CN1063157C - Industrial monoammonium phosphate and productive method for industrial monoammunium phosphate and calcium hydrogen phosphate fodder - Google Patents
Industrial monoammonium phosphate and productive method for industrial monoammunium phosphate and calcium hydrogen phosphate fodder Download PDFInfo
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- CN1063157C CN1063157C CN96117680A CN96117680A CN1063157C CN 1063157 C CN1063157 C CN 1063157C CN 96117680 A CN96117680 A CN 96117680A CN 96117680 A CN96117680 A CN 96117680A CN 1063157 C CN1063157 C CN 1063157C
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- phosphate
- phosphoric acid
- industrial monoammonium
- monoammonium phosphate
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Abstract
The present invention provides a production method of industrial monoammonium phosphate and a joint production method of the industrial monoammonium phosphate and feed calcium hydrogen phosphate. In the production of the industrial monoammonium phosphate, wet process phosphoric acid produced from medium-grade and low-grade phosphate ore with high impurity contents of iron, aluminum and magnesium is used as raw materials; the method for producing the industrial monoammonium phosphate has the orderly working procedures of sodium salts or potassium salts and phosphate ore powder adding for pretreatment, filtering, ammonium adding for primary neutralization, filtering, ammonium adding for secondary neutralization and spray drying. In the joint production method of the industrial monoammonium phosphate and the feed calcium hydrogen phosphate, a part of phosphoric acid purification liquid obtained after the primary neutralization and filtration is used for preparing the industrial monoammonium, the other part is used for preparing the feed calcium hydrogen phosphate, and two kinds of products can be obtained only through adding a small quantity of equipment.
Description
The present invention relates to the production method of industrial monoammonium phosphate and calcium hydrogen phosphate fodder.
Industrial monoammonium phosphate, calcium hydrogen phosphate fodder can phosphoric acid by wet process be raw material production all, but the data from collecting, their production method all has one of one's own and overlaps independently technical process.Chinese patent ZL92108090.5 provides a kind of production method of PHOSPHORIC ACID TECH.GRADE ammonium, this method is that the phosphoric acid by wet process that the Rock Phosphate (72Min BPL) below 10% or 10% makes is a raw material with iron, aluminium, magnesium addition total content, with in the ammonia and phosphoric acid by wet process and the ammonification slip carried out settlement separate, gained clear liquid through evaporation concentration, crystallisation by cooling, centrifugation, washing, dry industrial grade monoammonium phosphate product.Though this kind method can be produced industrial monoammonium phosphate with mid low grade phosphate rock, but have the following disadvantages: (1) directly neutralizes with the phosphoric acid by wet process ammonification of extraction, will make silicon contained in the phosphoric acid by wet process in N-process, form the silicon gel, thereby increase the viscosity of slip, influence settlement separate efficient, reduce the yield of industrial monoammonium phosphate; (2) adopt ammonification once to be neutralized to the required degree of neutralization of industrial monoammonium phosphate can increase P in the process that removes impurity
2O
5Loss; (3) setting of evaporation concentration, crystallisation by cooling, centrifugation, washing, drying process not only causes long flow path, increases the investment of equipment and the difficulty of operation, and can reduce the yield of industrial monoammonium phosphate.
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of production method of novel industrial monoammonium phosphate and the co-production method of industrial monoammonium phosphate and calcium hydrogen phosphate fodder, to reduce operation, reduce investment, to improve the yield of usage ratio of equipment and product.
The production method of industrial monoammonium phosphate provided by the present invention is a raw material with the phosphoric acid by wet process of the higher mid low grade phosphate rock production of iron, aluminium, magnesium addition content, comprises pre-treatment, filtration successively, once neutralizes, filtration, secondary neutralization, spraying drying operation.Pre-treatment is to add sodium salt or sylvite and ground phosphate rock in phosphoric acid by wet process, makes contained fluorine silicon ion SiF in they and the phosphoric acid by wet process
6 2-React with free sulfuric acid, to remove fluorine silicon ion SiF
6 2-With sulfate radical SO
4 2-Thereby, can avoid the formation and the voluminous phosphoric acid of silicon gel, the Na that is generated
2SiF
6Or K
2SiF
6Enter phosphorus ammonium composting system with phosphogypsum.Once neutralization is to feed gaseous ammonia in the filtrate of pre-treatment after-filtration gained, control 2.0≤pH＜4.0, the purpose of this operation is to remove iron, aluminium, magnesium and a spot of fluorine in the phosphoric acid by wet process and generate soluble phosphoric acid one ammonium, above-mentioned impurity generates calcium phosphate precipitation after ammonification, enter phosphorus ammonium composting system, experiment shows that the pH value of slip will make R greater than 4.0 during the ammonification removal of impurities
2O
5Loss increases, and therefore, the pH value of slip controlled well is a major issue.The secondary neutralization is once to feed gaseous ammonia in the neutralization filtration gained filtrate, and the pH value is controlled at 4.0～5.0, produces required pH value to reach monoammonium phosphate.
