CN103466642B - Method for preparing hydrogen fluoride (HF) and white carbon black by treating fluosilicic acid (H2SiF6) via organic alkali - Google Patents
Method for preparing hydrogen fluoride (HF) and white carbon black by treating fluosilicic acid (H2SiF6) via organic alkali Download PDFInfo
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Abstract
The invention particularly relates to a method for preparing hydrogen fluoride (HF) and white carbon black by treating fluosilicic acid (H2SiF6) via an organic alkali, which relates to the technical field of chemical engineering. The method comprises the following steps: a, extracting a H2SiF6 solution with an extractant; b, adding the organic alkali with a low boiling point into a H2SiF6-extractant solution to perform a reaction on the organic alkali and the H2SiF6 so as to generate SiO2 and an organic alkali fluoride salt which are filtered, thereby obtaining the white carbon black; c, heating the organic alkali fluoride salt to a certain temperature and distilling so as to remove the organic alkali with the low boiling point, thereby obtaining a HF-extractant solution; and d, heating, distilling and separating the HF-extractant solution so as to obtain the HF product and recycling the extractant after the regeneration of the extractant so as to extract the H2SiF6. According to the method, fluorine and silicon resources in byproducts in the phosphate fertilizer industry are efficiently and comprehensively utilized.
Description
Technical field
The present invention relates to a kind of method being prepared hydrogen fluoride and white carbon black by organic bases process silicate fluoride solution, especially for the method for the efficiency utilization of the rare silicofluoric acid resource of by-product in phosphoric acid by wet process and phophatic fertilizer production process.Belong to chemical technology field.
Background technology
Hydrogen fluoride is the basis of modern fluorine chemical, and be the most basic raw material producing various fluorine product, market demand is very big.Fluorine in current fluorine chemical is almost all from the exploitation of fluorite, but fluorite is as Nonrenewable resources, and too fast consumption has in recent years caused each side to pay attention to.Along with the management and control of country to fluorite output and the minimizing of output, the raw material of fluorine chemical enterprise certainly will be caused nervous, finally cause the cost of Fluorine contained chemicals.Therefore finding new fluorine source is a kind of trend; and in Rock Phosphate (72Min BPL), also contain a large amount of fluorine resources; strengthen and the utilization of this resource is of great significance phosphoric acid by wet process and phosphate fertilizer industry Sustainable development tool; not only be conducive to the environmental pollution improvement of phosphatic fertilizer company fluorinated tail gas, and have great strategic importance for the coordinated development and technical progress protecting the relevant industries such as fluorite resource, the industry of promotion fluorine, non-ferrous metals industry, the industry of phosphorus compound fertilizer.
At present, rare silicofluoric acid of phosphoric acid by wet process and phosphatic fertilizer company by-product, main employing is reacted with sodium salt and is produced Sodium Silicofluoride.Sodium Silicofluoride is the inorganic salt of low value, its market sales volume and price volalility larger, directly have influence on the normal production of phosphoric acid by wet process and phosphatic fertilizer company, in Sodium Silicofluoride production process, wastewater discharge is larger simultaneously, general enterprises all adopts neutralizing treatment to dilute rear direct discharge up to standard, and processing cost is higher.Present phosphoric acid by wet process and phosphatic fertilizer company all pay much attention to the technological development of by-product fluorine, silicon resource, and actively push forward the high-efficiency comprehensive utilization of fluorine, silicon resource, main route has following three: the silicofluoric acid of (1) phosphate fertilizer by-product is raw material production Neutral ammonium fluoride and white carbon black, and Neutral ammonium fluoride and sulfuric acid reaction generate hydrofluoric acid and ammonium sulfate.The subject matter that this route exists is: 1. white carbon black inferior quality, affects its price and purposes; 2. often produce 1 ton of hydrofluoric acid meeting by-product, 3.4 tons of ammonium sulfate, and ammonium sulfate market capacity is limited.(2) silicofluoric acid of phosphate fertilizer by-product is that raw material and aluminium hydroxide react and produces aluminum fluoride, by-product silica gel; The Sodium Silicofluoride of phosphate fertilizer by-product is that raw material and sodium carbonate react and produces Sodium Fluoride, by-product silica gel; Sodium Fluoride and aluminum fluoride synthetic cryolite.Mainly there is following problem in these routes: in the silica gel of 1. by-product Sodium Fluoride and aluminum fluoride content higher, be difficult to effective utilization; 2. be difficult to find efficient manner to realize being separated of Sodium Fluoride and silicon-dioxide and aluminum fluoride and silicon-dioxide, the quality of Sodium Fluoride, aluminum fluoride and sodium aluminum fluoride can be had influence on.(3) silicofluoric acid of phosphate fertilizer by-product and direct reaction of sulfuric acid, produces hydrogen fluoride and silicon tetrafluoride, and silicon tetrafluoride use water absorbs and generates silicofluoric acid and silica gel, silicofluoric acid circulation and sulfuric acid reaction; Mainly there is following problem in this route: is finally converted into silica gel after the silicon cycling 1. in this route, the silicofluoric acid that silica gel is residual and hydrogen fluoride higher, it utilizes the development that govern this technique; 2. in the process of silicofluoric acid and sulfuric acid reaction, the fluorine atom of 1/3rd is converted into hydrofluoric acid, and the fluorine atom of 2/3rds with getting back to silicofluoric acid, needs iterative cycles the fluorine in silicofluoric acid all could be changed into hydrofluoric acid by two steps conversions.
