CN103145131A - Resource comprehensive utilization method for recovering fluorine from wet-process phosphoric acid - Google Patents
Resource comprehensive utilization method for recovering fluorine from wet-process phosphoric acid Download PDFInfo
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- CN103145131A CN103145131A CN201310060645XA CN201310060645A CN103145131A CN 103145131 A CN103145131 A CN 103145131A CN 201310060645X A CN201310060645X A CN 201310060645XA CN 201310060645 A CN201310060645 A CN 201310060645A CN 103145131 A CN103145131 A CN 103145131A
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Abstract
The invention relates to a resource comprehensive utilization method for recovering fluorine from wet-process phosphoric acid. The method comprises the following steps of: absorbing SiF4 and HF gases generated in the wet-process phosphoric acid by using water, and preparing the gases into a hydrofluosilicic acid solution of which the mass percent concentration is 10-35%; mixing one of four solids including solid sodium sulfate, solid potassium sulfate, solid sodium chloride and solid potassium chloride with the hydrofluosilicic acid solution, and reacting for 0.1-2 hours at 30-80 DEG C under stirring to obtain a mixture; centrifugally separating the obtained mixture to obtain a solid and a filtrate; and washing the solid with water, and drying for 1-3 hours at 100-120 DEG C to obtain a sodium fluorosilicate or potassium fluorosilicate crystal. According to the method, a byproduct hydrofluosilicic acid in the wet-process phosphoric acid and sodium (potassium) sulfates or chlorides which are abundant and easily-available are used as raw materials, so that the cost is low, two products including sodium fluorosilicate and potassium fluorosilicate can be produced at the same time by using one set of equipment, and the maximum utilization ratio of the hydrofluosilicic acid can reach over 99%.
Description
Technical field
The present invention relates to a kind of comprehensive utilization of resources method that reclaims fluorine from phosphoric acid by wet process, belong to the inorganic chemical industry production technical field.
Background technology
Existing natural fluorine-containing ore resource mainly contains three kinds: fluorite (main component CaF
2), fluorine-containing 49%; Natural cryolite (main component Na
3AlF
6), fluorine-containing 45%; Fluorapatite, (main component Ca
5F (PO
4)
3), fluorine-containing 3% ~ 4%.Fluorite resource wherein, particularly an acid level fluorite has faced exhaustion, so that price goes up year by year, and China just is decided to be fluorite strategic resource and strict quota restrictions has been carried out in the outlet of fluorite many years ago, and natural cryolite quantity is rare, does not possess industrial utilization and is worth.Although the fluorine content of fluorapatite is lower, fluorine-containing resource has 90% above association in phosphorus ore, and phosphorus ore is distributed more widely, and reserves are much larger than front two kinds of ore resource, and therefore fluorine-containing total amount is very considerable.
In the phosphorous chemical industry such as the phosphate fertilizer take Rock Phosphate (72Min BPL) as raw material, yellow phosphorus, phosphoric acid and phosphoric acid salt were produced, the Main By product that produces was silicofluoric acid (H
2SiF
6), directly discharging can be to the environment harm.The productive rate of China's byproduct of phosphatic fertilizer is about 50kg/tP
2O
5If by the phosphate fertilizer aggregated capacity, will have every year 1500000 tons of silicofluoric acid to need to process.Therefore, make good use of silicofluoric acid to improve the utilization ratio of fluorine resource, reduce the discharging of by-product fluorine, create that to have high value-added product be the very important strategy and policy of development fluorine chemical more.Mostly prior art is H
2SiF
6Further be processed into Na
2SiF
6, K
2SiF
6Deng the inorganic fluoride salt product.The preparation of this class inorganic fluoride salt product is except being strict with its inner quality index, and also the special requirement that proposes crystal size, require product granularity large, to prevent the harm of dust from flying to environmental and human health impacts in transportation and use procedure.