The co-production method of industrial monoammonium phosphate provided by the present invention and calcium hydrogen phosphate fodder belongs to a total inventive concept with the production method of above-mentioned industrial monoammonium phosphate, purpose is to improve usage ratio of equipment, on the basis of manufacture monoammonium phosphate equipment, only increase small number of devices and just can have more a kind of product, concrete technical process is: with phosphoric acid by wet process through pre-treatment, filter, once neutralization, filter, the phosphoric acid purification liquid part of 2.0≤pH of gained＜4.0 is used to make monoammonium phosphate, a part adds the milk of lime secondary and is neutralized to pH value 6.0～7.0 and is settled out calcium hydrogen phosphate fodder, filtering separation obtains calcium hydrogen phosphate fodder product and diammonium phosphate filtrate, diammonium phosphate filtrate with carry out spraying drying after once the part phosphoric acid purification liquid that obtains of neutralization mixes and make the industrial monoammonium phosphate product.
In order to realize goal of the invention better, the present invention has also taked following technical measures:
Pre-treatment is under agitation carried out, and temperature is controlled at 40～70 ℃, and the time is 0.5～2.5 hour; The add-on of sodium salt or sylvite is pressed stoichiometric 105～120% calculating of fluorine content in the phosphoric acid by wet process, and the add-on of ground phosphate rock is pressed 5～20% of phosphoric acid by wet process amount and calculated; The sodium salt that is added is Na
2SO
4Or Na
2CO
3, the sylvite that is added is K
2SO
4
Once and the time, the reaction under agitation carry out, the time is 0.5～1 hour.
The industrial monoammonium phosphate per unit area yield, its secondary neutralization reaction is under agitation carried out, and the time is 0.5～1 hour.
The coproduction of industrial monoammonium phosphate and calcium hydrogen phosphate fodder, in the secondary and time institute's concentration of adding milk of lime be CaO content 8～10%, react and under agitation carry out, temperature is controlled at 40～50 ℃, the time is 1～2 hour.
Compared with prior art, the present invention has the following advantages:
1. being provided with of pretreatment process one is to have removed SiF contained in the phosphoric acid by wet process
6 2-Ion, thus avoided forming of the influence of silicon gel to solid-liquid separation, improved the yield of industrial monoammonium phosphate effectively; The 2nd, made full use of the chemical energy of free sulfuric acid, in voluminous phosphoric acid, removed the sulfate radical that influences industrial monoammonium phosphate purity again.
2. the phosphoric acid by wet process neutralization is divided into twice and finishes, help reducing P
2O
5Loss, improve its yield.
3. the direct spraying drying of industrial monoammonium phosphate solution after the purification separation is got product, both shortened technical process, saved evaporation concentration, crystallisation by cooling, centrifugation, washing, dry required facility investment and energy consumption again, production cost is reduced significantly.In addition, also can avoid the obstruction of filter plant, pipeline, prolong the equipment washing cycle, improve driving rate.
4. on the basis of industrial monoammonium phosphate technical process, secondary neutralization changed slightly and realize the coproduction of industrial monoammonium phosphate and calcium hydrogen phosphate fodder both having improved usage ratio of equipment, strengthened adaptability to changes again market.
5. combine with existing ammonium phosphate plant, need not again organizational system acid device, and can form the complete process flow of a cover slurry process phosphorus coproducing ammonium industrial monoammonium phosphate and calcium hydrogen phosphate fodder, improved P effectively
2O
5Utilization ratio and added value of product.
Below in conjunction with drawings and Examples method provided by the invention is further described.
Fig. 1 is the process flow sheet of industrial monoammonium phosphate production method provided by the present invention.
Fig. 2 is the process flow sheet of industrial monoammonium phosphate provided by the present invention and calcium hydrogen phosphate fodder co-production method.
Embodiment 1
The technical process of present embodiment as shown in Figure 1, concrete operations are as follows: get and contain P
2O
520% phosphoric acid by wet process places in the pretreatment reaction groove for 1000 kilograms, adds 17.2 kilograms of Na then
2SO
4And 56.25 kilograms of ground phosphate rock (contain P in the phosphorus ore
2O
532%), 68 ℃ of following stirring reactions 1 hour, filter and adopt filter press, the gained filter residue enters the composting system, gained filtrate is sent into a logical gaseous ammonia neutralization of neutralizer, when slip pH value reaches 3.5, stop logical ammonia, continue stirring reaction again and filtered in 40 minutes, filter and still adopt filter press, the gained filter residue enters the composting system, gained filtrate is sent into the logical gaseous ammonia neutralization of secondary neutralizer, when the pH value reaches 5.O, stops logical ammonia, continue again to stir 30 minutes, carry out spraying drying then and make 194.68 kilograms of industrial monoammonium phosphate products.
