CN103864043A - Method for co-producing feed-grade calcium phosphate and monopotassium phosphate by defluorinated wet- process on phosphoric acid - Google Patents
Method for co-producing feed-grade calcium phosphate and monopotassium phosphate by defluorinated wet- process on phosphoric acid Download PDFInfo
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Abstract
The invention relates to a method for co-producing feed-grade calcium phosphate and monopotassium phosphate by defluorinated wet-process phosphoric acid, which belongs to the field of chemical product preparation. The method comprises the following steps of: reacting a neutralizer I with defluorinated phosphoric acid to generate phosphate slurry, and filtering the slurry to obtain a solid phase I and a filtrate I, wherein the neutralizer I is at least one of calcium oxide, calcium carbonate and calcium hydroxide; and carrying out a neutralization reaction on the filtrate I and a neutralizer II; after the reaction, carrying out solid-liquid separation to obtain a solid phase II and a filtrate II; drying the solid phase I and the solid phase II and then adequately mixing to obtain the feed-grade calcium phosphate; and crystallizing the filtrate II to obtain high-purity monopotassium phosphate.
Description
Technical field
The method that the present invention relates to defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium primary phosphate, belongs to Chemicals preparation field.
Background technology
Secondary calcium phosphate is divided into four kinds of ranks by purposes: toothpaste grade calcium hydrophosphate, and be mainly used in toothpaste and produce as friction agent, food-grade calcium hydrogen phosphate, does raising agent for foodstuffs industry, and fertilizer grade secondary calcium phosphate, as phosphate fertilizer; Calcium hydrophosphate fodder, it is a kind of large phosphorus chemical product that has bright prospects, it is a kind of poultry, domestic animal feed additive that contains phosphorus, two kinds of elements of calcium, because phosphorus calcium ratio is wherein more approaching than with the phosphorus calcium in animal skeleton, can all be dissolved in again in animal hydrochloric acid in gastric juice simultaneously, so easily enter in animal body and participate in metabolism, the needed hormone of composition body, enzyme and VITAMIN, keep the phosphorus calcium ratio in bone, thereby prevent that animal from, because lacking the caused various diseases of phosphorus calcium, promoting animal body Fast Growth simultaneously.
Potassium primary phosphate is as the colourless or white rhomboidal crystal with gloss, it is a kind of phosphorus potash fertilizer of high density, it is high that it has nutritive ingredient, soluble in water, the feature of stable chemical nature, potassium primary phosphate is at modern medicine simultaneously, chemical industry chemistry, foodstuffs industry also has a wide range of applications, the production method of potassium primary phosphate is a lot, roughly be summarised as neutralisation, extraction process, ion exchange method, double decomposition, direct method, crystallization process and electrolytic process etc., in China, its production technique adopts neutralisation more, secondly also has organic extraction, double decomposition and ion exchange method.
In traditional technology, phosphoric acid by wet process and milk of lime are produced secondary calcium phosphate and are all adopted two sections of neutralisations, and one section of neutralization secondary calcium phosphate out can only be served as thick fertile cheap processing owing to containing a large amount of fluorine, and this has increased production cost greatly.And producing in the processing method of potassium primary phosphate, there is organic solvent costliness in organic extraction, and the problem such as the toxic bad processing of organic solvent, phosphorous recovery be low.Double decomposition exists rate of decomposition low, and unstable product quality is serious to equipment corrosion, neutralisation utilization be that thermal phosphoric acid is produced, this has increased production cost virtually.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium primary phosphate.
The method of defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt of the present invention and potassium primary phosphate, comprises the steps:
(a) one section of neutralization: get neutralizing agent I and phosphoric acid defluorination and carry out neutralization reaction, react complete, solid-liquid separation, obtains solid phase I and filtrate I, wherein, calcium constituent in neutralizing agent I in molar ratio: P in phosphoric acid defluorination
2o
5=0.4～2:1;
Wherein, described neutralizing agent I is at least one in calcium oxide, calcium carbonate and calcium hydroxide;
(b) two sections of neutralizations: get neutralizing agent II and filtrate I is carried out neutralization reaction, until reaction system pH=4～5, react complete, solid-liquid separation, obtains solid phase II and filtrate II, and solid phase II and solid phase I are mixed after drying and obtained feed-grade calcium phosphate salt, filtrate II is after crystallization, solid-liquid separation, obtains solid phase III, and solid phase III is potassium primary phosphate after drying;
Wherein, described neutralizing agent II is at least one in potassium hydroxide, salt of wormwood and saleratus.
