CN109437981A - Fertilizer triammonium polyphosphate and its production method containing microelement in metal - Google Patents
Fertilizer triammonium polyphosphate and its production method containing microelement in metal Download PDFInfo
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- CN109437981A CN109437981A CN201811611616.7A CN201811611616A CN109437981A CN 109437981 A CN109437981 A CN 109437981A CN 201811611616 A CN201811611616 A CN 201811611616A CN 109437981 A CN109437981 A CN 109437981A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
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Abstract
The present invention relates to fertilizer triammonium polyphosphates and its production method containing microelement in metal, belong to agricultural fertilizer production technical field.Present invention solves the technical problem that being that microelement is at high cost, solubility is low in existing water solubility.The present invention discloses fertilizer triammonium polyphosphate and its production method containing microelement in metal, and step includes a. pre-reaction；B. it polymerize；C. it is crushed, packs, mainly first mix excess phosphoric acid under condition of heating and stirring with trace mineral supplement in metal, condensing agent urea is then added, in condition of heating and stirring and NH3The lower progress polymerization reaction of partial pressure obtains ammonium polyphosphate semi-finished product.The fertilizer triammonium polyphosphate good water solubility containing microelement in metal that the present invention is prepared, the amount of microelement is high in metal in final products, and the ultimate density of soluble middle microelement is high in product, and method is easy, has good market prospects.
Description
Technical field
The invention belongs to agricultural fertilizer production technical fields, and in particular to the fertilizer grade polyphosphoric acid containing microelement in metal
Ammonium and its production method.
Background technique
In China, most phosphate rock resource is all used for the production of phosphate fertilizer, but there are phosphate fertilizer utilization efficiencies generally not high, phosphorus
Fertile kind also few problem, the absorptivity of traditional phosphate fertilizer phosphorus is very low, and approximately less than 20%.Phosphorus compound fertilizer both domestic and external exists at present
Serious excess capacity situation, and this trend is also being aggravated, therefore international fertilizer consumption in recent years is to high concentration, multiple
Combination, fluidization direction develop.
In agricultural production, surely belong to n-p-k three elements fertilizer using more, in recent years, people gradually recognize
The importance of middle microelement.It finds in practical applications, middle microelement is improved utilization rate of fertilizer, crop yield, reduction
The effect of generation of crop disease and insect and raising crop quality.
Since the water solubility of the middle microelement of inorganic states is universal poor, to be used in Water soluble fertilizer field, it is necessary first to solve
Certainly its dissolubility, for general at present method in the industry be first the middle microelement of inorganic states is made it is micro in water-soluble
Element, such as EDTA-ethylenediamine tetra-acetic acid type, then (such as potassium dihydrogen phosphates are tied with various water-soluble macroelement fertilizers again
Brilliant ammonium dihydrogen phosphate, potassium nitrate etc.) it is administered after physical mixed.However production technology is complicated, leads to micro member in water solubility
Element higher cost, and in EDTA type microelement due to chelate group ethylenediamine tetra-acetic acid it is more stable in the soil, very
It can not be all released effectively out ion in long a period of time, crop is difficult to absorb.
Ammonium polyphosphate is also known as ammonium polyphosphate or polycondensation ammonium phosphate (abbreviation APP).Ammonium polyphosphate is non-toxic and tasteless, does not generate corruption
Gas is lost, hygroscopicity is small.Ammonium polyphosphate has progressed into the production of compound fertilizer and liquid fertilizer, has especially obtained in developed country
To extensive use.Simultaneously industrialized production is succeeded in developing earliest in nineteen sixty-five Monsanto Chemicals, in the 1970s, Japan,
The states such as the former Soviet Union start mass production ammonium low polyphosphate and for agricultural fertilizer applications.
Summary of the invention
Present invention solves the technical problem that being that microelement is at high cost, solubility is low in existing water solubility.
Technical proposal that the invention solves the above-mentioned problems is to provide containing the fertilizer triammonium polyphosphate of microelement in metal
Production method, step include:
A. pre-reaction: excess phosphoric acid is mixed under condition of heating and stirring with trace mineral supplement in metal, is obtained pre-
Reaction slurry；
B. it polymerize: adds condensing agent urea into pre-reaction slurry made from step a, is uniformly mixed, in heating stirring item
Part and NH3The lower progress polymerization reaction of partial pressure obtains ammonium polyphosphate semi-finished product；
C. it is crushed, packs: the ammonium polyphosphate semi-finished product that b reacts are crushed and screened to obtain containing microelement in metal
Ammonium polyphosphate product.