Embodiment 2
The technical process of present embodiment such as Fig. 2 show, concrete operations are as follows: get and contain P
2O
520% phosphoric acid by wet process places in the pretreatment reaction groove for 1000 kilograms, adds 25 kilograms of K again
2SO
4And 72 kilograms of ground phosphate rock, 50 ℃ of following stirring reactions 2 hours, it is settlement separate to filter employing, the gained filter residue enters the composting system, gained filtrate is sent into a logical ammonia neutralization of neutralizer, when reaching 3.0, the pH value stops logical ammonia, continue again to stir and filtered in 1 hour, filter and adopt filter press, the gained filter residue enters the composting system, a gained phosphoric acid purification liquid part is sent into the batch mixing pipe and is made industrial monoammonium phosphate, a part is sent into the secondary neutralizer and is added milk of lime neutralization (concentration of milk of lime is CaO content 8%), temperature of reaction is controlled at 45 ℃, when the pH value reaches 6.5, stops to add milk of lime, continue again to stir 1 hour, be settled out calcium hydrogen phosphate fodder, filtering separation obtains 97.22 kilograms of calcium hydrogen phosphate fodder products and diammonium phosphate filtrate, carries out spraying drying after the phosphoric acid purification liquid of sending to after diammonium phosphate filtrate is sent into the batch mixing pipe and once neutralized mixes and makes 134.21 kilograms of industrial monoammonium phosphate products.
Adopt industrial monoammonium phosphate purity that this law makes more than 90%, its N 〉=11.0%, P
2O
5〉=56.0%; Calcium hydrogen phosphate fodder is: P
2O
5〉=37%, CaO 〉=30%, F≤O.1%.
Claims (7)
1. the production method of an industrial monoammonium phosphate, phosphoric acid by wet process with the higher mid low grade phosphate rock production of iron, aluminium, magnesium addition content is a raw material, it is characterized in that comprising pre-treatment, filtration successively, once neutralize, filtration, secondary neutralization, spraying drying operation, pre-treatment is to add sodium salt or sylvite and ground phosphate rock in phosphoric acid by wet process, makes contained fluorine silicon ion SiF in they and the phosphoric acid by wet process
6 2-React with free sulfuric acid, to remove fluorine silicon ion SiF
6 2-With sulfate radical SO
4 2-Thereby, voluminous phosphoric acid, once neutralization is to feed gaseous ammonia in the filtrate of pre-treatment after-filtration gained, control 2.0≤pH＜4.0, the secondary neutralization is to feed gaseous ammonia in once He in the after-filtration gained filtrate, the pH value is controlled at 4.0～5.0.
2. the production method of industrial monoammonium phosphate according to claim 1 is characterized in that pre-treatment under agitation carries out, and temperature is controlled at 40～70 ℃, and the time is 0.5～2.5 hour.
3. the production method of industrial monoammonium phosphate according to claim 1 and 2, the add-on of sodium salt or sylvite is calculated by fluorine content in the phosphoric acid by wet process stoichiometric 105～120% when it is characterized in that pre-treatment, the add-on of ground phosphate rock is pressed 5～20% of phosphoric acid by wet process amount and is calculated, and the sodium salt that is added is Na
2SO
4Or Na
2CO
3, the sylvite that is added is K
2SO
4
4. the production method of industrial monoammonium phosphate according to claim 1, it is characterized in that once in and the time, reaction is under agitation carried out, the time is 0.5～1 hour.
5. the production method of industrial monoammonium phosphate according to claim 1, it is characterized in that in the secondary and the time, reaction is under agitation carried out, the time is 0.5～1 hour.
6. the co-production method of industrial monoammonium phosphate and calcium hydrogen phosphate fodder, with iron, aluminium, the phosphoric acid by wet process of the mid low grade phosphate rock production that magnesium addition content is higher is a raw material, it is characterized in that technical process is: with phosphoric acid by wet process through pre-treatment, filter, once neutralization, filter, the phosphoric acid purification liquid part of 2.0≤pH of gained＜4.0 is used to make monoammonium phosphate, a part adds the milk of lime secondary and is neutralized to pH value 6.0～7.0 and is settled out calcium hydrogen phosphate fodder, filtering separation obtains calcium hydrogen phosphate fodder product and diammonium phosphate filtrate, diammonium phosphate filtrate with carry out spraying drying after once the part phosphoric acid purification liquid that obtains of neutralization mixes and make the industrial monoammonium phosphate product.
