CN106044733A - Novel method for removing arsenic in phosphorite-produced calcium hydrophosphate - Google Patents
Novel method for removing arsenic in phosphorite-produced calcium hydrophosphate Download PDFInfo
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- CN106044733A CN106044733A CN201610386762.9A CN201610386762A CN106044733A CN 106044733 A CN106044733 A CN 106044733A CN 201610386762 A CN201610386762 A CN 201610386762A CN 106044733 A CN106044733 A CN 106044733A
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- calcium
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- sulphuric acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/324—Preparation from a reaction solution obtained by acidifying with an acid other than orthophosphoric acid
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
- C05B11/04—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid
- C05B11/08—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid using sulfuric acid
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a novel method for removing arsenic in phosphorite-produced calcium hydrophosphate. The novel method is characterized by including the following steps of ore pulp preparing, sulfuric acid acidolysis reacting, primary neutralizing fluoride removing, primary neutralizing arsenic removing, sodium sulphide regenerating, secondary neutralizing and trinary neutralizing. The novel method has the advantages that on the basis of the prior art, fluoride removing and arsenic removing are separated, the content of arsenic in the fertilizer-level calcium hydrophosphate is reduced, the product obtained after arsenic removing regenerates sodium sulphide through strong acid, it is achieved that sodium sulphide is recycled, and cost is reduced.
Description
Technical field
The invention belongs to produce dearsenicating method in calcium hydrogen phosphate technique, be specifically related in a kind of Phosphate Rock acid hydrogen calcium remove
The new method of arsenic.
Background technology
With sulphuric acid, phosphoric acid for during raw material production calcium hydrophosphate fodder, bring into from phosphorus ore or smelt sulphuric acid
Certain arsenic impurities, thus lead the standard-required beyond product of the arsenic content in calcium monophosphate product.
At present, in most calcium hydrogen phosphate enterprises and industrial grade phosphate manufacturing enterprise removing product, the method for arsenic is main
It is, with sodium sulfide or phosphorus pentasulfide, thermal phosphoric acid or phosphoric acid by wet process are carried out dearsenization process.And calcium hydrogen phosphate fodder Qing Gai enterprise
The method of dearsenization mainly with sodium sulfide in phosphoric acid by wet process, one section or two-stage nitration and slip carries out dearsenization process, during dearsenization
Being recycled hydrogen sulfide in the waste gas produced, the arsenic sulfide of generation then enter into white fertile central, cause in white fertilizer
Arsenic is higher.In order to solve such problem, the present invention provides the arsenic content that on the one hand a kind of new arsenic removal flow process decreases in white fertilizer,
On the other hand the method that can again produce sodium sulfide.
Summary of the invention
It is an object of the invention to provide the new method of arsenic removal in a kind of Phosphate Rock acid hydrogen calcium.
The object of the present invention is achieved like this, and in a kind of Phosphate Rock acid hydrogen calcium, the new method of arsenic removal is by following steps
Constitute:
Step A ore pulp makes: is crushed in disintegrating machine by rock phosphate in powder, carries out slurrying by ball crusher, obtains phosphorus ore ore pulp,
Maturation 1～3 day in maturation pool；
Step B sulfuric acid solution reacts: is initially charged the sulphuric acid of 40-50% by adding sulphuric acid in phosphorus ore ore pulp in extraction tank, then exists
Add the sulphuric acid of 70-90%, fully filtered by filter after reaction, obtain ardealite and filtrate, filtrate is drained into phosphorus
Acid precipitation pond, and add a certain amount of coagulating sedimentation agent, obtain phosphoric acid liquid 1；
Step C mono-section neutralizes fluorine removal: phosphoric acid liquid 1 is put into reaction tank, and adds calcium hydroxide or calcium carbonate suspension, fill
Dividing reaction, the PH value of solution is 1.1～1.4, obtains white fertilizer, and the supernatant by centrifugal for thick paste after completion of the reaction；