In order to react fully, be conducive to stir, do not produce parcel phenomenon, described in preferred steps (a), neutralizing agent I can be substituted by milk of lime; More preferably the preparation method of milk of lime is as follows: water in molar ratio: unslaked lime=1.6～12:1 water intaking and unslaked lime, mix and obtain milk of lime.
Further, preferred described water: unslaked lime=6.5～10:1 in molar ratio.
In order to guarantee reaction mass, cost-saving, neutralization reaction in step (a), preferable reaction temperature T
1=40～100 ℃, preferred reaction time t
1=0.5～2h.More preferably described temperature of reaction T
1=70～80 ℃; More preferably described reaction times t
1=1h.
Further, phosphoric acid defluorination P described in preferred steps (a)
2o
5concentration is 20～55wt%, preferably phosphoric acid defluorination P
2o
5concentration is 42～46wt%.
In order to guarantee that the fluorine content in product does not exceed standard, P in mass ratio in phosphoric acid defluorination in preferred steps (a)
2o
5the ratio of/F is greater than 250; Preferably P in mass ratio in phosphoric acid defluorination
2o
5/ F=350～500.
In order not introduce new impurity, guarantee quality product, in preferred steps (a), the purity of neutralizing agent I is greater than 95wt%.
Further, calcium constituent in neutralizing agent I in molar ratio in preferred steps (a): P in phosphoric acid defluorination
2o
5=0.8～1.2:1.
In order to make reaction carry out more thoroughly, described in preferred steps (b), pH is 4.4～4.7.
In order to guarantee reaction mass, cost-saving, neutralization reaction described in step (b), preferable reaction temperature T
2≤ 100 ℃, preferred reaction time t
2=0.5～2h, more preferably described temperature of reaction T
2=80～95 ℃; More preferably described reaction times t
2=1～1.5h.
In order to remove the purity of the impurity raising potassium primary phosphate in potassium primary phosphate, after concentrating described in preferred steps (b), adopt crystallisation by cooling or spraying dry, the temperature of crystallisation by cooling is 20～55 ℃, more preferably the temperature of crystallisation by cooling is 25～35 ℃.
The reaction equation of the method for defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt of the present invention and potassium primary phosphate is as follows:
Ca(OH)
2+2H
3PO
4=Ca(H
2PO
4)
2+2H
2O
Ca(H
2PO
4)
2+Ca(OH)
2+2H
2O=2CaHPO
4·2H
2O
H
3PO
4+KOH=KH
2PO
4+H
2O
The present invention has following beneficial effect:
1, compared with traditional wet process acid secondary calcium phosphate processed, a step neutralization get final product to calcium hydrophosphate fodder, centre does not produce thick fertilizer, this has improved the utilization ratio of phosphorus greatly, has saved production cost.
2, neutralizing agent II solid directly joins reaction in phosphoric acid (filtrate), adds compared with potassium hydroxide solution with traditional, has reduced evaporation of water amount, at T
2after under≤100 ℃ of conditions, reaction finishes, the concentration of potassium dihydrogen phosphate is very high, directly crystallisation by cooling, and this has saved the step of evaporation concentration, and the operational path of simplification, has saved the energy, has reduced production cost.
3, phosphoric acid by wet process replaces thermal phosphoric acid to produce calcium phosphate salt and potassium primary phosphate, has reduced production cost.The strict add-on of controlling calcium constituent, tool has guaranteed the quality of secondary calcium phosphate, has also reduced the impact of impurity on potassium primary phosphate, has improved the quality of potassium primary phosphate.
Embodiment
Technical problem to be solved by this invention is to provide a kind of method of defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium primary phosphate.
