CN100395178C - Method of producing zinc phosphate using phosphorus fertilizer - Google Patents

Method of producing zinc phosphate using phosphorus fertilizer Download PDF

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Publication number
CN100395178C
CN100395178C CNB2006100107752A CN200610010775A CN100395178C CN 100395178 C CN100395178 C CN 100395178C CN B2006100107752 A CNB2006100107752 A CN B2006100107752A CN 200610010775 A CN200610010775 A CN 200610010775A CN 100395178 C CN100395178 C CN 100395178C
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phosphate
zinc
solution
fertilizer
salt
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CN1830761A (en
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宁平
马兴良
瞿广飞
李军燕
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The present invention relates to a method for producing zinc phosphate by using phosphate fertilizer, which comprises the following steps: fertilizer-grade ammonium phosphate salt and soluble zinc salt are respectively dissolved in hot water to obtain ammonium phosphate solution and zinc salt solution; the molar ratio of phosphate radical ions and zinc ions in the prepared ammonium phosphate solution and the prepared zinc salt solution is 0.7 to 1: 1, and according to the proportion, the two kinds of prepared solution are added in a container with a stirrer; the solution temperature is kept at 50 DEG C to 80 DEG C, and the pH value of the mixed solution is regulated between 6.5 and 8.5 with alkali lye; after slaking reaction for 10 to 20 minutes, the mixed solution is filtered, and filter cakes are washed with hot water to obtain wet zinc phosphate which is dried at normal pressure to obtain zinc phosphate products. Fertilizer-grade ammonium phosphate has the advantages of wide sources, low prices and low production cost.