Step D mono-section neutralizes arsenic removal: by adding sodium sulfide solution arsenic removal in the supernatant in step C, produce during reaction
Hydrogen sulfide gas, uses sodium hydroxide to absorb, after completion of the reaction quiescent setting be centrifuged and be precipitated 1 and solution 1；
The regenerative vulcanized sodium of step E: precipitation 1 being joined and have been loaded with in the middle of the reactor of sulphuric acid, the concentration of sulphuric acid is 40-50%, raw
Become hydrogen sulfide, use the aqueous solution containing sodium hydroxide to collect hydrogen sulfide gas and generate in sodium sulfide reactor remaining molten containing arsenic
Liquid can be used to produce containing arsenic goods raw material；
Step F two-stage nitration neutralize: by solution 1 add aqua calcis, fully react, the PH value to solution be 2.8～
3.6, sedimentation, filter, obtain solution 2, filtration cakes torrefaction, obtain calcium hydrophosphate fodder；
Step G tri-sections neutralization: adding aqua calcis in solution 2, fully react, the PH value to solution is 6.5～7.0,
Three sections neutralize feed liquid sedimentation, filter filtration cakes torrefaction, obtain calcium hydrophosphate fodder；
The invention have the advantages that 1, neutralized fluorine removal, one section of neutralization arsenic removal by one section, by the step of arsenic removal and fluorine removal separately, can subtract
The content of arsenic in few white fertilizer；2, one section of neutralization arsenic removal and fluorine removal separately can make the hydrogen sulfide of generation preferably be collected, and
And one section of hydrogen sulfide neutralizing the hydrogen sulfide produced in arsenic removal and the generation of step E can absorb with same device；3, the sulfur generated
Change arsenic precipitation by regeneration, generation sodium sulfide recycling；4 steps E solution containing arsenic can be as the raw material producing arsenic goods
5, by the way of twice adds sulphuric acid, reduce the calcium sulfate precipitation parcel to mineral, improve extraction yield.
Detailed description of the invention
Embodiment 1
Step A ore pulp makes: is crushed in disintegrating machine by rock phosphate in powder, carries out slurrying by ball crusher, obtains phosphorus ore ore pulp,
Maturation 1 day in maturation pool；
Step B sulfuric acid solution reacts: is initially charged the sulphuric acid of 40% by adding sulphuric acid in phosphorus ore ore pulp in extraction tank, is then adding
Enter the sulphuric acid of 70%, fully filtered by filter after reaction, obtain ardealite and filtrate, filtrate is drained into phosphoric acid and sinks
Pond, shallow lake, and add a certain amount of coagulating sedimentation agent, obtain phosphoric acid liquid 1；
Step C mono-section neutralizes fluorine removal: phosphoric acid liquid 1 is put into reaction tank, and adds calcium hydroxide or calcium carbonate suspension, fill
Dividing reaction, the PH value of solution is 1.1, obtains white fertilizer, and the supernatant by centrifugal for thick paste after completion of the reaction；
Step D mono-section neutralizes arsenic removal: by adding sodium sulfide solution arsenic removal in the supernatant in step C, produce during reaction
Hydrogen sulfide gas, uses sodium hydroxide to absorb, after completion of the reaction quiescent setting be centrifuged and be precipitated 1 and solution 1；
The regenerative vulcanized sodium of step E: precipitation 1 being joined and have been loaded with in the middle of the reactor of sulphuric acid, the concentration of sulphuric acid is 40%, generates
Hydrogen sulfide, using the aqueous solution containing sodium hydroxide to collect remaining solution in hydrogen sulfide gas generation sodium sulfide reactor can use
Produce containing arsenic goods raw material；
Step F two-stage nitration neutralizes: by adding aqua calcis in solution 1, fully reacting, the PH value to solution is 2.8, heavy
Fall, filters, obtains solution 2, filtration cakes torrefaction, obtain calcium hydrophosphate fodder；
Step G tri-sections neutralization: adding aqua calcis in solution 2, fully react, the PH value to solution is 6.5, three sections
Neutralization feed liquid settles, and filters filtration cakes torrefaction, obtains calcium hydrophosphate fodder；
Arsenic in white fertilizer reduces 92%, and the response rate of sodium sulfide arrives 81%.