The method of defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt of the present invention and potassium primary phosphate, comprises the steps:
(a) one section of neutralization: get neutralizing agent I and phosphoric acid defluorination and carry out neutralization reaction, react complete, solid-liquid separation, obtains solid phase I and filtrate I, wherein, calcium constituent in neutralizing agent I in molar ratio: P in phosphoric acid defluorination
2o
5=0.4～2:1;
Wherein, described neutralizing agent I is at least one in calcium oxide, calcium carbonate and calcium hydroxide;
(b) two sections of neutralizations: get neutralizing agent II and filtrate I is carried out neutralization reaction, until reaction system pH=4～5, react complete, solid-liquid separation, obtains solid phase II and filtrate II, and solid phase II and solid phase I are mixed after drying and obtained feed-grade calcium phosphate salt, filtrate II is after crystallization, solid-liquid separation, obtains solid phase III, and solid phase III is potassium primary phosphate after drying;
Wherein, described neutralizing agent II is at least one in potassium hydroxide, salt of wormwood and saleratus.
In order to react fully, be conducive to stir, do not produce parcel phenomenon, described in preferred steps (a), neutralizing agent I can be substituted by milk of lime; More preferably the preparation method of milk of lime is as follows: water in molar ratio: unslaked lime=1.6～12:1 water intaking and unslaked lime, mix and obtain milk of lime.
Further, preferred described water: unslaked lime=6.5～10:1 in molar ratio.
In order to guarantee reaction mass, cost-saving, neutralization reaction in step (a), preferable reaction temperature T
1=40～100 ℃, preferred reaction time t
1=0.5～2h.More preferably described temperature of reaction T
1=70～80 ℃; More preferably described reaction times t
1=1h.
Further, phosphoric acid defluorination P described in preferred steps (a)
2o
5concentration is 20～55wt%, preferably phosphoric acid defluorination P
2o
5concentration is 42～46wt%.
In order to guarantee that the fluorine content in product does not exceed standard, P in mass ratio in phosphoric acid defluorination in preferred steps (a)
2o
5the ratio of/F is greater than 250; Preferably P in mass ratio in phosphoric acid defluorination
2o
5/ F=350～500.
In order not introduce new impurity, guarantee quality product, in preferred steps (a), the purity of neutralizing agent I is greater than 95wt%.
Further, calcium constituent in neutralizing agent I in molar ratio in preferred steps (a): P in phosphoric acid defluorination
2o
5=0.8～1.2:1.
In order to make reaction carry out more thoroughly, described in preferred steps (b), pH is 4.4～4.7.
In order to guarantee reaction mass, cost-saving, neutralization reaction described in step (b), preferable reaction temperature T
2≤ 100 ℃, preferred reaction time t
2=0.5～2h, more preferably described temperature of reaction T
2=80～95 ℃; More preferably described reaction times t
2=1～1.5h.
In order to remove the purity of the impurity raising potassium primary phosphate in potassium primary phosphate, after concentrating described in preferred steps (b), adopt crystallisation by cooling or spraying dry, the temperature of crystallisation by cooling is 20～55 ℃, more preferably the temperature of crystallisation by cooling is 25～35 ℃.
The reaction equation of the method for defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt of the present invention and potassium primary phosphate is as follows:
Ca(OH)
2+2H
3PO
4=Ca(H
2PO
4)
2+2H
2O
Ca(H
2PO
4)
2+Ca(OH)
2+2H
2O=2CaHPO
4·2H
2O
H
3PO
4+KOH=KH
2PO
4+H
2O
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
The method of embodiment 1 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium primary phosphate
(a) get the milk of lime and the phosphoric acid defluorination that prepare, phosphoric acid defluorination P
2o
5concentration is 20wt%, by P in calcium constituent in milk of lime and phosphoric acid defluorination
2o
5molar ratio be that 0.4:1 joins in neutralization reaction groove I slowly, be under the condition of 40 ℃ in temperature of reaction, stirring reaction 0.5h, react complete, reaction slurry is after solid-liquid separation, and (filter residue can wash three times, the washing lotion of washing can proceed in neutralization reaction groove II together with filtrate for the first time), obtain solid phase I and filtrate I, solid phase I is calcium phosphate salt after drying, and filtrate I proceeds in neutralization reaction groove II;
Wherein, the preparation method of milk of lime is as follows: water in molar ratio: unslaked lime=2:1 water intaking and unslaked lime, mix and obtain milk of lime;
(b) second step neutralisation potassium dihydrogen phosphate making: the filtrate I of getting in potassium hydroxide and neutralization reaction groove II is carried out neutralization reaction.Under the condition of temperature 50 C, stirring reaction 2h, now reaction system pH=4, after reaction finishes, carries out solid-liquid separation while hot, obtains solid phase II and filtrate II.After the oven dry of solid phase II, carry out fully mixing to obtain feed-grade calcium phosphate salt with the solid phase I after oven dry, filtrate II is after concentrated, and 20 ℃ of crystallisation by cooling, carry out, after liquid-solid separation, obtaining solid phase III, and solid phase III is highly purified potassium primary phosphate after drying.
