CN103818891A - Method for preparing fine sodium phosphates from fertilizer-grade dicalcium phosphate - Google Patents

Method for preparing fine sodium phosphates from fertilizer-grade dicalcium phosphate Download PDF

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CN103818891A
CN103818891A CN201410071102.2A CN201410071102A CN103818891A CN 103818891 A CN103818891 A CN 103818891A CN 201410071102 A CN201410071102 A CN 201410071102A CN 103818891 A CN103818891 A CN 103818891A
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reaction
sodium
solid
sent
fertilizer
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CN103818891B (en
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曾润国
周桂民
冯发均
魏家贵
周永祥
刘泽祥
韦文相
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Kunming Chuanjinnuo Chemical Shares Co Ltd
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Kunming Chuanjinnuo Chemical Shares Co Ltd
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Abstract

The invention relates to a method for preparing fine sodium phosphates from fertilizer-grade dicalcium phosphate. The method comprises the following steps: pulping, metathesis reaction, filtering, desulphurization, neutralization, filtering, refining, concentration, crystallization and preparation of sodium phosphates. The method has the following advantages: 1, as the environment for a replacement reaction between fertilizer-grade dicalcium phosphate and sodium bisulfate is acidic, impurities of fertilizer-grade dicalcium phosphate, such as iron, aluminium, fluorine and the like, do not participate in the reaction but are left in a solid phase so as to lay a foundation for the preparation of high-quality sodium phosphates; 2, by reference to a conventional phosphoric acid extraction technology from dehydrate, uniform and bulky gypsum can be generated during filtration and washing processes in the reaction such that yield of phosphorus pentoxide is high; and 3, as fertilizer-grade dicalcium phosphate is selected as a desulfurizer during the desulphurization process, desulphurization cost is reduced.