Wherein, 50-100 DEG C of temperature of step a pre-reaction, reaction time 10-30min.
Wherein, the P in metal described in step a in trace mineral supplement and phosphoric acid2O5Mass ratio is 10%~30%；
Preferably, the P in metal in trace mineral supplement and phosphoric acid2O5Mass ratio is 15%~25%.
Wherein, the control of step a speed of agitator is 300rpm, average linear velocity 2-3m/s.
Wherein, the additional amount of condensing agent urea is P in phosphoric acid in step b2O5The 70%-90% of quality, the amount of being preferably added
It is 80%.
Wherein, the control of step b polymerization temperature is at 100~350 DEG C；Preferred polymerization temperature control is at 150~300 DEG C；More
Preferred polymerization temperature control is at 200 DEG C；Polymerization time was controlled at 1~3 hour, and preferred polymerization time control is in 2h.
Wherein, NH in step b3Partial pressure control is in 0.1~0.5KPa；Preferred NH3Partial pressure control is in 0.2KPa.
Wherein, the control of step b speed of agitator is 200rpm, average linear velocity 0.5-1.0m/s.
Wherein, trace mineral supplement is in the metal inorganic salt of Ca, Fe, Zn, Mn, Cu or Mg in metal described in step a
At least one.
Wherein, metal inorganic salt is at least one of sulfate, nitrate or chloride.
Further, ammonium hydroxide can be made through water or acid solution absorption processing in the tail gas that polymerization reaction generates by step b of the present invention
Or ammonium salt.
The present invention also provides the fertilizer triammonium polyphosphate prepared by the preparation method containing microelement in metal,
The degree of polymerization wherein containing microelement ammonium polyphosphate in metal is 8~20, and aggregate rate is 95% or more.
Beneficial effects of the present invention:
Trace mineral supplement in excess phosphoric acid and metal is first carried out pre-reaction by the present invention, and condensing agent urea is then added
Carry out polymerization reaction, middle microelement dispersibility is more preferable, mass-and heat-transfer faster, and PO4 combination more closely, can be promoted final
In product in metal microelement amount；
The present invention, can by the control to condensing agent additional amount in polymerization process, reaction temperature time, ammonia partial pressure
Aggregate rate is controlled 95% or more, the degree of polymerization is in 8-20；
The fertilizer triammonium polyphosphate good water solubility containing microelement in metal that the present invention is prepared, it is soluble in product
The ultimate density of middle microelement is high；
The method of the present invention is easy, it is only necessary to the gold of high quality can be produced using common chemical industry equipment and industrial chemicals
Trace element water-soluble ammonium polyphosphate fertilizer, has good market prospects in category.
Figure of description
Fig. 1 is the process flow chart of the invention containing the fertilizer triammonium polyphosphate production method of microelement in metal.
Specific embodiment
The forming process of ammonium polyphosphate is exactly the dehydrating condensation process of phosphoric acid, that is, the polymerization process of phosphoric acid, phosphorus in fact
The polymerization process of acid is shown below:
It was found that phosphoric acid can provide multipair lone pair electrons in the course of the polymerization process, be not it is very stable, easily and metal ion
Form chelating ring-type or netted water-soluble complex ion such as:
In addition, the aqueous solution of ammonium polyphosphate will be hydrolyzed slowly under the conditions of certain temperature and acid-base property, by phosphorus oxygen
Cyclic compound, chain compound and branched high-molecular compound are gradually hydrolyzed into phosphoric acid normal salt, lose sequestering power gradually.
Microelement in metal is added in the invention before polymerization reaction occurs for phosphoric acid, provides containing micro- in metal
The production method of the fertilizer triammonium polyphosphate of secondary element, step include:
A. pre-reaction: excess phosphoric acid is mixed under condition of heating and stirring with trace mineral supplement in metal, is obtained pre-
Reaction slurry；
B. it polymerize: condensing agent urea is added into pre-reaction slurry made from step a, in condition of heating and stirring and NH3Point
Pressure carries out polymerization reaction and obtains ammonium polyphosphate semi-finished product；
C. it is crushed, packs: the ammonium polyphosphate semi-finished product that b reacts are crushed and screened to obtain containing microelement in metal
Ammonium polyphosphate product.
The present invention is dissolved inorganic middle microelement with excessive phosphoric acid in step a, to reach inorganic middle microelement
It is purpose existing for ionic state in the solution, while can also greatly promotes inorganic middle microelement in acid by heating and stirring
Solubility, and then promote its amount in the final product.
Wherein, 50-100 DEG C of temperature of step a pre-reaction, reaction time 10-30min.