Description

Method with the production of phosphate fertilizer zinc phosphate
One, affiliated technical field: chemical industry of inorganic salt field
Two, background technology:
Zinc phosphate Zn 3(PO 4) 2χ H 2O (χ is 0,2,4) is mainly used in environmental friendly, anti-corrosive pigment, ferrous metal phosphatization, is used for glass, enamel, pottery etc. on a small quantity, at present industrialized preparing process has two classes, and is as follows:
1, neutralisation
Add dilute phosphoric acid neutralization, slaking, filtration, drying in the Zinc oxide water slurries and get.
3ZnO+2H 3PO 4+H 2O→Zn 3(PO 4) 2·4H 2O↓
Production technique is complicated.The ratio of the amount of substance of used zinc oxide and phosphoric acid is 3: 1, and zinc oxide can not transform fully.Zinc oxide and product Zinc phosphate tetrahydrate are almost insoluble in water, and this reaction essence is a precipitation conversion reaction.Must power consumption again consuming time with traditional indirect heating method.
2, double decomposition
Alkali metal phosphate and soluble zinc salt react at hot aqueous phase, adjust the pH value, and filtration, washing, fragmentation, drying make.
2MOH+2M 2HPO 4+3Zn 2++2H 2O→Zn 3(PO 4) 2·4H 2O↓+M +
2M 3PO 4+3Zn 2++4H 2O→Zn 3(PO 4) 2·4H 2O↓+6M +
Wherein: M is a basic metal.
In neutralisation, raw material zinc oxide and phosphoric acid are technical grade product, and price is higher, and production cost is higher.In double decomposition, though the employing soluble zinc salt is a raw material, unit weight zinc price is low than zinc oxide, is raw material owing to adopt the technical grade alkali metal phosphate, and cost is also higher.
English Patent BP 962182 discloses a kind of zinc phosphate production method, and adopting soluble zinc salt and phosphoric acid salt is raw material, and replacement(metathesis)reaction is carried out in two steps, produces four water zinc phosphates, and this method must be used purer raw material, the production cost height.
U.S. Pat-A 4294808 discloses a kind of method from zinc oxide and phosphoric acid production zinc phosphate, zinc oxide at first in water by means of spiral pump under the condition of 3000rpm~10000rpm, circulate dispersion, fragmentation, add phosphoric acid further reaction, slaking under spiral pump circulation dispersion condition again, after filtration, the dry product that gets.This technology belongs to neutralisation, though speed of reaction and production efficiency are higher, technology is simple, must use higher zinc oxide of purity and PHOSPHORIC ACID TECH.GRADE to be raw material, and the raw materials for production cost is higher.
It is the method for raw material preparation of zinc phosphate with purification of wet process phosphoric acid and zinc oxide that Chinese patent 1164508 (publication number) discloses a kind of, it is characterized in that used zinc oxide is the inferior rudimentary zinc oxide of inexpensive matter, zinc oxide content is 50%~95%, through acid (mixing acid of sulfuric acid and small amounts of phosphoric acid) dissolving, zinc change over to liquid phase and through purify must contain zinc 10%~18% after concentrating solution again with contain P 2O 5The mixed organic solvents of 11%~17% (and containing butanols>60%, TBP<40%) is pressed P mutually 2O 5React with the stoichiometric of Zn.There are three shortcomings in this method: the one, solution behind the sour molten zinc oxide is because impurity exists, or this solution must be further purified, or the product foreign matter content is higher, and purity is low; The 2nd, sour dissolved oxygen zinc solution must concentrate, and consumes more energy; The 3rd, reaction generates wet product and contains organic solvent, also will consume than macro-energy if organic solvent reclaims, and because of the TBP boiling point is higher than zinc phosphate two water thing dehydration temperaturres, product is difficult to crystallization control water number amount.
Chinese patent 1460637 (publication number) discloses employing low-heat solid state reaction direct synthesis technique, concrete technology is, with zinc salt powder, inorganic phosphate powder is basic raw material, add template, under 15~150 ℃, non-pressurized condition, mix the back and grind, then allow the reaction mixture insulation leave standstill, wash the inorganic salt by-product of solubility in the dereaction mixture then with water, filter, oven dry obtains nano level zinc phosphate crystal after the pulverizing.Above-described synthesis of nano zinc phosphate crystalline method, its proportioning raw materials is: zinc salt: inorganic phosphate=1.0~2.5: 1.0 (mol ratios), template then account for 0.1~15% of entire reaction thing weight.This technology essence is to prepare zinc phosphate with replacement(metathesis)reaction, and two kinds of material purities are had relatively high expectations, and production cost is also higher.