Embodiment 2
Step A ore pulp makes: is crushed in disintegrating machine by rock phosphate in powder, carries out slurrying by ball crusher, obtains phosphorus ore ore pulp,
Maturation 2 days in maturation pool；
Step B sulfuric acid solution reacts: is initially charged the sulphuric acid of 45% by adding sulphuric acid in phosphorus ore ore pulp in extraction tank, is then adding
Enter the sulphuric acid of 80%, fully filtered by filter after reaction, obtain ardealite and filtrate, filtrate is drained into phosphoric acid and sinks
Pond, shallow lake, and add a certain amount of coagulating sedimentation agent, obtain phosphoric acid liquid 1；
Step C mono-section neutralizes fluorine removal: phosphoric acid liquid 1 is put into reaction tank, and adds calcium hydroxide or calcium carbonate suspension, fill
Dividing reaction, the PH value of solution is 1.2, obtains white fertilizer, and the supernatant by centrifugal for thick paste after completion of the reaction；
Step D mono-section neutralizes arsenic removal: by adding sodium sulfide solution arsenic removal in the supernatant in step C, produce during reaction
Hydrogen sulfide gas, uses sodium hydroxide to absorb, after completion of the reaction quiescent setting be centrifuged and be precipitated 1 and solution 1；
The regenerative vulcanized sodium of step E: precipitation 1 being joined and have been loaded with in the middle of the reactor of sulphuric acid, the concentration of sulphuric acid is 45%, generates
Hydrogen sulfide, using the aqueous solution containing sodium hydroxide to collect remaining solution in hydrogen sulfide gas generation sodium sulfide reactor can use
Produce containing arsenic goods raw material；
Step F two-stage nitration neutralizes: by adding aqua calcis in solution 1, fully reacting, the PH value to solution is 3.2, heavy
Fall, filters, obtains solution 2, filtration cakes torrefaction, obtain calcium hydrophosphate fodder；
Step G tri-sections neutralization: adding aqua calcis in solution 2, fully react, the PH value to solution is 6.7, three sections
Neutralization feed liquid settles, and filters filtration cakes torrefaction, obtains calcium hydrophosphate fodder；
Arsenic in white fertilizer reduces 91%, and the response rate of sodium sulfide arrives 79%.
Embodiment 3
Step A ore pulp makes: is crushed in disintegrating machine by rock phosphate in powder, carries out slurrying by ball crusher, obtains phosphorus ore ore pulp,
Maturation 3 days in maturation pool；
Step B sulfuric acid solution reacts: is initially charged the sulphuric acid of 50% by adding sulphuric acid in phosphorus ore ore pulp in extraction tank, is then adding
Enter the sulphuric acid of 90%, fully filtered by filter after reaction, obtain ardealite and filtrate, filtrate is drained into phosphoric acid and sinks
Pond, shallow lake, and add a certain amount of coagulating sedimentation agent, obtain phosphoric acid liquid 1；
Step C mono-section neutralizes fluorine removal: phosphoric acid liquid 1 is put into reaction tank, and adds calcium hydroxide or calcium carbonate suspension, fill
Dividing reaction, the PH value of solution is 1.4, obtains white fertilizer, and the supernatant by centrifugal for thick paste after completion of the reaction；
Step D mono-section neutralizes arsenic removal: by adding sodium sulfide solution arsenic removal in the supernatant in step C, produce during reaction
Hydrogen sulfide gas, uses sodium hydroxide to absorb, after completion of the reaction quiescent setting be centrifuged and be precipitated 1 and solution 1；
The regenerative vulcanized sodium of step E: precipitation 1 being joined and have been loaded with in the middle of the reactor of sulphuric acid, the concentration of sulphuric acid is 450%, generates
Hydrogen sulfide, using the aqueous solution containing sodium hydroxide to collect remaining solution in hydrogen sulfide gas generation sodium sulfide reactor can use
Produce containing arsenic goods raw material；
Step F two-stage nitration neutralizes: by adding aqua calcis in solution 1, fully reacting, the PH value to solution is 3.6, heavy
Fall, filters, obtains solution 2, filtration cakes torrefaction, obtain calcium hydrophosphate fodder；
Step G tri-sections neutralization: adding aqua calcis in solution 2, fully react, the PH value to solution is 7.0, three sections
Neutralization feed liquid settles, and filters filtration cakes torrefaction, obtains calcium hydrophosphate fodder；
Arsenic in white fertilizer reduces 89%, and the response rate of sodium sulfide arrives 83%.