Wherein, the P in metal described in step a in trace mineral supplement and phosphoric acid2O5Mass ratio is 10%~30%；
Preferably, the P in metal in trace mineral supplement and phosphoric acid2O5Mass ratio is 15%~25%.
Wherein, the control of step a speed of agitator is 300rpm, average linear velocity 2-3m/s.
Wherein, wherein the additional amount of condensing agent urea is P in phosphoric acid in step b2O5The 70%-90% of quality, preferably
Additional amount is 80%.
Wherein, the control of step b polymerization temperature is at 100~350 DEG C；Preferred polymerization temperature control is at 150~300 DEG C；More
Preferred polymerization temperature control is at 200 DEG C；Polymerization time was controlled at 1~3 hour, and preferred polymerization time control is in 2h.
Wherein, step bNH3Partial pressure control is in 0.1~0.5MPa；Preferred NH3Partial pressure control is in 0.2MPa.
Wherein, the control of step b speed of agitator is 200rpm, average linear velocity 0.5-1.0m/s.
Wherein, trace mineral supplement is in the metal inorganic salt of Ca, Fe, Zn, Mn, Cu or Mg in metal described in step a
At least one.
Wherein, metal inorganic salt is at least one of sulfate, nitrate or chloride.
Further, ammonium hydroxide can be made through water or acid solution absorption processing in the tail gas that polymerization reaction generates by step b of the present invention
Or ammonium salt.
The present invention also provides the fertilizer triammonium polyphosphate prepared by the preparation method containing microelement in metal,
The degree of polymerization wherein containing microelement ammonium polyphosphate in metal is 8~20, and aggregate rate is 95% or more.
The following further explains the present invention by way of examples.
The raw materials used in the present invention source and index are described as follows:
Phosphoric acid is that phosphorus ore produces to obtain via wet processing, and urea is outsourcing bulk product, and index meets national standard
The requirement of " 2440-2017 urea ", various middle microelements are feed grade specification, and main content is 90% or so, and specific targets are such as
Shown in table 1~3.
The detection method of ammonium polyphosphate product is with reference to professional standard " HG/T 2770-2008 " and agriculture ministerial standard " NY/
T1977-2010 water-soluble fertilizer ".
1 phosphoric acid by wet process index of table
| Index | P2O5Always | CaO | MgO | Fe2O3 | Al2O3 | SO4 2- | F |
| Percentage composition % | 54.34 | 0.30 | 2.04 | 0.46 | 0.15 | 2.76 | 0.31 |
2 urea index of table
| Index | N is total | Moisture | Biuret |
| Percentage composition % | 46.3 | 0.3 | 0.4 |
The mass percentage concentration of middle microelement simple substance in 3 feed grade inorganic salts of table
Embodiment 1
It negates using phosphatase 11 500g, is heated to 60~80 DEG C, calcium sulfate 240g is added, reacts 20 under stirring condition
Minute；Then it adds urea 960g to be uniformly mixed, the slurry mixed is poured into polymerizer, which is a band folder
The stainless steel reaction tank of set is passed through thermal medium indirect heating in collet, provides polymerization institute's calorific requirement, and polymerizer is also equipped with a height
Fast blender plays the role of defoaming and mixing, controls in polymerizer 210 DEG C of temperature, and carry out closed, it is ensured that certain ammonia point
Pressure after heat preservation 2 hours, is taken out, cooling crush is up to product as material solidifies.Product good water solubility dissolves in 25 DEG C of water
It spends up to 5g/100g water, dissolution rear solution is completely limpid, and product index is as shown in table 4.
Embodiment 2
It negates using phosphatase 11 500g, is heated to 60~80 DEG C, magnesium sulfate 240g is added, reacts 20 under stirring condition
Minute；Then it adds urea 960g to be uniformly mixed, the slurry mixed is poured into polymerizer, control temperature in polymerizer
180 DEG C, and carry out closed, it is ensured that certain ammonia partial pressure, as material solidifies, after heat preservation 2 hours, taking-up, cooling crush to obtain the final product
Product.Product good water solubility, solubility is up to 5g/100g water in 25 DEG C of water, and dissolution rear solution is completely limpid, product index
As shown in table 4.
Embodiment 3
It negates using phosphatase 11 500g, is heated to 60~80 DEG C, ferrous sulfate 200g is added, is reacted under stirring condition
20 minutes；Then it adds urea 1033g to be uniformly mixed, the slurry mixed is poured into polymerizer, control temperature in polymerizer
250 DEG C of degree, and carry out closed, it is ensured that certain ammonia partial pressure.As material solidifies, after heat preservation 2 hours, take out, cooling crush is
Obtain product.Product good water solubility, solubility is up to 5g/100g water in 25 DEG C of water, and dissolution rear solution is completely limpid, and product refers to
Mark is as shown in table 4.