In embodiment 1, partial data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P
2o
521.92%, F0.098%, Fe
2o
30.57%, Al
2o
30.45%, MgO0.63%, SO
31.32%;
The each component of calcium phosphate salt is as follows, is all weight percentage: P
2o
548.79%, Ca15.21%, F0.16%, SO
32.32%;
The each component of potassium primary phosphate is as follows, is all weight percentage: KH
2pO
498.42%, K28.11%, F0.008%.
From GB/T22549-2008, mixed phosphate calcium salt has reached the standard of calcium hydrophosphate fodder, by whole technique is carried out after material balance, and P in phosphoric acid defluorination
2o
5yield is 97.1%.
The method of embodiment 2 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium primary phosphate
(a) get the milk of lime and the phosphoric acid defluorination that prepare, phosphoric acid defluorination P
2o
5concentration is 55wt%, by P in calcium constituent in milk of lime and phosphoric acid defluorination
2o
5molar ratio be that 2:1 joins in neutralization reaction groove I slowly, be under the condition of 100 ℃ in temperature of reaction, stirring reaction 2h, react complete, reaction paste is after solid-liquid separation, and (filter residue can wash three times, the washing lotion of washing can proceed in neutralizing well II together with filtrate for the first time), obtaining solid phase I and filtrate I, is calcium phosphate salt after solid phase I drying, and filtrate I proceeds in neutralizing well II;
Wherein, the preparation method of milk of lime is as follows: water in molar ratio: milk of lime=12:1 water intaking and unslaked lime, mix and obtain milk of lime;
(b) second step neutralisation potassium dihydrogen phosphate making: the filtrate I of getting in potassium hydroxide and neutralization reaction groove II is carried out neutralization reaction.Under the condition of temperature 50 C, stirring reaction 0.5h, now reaction system pH=5, after reaction finishes, carries out solid-liquid separation while hot, obtains solid phase II and filtrate II.After the oven dry of solid phase II, carry out fully mixing to obtain feed-grade calcium phosphate salt with the solid phase I after oven dry, filtrate II is after concentrated, and 55 ℃ of crystallisation by cooling, carry out, after liquid-solid separation, obtaining solid phase III, and solid phase III is highly purified potassium primary phosphate after drying.
In embodiment 2, partial data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P
2o
535.01%, F0.089%, Fe
2o
30.51%, Al
2o
30.57%, MgO0.64%, SO
31.35%;
The each component of calcium phosphate salt is as follows, is all weight percentage: P
2o
549.12%, Ca15.51%, F0.18%, SO
32.40%;
The each component of potassium primary phosphate is as follows, is all weight percentage: KH
2pO
498.69%, K28.36%, F0.012%;
From GB/T22549-2008, mixed phosphate calcium salt has reached the standard of calcium hydrophosphate fodder, by whole technique is carried out after material balance, and P in phosphoric acid defluorination
2o
5yield is 97.28%.
