CN101973568B - Comprehensive utilization method of gypsum containing fluorine and fluosilicic acid as byproduct of phosphatic fertilizer - Google Patents
Comprehensive utilization method of gypsum containing fluorine and fluosilicic acid as byproduct of phosphatic fertilizer Download PDFInfo
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- CN101973568B CN101973568B CN 201010287414 CN201010287414A CN101973568B CN 101973568 B CN101973568 B CN 101973568B CN 201010287414 CN201010287414 CN 201010287414 CN 201010287414 A CN201010287414 A CN 201010287414A CN 101973568 B CN101973568 B CN 101973568B
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Abstract
The invention relates to a comprehensive utilization method of gypsum containing fluorine and fluosilicic acid as a byproduct of phosphatic fertilizer, in particular to the field of the comprehensive utilization of wastes in inorganic chemical industry, which comprises the following steps: a. ammonizing and filtering the fluosilicic acid to prepare an ammonium fluoride solution, stirring the excessive 0% to 15% of the ammonium fluoride solution and gypsum powder containing the fluorine at the temperature of 60 to 80 DEG C to prepare a slurry; b. filtering the slurry to prepare ammonium sulfate mother liquor with the concentration of 10% to 38%, and washing, drying and crushing filter cakes to prepare CaF2 solid powder; c. placing the solid powder into a sulfuric acid-fluorite method system to prepare hydrogen fluoride (HF), wherein the gypsum containing the fluorine generated in the course of preparing the HF can be recycled; and d. utilizing the ammonium sulfate mother liquor generated in the step b to prepare ammonium sulfate for agriculture. The method of the invention can be suitable for the fluosilicic acid and ammonium fluoride with different concentrations and has the advantages that no waste is exhausted in the integral comprehensive utilization system; white carbon black and the ammonium sulfate product for agriculture can be cogenerated; and the prepared calcium fluoride solid powder and the sulfuric acid have no side reaction in the course of reacting for preparing hydrofluoric acid.
Description
Technical field
The present invention relates to inorganic chemical industry and produce the waste ' s reclamation field, specifically utilize fluorgypsum and phosphate fertilizer industry by-product fluosilicic acid to produce HF, simultaneously the method for comprehensive utilization of co-producing white carbon black, agricultural ammonium sulfate.
Background technology
Silicofluoric acid is normally produced the byproduct of phosphoric acid by wet process and general calcium.China's phosphate fertilizer production in 2005, the P of folding 100%
2O
5Be 1,125 ten thousand tons, but by-product fluosilicic acid is by 100% H
2SiF
6Calculate then above 500,000 tons.At present, China's silicofluoric acid major part is the form recovery with Sodium Silicofluoride, but the Sodium Silicofluoride purposes is narrow, deficiency in economic performance, usually unsalable, had a strong impact on the development that enthusiasm that manufacturer reclaims silicofluoric acid has also restricted phosphate fertilizer industry simultaneously, this has not only caused the serious waste of fluorine, silicon resource, and has polluted to a great extent environment.
Fluorgypsum refers to that sulfuric acid and fluorite produce hydrofluoric byproduct, and main component is calcium sulfate, belongs to high-risk solid waste.At present, fluorgypsum mainly is to store up processing, after few part fluorgypsum mainly passes through harmless treatment, as the main production starting material of the building material mades such as gypsum block, gypsum sheet material, gypsum decorative product, brushing gypsum.
Agricultural ammonium sulfate is applicable to various soil and crop as traditional nitrogen fertilizers, is that China uses and produce the earliest a nitrogen fertilizers.Account at present 0.7% of China's nitrogenous fertilizer ultimate production.Ammonium sulfate acceptable end product nitrogen content is more than 21%, and ammonium sulfate also contains 25% sulphur except nitrogenous, also is a kind of important sulfur fertilizer.