Embodiment 4
It negates using phosphatase 11 500g, is heated to 60~80 DEG C, zinc sulfate 170g is added, reacts 20 under stirring condition
Minute；Then it adds urea 900g to be uniformly mixed, the slurry mixed is poured into polymerizer, control temperature in polymerizer
190 DEG C, and carry out closed, it is ensured that certain ammonia partial pressure.As material solidifies, after heat preservation 2 hours, taking-up, cooling crush to obtain the final product
Product.Product good water solubility, solubility is up to 5g/100g water in 25 DEG C of water, and dissolution rear solution is completely limpid, product index
As shown in table 4.
Embodiment 5
It negates using phosphatase 11 500g, is heated to 60~80 DEG C, manganese sulfate 160g is added, reacts 20 under stirring condition
Minute；Then it adds urea 880g to be uniformly mixed, the slurry mixed is poured into polymerizer, which is a band folder
The stainless steel reaction tank of set is passed through thermal medium indirect heating in collet, provides polymerization institute's calorific requirement, and polymerizer is also equipped with a height
Fast blender, plays the role of defoaming and mixing.160 DEG C of temperature are controlled in polymerizer, and is carried out closed, it is ensured that certain ammonia point
Pressure.As material solidifies, after heat preservation one hour, take out, cooling crush is up to product.Product good water solubility, it is molten in 25 DEG C of water
Xie Du is up to 5g/100g water, and dissolution rear solution is completely limpid, and product index is as shown in table 4.
Embodiment 6
It negates using phosphatase 11 500g, is heated to 60~80 DEG C, ferrous sulfate 100g, zinc sulfate 80g, sulfuric acid is added
Manganese 80g, magnesium sulfate 50g react 20 minutes under stirring condition；Then urea 1102g is added, after mixing, is added to poly-
In clutch, 160 DEG C of temperature are controlled in polymerizer, and carry out closed, it is ensured that certain ammonia partial pressure, as material solidifies, heat preservation one
It after hour, takes out, cooling crush is up to product.Product good water solubility, solubility is up to 5g/100g water, dissolution in 25 DEG C of water
Rear solution is completely limpid, and product index is as shown in table 4.
Table 4
Claims (10)
1. the production method containing the fertilizer triammonium polyphosphate of microelement in metal, it is characterised in that the following steps are included:
A. pre-reaction: excess phosphoric acid is mixed under condition of heating and stirring with trace mineral supplement in metal, obtains pre-reaction
Slurry；
B. it polymerize: condensing agent urea is added into pre-reaction slurry made from step a, in condition of heating and stirring and NH3Under partial pressure into
Row polymerization reaction obtains ammonium polyphosphate semi-finished product；
C. be crushed, pack: by ammonium polyphosphate semi-finished product that b reacts through cooling, crush and screen to obtain containing micro member in metal
The ammonium polyphosphate product of element.
2. the production method according to claim 1 containing the fertilizer triammonium polyphosphate of microelement in metal, feature exist
In: the P in metal described in step a in trace mineral supplement and phosphoric acid2O5Mass ratio is 10%~30%；Preferably 15%
~25%.
3. the production method according to claim 1 or 2 containing the fertilizer triammonium polyphosphate of microelement in metal, feature
It is that step a at least meets following one of them:
50-100 DEG C of pre-reaction temperature, reaction time 10-30min；
Speed of agitator control is 300rpm, average linear velocity 2-3m/s.
4. described in any item production methods containing the fertilizer triammonium polyphosphate of microelement in metal according to claim 1~3,
It is characterized by: the additional amount of step b condensing agent urea is P in phosphoric acid2O5The 70%-90% of quality, the amount of being preferably added are
80%.
5. the production method according to any one of claims 1 to 4 containing the fertilizer triammonium polyphosphate of microelement in metal,
It is characterized by: the control of step b polymerization temperature is at 100~350 DEG C；Preferred polymerization temperature control is at 150~300 DEG C；It is more excellent
The polymerization temperature of choosing is controlled at 200 DEG C；Polymerization time was controlled at 1~3 hour, and preferred polymerization time control is in 2h.
6. described in any item production methods containing the fertilizer triammonium polyphosphate of microelement in metal according to claim 1~5,
It is characterized by: NH in step b3Partial pressure control is in 0.1~0.5KPa；Preferred NH3Partial pressure control is in 0.2KPa.
