CN102115441A - Method for producing industrial calcium oxalate and phosphoric acid by utilizing phosphogypsum - Google Patents
Method for producing industrial calcium oxalate and phosphoric acid by utilizing phosphogypsum Download PDFInfo
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- CN102115441A CN102115441A CN2010106155440A CN201010615544A CN102115441A CN 102115441 A CN102115441 A CN 102115441A CN 2010106155440 A CN2010106155440 A CN 2010106155440A CN 201010615544 A CN201010615544 A CN 201010615544A CN 102115441 A CN102115441 A CN 102115441A
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- filter residue
- phosphogypsum
- phosphoric acid
- acid
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Abstract
The invention provides a method for producing industrial calcium oxalate and phosphoric acid by utilizing phosphogypsum, which comprises the following steps of: crushing the phosphogypsum into coarse powder with the granularity of 80 to 100 meshes, fully mixing with water, and filtering to obtain filter residue one and filtrate one; reacting the filter residue one with excessive sulfuric acid, and filtering to obtain filter residue two and filtrate two; reacting the filtrate residue two with excessive hydrochloric acid, and filtering a reaction product to obtain filtrate three and filter residue mainly containing calcium sulfate; washing, drying and crushing the filter residue three to obtain the calcium sulfate; mixing the obtained calcium sulfate with water, reacting with oxalic acid to obtain a calcium oxalate precipitate and sulfuric acid, and filtering and separating to obtain calcium oxalate filter cakes and sulfuric acid filtrate; washing, crushing and drying the obtained calcium oxalate filter cakes to obtain a calcium oxalate product; and combining the filtrate one, the filtrate two and the filtrate three, distilling under reduced pressure, condensing to collect phosphoric acid to obtain the phosphoric acid, and burying residual.
Description
Technical field
The present invention relates to phosphogypsum, particularly, relate to a kind of method of utilizing phosphogypsum manufacture caoxalate and phosphoric acid.
Background technology
Phosphogypsum is meant in phosphoric acid production, the solid slag that produces during with sulfuric acid treating phosphorite, and its main component is a calcium sulfate.Contain multiple other impurity in addition, as insoluble impurities: as the phosphoric acid salt and the vitriol of quartz, undecomposed phosphatic rock, fluorochemical and fluorine, aluminium, magnesium; Soluble impurity: as water-soluble P
2O
5, fluorochemical that solubleness is lower and vitriol.In addition, also contain arsenic, copper, zinc, iron, manganese, lead, cadmium, mercury and radioelement in the phosphogypsum, equal trace extremely, and great majority are insoluble solid, its hazardness can be ignored.Institute's fluoride, free phosphoric acid, P in the phosphogypsum
2O
5, impurity such as phosphoric acid salt is to cause phosphogypsum to cause the principal element of environmental pollution in the process of storing up.The improvement of phosphogypsum and to utilize problem be a global difficult problem.
China is as first production of phosphate fertilizer state in the world, also is simultaneously first phosphogypsum by-product state.According to incompletely statistics, the domestic phosphogypsum slag of storing up reaches more than 100,000,000 ton at present, also will newly produce tens million of tons every year.Because the phosphogypsum generation is huge, the market capacity of phosphogypsum comprehensive utilization product is limited, also can't accomplish in a short time phosphogypsum is all utilized, and can only adopt air storage to handle.Storing up in a large number of phosphogypsum, injustice has been occupied land resources, has caused the pollution of atmosphere, water system and soil owing to wind erosion, weathering.The Long contact time phosphogypsum may cause people's death or pathology certainly.
For this reason, be necessary to explore the industry application method thereof of phosphogypsum, give full play to its potential economic worth.
Summary of the invention
For this reason, the application provides a kind of method of utilizing phosphogypsum manufacture caoxalate and phosphoric acid, and this method is effectively extracted the calcium sulfate in the phosphogypsum, for the industrial application of phosphogypsum provides new approach.
The main component of phosphogypsum is a calcium sulfate, contains multiple other impurity in addition, as insoluble impurities: the phosphoric acid salt and the vitriol of quartzy, undecomposed phosphatic rock, fluorochemical and fluorine, aluminium, magnesium; Soluble impurity: as P
2O
5, fluorochemical that solubleness is lower and vitriol.
The application's technical scheme is as follows: a kind of method of utilizing phosphogypsum manufacture caoxalate and phosphoric acid, this method comprises following concrete steps: it is 80-100 purpose meal that phosphogypsum is pulverized, place reactor and water thorough mixing, make the water-soluble after-filtration of soluble impurity in the phosphogypsum, obtain filter residue one and filtrate one; Be water-fast impurity in the filter residue one, it mainly contains calcium sulfate, calcium phosphate, and the phosphoric acid salt of a spot of other insoluble impuritiess such as fluorochemical and fluorine, aluminium, magnesium and vitriol etc.; With filter residue one and excess sulfuric acid reaction, at this moment, calcium phosphate in the filter residue one and sulfuric acid reaction generate insoluble calcium sulfate and soluble phosphoric acid, after the filtration, obtain filter residue two and filtrate two; Filter residue two mainly contains the phosphoric acid salt and the vitriol of calcium sulfate and a spot of other insoluble impuritiess such as fluorochemical and fluorine, aluminium, magnesium, filter residue two reacts with excessive hydrochloric acid again, at this moment, insoluble calcium phosphate is converted to the phosphoric acid and the calcium chloride of solubility, and the phosphoric acid salt of insoluble fluorine, aluminium, magnesium also is converted to the phosphoric acid and the muriate of solubility; Reactant refilters, and obtains the filter residue three of filtrate three and main sulfur acid calcium and a small amount of vitriol; Gained filter residue three promptly obtains highly purified calcium sulfate through washing, crushed after being dried; The calcium sulfate that gained is high-purity mixes back and oxalic acid reaction with water, obtain calcium oxalate precipitation and sulfuric acid, separates after filtration, obtains caoxalate filter cake and sulfuric acid filtrate; Sulphuric acid soln returns with filter residue one reaction and reuses; Gained caoxalate filter cake obtains the caoxalate product through washing, pulverizing and dry.