HF is as the basic material of fluorine industry, and hydrofluoric acid (hydrogen fluoride) nearly all is to decompose fluorite (CaF with sulfuric acid
2) obtain.Because the standing stock of fluorite are very little in the world, having verified at present only to have 6,500 ten thousand tons for the reserves of exploitation, and concentrates on several countries few in number.In addition, some fluorochemicals are present space flight, and the industrial indispensable goods and materials such as national defence relate to national security.So some countries manage fluorite as strategic resource.Though China is fluorite resource big country, present fluorite in the world is consumed with annual 4000000 tons speed, considers from strategic height, and China has also taked restriction exploitation and outlet measure.The technique for preparing hydrofluoric acid by the synthetic fluorite of phosphate fertilizer by-product fluosilicic acid yet there are no report.In addition, the fluorine resource from the phosphate fertilizer by-product fluosilicic acid in the fluorine resource comparison fluorite just becomes the original suitable advantage that has, and this also is the economic technology basis that takes full advantage of the phosphate fertilizer by-product fluosilicic acid.
Summary of the invention
Purpose of the present invention is intended to overcome the defective of prior art, provide a kind of gypsum containing fluorine and fluosilicic acid as byproduct of phosphatic fertilizer to produce HF simultaneously co-producing white carbon black, agricultural ammonium sulfate, and the hydrofluoric acid of producing can be up to state standards, thus the method for the comprehensive utilization of the gypsum containing fluorine of the comprehensive utilization of realization phosphate fertilizer by-product fluosilicic acid and fluosilicic acid as byproduct of phosphatic fertilizer.
The percentage number average that adopts among the present invention is mass percent.
The method of the comprehensive utilization of gypsum containing fluorine of the present invention and fluosilicic acid as byproduct of phosphatic fertilizer, the method may further comprise the steps:
A. first with silicofluoric acid and ammonification, filtration, obtain ammonium fluoride solution concentration and be 5%～22% ammonium fluoride solution, concentration is 5%～22% ammonium fluoride solution, and excessive 0%～15% stirs under 60～80 ℃ condition with the fluorgypsum powder, after reaction in 1～2.5 hour, get slip;
B. slurry filtration obtains concentration and is 10%～38% ammonium sulfate liquor, and filter cake obtains CaF through washing, dry, fragmentation
2Pressed powder;
C. pressed powder is put into sulfuric acid-fluorite genealogy of law system and produced HF, the produced simultaneously gypsum containing fluorine of producing HF recycles;
D. the ammonium sulfate liquor of step b generation is for the production of agricultural ammonium sulfate.
The described Neutral ammonium fluoride concentration of step a is 5%～22% to keep simultaneously overrate 0%～15%.
The agricultural ammonium sulfate of the described preparation of steps d is through concentrated, the agricultural ammonium sulfate of crystalline with the by-product ammonium sulfate liquor.
The method of comprehensive utilization of described gypsum containing fluorine and fluosilicic acid as byproduct of phosphatic fertilizer, the CaF that its reaction generates
2Pressed powder purity is greater than 92%.Ammonium fluoride solution and fluorgypsum reaction conversion ratio reach more than 97%.
The method of comprehensive utilization of described gypsum containing fluorine and fluosilicic acid as byproduct of phosphatic fertilizer, whole reaction is in neutral environment, PH=6～8.
The described fluorgypsum powder of step a comprises that the fluorite method produces the gypsum of hydrofluoric acid process by-product and the gypsum that present method is produced hydrofluoric acid process by-product, and wherein calcium sulphate content is greater than 90%, granularity-200 order 〉=90%.
The method of the comprehensive utilization of gypsum containing fluorine of the present invention and fluosilicic acid as byproduct of phosphatic fertilizer, from the angle of comprehensive utilization of resources, having designed one is the Acid of Hydrofluoric Acid Production route of main raw material from fluorgypsum and fluosilicic acid as byproduct of phosphatic fertilizer.Utilize the phosphate fertilizer by-product fluosilicic acid to obtain cheap fluorine source, have good economic benefit and social benefit.By test, prove that prepared Calcium Fluoride (Fluorspan) can generate hydrofluoric acid with strong sulfuric acid response, and higher transformation efficiency is arranged, and the hydrofluoric acid of producing satisfies the national standard requirement.
