried the ammonium sulfate product that promptly makes as fertilizer.
Embodiment 14:
A kind of phosphogypsum ball grinds the standby method of making the ammonium sulfate of fertilizer, comprises the following steps:
A, batching: get and contain CaSO 4.2H 2The weight percentage of O is that 86.285% phosphogypsum, bicarbonate of ammonia and water are raw material; According to CaSO 4.2H 2O and NH 4HCO 3The stoichiometric ratio of reaction is with CaSO 4.2H 2The consumption of O excessive by weight percentage 5%; Press the CaSO in the phosphogypsum 4.2H 2O content is converted to the consumption of required phosphogypsum and bicarbonate of ammonia, and by water: the part by weight of (phosphogypsum+bicarbonate of ammonia)=0.25 adds water;
The consumption m of phosphogypsum in the batching PhosphogypsumConsumption m with bicarbonate of ammonia Bicarbonate of ammoniaPart by weight be as can be known as calculated:
m Phosphogypsum/ m Bicarbonate of ammonia=1.33
B, ball-milling reaction: phosphogypsum, bicarbonate of ammonia and water are dropped in the ball mill, are 3 input abrading-balls by ratio of grinding media to material (weight ratio), at normal temperatures, behind the ball-milling reaction 50min, are dried the ammonium sulfate product that promptly makes as fertilizer.
Embodiment 15:
A kind of phosphogypsum ball grinds the standby method of making the ammonium sulfate of fertilizer, comprises the following steps:
A, batching: get and contain CaSO 4.2H 2The weight percentage of O is that 86.285% phosphogypsum, bicarbonate of ammonia and water are raw material; According to CaSO 4.2H 2O and NH 4HCO 3The stoichiometric ratio of reaction is with CaSO 4.2H 2The consumption of O excessive by weight percentage 13%; Press the CaSO in the phosphogypsum 4.2H 2O content is converted to the consumption of required phosphogypsum and bicarbonate of ammonia, and by water: the part by weight of (phosphogypsum+bicarbonate of ammonia)=0.20 adds water;
The consumption m of phosphogypsum in the batching PhosphogypsumConsumption m with bicarbonate of ammonia Bicarbonate of ammoniaPart by weight be as can be known as calculated:
m Phosphogypsum/ m Bicarbonate of ammonia=1.43
B, ball-milling reaction: phosphogypsum, bicarbonate of ammonia and water are dropped in the ball mill, are 5 input abrading-balls by ratio of grinding media to material (weight ratio), at normal temperatures, behind the ball-milling reaction 60min, are dried the ammonium sulfate product that promptly makes as fertilizer.
The invention is not restricted to the foregoing description, content of the present invention is described all can implement and have described good result.

Claims (1)

1. a phosphogypsum ball grinds the standby method of making the ammonium sulfate of fertilizer, it is characterized in that comprising the following steps:
A, batching: getting phosphogypsum, bicarbonate of ammonia and water is raw material; According to CaSO 4.2H 2O and NH 4HCO 3The stoichiometric ratio of reaction is with CaSO 4.2H 2The consumption of O excessive by weight percentage 1%～20%; Press the CaSO in the phosphogypsum 4.2H 2O content is converted to the consumption of required phosphogypsum and bicarbonate of ammonia, and by water: the part by weight of (phosphogypsum+bicarbonate of ammonia)=0.05～0.25 adds water;
B, ball-milling reaction: phosphogypsum, bicarbonate of ammonia and water are dropped in the ball mill, are 3～5 input abrading-balls by ball material weight ratio, at normal temperatures, behind ball-milling reaction 20min～60min, are dried the ammonium sulfate product that promptly makes as fertilizer.
CN 200910059716 2009-06-23 2009-06-23 Method for preparing ammonium sulfate as fertilizer by phosphogypsum through ball milling Expired - Fee Related CN101585547B (en)

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Publication number Priority date Publication date Assignee Title
CN101798240A (en) * 2010-03-23 2010-08-11 西南科技大学 Method for preparing urea gypsum fertilizer by ball milling of gypsum
CN102583443B (en) * 2012-04-09 2014-05-07 瓮福（集团）有限责任公司 Method for producing ammonium sulfate by using ammonium bicarbonate as main raw material
RU2510366C2 (en) * 2012-05-29 2014-03-27 Общество с ограниченной ответственностью Инженерно-производственная компания "ИНТЕРФОС" Method of processing phosphogypsum to ammonium sulphate and phosphochalk
CN103333033B (en) * 2013-06-24 2015-08-05 西南科技大学 The preparation method of low urea formaldehyde resin-gypsum-bentonite base slow release fertilizer
CN106044798A (en) * 2016-08-25 2016-10-26 太仓市新星轻工助剂厂 Ammonium sulfate preparation method
CN113336242A (en) * 2021-05-11 2021-09-03 太仓市业洪净水新材料有限公司 Preparation method of phosphogypsum solid-phase ball milling of ammonium sulfate for water treatment

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