Three, summary of the invention
1, the objective of the invention is to overcome the existing raw materials used deficiency of producing, providing a kind of is raw material from fertilizer grade ammonium phosphate, prepares the method for zinc phosphate through impurity and purification, metathesis, the wide material sources of fertilizer grade ammonium phosphate, cheap, and production cost is low.
2, invention is finished according to the following steps
1), raw material is the fertilizer grade ammonium phosphate salt, soluble zinc salt.The fertilizer grade ammonium phosphate salt comprises monoammonium phosphate (MAP) or diammonium phosphate (DAP); Soluble zinc salt comprises zinc sulfate, zinc chloride or zinc nitrate;
2) technological process of the present invention
(1), ammonium phosphate prepares ammonium phosphate solution
It is in 1~2 times 50 ℃~80 ℃ the water that 1 part of fertilizer grade ammonium phosphate is dissolved in weight ratio, and 25~60 minutes after-filtration of insulation ageing, the filtering and removing insoluble impurities.Filter residue is with 50 ℃~80 ℃ hot washes washing 1~2 time, wash water and filtrate merge ammonium phosphate solution, filter residue can be used as the fertiliser production raw material;
(2), zinc solution preparation
Soluble zinc salt under agitation is dissolved in 50 ℃~80 ℃ hot water, and heat filtering is removed the mechanical impurity that wherein may contain, and makes the zinc solution of 20wt%~45wt%;
(3), replacement(metathesis)reaction
In ammonium phosphate solution that makes and zinc solution, phosphate anion and zine ion mol ratio are 0.7~1: 1 ratio, two kinds of solution that make are added mixing in the container of being with stirring, keep 50 ℃~80 ℃ of solution temperatures, adjust between the pH of mixed value 6.5~8.5 with alkali lye, (alkali lye comprises sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor), slaking is sent out and is answered 10~20 minutes after-filtration, filter cake obtains wet zinc phosphate with 50 ℃~80 ℃ hot washes of 2~5 times of its weight 2~3 times;
(4), drying
Wet zinc phosphate in 90 ℃~110 ℃ dryings 10~30 minutes, obtains the zinc phosphate product under normal pressure.
3, the advantage that compared with prior art had of present technique
1, adopting fertilizer grade ammonium phosphate is raw material, and it is wide, cheap to have a source, and production cost is low.
2, make because of adopting raw material fertilizer grade ammonium phosphate and zinc sulfate to be wet method, thereby this technology belongs to energy-saving technology.
Four, description of drawings:
Fig. 1 is a process flow sheet of the present invention
Five, embodiment
Embodiment 1:
1.25kg the fertilizer grade diammonium phosphate is under agitation dissolved in 75 ℃ of hot water of 1.5kg, keeps 75 ℃ of temperature, 35 minutes after-filtration, and filter residue merges with 70 ℃ of hot washes 1 time, washing lotion and filtrate; 2.6kg zinc sulfate (ZnSO 47H 2O) be dissolved in the zinc solution that makes in 2.0kg, the 70 ℃ of hot water, after filtration; The solution of two kinds of feedstock production adds in the stirred reactor, and temperature of reaction keeps 50 ℃, and after stock liquid added, adjusting the pH value with 40wt% sodium hydroxide was 6.8, and reaction solution is kept 20 minutes after-filtration of this temperature again; Filter cake gets the zinc phosphate wet cake with 3 times of 70 ℃ of hot washes of its weight 3 times; Under normal pressure,, obtain the product zinc phosphate in 110 ℃ of dryings 20 minutes.Analytical results such as table 1:
Table 1 embodiment 1 product analysis result
?Zn,% 50.8
?P 2O 5,% 48.2
?SO 4 2-,% 0.08
Burning decrement, % 7.4
Above-mentioned products obtained therefrom is Zn 3(PO 4) 22H 2O.
Embodiment 2:
3kg fertilizer grade monoammonium phosphate under agitation dissolves in 75 ℃ of hot water of 3.5kg, keeps 75 ℃ of 35 minutes after-filtration, and filter residue merges with 60 ℃ of hot washes 2 times, washing lotion and filtrate; 7 kg zinc sulfate (ZnSO 47H 2O) be dissolved in the zinc solution that filtration makes 45wt% in 5kg, the 70-80 ℃ hot water, filter; Above-mentioned two kinds of solution join in the stirred reactor simultaneously, and temperature of reaction keeps 70-80 ℃, and after solution added, adjusting the pH value with 40wt% sodium hydroxide was 7.2-8, and reactant is kept 18 minutes after-filtration of this temperature again; Filter cake gets the zinc phosphate wet cake with 4 times of 80 ℃ of hot washes of its weight 2 times; Under normal pressure,, obtain the product zinc phosphate in 110 ℃ of dryings 18 minutes.Analytical results sees Table 2:
Table 2 embodiment 2 product analysis results
Zn,% 50.9
?P 2O 5,% 48.1
?SO 4 2-,% 0.06
Burning decrement, % 7.5
Above-mentioned products obtained therefrom is Zn 3(PO 4) 22H 2O.