Main chemical reactions principle of the present invention is:
2NH
4F+CaSO
4→CaF
2↓+(NH
4)
2SO
4
CaF
2+H
2SO
4→CaSO
4+HF↑
The method of the comprehensive utilization of gypsum containing fluorine of the present invention and fluosilicic acid as byproduct of phosphatic fertilizer, the advantage that has is: the present invention has adopted fluorgypsum and phosphate fertilizer by-product fluosilicic acid to prepare the hydrofluoric acid novel process, do not have waste discharge in the whole flow process, meet the requirement of environmental friendliness chemistry.In whole preparation process, reaction conditions is gentle, and operational condition is easier to control, can be used for the Calcium Fluoride (Fluorspan) pressed powder of sulfuric acid-fluorite method production usefulness.Method of the present invention according to the difference of silicofluoric acid, Neutral ammonium fluoride concentration, can obtain the Calcium Fluoride (Fluorspan) pressed powder for sulfuric acid-fluorite method production usefulness applicable to silicofluoric acid and the Neutral ammonium fluoride of different concns under different processing parameter conditions.And in the system of whole comprehensive utilization, do not have waste discharge, but and co-producing white carbon black, agricultural ammonium sulfate product, there is not side reaction in prepared Calcium Fluoride (Fluorspan) pressed powder producing in the hydrofluoric acid process with sulfuric acid reaction.
Description of drawings
Fig. 1 is preparation method's of the present invention process flow diagram.
Embodiment
By specific embodiment given below, can further understand the present invention, but be not limited to method described in the example.
Embodiment 1
In 60 ℃ water-bath, to in the reactor that stirs, add 777g, the ammonium fluoride solution of overrate 5%, 10% progressively adds fluorgypsum pressed powder 173.74g, reacts 2 hours.Slip after filtration, filter cake through the washing, drying.Sample presentation is analyzed, and ammonium sulfate concentrations is 14.26% in the mother liquor, and butt Calcium Fluoride (Fluorspan) product purity is 93.43%.
Embodiment 2
In 80 ℃ water-bath, to in the reactor that stirs, add 647.5g, the ammonium fluoride solution of overrate 5%, 18% progressively adds fluorgypsum pressed powder 260.61g, reacts 2.5 hours.Slip after filtration, filter cake through the washing, drying.Sample presentation is analyzed, and ammonium sulfate concentrations is 28.12% in the mother liquor, and butt Calcium Fluoride (Fluorspan) product purity is 92.10%.
Embodiment 3
In 80 ℃ water-bath, to in the reactor that stirs, add 851g (overrate 15%), 10% ammonium fluoride solution progressively adds fluorgypsum pressed powder 173.74g, reacts 2.5 hours.Slip after filtration, filter cake through the washing, drying.Sample presentation is analyzed, and ammonium sulfate concentrations is 14.82% in the mother liquor, and butt Calcium Fluoride (Fluorspan) product purity is 92.62%.
Embodiment 4
In 60 ℃ water-bath, to in the reactor that stirs, add 709.17g, the ammonium fluoride solution of overrate 15%, 18% progressively adds fluorgypsum pressed powder 260.61g, reacts 2.5 hours.Slip after filtration, filter cake through the washing, drying.Sample presentation is analyzed, and ammonium sulfate concentrations is 24.56% in the mother liquor, and butt Calcium Fluoride (Fluorspan) product purity is 94.06%.
Embodiment 5
In 80 ℃ water-bath, to in the reactor that stirs, add 750.2g, the ammonium fluoride solution of overrate 5%, 5% progressively adds fluorgypsum pressed powder 83.03g, reacts 2.5 hours.Slip after filtration, filter cake through the washing, drying.Sample presentation is analyzed, and ammonium sulfate concentrations is 10.40% in the mother liquor, and butt Calcium Fluoride (Fluorspan) product purity is 96.75%.
Embodiment 6
Choose the butt CaF of test preparation
2The Calcium Fluoride (Fluorspan) product 50g of content 94.06%, concentration is 97% the vitriol oil, excessive ratio 1.05 adds 63.96g under the condition of other conditions with the fluorite method, heated and stirred reaction in cylinder of steel, water absorbs to produce hydrofluoric acid.After the analytical reaction in the material F content be 0.54%, the quality of gained hydrofluoric acid is: HF%=40.08%, H
2SiF
6%=0.03%, H
2SO
4%=0.04%.