Description

A kind of method of producing meticulous sodium phosphate salt with fertilizer grade secondary calcium phosphate
Technical field
The invention belongs to fine phosphate production technical field, be specifically related to a kind of method of utilizing fertilizer grade secondary calcium phosphate preparing phosphoric acid sodium salt.
Background technology
Sodium phosphate salt finished product price is higher in the market, and various sodium phosphate salts are except thermal phosphoric acid neutralisation product, and that the product of other side manufacture has is impure more, class is on the low side; Some raisings quality, but aborning raw material and heat exhaustion large, thereby increase cost.The cost of thermal phosphoric acid neutralisation is higher, thereby has limited its use.
Summary of the invention
For above situation, the present invention has developed and a kind ofly can produce the sodium phosphate salt new process of production that detrimental impurity is lower, cost is low, quality is high, can create the novel technique of good economic benefits.
Beneficial effect of the present invention and advantage are mainly reflected in following several respects:
1, want by-product fertilizer grade secondary calcium phosphate in feed-grade calcium phosphate salt production process, if being reacted with sodium sulfate, manufactures in sulfuric acid sodium pyrosulfate, carry out replacement(metathesis)reaction preparing phosphoric acid one sodium (can continue with in sodium carbonate, sodium hydroxide and preparing phosphoric acid disodium, tertiary sodium phosphate) with fertilizer grade secondary calcium phosphate again, so just the production of the production of feed-grade calcium phosphate salt and sodium phosphate salt can be combined, can solve thus because feed-grade calcium phosphate salt productive profit space is little, can only raise by pursuit/fertilizer recently improves a difficult problem for output and economic benefit.
2, by effective utilization that fertilizer grade secondary calcium phosphate is worth, the impact of the low feed calcium salt yield of consideration that can be not too much in the time producing the feed-grade calcium phosphate salt of low fluorine or ultralow fluorine on economic benefit;
3, for the fertilizer grade secondary calcium phosphate take high quality, low value provides a kind of new processing method as raw material production sodium phosphate salt.The fertilizer grade secondary calcium phosphate that feed-grade calcium phosphate salt is produced in producing due to the production of the sodium phosphate salt of high added value has become a main product, rather than low value-added byproduct in the past, has created a large amount of profits.
The object of the invention is to overcome prior art deficiency, a kind of method that can use fertilizer grade secondary calcium phosphate to produce meticulous sodium phosphate salt is provided.The every reaction equation the present invention relates to is as follows:
Na 2SO 4+H 2SO 4=NaHSO 4
NaHSO 4+CaHPO 4.2H 2O?+2H 2O?=CaSO 4.2H 2O↓+?NaH 2PO 4.2H 2O
Implementation step of the present invention comprises: slurrying-replacement(metathesis)reaction-filtration-desulfurization-neutralization-filtration-refining-concentrated-crystallization-sodium phosphate salt, specifically comprises following operation:
A, fertilizer grade secondary calcium phosphate is added to clear water make slip, its solid content is 15-55%;
B, sodium sulfate react 0.5-2 hours by equimolar amount with sulfuric acid in reactive tank, extracting sulfuric acid hydrogen sodium;
C, the fertilizer grade secondary calcium phosphate after slurrying and sodium pyrosulfate are added to (equimolar amount) according to phosphorus: sodium=1:1, stirring reaction 1.5-3 hours, temperature of reaction is controlled at 65-85 ℃;
D, the slip after completely reacted is carried out to solid-liquid separation, solid is sent to slag field and banks up, and clear liquid is sent to lower operation processing;
After E, filtration, gained clear liquid adds fertilizer grade secondary calcium phosphate to deviate from unnecessary SO again 3(by SO in filtrate 3content equimolar amount adds fertilizer grade secondary calcium phosphate), stirring reaction 1.5---3 hours, after sedimentation, thick slurry was sent to the reaction of C operation, and clear liquid is sent to lower operation;
Clear liquid after F, clarification adds sodium carbonate solution again, is neutralized to pH value 4.2-4.6, reaction makes monosodium phosphate solution for 0.5-2 hours;
G, neutralizer after completely reacted are sent to plate and frame filter and carry out solid-liquid separation;
The clear liquid of H, solid-liquid separation is concentrated into proportion 1.22-1.26 g/ml;
I, by this concentrated solution crystallisation by cooling to 60-70 ℃, through centrifugation, solid is sent to lower operation dries;
J, the mother liquor after centrifugation is returned respectively toward F, I workshop section and continues reaction depending on its impurity situation
K, solid after centrifugal, again through fluidised bed drying, can obtain NaH 2pO 4.2H 2o finished product.
The invention has the advantages that:
1, because the environment of fertilizer grade secondary calcium phosphate and sodium pyrosulfate generation replacement(metathesis)reaction is acid, therefore the magazine of fertilizer grade secondary calcium phosphate will all not participate in reaction and stay in solid phase as iron, aluminium, fluorine etc. in the process of this reaction, thereby lay a good foundation for the sodium phosphate salt of producing high-quality;