In sum, very necessary research produces hydrofluoric new technology from phosphate fertilizer by-product silicofluoric acid, can accomplish reasonable employment to silicon resource wherein simultaneously.
Summary of the invention
The object of the invention is to overcome and existing irrational technological deficiency is utilized to phosphate fertilizer and phosphoric acid by wet process by-product fluosilicic acid, a kind of method utilizing phosphatic fertilizer company fluosilicic acid as byproduct to produce hydrogen fluoride and white carbon black is provided, a kind of method of production of phosphate fertilizer by-product fluosilicic acid can be utilized efficiently.
A kind of method and technology scheme preparing hydrogen fluoride and white carbon black by organic bases process silicofluoric acid of the present invention is: containing following processing step be:
A. extraction agent extraction silicate fluoride solution is first used;
B. in silicofluoric acid-extraction agent solution, lower boiling organic bases is added, lower boiling organic bases and H
2siF
6reaction generates SiO
2with organic bases fluoride salt, filter and obtain white carbon black;
C., under organic bases fluoride salt being heated to certain temperature, the lower boiling organic bases of distillation removing, obtains HF-extraction agent solution;
D. carry out intensification fractionation by distillation to HF-extraction agent solution, obtain HF product, extractant regeneration Posterior circle returns extraction silicofluoric acid.
In described step a, extraction agent is preferably three positive heptyl amices, tri-n-octyl amine, tri-iso-octylamine, tri-n-nonylamine or three n-Decylamines, the concentration of silicofluoric acid is 5%-20%, extraction temperature is 20-95 DEG C, and extraction time is 0.5-3 h, and the mass ratio of extraction agent and silicofluoric acid is 0.6:1-1.5:1.
In described step b, lower boiling organic bases is preferably Trimethylamine 99, triethylamine or tripropyl amine, and temperature of reaction is 20-95 DEG C, and the reaction times is 0.5-12h, and the mol ratio of organic bases and silicofluoric acid is 1:1-1.5:1.
In described step c, temperature of reaction is 50-100 DEG C, and distillation pressure is 0.1-1 bar, and the reaction times is 2-10 h.
In described steps d, temperature of reaction is 120-180 DEG C, and distillation pressure is 0.1-1 bar, and the reaction times is 2-10 h.
Principle of the present invention, is described according to following equation and illustrates:
Novelty of the present invention is: (1) avoids needs the process through preparing Calcium Fluoride (Fluorspan) or other fluoride salts to produce hydrogen fluoride by silicofluoric acid raw material, adopt initiative method directly to utilize rare silicofluoric acid of phosphoric acid by wet process by-product, operational path is novel.(2) principle is that silicofluoric acid and water react and produces hydrogen fluoride and white carbon black (effective ingredient is: SiO
2), consumption only have silicofluoric acid and water, do not need to consume sulfuric acid or other raw materials, organic bases recycles as reaction medium with extraction agent.(3) disposable being separated by all fluorine in silicofluoric acid hydrogen fluoride can be become.(4) producing hydrofluoric while, can accomplish controlled to the quality of silicon-dioxide.
The aspect that the present invention is above-mentioned and additional and advantage, will become obvious and easy understand from description in conjunction with the embodiments.
Environmental value of the present invention is to accomplish the comprehensive utilization to fluorine silicon two spike-type cultivars, and does not have the waste of contaminate environment to produce.
What economic worth of the present invention was to consume only has silicofluoric acid and water, does not need to consume sulfuric acid or other raw materials, and obtains hydrogen fluoride and the white carbon black of high value simultaneously, accomplished to utilize the comprehensive high-efficiency of fluorine silicon resource.
Accompanying drawing explanation
By embodiment, the present invention is described by reference to the accompanying drawings in detail below, to becoming detailed in the description of embodiment and easy understand the present invention is above-mentioned or additional aspect and advantage.
Fig. 1 is present invention process schema.