Claims (4)
1. a new method for arsenic removal in Phosphate Rock acid hydrogen calcium, is characterized in that: described method is made up of following steps:
Step A ore pulp makes: is crushed in disintegrating machine by rock phosphate in powder, carries out slurrying by ball crusher, obtains phosphorus ore ore pulp,
Maturation 1～3 day in maturation pool；
Step B sulfuric acid solution reacts: carried out by filter after adding sulphuric acid, fully reaction in phosphorus ore ore pulp in extraction tank
Filter, obtain ardealite and filtrate, filtrate is drained into phosphoric acid precipitates pond, and adds a certain amount of coagulating sedimentation agent, obtain phosphorus
Acid solution 1；
Step C mono-section neutralizes fluorine removal: phosphoric acid liquid 1 is put into reaction tank, and adds calcium hydroxide or calcium carbonate, the most instead
Should, the PH value of solution is 1.1～1.4, obtains white fertilizer and the supernatant by centrifugal for thick paste after completion of the reaction；
Step D mono-section neutralizes arsenic removal: by adding sodium sulfide solution arsenic removal in the supernatant in step C, produce during reaction
Hydrogen sulfide gas, uses sodium hydroxide to absorb, after completion of the reaction quiescent setting be centrifuged and be precipitated 1 and solution 1；
The regenerative vulcanized sodium of step E: precipitation 1 is joined and has been loaded with in the middle of the reactor of sulphuric acid, generate hydrogen sulfide, use containing hydrogen
The aqueous solution of sodium oxide is collected hydrogen sulfide gas and is generated sodium sulfide；
Step F two-stage nitration neutralizes: adding aqua calcis in solution 1, fully react, the PH value to solution is 2.8～3.6,
Sedimentation, filters, obtains solution 2, filtration cakes torrefaction, obtain calcium hydrophosphate fodder；
Step G tri-sections neutralization: adding aqua calcis in solution 2, fully react, the PH value to solution is 6.5～7.0,
Three sections neutralize feed liquid sedimentation, filter filtration cakes torrefaction, obtain calcium hydrophosphate fodder.
In a kind of Phosphate Rock acid hydrogen calcium the most according to claim 1, the new method of arsenic removal, is characterized in that: described step
The step adding sulphuric acid in rapid B is to be initially charged the sulphuric acid of 40-50%, then at the sulphuric acid adding 70-90%.
In a kind of Phosphate Rock acid hydrogen calcium the most according to claim 1, the new method of arsenic removal, is characterized in that: described step
In rapid C, calcium hydroxide or calcium carbonate can make suspension.
In a kind of Phosphate Rock acid hydrogen calcium the most according to claim 1, the new method of arsenic removal, is characterized in that: described step
In rapid E, the concentration of sulphuric acid in the middle of reactor is 40-50%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610386762.9A CN106044733A (en) | 2016-06-05 | 2016-06-05 | Novel method for removing arsenic in phosphorite-produced calcium hydrophosphate |
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| CN201610386762.9A CN106044733A (en) | 2016-06-05 | 2016-06-05 | Novel method for removing arsenic in phosphorite-produced calcium hydrophosphate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110255502A (en) * | 2019-06-14 | 2019-09-20 | 贵州新东浩化工材料科技有限公司 | White fertilizer hydrogen fluoride coproduction richness calcium and general calcium technique |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183378A (en) * | 1995-10-20 | 1998-06-03 | 四川联合大学 | Method for producing feed calcium hydrogen phosphate |
| CN1772601A (en) * | 2004-11-12 | 2006-05-17 | 自贡鸿鹤化工股份有限公司 | Hydrochloric acid process of producing feed level calcium diphosphate and gypsum coproduct |
| CN102701170A (en) * | 2012-06-15 | 2012-10-03 | 昆明川金诺化工股份有限公司 | Process method for removing arsenic from feed-grade calcium hydrogen phosphate prepared from wet-process phosphoric acid |
-
2016
- 2016-06-05 CN CN201610386762.9A patent/CN106044733A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183378A (en) * | 1995-10-20 | 1998-06-03 | 四川联合大学 | Method for producing feed calcium hydrogen phosphate |
| CN1772601A (en) * | 2004-11-12 | 2006-05-17 | 自贡鸿鹤化工股份有限公司 | Hydrochloric acid process of producing feed level calcium diphosphate and gypsum coproduct |
| CN102701170A (en) * | 2012-06-15 | 2012-10-03 | 昆明川金诺化工股份有限公司 | Process method for removing arsenic from feed-grade calcium hydrogen phosphate prepared from wet-process phosphoric acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110255502A (en) * | 2019-06-14 | 2019-09-20 | 贵州新东浩化工材料科技有限公司 | White fertilizer hydrogen fluoride coproduction richness calcium and general calcium technique |
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Application publication date: 20161026 |