The method of embodiment 3 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium primary phosphate
(a) get the milk of lime and the phosphoric acid defluorination that prepare, phosphoric acid defluorination P
2o
5concentration is 42wt%, by P in calcium constituent in milk of lime and phosphoric acid defluorination
2o
5molar ratio be that 0.8:1 joins in neutralization reaction groove I slowly, be under the condition of 80 ℃ in temperature of reaction, stirring reaction 1h, react complete, reaction slurry is (filter residue can wash three times, and the washing lotion of washing can proceed in neutralization reaction groove II together with filtrate for the first time) after solid-liquid separation, obtains solid phase I and filtrate I, solid phase I is calcium phosphate salt after drying, and filtrate I proceeds in neutralization reaction groove II;
Wherein, the preparation method of milk of lime is as follows: water in molar ratio: unslaked lime=6.5:1 water intaking and unslaked lime, mix and obtain milk of lime;
(b) second step neutralisation potassium dihydrogen phosphate making: the filtrate I of getting in potassium hydroxide and neutralization reaction groove II is carried out neutralization reaction.Under the condition of 80 ℃ of temperature, stirring reaction 1.5h, now reaction system pH=4.4, after reaction finishes, carries out solid-liquid separation while hot, obtains solid phase II and filtrate II.After the oven dry of solid phase II, carry out fully mixing to obtain feed-grade calcium phosphate salt with the solid phase I after oven dry, filtrate II is after concentrated, and 35 ℃ of crystallisation by cooling, carry out, after liquid-solid separation, obtaining solid phase III, and solid phase III is highly purified potassium primary phosphate after drying.
In embodiment 3, partial data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P
2o
541.32%, F0.11%, Fe
2o
30.58%, Al
2o
30.63%, MgO0.72%, SO
31.45%;
The each component of calcium phosphate salt is as follows, is all weight percentage: P
2o
549.35%, Ca15.61%, F0.17%, SO
32.30%;
The each component of potassium primary phosphate is as follows, is all weight percentage: KH
2pO
499.23%, K28.22%, F0.01%;
From GB/T22549-2008, mixed phosphate calcium salt has reached the standard of calcium hydrophosphate fodder, by whole technique is carried out after material balance, and P
2o
5yield is 97.40%.
The method of embodiment 4 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium primary phosphate
(a) get the milk of lime and the phosphoric acid defluorination that prepare, phosphoric acid defluorination P
2o
5concentration is 46wt%, by P in calcium constituent in milk of lime and phosphoric acid defluorination
2o
5molar ratio be that 1.2:1 joins in neutralization reaction groove I slowly, be under the condition of 70 ℃ in temperature of reaction, stirring reaction 1h, react complete, reaction slurry is (filter residue can wash three times, and the washing lotion of washing can proceed in neutralization reaction groove II together with filtrate for the first time) after solid-liquid separation, obtains solid phase I and filtrate I, solid phase I is calcium phosphate salt after drying, and filtrate I proceeds in neutralization reaction groove II;
Wherein, the preparation method of milk of lime is as follows: water in molar ratio: unslaked lime=10:1 water intaking and unslaked lime, mix and obtain milk of lime;
(b) second step neutralisation potassium dihydrogen phosphate making: the filtrate I of getting in potassium hydroxide and neutralization reaction groove II is carried out neutralization reaction.Under the condition of 95 ℃ of temperature, stirring reaction 1h, now reaction system pH=4.7, after reaction finishes, carries out solid-liquid separation while hot, obtains solid phase II and filtrate II.After the oven dry of solid phase II, carry out fully mixing to obtain feed-grade calcium phosphate salt with the solid phase I after oven dry, filtrate II is after concentrated, and 20 ℃ of crystallisation by cooling, carry out, after liquid-solid separation, obtaining solid phase III, and solid phase III is highly purified potassium primary phosphate after drying.
In embodiment 4, partial data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P
2o
545.76%, F0.093%, Fe
2o
30.63%, Al
2o
30.67%, MgO0.68%, SO
31.38%;
The each component of calcium phosphate salt is as follows, is all weight percentage: P
2o
549.68%, Ca15.71%, F0.16%, SO
32.34%;
The each component of potassium primary phosphate is as follows, is all weight percentage: KH
2pO
499.18%, K28.32%, F0.0081%;
From GB/T22549-2008, mixing filter residue has reached the standard of calcium hydrophosphate fodder, by whole technique is carried out after material balance, and P in phosphoric acid defluorination
2o
5yield is 97.59%.