Embodiment
Described embodiment, only for explaining the present invention, and can not be interpreted as limitation of the present invention.
The method that organic bases process silicofluoric acid of the present invention prepares hydrogen fluoride and silicon-dioxide comprises following several step: first a. uses extraction agent to extract silicate fluoride solution; B. in silicofluoric acid-extraction agent solution, lower boiling organic bases is added, organic bases and H
2siF
6reaction generates SiO
2with organic bases fluoride salt, filter and obtain white carbon black; C., under organic bases fluoride salt being heated to certain temperature, the lower boiling organic bases of distillation removing, obtains HF-extraction agent solution; D. carry out intensification fractionation by distillation to HF-extraction agent solution, obtain HF product, extractant regeneration Posterior circle returns extraction silicofluoric acid.
In step a, extraction agent is preferably three positive heptyl amices, tri-n-octyl amine, tri-iso-octylamine, tri-n-nonylamine, three n-Decylamines, the concentration of silicofluoric acid is 5%-20%, extraction temperature is 20-95 DEG C, and extraction time is 0.5-3 h, and the mass ratio of extraction agent and silicofluoric acid is 0.6:1-1.5:1.
In step b, organic bases is preferably Trimethylamine 99, triethylamine, tripropyl amine, and temperature of reaction is 20-95 DEG C, and the reaction times is 0.5-12h, and the mol ratio of organic bases and silicofluoric acid is 1:1-1.5:1.
In step c, temperature of reaction is 50-100 DEG C, and distillation pressure is 0.1-1 bar, and the reaction times is 2-10 h.
In steps d, temperature of reaction is 120-180 DEG C, and distillation pressure is 0.1-1 bar, and the reaction times is 2-10 h.
New process of the present invention can adopt existing technology and realize through the unit equipment that large-scale industrial production is verified.
embodiment 1
Be positive heptyl amice 80 g of silicate fluoride solution 100 g and three of 10% by massfraction, after temperature is elevated to 60 DEG C gradually, mix and blend 2 h.Then, separatory removing aqueous phase, in organic phase, add 71 g tripropyl amines, react 3 h, suction filtration obtains solid and filtrate.Solid water is carried out washing drying and obtain white carbon black.Be that under the pressure of 200 mabr, temperature 90 DEG C steams tripropyl amines all in the middle of system, and then system temperature system pressure remains unchanged in system by filtrate, continue to be warmed up to 150 DEG C, obtain HF.
embodiment 2
Be positive heptyl amice 80 g of silicate fluoride solution 100 g and three of 10% by massfraction, after temperature is elevated to 60 DEG C gradually, mix and blend 2 h.Then, separatory removing aqueous phase, in organic phase, add 30 g Trimethylamine 99s, react 1.5 h, suction filtration obtains solid and filtrate.Solid water is carried out washing drying and obtain white carbon black.Be that under the pressure of 0.2 bar, temperature 80 DEG C steams Trimethylamine 99s all in the middle of system, and then system temperature system pressure remains unchanged in system by filtrate, continue to be warmed up to 120 DEG C, obtain HF.
embodiment 3
Be silicate fluoride solution 50 g and tri-n-octyl amine 80 g of 20% by massfraction, after temperature is elevated to 60 DEG C gradually, mix and blend 1.5 h.Then, separatory removing aqueous phase, in organic phase, add 36 g Trimethylamine 99s, react 1.5 h, suction filtration obtains solid and filtrate.Solid water is carried out washing drying and obtain white carbon black.By filtrate at ambient pressure, temperature 90 DEG C steams Trimethylamine 99s all in the middle of system, and then system temperature system pressure remains unchanged, and continues to be warmed up to 120 DEG C, obtains HF.
embodiment 4
Be silicate fluoride solution 50 g and TNA trinonylamine 100 g of 10% by massfraction, after temperature is elevated to 80 DEG C gradually, mix and blend 2 h.Then, separatory removing aqueous phase, in organic phase, add 36 g Trimethylamine 99s, react 2 h, suction filtration obtains solid and filtrate.Solid water is carried out washing drying and obtain white carbon black.By filtrate at ambient pressure, temperature 100 DEG C steams Trimethylamine 99s all in the middle of system, and then system temperature system pressure remains unchanged, and continues to be warmed up to 130 DEG C, obtains HF.
embodiment 5
Be silicate fluoride solution 50 g and trioctylamine 80 g of 20% by massfraction, after temperature is elevated to 60 DEG C gradually, mix and blend 1.5 h.Then, separatory removing aqueous phase, in organic phase, add 63 g triethylamines, react 3 h, suction filtration obtains solid and filtrate.Solid water is carried out washing drying and obtain white carbon black.By filtrate under 0.1 bar pressure, temperature 100 DEG C steams triethylamines all in the middle of system, and then system temperature system pressure remains unchanged, and continues to be warmed up to 120 DEG C, obtains HF.