7. the co-production method of industrial monoammonium phosphate according to claim 6 and calcium hydrogen phosphate fodder is characterized in that pre-treatment under agitation carries out, and temperature is controlled at 40～70 ℃, and the time is 0.5～2.5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117680A CN1063157C (en) | 1996-08-26 | 1996-08-26 | Industrial monoammonium phosphate and productive method for industrial monoammunium phosphate and calcium hydrogen phosphate fodder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117680A CN1063157C (en) | 1996-08-26 | 1996-08-26 | Industrial monoammonium phosphate and productive method for industrial monoammunium phosphate and calcium hydrogen phosphate fodder |
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| Publication Number | Publication Date |
|---|---|
| CN1174812A CN1174812A (en) | 1998-03-04 |
| CN1063157C true CN1063157C (en) | 2001-03-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96117680A Expired - Fee Related CN1063157C (en) | 1996-08-26 | 1996-08-26 | Industrial monoammonium phosphate and productive method for industrial monoammunium phosphate and calcium hydrogen phosphate fodder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020256B (en) * | 2010-11-22 | 2012-05-23 | 马健 | Method for producing industrial and agricultural monoammonium phosphate and magnesium ammonium phosphate with wet-process phosphoric acid |
| CN102942166A (en) * | 2012-11-14 | 2013-02-27 | 贵州开磷（集团）有限责任公司 | Method for preparing toothpaste/food/medicine grade calcium hydrophosphate from phosphoric acid by wet process |
| CN102992289B (en) * | 2012-12-27 | 2014-09-17 | 广西明利化工有限公司 | Method for producing food-grade phosphoric acid |
| CN103848407B (en) * | 2013-04-02 | 2016-01-13 | 襄阳泽东化工集团有限公司 | A kind of production method of monoammonium phosphate |
| CN103771380B (en) * | 2013-11-08 | 2016-06-29 | 昆明川金诺化工股份有限公司 | A kind of method utilizing Wet-process Phosphoric Acid Production industrial phosphoric acid salt |
| CN103864043B (en) * | 2014-04-04 | 2016-09-28 | 中化云龙有限公司 | Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate |
| CN103864039B (en) * | 2014-04-04 | 2015-10-28 | 中化云龙有限公司 | The method of phosphoric acid defluorination coproduction PHOSPHORIC ACID TECH.GRADE ammonium dihydrogen and feed-grade calcium phosphate salt |
| JP6268054B2 (en) * | 2014-07-09 | 2018-01-24 | 株式会社アナック | Method and apparatus for producing fertilizer by treating phosphoric acid mixed acid waste liquid |
| CN104445121B (en) * | 2014-11-21 | 2017-02-08 | 贵州开磷集团股份有限公司 | Mono-ammonium phosphate produced by using wet process phosphoric acid and production method of mono-ammonium phosphate |
| CN105174237B (en) * | 2015-09-22 | 2018-03-13 | 贵州开磷集团股份有限公司 | A kind of phosphoric acid by wet process prepares sodium dihydrogen phosphate method |
| CN105174238B (en) * | 2015-09-22 | 2018-03-13 | 贵州开磷集团股份有限公司 | A kind of phosphoric acid by wet process prepares dipotassium hydrogen phosphate method |
| CN105174239B (en) * | 2015-09-22 | 2018-03-13 | 贵州开磷集团股份有限公司 | A kind of phosphoric acid by wet process prepares disodium hydrogen phosphate method |
| CN106800285A (en) * | 2017-01-10 | 2017-06-06 | 四川龙蟒磷化工有限公司 | The production method of calcium hydrophosphate fodder |
| CN114014287A (en) * | 2021-11-08 | 2022-02-08 | 宜都兴发化工有限公司 | Wet-process phosphoric acid purification method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103677A (en) * | 1985-05-15 | 1986-11-12 | 窒素股份有限公司 | Method with producing purified monoammonium phosphate from wet process phosphoric acid |
| CN1064858A (en) * | 1992-04-11 | 1992-09-30 | 四川省德阳市什邡化肥总厂 | Coproduction of fertilizer grade and pure monoammonium phosphate by wet-process phosphoric acid |
-
1996
- 1996-08-26 CN CN96117680A patent/CN1063157C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103677A (en) * | 1985-05-15 | 1986-11-12 | 窒素股份有限公司 | Method with producing purified monoammonium phosphate from wet process phosphoric acid |
| CN1064858A (en) * | 1992-04-11 | 1992-09-30 | 四川省德阳市什邡化肥总厂 | Coproduction of fertilizer grade and pure monoammonium phosphate by wet-process phosphoric acid |
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| Publication number | Publication date |
|---|---|
| CN1174812A (en) | 1998-03-04 |
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