Gained filtrate one, after filtrate two and filtrate three merged, through underpressure distillation, phosphoric acid was collected in condensation, obtains highly purified phosphoric acid, and residuum is buried.
The method of utilizing phosphogypsum production manufacture caoxalate and phosphoric acid of the present invention, this method is effectively extracted the calcium sulfate in the phosphogypsum, for the industrial application of phosphogypsum provides new approach.
Embodiment
Embodiment 1:
A kind of method of utilizing phosphogypsum manufacture caoxalate and phosphoric acid, it is 80 purpose meal that the 500kg phosphogypsum is pulverized, and places reactor and water thorough mixing, makes the water-soluble after-filtration of soluble impurity in the phosphogypsum, obtains filter residue one and filtrate one; With filter residue one and excess sulfuric acid reaction, after the filtration, obtain filter residue two and filtrate two; Filter residue two reacts with excessive hydrochloric acid again, and reactant refilters, and obtains the filter residue three of filtrate three and main sulfur acid calcium; Gained filter residue three promptly obtains calcium sulfate through washing, crushed after being dried; Gained calcium sulfate is mixed back and oxalic acid reaction with water, obtain calcium oxalate precipitation and sulfuric acid, separate after filtration, obtain caoxalate filter cake and sulfuric acid filtrate; Sulphuric acid soln returns with filter residue one reaction and reuses; Gained caoxalate filter cake obtains the caoxalate product through washing, pulverizing and dry; Gained filtrate one, after filtrate two and filtrate three merged, through underpressure distillation, phosphoric acid was collected in condensation, obtains phosphoric acid, and residuum is buried.
Embodiment 2:
A kind of method of utilizing phosphogypsum manufacture caoxalate and phosphoric acid, it is 100 purpose meal that the 500kg phosphogypsum is pulverized, and places reactor and water thorough mixing, makes the water-soluble after-filtration of soluble impurity in the phosphogypsum, obtains filter residue one and filtrate one; With filter residue one and excess sulfuric acid reaction, after the filtration, obtain filter residue two and filtrate two; Filter residue two reacts with excessive hydrochloric acid again, and reactant refilters, and obtains the filter residue three of filtrate three and main sulfur acid calcium; Gained filter residue three promptly obtains calcium sulfate through washing, crushed after being dried; Gained calcium sulfate is mixed back and oxalic acid reaction with water, obtain calcium oxalate precipitation and sulfuric acid, separate after filtration, obtain caoxalate filter cake and sulfuric acid filtrate; Sulphuric acid soln returns with filter residue one reaction and reuses; Gained caoxalate filter cake obtains the caoxalate product through washing, pulverizing and dry; Gained filtrate one, after filtrate two and filtrate three merged, through underpressure distillation, phosphoric acid was collected in condensation, obtains phosphoric acid, and residuum is buried.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, its framework form can be flexible and changeable, can the subseries product.Just make some simple deduction or replace, all should be considered as belonging to the scope of patent protection that the present invention is determined by claims of being submitted to.
Claims (1)
1. method of utilizing phosphogypsum manufacture caoxalate and phosphoric acid, it is characterized in that, comprise following concrete steps: it is 80-100 purpose meal that phosphogypsum is pulverized, place reactor and water thorough mixing, make the water-soluble after-filtration of soluble impurity in the phosphogypsum, obtain filter residue one and filtrate one; With filter residue one and excess sulfuric acid reaction, after the filtration, obtain filter residue two and filtrate two; Filter residue two reacts with excessive hydrochloric acid again, and reactant refilters, and obtains the filter residue three of filtrate three and main sulfur acid calcium; Gained filter residue three promptly obtains calcium sulfate through washing, crushed after being dried; Gained calcium sulfate is mixed back and oxalic acid reaction with water, obtain calcium oxalate precipitation and sulfuric acid, separate after filtration, obtain caoxalate filter cake and sulfuric acid filtrate; Sulphuric acid soln returns with filter residue one reaction and reuses; Gained caoxalate filter cake obtains the caoxalate product through washing, pulverizing and dry; Gained filtrate one, after filtrate two and filtrate three merged, through underpressure distillation, phosphoric acid was collected in condensation, obtains phosphoric acid, and residuum is buried.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106155440A CN102115441A (en) | 2010-12-31 | 2010-12-31 | Method for producing industrial calcium oxalate and phosphoric acid by utilizing phosphogypsum |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106155440A CN102115441A (en) | 2010-12-31 | 2010-12-31 | Method for producing industrial calcium oxalate and phosphoric acid by utilizing phosphogypsum |
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| CN102115441A true CN102115441A (en) | 2011-07-06 |
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|---|---|---|---|
| CN2010106155440A Pending CN102115441A (en) | 2010-12-31 | 2010-12-31 | Method for producing industrial calcium oxalate and phosphoric acid by utilizing phosphogypsum |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642852A (en) * | 2013-11-29 | 2014-03-19 | 大连创达技术交易市场有限公司 | Preparation method of oxalate |
-
2010
- 2010-12-31 CN CN2010106155440A patent/CN102115441A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642852A (en) * | 2013-11-29 | 2014-03-19 | 大连创达技术交易市场有限公司 | Preparation method of oxalate |
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Application publication date: 20110706 |