7. described in any item production methods containing the fertilizer triammonium polyphosphate of microelement in metal according to claim 1~6,
It is characterized by: the control of step b speed of agitator is 200rpm, average linear velocity 0.5-1.0m/s.
8. described in any item production methods containing the fertilizer triammonium polyphosphate of microelement in metal according to claim 1~7,
It is characterized by: trace mineral supplement is in the metal inorganic salt of Ca, Fe, Zn, Mn, Cu or Mg in metal described in step a
It is at least one.
9. the production method according to claim 8 containing the fertilizer triammonium polyphosphate of microelement in metal, feature exist
In: the metal inorganic salt is at least one of sulfate, nitrate or chloride.
10. the fertilizer grade polyphosphoric acid containing microelement in metal being prepared by any one of claim 1~9 preparation method
Ammonium, it is characterised in that: the ammonium polyphosphate degree of polymerization containing microelement in metal is 8~20, and aggregate rate is 95% or more.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135556A (en) * | 2021-05-25 | 2021-07-20 | 贵州川恒化工股份有限公司 | Method for preparing agricultural grade polyphosphoric acid |
| CN113248322A (en) * | 2021-05-25 | 2021-08-13 | 贵州川恒化工股份有限公司 | Preparation method of soluble medium-trace element fertilizer |
| CN114249610A (en) * | 2021-12-30 | 2022-03-29 | 瓮福达州化工有限责任公司 | Preparation process and device of ammonium potassium polyphosphate containing chelated medium and trace elements |
| CN114478076A (en) * | 2022-01-18 | 2022-05-13 | 贵州川恒化工股份有限公司 | Preparation method of zinc-rich phosphorus-nitrogen type liquid fertilizer stock solution |
| WO2022142861A1 (en) * | 2020-12-28 | 2022-07-07 | 瓮福（集团）有限责任公司 | Method for preparing high-solubility nitrogen-phosphorus water-soluble fertilizer |
| CN116474622A (en) * | 2023-06-26 | 2023-07-25 | 昆明云盘山农牧科技有限公司 | Production device for preparing monopotassium phosphate by wet-process phosphoric acid |
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| CN103787726A (en) * | 2014-02-21 | 2014-05-14 | 山东泰宝生物科技股份有限公司 | Ammonium polyphosphate water soluble fertilizer and preparation method thereof |
| CN108610145A (en) * | 2018-06-07 | 2018-10-02 | 什邡市长丰化工有限公司 | A kind of production method of water-soluble poly ammonium phosphate chelated microelement |
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2018
- 2018-12-27 CN CN201811611616.7A patent/CN109437981A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103787726A (en) * | 2014-02-21 | 2014-05-14 | 山东泰宝生物科技股份有限公司 | Ammonium polyphosphate water soluble fertilizer and preparation method thereof |
| CN108610145A (en) * | 2018-06-07 | 2018-10-02 | 什邡市长丰化工有限公司 | A kind of production method of water-soluble poly ammonium phosphate chelated microelement |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022142861A1 (en) * | 2020-12-28 | 2022-07-07 | 瓮福（集团）有限责任公司 | Method for preparing high-solubility nitrogen-phosphorus water-soluble fertilizer |
| CN113135556A (en) * | 2021-05-25 | 2021-07-20 | 贵州川恒化工股份有限公司 | Method for preparing agricultural grade polyphosphoric acid |
| CN113248322A (en) * | 2021-05-25 | 2021-08-13 | 贵州川恒化工股份有限公司 | Preparation method of soluble medium-trace element fertilizer |
| CN113135556B (en) * | 2021-05-25 | 2022-11-18 | 贵州川恒化工股份有限公司 | Method for preparing agricultural grade polyphosphoric acid |
| CN114249610A (en) * | 2021-12-30 | 2022-03-29 | 瓮福达州化工有限责任公司 | Preparation process and device of ammonium potassium polyphosphate containing chelated medium and trace elements |
| CN114478076A (en) * | 2022-01-18 | 2022-05-13 | 贵州川恒化工股份有限公司 | Preparation method of zinc-rich phosphorus-nitrogen type liquid fertilizer stock solution |
| CN116474622A (en) * | 2023-06-26 | 2023-07-25 | 昆明云盘山农牧科技有限公司 | Production device for preparing monopotassium phosphate by wet-process phosphoric acid |
| CN116474622B (en) * | 2023-06-26 | 2023-09-22 | 昆明云盘山农牧科技有限公司 | Production device for preparing monopotassium phosphate by wet-process phosphoric acid |
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Application publication date: 20190308 |