Claims (5)

1. method with the production of phosphate fertilizer zinc phosphate, it is characterized in that: method is finished according to the following steps,
Raw material is the fertilizer grade ammonium phosphate salt, soluble zinc salt;
It is in 1~2 times of hot water that 1 part of fertilizer grade ammonium phosphate is dissolved in weight ratio, and 25~60 minutes after-filtration of insulation ageing, the filtering and removing insoluble impurities, and the filter residue hot water washing, wash water and filtrate combination system get ammonium phosphate solution;
Soluble zinc salt under agitation is dissolved in the hot water, and heat filtering is removed mechanical impurity wherein, and making concentration is 20wt%~45wt% zinc solution;
In ammonium phosphate solution that makes and zinc solution, phosphate anion and zine ion mol ratio are 0.7~1: 1 ratio, two kinds of solution that make are added mixing in the container of being with stirring, keep 50 ℃~80 ℃ of solution temperatures, adjust between the pH of mixed value 6.5~8.5 10~20 minutes after-filtration of slaking reaction, filter cake hot wash with alkali lye, obtain wet zinc phosphate, wet zinc phosphate drying under normal pressure obtains the zinc phosphate product.
2. the method with the production of phosphate fertilizer zinc phosphate according to claim 1, it is characterized in that: described fertilizer grade ammonium phosphate salt comprises monoammonium phosphate or diammonium phosphate; Soluble zinc salt comprises zinc sulfate, zinc chloride or zinc nitrate.
3. the method with the production of phosphate fertilizer zinc phosphate according to claim 1, it is characterized in that: the hot water that dissolving phosphoric acid ammonium, zinc salt and washing leaching cake, filter residue are used is 50 ℃~80 ℃.
4. according to claim 1 or 3 described methods with production of phosphate fertilizer zinc phosphates, it is characterized in that: filter cake is with the hot wash of 2~5 times of its weight 2~3 times.
5. the method with the production of phosphate fertilizer zinc phosphate according to claim 1 is characterized in that: wet zinc phosphate was in 90 ℃~110 ℃ dryings 10~30 minutes.
CNB2006100107752A 2006-03-24 2006-03-24 Method of producing zinc phosphate using phosphorus fertilizer Expired - Fee Related CN100395178C (en)

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Publication number Priority date Publication date Assignee Title
CN106115647A (en) * 2016-06-16 2016-11-16 重庆天原化工有限公司 A kind of indirect method produces High Quality Zinc Phosphate technique
CN117550574A (en) * 2023-07-21 2024-02-13 四川科尔瑞环保科技有限责任公司 Synthetic method for preparing zinc phosphate by taking zinc-containing solution as raw material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0009717A1 (en) * 1978-09-28 1980-04-16 Hoechst Aktiengesellschaft Process for the production of particulate zinc phosphate
US4294808A (en) * 1978-09-20 1981-10-13 Hoechst Aktiengesellschaft Production of anticorrosive pigments containing phosphorus
US4400365A (en) * 1980-12-11 1983-08-23 Goslarer Farbenwerke Method for the manufacture of aluminum zinc phosphate hydrates or basic aluminum zinc phosphate hydrates
JP2000154010A (en) * 1998-11-18 2000-06-06 Fuji Chem Ind Co Ltd Fine particle zinc phosphate, its production and rust preventive pigment using that

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4294808A (en) * 1978-09-20 1981-10-13 Hoechst Aktiengesellschaft Production of anticorrosive pigments containing phosphorus
EP0009717A1 (en) * 1978-09-28 1980-04-16 Hoechst Aktiengesellschaft Process for the production of particulate zinc phosphate
US4400365A (en) * 1980-12-11 1983-08-23 Goslarer Farbenwerke Method for the manufacture of aluminum zinc phosphate hydrates or basic aluminum zinc phosphate hydrates
JP2000154010A (en) * 1998-11-18 2000-06-06 Fuji Chem Ind Co Ltd Fine particle zinc phosphate, its production and rust preventive pigment using that

Non-Patent Citations (4)

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低纯度氧化锌制备磷酸锌的研究. 陈云华,赵宾,张恒津.云南化工,第28卷第3期. 2001 *
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