The method of embodiment 5 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium primary phosphate
(a) get calcium hydroxide and phosphoric acid defluorination, phosphoric acid defluorination P
2o
5concentration is 35wt%, by P in calcium constituent in calcium hydroxide and phosphoric acid defluorination
2o
5molar ratio be that 1:1 joins in neutralization reaction groove I slowly, be under the condition of 75 ℃ in temperature of reaction, stirring reaction 1h, react complete, reaction slurry is (filter residue can wash three times, and the washing lotion of washing can proceed in neutralization reaction groove II together with filtrate for the first time) after solid-liquid separation, obtains solid phase I and filtrate I, solid phase I is calcium phosphate salt after drying, and filtrate I proceeds in neutralization reaction groove II;
(b) second step neutralisation potassium dihydrogen phosphate making: the filtrate I of getting in salt of wormwood and neutralization reaction groove II is carried out neutralization reaction.Under the condition of 85 ℃ of temperature, stirring reaction 1.5h, now reaction system
ph=4.8, after reaction finishes, carries out solid-liquid separation while hot, obtains solid phase II and filtrate II.After the oven dry of solid phase II, carry out fully mixing to obtain feed-grade calcium phosphate salt with the solid phase I after oven dry, filtrate II is after concentrated, and 45 ℃ of crystallisation by cooling, carry out, after liquid-solid separation, obtaining solid phase III, and solid phase III is highly purified potassium primary phosphate after drying.
In embodiment 5, partial data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P
2o
546.76%, F0.089%, Fe
2o
30.63%, Al
2o
30.61%, MgO0.7%, SO
31.35%;
The each component of calcium phosphate salt is as follows, is all weight percentage: P
2o
549.89%, Ca15.84%, F0.13%, SO
32.36%;
The each component of potassium primary phosphate is as follows, is all weight percentage: KH
2pO
499.58%, K28.4%, F0.0054%;
From GB/T22549-2008, mixing filter residue has reached the standard of calcium hydrophosphate fodder, by whole technique is carried out after material balance, and P in phosphoric acid defluorination
2o
5yield is 98.59%.
The method of embodiment 6 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium primary phosphate
(a) get calcium carbonate and phosphoric acid defluorination, phosphoric acid defluorination P
2o
5concentration is 52wt%, by P in calcium constituent in calcium carbonate and phosphoric acid defluorination
2o
5molar ratio be that 1.6:1 joins in neutralization reaction groove I slowly, be under the condition of 70 ℃ in temperature of reaction, stirring reaction 1.5h, react complete, reaction slurry is (filter residue can wash three times, and the washing lotion of washing can proceed in neutralization reaction groove II together with filtrate for the first time) after solid-liquid separation, obtains solid phase I and filtrate I, solid phase I is calcium phosphate salt after drying, and filtrate I proceeds in neutralization reaction groove II;
(b) second step neutralisation potassium dihydrogen phosphate making: the filtrate I of getting in salt of wormwood and neutralization reaction groove II is carried out neutralization reaction.Under the condition of 100 ℃ of temperature, stirring reaction 1.5h, now reaction system pH=4.8, after reaction finishes, carries out solid-liquid separation while hot, obtains solid phase II and filtrate II.After the oven dry of solid phase II, carry out fully mixing to obtain feed-grade calcium phosphate salt with the solid phase I after oven dry, filtrate II is after concentrated, and 45 ℃ of crystallisation by cooling, carry out, after liquid-solid separation, obtaining solid phase III, and solid phase III is highly purified potassium primary phosphate after drying.
In embodiment 6, partial data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P
2o
546.76%, F0.095%, Fe
2o
30.62%, Al
2o
30.63%, MgO0.64%, SO
31.35%;
The each component of calcium phosphate salt is as follows, is all weight percentage: P
2o
549.71%, Ca15.82%, F0.14%, SO
32.3%;
The each component of potassium primary phosphate is as follows, is all weight percentage: KH
2pO
499.38%, K28.36%, F0.0079%;
From GB/T22549-2008, mixing filter residue has reached the standard of calcium hydrophosphate fodder, by whole technique is carried out after material balance, and P in phosphoric acid defluorination
2o
5yield is 97.69%.