embodiment 6
Be silicate fluoride solution 100 g and trioctylamine 80 g of 10% by massfraction, after temperature is elevated to 60 DEG C gradually, mix and blend 1.5 h.Then, separatory removing aqueous phase, in organic phase, add 32 g Trimethylamine 99s, react 1.5 h, suction filtration obtains solid and filtrate.Solid water is carried out washing drying and obtain white carbon black.By filtrate under 0.2 bar pressure, temperature 70 DEG C steams Trimethylamine 99s all in the middle of system, and then system temperature system pressure remains unchanged, and continues to be warmed up to 180 DEG C, obtains HF.
Claims (5)
1. prepared a method for hydrogen fluoride and white carbon black by organic bases process silicofluoric acid, it is characterized in that containing following processing step be:
A. extraction agent extraction silicate fluoride solution is first used;
B. in silicofluoric acid-extraction agent solution, lower boiling organic bases is added, lower boiling organic bases and H
2siF
6reaction generates SiO
2with organic bases fluoride salt, filter and obtain white carbon black;
C., under organic bases fluoride salt being heated to certain temperature, the lower boiling organic bases of distillation removing, obtains HF-extraction agent solution;
D. carry out intensification fractionation by distillation to HF-extraction agent solution, obtain HF product, extractant regeneration Posterior circle returns extraction silicofluoric acid;
In step a, extraction agent is three positive heptyl amices, tri-n-octyl amine, tri-iso-octylamine, tri-n-nonylamine or three n-Decylamines,
In step b, lower boiling organic bases is Trimethylamine 99, triethylamine or tripropyl amine.
2., by method according to claim 1, it is characterized in that, in step a, the concentration of silicofluoric acid is 5%-20%, and extraction temperature is 20-95 DEG C, and extraction time is 0.5-3 h, and the mass ratio of extraction agent and silicofluoric acid is 0.6:1-1.5:1.
3., by method according to claim 1, it is characterized in that, in step b, temperature of reaction is 20-95 DEG C, and the reaction times is 0.5-12h, and the mol ratio of organic bases and silicofluoric acid is 1:1-1.5:1.
4. by method according to claim 1, it is characterized in that, in step c, temperature of reaction is 50-100 DEG C, and distillation pressure is 0.1-1 bar, and the reaction times is 2-10 h.
5. by method according to claim 1, it is characterized in that, in steps d, temperature of reaction is 120-180 DEG C, and distillation pressure is 0.1-1 bar, and the reaction times is 2-10 h.
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| CN104445074B (en) * | 2014-12-11 | 2016-09-14 | 云南省化工研究院 | The method that dilute hexafluosilicic acid prepares anhydrous hydrogen fluoride coproduction Silicon fluoride. is processed by solvent extraction |
| CN105366643B (en) * | 2015-12-18 | 2018-04-10 | 云南省化工研究院 | A kind of method that dilute fluosilicic acid of solvent extraction prepares fluoride salt co-producing white carbon black |
| CN105502435B (en) * | 2015-12-18 | 2017-09-22 | 云南天安化工有限公司 | A kind of method that ammonium fluoride is prepared by tertiary amine fluosilicic acid |
| CN108046304A (en) * | 2017-12-14 | 2018-05-18 | 云南云天化股份有限公司 | A kind of tertiary amine extracts the method that dilute fluosilicic acid prepares calcirm-fluoride combined producting ammonium chloride |
| CN108176705B (en) * | 2018-03-29 | 2020-04-10 | 中化云龙有限公司 | Treatment method for residue after extracting and purifying phosphogypsum by organic solvent |
| CN115433580B (en) * | 2022-10-27 | 2023-08-18 | 湖北九宁化学科技有限公司 | Production method of etching solution in photoelectric industry |
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|---|---|---|---|---|
| CN1721044A (en) * | 2005-05-24 | 2006-01-18 | 夏克立 | Fluorine-containing waste gas utilization method in phosphorus fertilizer production |
| CN103172074A (en) * | 2013-01-17 | 2013-06-26 | 洛阳氟钾科技有限公司 | Process for decomposing potassium feldspar by adopting low-temperature semidry method for comprehensive utilization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721044A (en) * | 2005-05-24 | 2006-01-18 | 夏克立 | Fluorine-containing waste gas utilization method in phosphorus fertilizer production |
| CN103172074A (en) * | 2013-01-17 | 2013-06-26 | 洛阳氟钾科技有限公司 | Process for decomposing potassium feldspar by adopting low-temperature semidry method for comprehensive utilization |
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