The product quality analysis of embodiment 1～5 the results are shown in following table:
Claims (6)
1. the method for comprehensive utilization of a gypsum containing fluorine and fluosilicic acid as byproduct of phosphatic fertilizer is characterized in that, the steps include:
A. first with silicofluoric acid ammonification, filtration, obtain ammonium fluoride solution concentration and be 5%～22% ammonium fluoride solution, concentration is 5%～22% ammonium fluoride solution, and excessive 0%～15% stirs under 60～80 ℃ condition with the fluorgypsum powder, after reaction in 1～2.5 hour, get slip;
B. slurry filtration obtains concentration and is 10%～38% ammonium sulfate liquor, and filter cake obtains CaF through washing, dry, fragmentation
2Pressed powder;
C. pressed powder is put into sulfuric acid-fluorite genealogy of law system and produced HF, the produced simultaneously gypsum containing fluorine of producing HF recycles;
D. the ammonium sulfate liquor of step b generation is through concentrated, the agricultural ammonium sulfate of crystalline.
2. the method for comprehensive utilization of gypsum containing fluorine according to claim 1 and fluosilicic acid as byproduct of phosphatic fertilizer is characterized in that, Neutral ammonium fluoride concentration is 5%～22% to keep simultaneously overrate 0%～15%.
3. the method for comprehensive utilization of gypsum containing fluorine according to claim 1 and fluosilicic acid as byproduct of phosphatic fertilizer is characterized in that, the CaF that reaction generates
2Pressed powder purity is greater than 92%.
4. the method for comprehensive utilization of gypsum containing fluorine according to claim 1 and fluosilicic acid as byproduct of phosphatic fertilizer is characterized in that ammonium fluoride solution and fluorgypsum reaction conversion ratio reach more than 97%.
5. the method for comprehensive utilization of gypsum containing fluorine according to claim 1 and fluosilicic acid as byproduct of phosphatic fertilizer is characterized in that, reaction is in neutral environment, pH=6～8.
6. the method for comprehensive utilization of gypsum containing fluorine according to claim 1 and fluosilicic acid as byproduct of phosphatic fertilizer, it is characterized in that, the fluorgypsum powder comprises the gypsum of fluorite method production hydrofluoric acid process by-product and the gypsum of producing hydrofluoric acid process by-product, wherein calcium sulphate content is greater than 90%, granularity-200 order 〉=90%.
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| CN102502753B (en) * | 2011-11-18 | 2013-01-16 | 昆明道尔森科技有限公司 | Synthetic method of calcium fluoride |
| CN108455647B (en) * | 2018-01-10 | 2021-01-15 | 湖北三宁化工股份有限公司 | Method for producing calcium fluoride and by-products of white carbon black and ammonium sulfate by phosphoric acid by-product phosphogypsum and fluosilicic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3195979A (en) * | 1961-12-18 | 1965-07-20 | Int Minerals & Chem Corp | Process of preparing hydrogen fluoride from fluosilicic acid |
| US3923964A (en) * | 1973-06-11 | 1975-12-02 | Gustave E Kidde | Process for the production of calcium fluoride from fluosilicates and by-product gypsum |
| CN1554570A (en) * | 2003-12-22 | 2004-12-15 | 云南三环化工有限公司 | Method for comprehensively utilizing phosphate fertilizer by-product |
-
2010
- 2010-09-20 CN CN 201010287414 patent/CN101973568B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3195979A (en) * | 1961-12-18 | 1965-07-20 | Int Minerals & Chem Corp | Process of preparing hydrogen fluoride from fluosilicic acid |
| US3923964A (en) * | 1973-06-11 | 1975-12-02 | Gustave E Kidde | Process for the production of calcium fluoride from fluosilicates and by-product gypsum |
| CN1554570A (en) * | 2003-12-22 | 2004-12-15 | 云南三环化工有限公司 | Method for comprehensively utilizing phosphate fertilizer by-product |
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