The method of embodiment 7 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium primary phosphate
(a) get calcium oxide and phosphoric acid defluorination, phosphoric acid defluorination P
2o
5concentration is 28wt%, by P in calcium constituent in calcium oxide and phosphoric acid defluorination
2o
5molar ratio be that 1.6:1 joins in neutralization reaction groove I slowly, be under the condition of 70 ℃ in temperature of reaction, stirring reaction 1.5h, react complete, reaction slurry is (filter residue can wash three times, and the washing lotion of washing can proceed in neutralization reaction groove II together with filtrate for the first time) after solid-liquid separation, obtains solid phase I and filtrate I, solid phase I is calcium phosphate salt after drying, and filtrate I proceeds in neutralization reaction groove II;
Wherein, the preparation method of milk of lime is as follows: water in molar ratio: unslaked lime=12:1 water intaking and unslaked lime, mix and obtain milk of lime;
(b) second step neutralisation potassium dihydrogen phosphate making: the filtrate I of getting in saleratus and neutralization reaction groove II is carried out neutralization reaction.Under the condition of 100 ℃ of temperature, stirring reaction 1.5h, now reaction system pH=4.8, after reaction finishes, carries out solid-liquid separation while hot, obtains solid phase II and filtrate II.After the oven dry of solid phase II, carry out fully mixing to obtain feed-grade calcium phosphate salt with the solid phase I after oven dry, filtrate II is after concentrated, and 45 ℃ of crystallisation by cooling, carry out, after liquid-solid separation, obtaining solid phase III, and solid phase III is highly purified potassium primary phosphate after drying.
In embodiment 7, partial data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P
2o
546.51%, F0.09%, Fe
2o
30.65%, Al
2o
30.61%, MgO0.64%, SO
31.32%;
The each component of calcium phosphate salt is as follows, is all weight percentage: P
2o
549.72%, Ca15.68%, F0.17%, SO
32.3%;
The each component of potassium primary phosphate is as follows, is all weight percentage: KH
2pO
499.23%, K28.31%, F0.0082%;
From GB/T22549-2008, mixing filter residue has reached the standard of calcium hydrophosphate fodder, by whole technique is carried out after material balance, and P in phosphoric acid defluorination
2o
5yield is 97.65%.
Claims (10)
1. the method for defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium primary phosphate, is characterized in that: comprise the steps:
(a) one section of neutralization: get neutralizing agent I and phosphoric acid defluorination and carry out neutralization reaction, react complete, solid-liquid separation, obtains solid phase I and filtrate I, wherein, calcium constituent in neutralizing agent I in molar ratio: P in phosphoric acid defluorination
2o
5=0.4～2:1;
Wherein, described neutralizing agent I is at least one in calcium oxide, calcium carbonate and calcium hydroxide;
(b) two sections of neutralizations: get neutralizing agent II and filtrate I is carried out neutralization reaction, until reaction system pH=4～5, react complete, solid-liquid separation, obtains solid phase II and filtrate II, and solid phase II and solid phase I are mixed after drying and obtained feed-grade calcium phosphate salt, filtrate II is after crystallization, solid-liquid separation, obtains solid phase III, and solid phase III is potassium primary phosphate after drying;
Wherein, described neutralizing agent II is at least one in potassium hydroxide, salt of wormwood and saleratus.
2. the method for defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 1 and potassium primary phosphate, is characterized in that: described in step (a), neutralizing agent I can be substituted by milk of lime; Preferably the preparation method of milk of lime is as follows: water in molar ratio: unslaked lime=1.6～12:1 water intaking and unslaked lime, mix and obtain milk of lime; More preferably described water: unslaked lime=6.5～10:1 in molar ratio.
3. the method for defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 1 and 2 and potassium primary phosphate, is characterized in that: neutralization reaction in step (a), temperature of reaction T
1=40～100 ℃, reaction times t
1=0.5～2h.
4. the method for defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 3 and potassium primary phosphate, is characterized in that: described temperature of reaction T
1=70～80 ℃; Described reaction times t
1=1h.
5. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in claim 1～4 any one and the method for potassium primary phosphate, it is characterized in that: phosphoric acid defluorination P described in step (a)
2o
5concentration is 20～55wt%, preferably phosphoric acid defluorination P
2o
5concentration is 42～46wt%.
6. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in claim 1～5 any one and the method for potassium primary phosphate, it is characterized in that: P in mass ratio in phosphoric acid defluorination in step (a)
2o
5the ratio of/F is greater than 250; Preferably P in mass ratio in phosphoric acid defluorination
2o
5/ F=350～500.
7. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in claim 1～6 any one and the method for potassium primary phosphate, it is characterized in that: in step (a), the purity of neutralizing agent I is greater than 95wt%.
8. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in claim 1～7 any one and the method for potassium primary phosphate, it is characterized in that: calcium constituent in neutralizing agent I in molar ratio in step (a): P in phosphoric acid defluorination
2o
5=0.8～1.2:1.
9. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in claim 1～8 any one and the method for potassium primary phosphate, it is characterized in that: neutralization reaction described in step (b), temperature of reaction T
2≤ 100 ℃, reaction times t
2=0.5～2h, preferred described temperature of reaction T
2=80～95 ℃; Preferred described reaction times t
2=1～1.5h; Described in step (b), pH is 4.4～4.7.
10. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in claim 1～9 any one and the method for potassium primary phosphate, it is characterized in that: after concentrated described in step (b), adopt crystallisation by cooling or spraying dry, the temperature of crystallisation by cooling is 20～55 ℃, and preferably the temperature of crystallisation by cooling is 25～35 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417516A (en) * | 2015-12-18 | 2016-03-23 | 瓮福（集团）有限责任公司 | Production method for feed-grade monocalcium phosphate |
| CN108726498A (en) * | 2018-06-27 | 2018-11-02 | 湖北吉星化工集团有限责任公司 | A kind of toothpaste grade dicalcium phosphate dihydrate mother liquor recycling method |
| CN110395704A (en) * | 2018-04-24 | 2019-11-01 | 四川大学 | The method of phosphoric acid by wet process coproduction PHOSPHORIC ACID TECH.GRADE potassium dihydrogen and calcium hydrophosphate fodder |
| CN113955730A (en) * | 2021-12-07 | 2022-01-21 | 安徽科宝生物工程有限公司 | Calcium hydrogen phosphate and production process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033261A (en) * | 1987-11-25 | 1989-06-07 | 沈阳化工综合利用研究所 | A kind of method of producing ammonium phosphate |
| CN1108055A (en) * | 1994-12-30 | 1995-09-13 | 吴隽 | Feed-stuff grade calcium hydrophosphate prodn. defluorination method circulating |
| CN1174812A (en) * | 1996-08-26 | 1998-03-04 | 四川联合大学 | Industrial monoammonium phosphate and productive method for industrial monoammunium phosphate and calcium hydrogen phosphate fodder |
| CN1463916A (en) * | 2002-06-28 | 2003-12-31 | 李光明 | Process for production of fodder level di-calcium phosphate |
-
2014
- 2014-04-04 CN CN201410134882.0A patent/CN103864043B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033261A (en) * | 1987-11-25 | 1989-06-07 | 沈阳化工综合利用研究所 | A kind of method of producing ammonium phosphate |
| CN1108055A (en) * | 1994-12-30 | 1995-09-13 | 吴隽 | Feed-stuff grade calcium hydrophosphate prodn. defluorination method circulating |
| CN1174812A (en) * | 1996-08-26 | 1998-03-04 | 四川联合大学 | Industrial monoammonium phosphate and productive method for industrial monoammunium phosphate and calcium hydrogen phosphate fodder |
| CN1463916A (en) * | 2002-06-28 | 2003-12-31 | 李光明 | Process for production of fodder level di-calcium phosphate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417516A (en) * | 2015-12-18 | 2016-03-23 | 瓮福（集团）有限责任公司 | Production method for feed-grade monocalcium phosphate |
| CN110395704A (en) * | 2018-04-24 | 2019-11-01 | 四川大学 | The method of phosphoric acid by wet process coproduction PHOSPHORIC ACID TECH.GRADE potassium dihydrogen and calcium hydrophosphate fodder |
| CN110395704B (en) * | 2018-04-24 | 2020-12-22 | 四川大学 | Method for co-producing industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid |
| CN108726498A (en) * | 2018-06-27 | 2018-11-02 | 湖北吉星化工集团有限责任公司 | A kind of toothpaste grade dicalcium phosphate dihydrate mother liquor recycling method |
| CN113955730A (en) * | 2021-12-07 | 2022-01-21 | 安徽科宝生物工程有限公司 | Calcium hydrogen phosphate and production process thereof |
| CN113955730B (en) * | 2021-12-07 | 2023-02-21 | 安徽科宝生物工程有限公司 | Calcium hydrogen phosphate and production process thereof |
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| CN103864043B (en) | 2016-09-28 |
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