2, this reaction simulation is with reference to conventional two water thing phosphoric acid extraction techniques, in the time of filtration washing because bearing evenly thick gypsum, therefore Vanadium Pentoxide in FLAKES yield of the present invention is high;
3, the present invention selects and adds fertilizer grade secondary calcium phosphate as sweetening agent at desulfurization process, has reduced desulphurization cost.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
embodiment 1
Take 1 ton of wet fertilizer grade secondary calcium phosphate as raw material, its P 2o 5content is 15.25%, CaO content 14.2%, the sulfuric acid with 98% and Na 2sO 4.10H 2o reaction extracting sulfuric acid hydrogen sodium, test by the inventive method:
A, the fertilizer grade secondary calcium phosphate that will wet add clear water slurrying, and its solid content is 31.2%, proportion 1.29g/ml;
B, with 429kg Na 2sO 4.10H 2o(is formulated as the solution of 1.35 g/ml) in reactive tank, react 0.5 hour extracting sulfuric acid hydrogen sodium by equimolar amount with 127kg, 98% sulfuric acid;
C, the fertilizer grade secondary calcium phosphate after slurrying and sodium pyrosulfate are added to (equimolar amount) according to phosphorus and sodium 1:1, stirring reaction 2 hours, temperature of reaction is controlled at 75 ℃;
D, the material after completely reacted will be sent to solid-liquid separation on band filter, solid is sent to slag field and piles up, and clear liquid is sent to lower operation processing;
After E, filtration, gained clear liquid adds 100kg fertilizer grade secondary calcium phosphate to deviate from unnecessary SO again 3(by SO in filtrate 3content equimolar amount adds fertilizer grade secondary calcium phosphate), stirring reaction 2 hours, after clarification, thick slurry is sent to the reaction of B operation, and clear liquid is sent to lower operation;
Clear liquid after F, clarification adds sodium carbonate solution to be neutralized to pH value 4.40 again, amounts to the sodium carbonate solution 60.2kg that adds 30%, reacts and within 30 minutes, makes monosodium phosphate solution;
G, neutralizer after completely reacted are sent to plate and frame filter and carry out solid-liquid separation;
H, the clear liquid of solid-liquid separation is concentrated into proportion 1.24g/ml;
I, by this concentrated solution crystallisation by cooling to 65 ℃, through centrifugation, solid is sent to lower operation dries;
J, the mother liquor after centrifugation is returned toward I workshop section and continues reaction;
K, solid after centrifugal, again through fluidised bed drying, obtain 245.2kgNaH 2pO 4.2H 2o finished product, its phosphorus yield is 65.3%.
This NaH by analysis 2pO 4.2H 2o reaches acceptable end product standard completely.
280kg AMSP can be obtained by one ton of wet fertilizer grade monocalcium phosphate of above-mentioned technique, 510kg fertilizer grade monocalcium phosphate can be obtained by directly drying in the past fertilizer grade monocalcium phosphate.
embodiment 2
Take 1 ton of wet fertilizer grade secondary calcium phosphate as raw material, its P 2o 5content is 14.78%, CaO content 13.9%, the sulfuric acid with 98% and Na 2sO 4.10H 2o pharmacy response, carries out lab scale by the inventive method:
A, the fertilizer grade secondary calcium phosphate that will wet add clear water slurrying, and its solid content is 33.5%, proportion 1.31g/ml;
B, with 420kg Na 2sO 4.10H 2o(is formulated as the solution of 1.33 g/ml) with 122kg, 98% sulfuric acid be raw material, in reactive tank, react extracting sulfuric acid hydrogen sodium 0.5 hour by equimolar amount;
C, by the fertilizer grade secondary calcium phosphate after slurrying and sodium pyrosulfate according to phosphorus with receive 1:1 and add (equimolar amount), stirring reaction 2 hours, temperature of reaction is at 72 ℃;
D, the material after completely reacted will be sent to solid-liquid separation on band filter, solid is sent to slag field and banks up, and clear liquid is sent to lower operation processing;
After E, filtration, gained clear liquid adds 95kg fertilizer grade secondary calcium phosphate to deviate from unnecessary SO again 3(by SO in filtrate 3content equimolar amount adds fertilizer grade secondary calcium phosphate), stirring reaction 2 hours, after clarification, thick slurry is sent to the reaction of B operation, and clear liquid is sent to lower operation;
Clear liquid after F, clarification adds sodium carbonate solution to be neutralized to pH value 4.6 again, amounts to the sodium carbonate solution 65.4kg that adds 30%, reacts and within 30 minutes, makes monosodium phosphate;
G, neutralizer after completely reacted are sent to plate and frame filter and carry out solid-liquid separation;
H, the clear liquid of solid-liquid separation is concentrated into proportion 1.26g/ml;
I, by this concentrated solution crystallisation by cooling to 68 ℃, through centrifugation, solid is sent to lower operation dries;
J, the mother liquor after centrifugation is returned toward I workshop section and continues reaction;
K, solid after centrifugal, again through fluidised bed drying, obtain 256.4kgNaH 2pO 4.2H 2o finished product, its phosphorus total recovery 70.6%.
This NaH by analysis 2pO 4.2H 2o reaches acceptable end product standard completely.

Claims (1)

1. a method of producing meticulous sodium phosphate salt with fertilizer grade secondary calcium phosphate, is characterized in that, step comprises: slurrying-replacement(metathesis)reaction-filtration-desulfurization-neutralization-filtration-refining-concentrated-crystallization-sodium phosphate salt, specifically comprises following operation:
A, fertilizer grade secondary calcium phosphate is added to clear water make slip, its solid content is 15-55%;
B, sodium sulfate react 0.5-2 hours by equimolar amount with sulfuric acid in reactive tank, extracting sulfuric acid hydrogen sodium;
C, by the fertilizer grade secondary calcium phosphate after slurrying and sodium pyrosulfate according to phosphorus: sodium=1:1 adds, stirring reaction 1.5-3 hours, temperature of reaction is controlled at 65-85 ℃;
D, the slip after completely reacted is carried out to solid-liquid separation, solid is sent to slag field and banks up, and clear liquid is sent to lower operation processing;
After E, filtration, gained clear liquid adds fertilizer grade secondary calcium phosphate to deviate from unnecessary SO again 3, by SO in filtrate 3content equimolar amount adds fertilizer grade secondary calcium phosphate, stirring reaction 1.5-3 hours, and after sedimentation, thick slurry is sent to the reaction of C operation, and clear liquid is sent to lower operation;
Clear liquid after F, clarification adds sodium carbonate solution again, is neutralized to pH value 4.2-4.6, reaction makes monosodium phosphate solution for 0.5-2 hours;
G, neutralizer after completely reacted are sent to plate and frame filter and carry out solid-liquid separation;
The clear liquid of H, solid-liquid separation is concentrated into proportion 1.22-1.26 g/ml;
I, by this concentrated solution crystallisation by cooling to 60-70 ℃, through centrifugation, solid is sent to lower operation dries;
J, the mother liquor after centrifugation is returned respectively toward F, I workshop section and continues reaction depending on its impurity situation
K, solid after centrifugal, again through fluidised bed drying, can obtain NaH 2pO 4.2H 2o finished product.
CN201410071102.2A 2014-02-28 2014-02-28 The method of meticulous sodium phosphate salt produced by a kind of fertilizer grade secondary calcium phosphate Active CN103818891B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104276555A (en) * 2014-09-19 2015-01-14 贵阳中化开磷化肥有限公司 Method for preparing monosodium phosphate and byproduct fertilizer specially used for buckwheat

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1567634A1 (en) * 1966-09-03 1970-09-10 Kloeckner Humboldt Deutz Ag Process for the production of phosphoric acid and / or soluble phosphoric acid salts
US3697246A (en) * 1970-10-16 1972-10-10 Pennzoil United Inc Potassium phosphate manufacture
US3956464A (en) * 1970-10-16 1976-05-11 Pennzoil Company Preparation of phosphates
CN101175691A (en) * 2005-03-31 2008-05-07 卡吉尔公司 Process for producing high purity phosphates
CN101203456A (en) * 2005-05-20 2008-06-18 卡吉尔公司 Processes for producing phosphates
CN103058158A (en) * 2013-02-05 2013-04-24 瓮福（集团）有限责任公司 Method for preparing monopotassium phosphate from fertilizer grade calcium hydrophosphate
CN103058157A (en) * 2013-02-26 2013-04-24 贵州开磷（集团）有限责任公司 Production method of industrial grade diammonium phosphate with wet-process phosphoric acid

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1567634A1 (en) * 1966-09-03 1970-09-10 Kloeckner Humboldt Deutz Ag Process for the production of phosphoric acid and / or soluble phosphoric acid salts
US3697246A (en) * 1970-10-16 1972-10-10 Pennzoil United Inc Potassium phosphate manufacture
US3956464A (en) * 1970-10-16 1976-05-11 Pennzoil Company Preparation of phosphates
CN101175691A (en) * 2005-03-31 2008-05-07 卡吉尔公司 Process for producing high purity phosphates
CN101203456A (en) * 2005-05-20 2008-06-18 卡吉尔公司 Processes for producing phosphates
CN103058158A (en) * 2013-02-05 2013-04-24 瓮福（集团）有限责任公司 Method for preparing monopotassium phosphate from fertilizer grade calcium hydrophosphate
CN103058157A (en) * 2013-02-26 2013-04-24 贵州开磷（集团）有限责任公司 Production method of industrial grade diammonium phosphate with wet-process phosphoric acid

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
王盼等: "磷酸氢钙生产磷酸二氢钾的工艺研究", 《无机盐工业》, vol. 43, no. 2, 28 February 2011 (2011-02-28) *
赵世忠: "磷酸二氢钾概况", 《无机盐工业》, 31 December 1981 (1981-12-31), pages 39 - 44 *
陈嘉甫、谭光薰: "《磷酸盐的生产与应用》", 31 December 1989, article "正磷酸钾盐的生产原理和生产方法" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104276555A (en) * 2014-09-19 2015-01-14 贵阳中化开磷化肥有限公司 Method for preparing monosodium phosphate and byproduct fertilizer specially used for buckwheat
CN104276555B (en) * 2014-09-19 2016-08-17 贵州开磷集团股份有限公司 A kind of method preparing sodium dihydrogen phosphate by-product Semen Fagopyri Esculenti special fertilizer

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