There are many drawbacks in Sodium Silicofluoride, the traditional production technique of potassium silicofluoride.Chinese patent literature CN95100688.6 discloses a kind of Na of preparation
2SiF
6Production technique, namely take fluorite as main raw material, at NH
4 +Do under the condition of catalyzer, make CaF
2And SiO
2With dilute sulphuric acid reaction preparation H
2SiF
6Solution, then make Na with the sodium salt reaction
2SiF
6The limitation of this technique is: raw material is rare fluorite resource, and production cost is high and do not meet the strategy of sustainable development; Will be with NH in reaction
4 +Make catalyzer, technique is loaded down with trivial details, operation inconvenience; The Na that makes
2SiF
6Finished particle is tiny, and quality has much room for improvement.Chinese patent literature CN02137889.4, take sodium-chlor or Klorvess Liquid as raw material and silicofluoric acid reactive crystallization, discharge on the top of reaction mother liquor autoreactor, and crystallization is from the bottom sedimentation, wash in thickener and separate through entering after washing, more both having got finished product after drying after filtration; The weak point of this technique is: simple chlorate solution take sodium or potassium is as raw material, and kind is more single; And the mother liquor of the first step reaction is directly discharged, and salts solution is not fully utilized, and causes to a certain extent the wasting of resources, the waste liquid amount of discharge is increased, the weighting ring environment pollution.Chinese patent literature CN101284669A(application number 200810018141.0) disclose the technique that a kind of sodium sulphate method is produced Sodium Silicofluoride, specifically comprised the following steps: (1) is 1: 1.0～1.2 silicofluoric acid and metabisulfite solution reaction crystallization with mol ratio; (2) throw in solid sulphuric acid sodium salt in above-mentioned reaction solution, until the mass percent concentration of sodium sulfate is 15～20%; (3) separate fluorine water glass; (4) the mother liquor salts solution enters circulation salt, reaction process again; This technique weak point is: simple chlorate solution take sodium or potassium is as raw material, and range of product is comparatively single; Except reaction raw materials, dropped into excessive sodium sulfate in order to form circulationization salt in reaction system, salt concn is increased, affect crystal and grow up, increased simultaneously cost; Have waste water to produce, environmental pollution is larger.
Summary of the invention
For the deficiencies in the prior art, in order better resource to be fully utilized, the invention provides a kind of comprehensive utilization of resources method that reclaims fluorine from phosphoric acid by wet process.
The term explanation:
Phosphoric acid by wet process of the present invention refers to the phosphoric acid that obtains with the sulfuric acid solution phosphorus ore, and by concentrated to the phosphoric acid by wet process heating, the part fluoro-gas is overflowed, and related chemical equation is as follows:
Ca
5F(PO
4)
3+H
2SO
4=CaSO
4·2H
2O↓+HF+H
3PO
4
6HF+SiO
2=H
2SiO
6+2H
2O
H
2SiO
6=SiF
4↑+2HF↑。
Technical scheme of the present invention is as follows:
A kind of comprehensive utilization of resources method that reclaims fluorine from phosphoric acid by wet process comprises the following steps:
(1) with the SiF of the generation in phosphoric acid by wet process
4Absorb with HF gas water, make mass percentage concentration and be 10% ~ 35% silicate fluoride solution;
(2) solid sodium sulfate, solid sulphuric acid potassium, solid sodium chloride or the solid Repone K silicate fluoride solution with step (1) is mixed, 30 ~ 80 ℃ of stirring reactions 0.1 ~ 2 hour get mixture;
When solid was sodium sulfate or vitriolate of tartar, silicofluoric acid: the mol ratio of sodium sulfate or vitriolate of tartar was 1.0: (0.8～1.0); Perhaps, when solid was sodium-chlor or Repone K, silicofluoric acid: the mol ratio of sodium-chlor or Repone K was 1: (1.6 ~ 2.0);
(3) with the centrifugation of step (2) gained mixture, get solid and filtrate; Solid obtained Sodium Silicofluoride or potassium silicofluoride crystal in 1 ~ 3 hour through water washing, 100～120 ℃ of dryings.
Preferred according to the present invention, the described temperature of reaction of step (2) is 40 ~ 70 ℃.
Preferred according to the present invention, step (3) also comprises to be processed and recycles described filtrate, and step is as follows:
When the solid of step (2) was sodium sulfate or vitriolate of tartar, it was 90 ~ 98% that filtrate is concentrated into the sulfuric acid massfraction, gets the vitriol oil.The vitriol oil is used for preparing phosphoric acid with Rock Phosphate (72Min BPL) reaction wet method;
Perhaps, when the solid of step (2) was sodium-chlor or Repone K, in filtrate, the mass concentration of hydrogenchloride was 15 ~ 33%.Directly sell as byproduct hydrochloric acid.
Chemical equation related in technical solution of the present invention is as follows:
SiF
4+2HF=H
2Si
2F
6
3SiF
4+2H
2O=2H
2SiF
6+SiO
2↓
H
2SiF
6+Na
2SO
4/K
2SO
4=Na
2SiF
6/K
2SiF
6+H
2SO
4
H
2SiF
6+2NaCl/KCl=Na
2SiF
6/K
2SiF
6+2HCl
The present invention will utilize defluorinating agent the fluorine of 2% left and right contained in phosphoric acid to be deviate to form the silicofluoride of insoluble after wet phosphoric acid purifying, obtain the silicofluoride product through sedimentation, washing, separation oven dry, reaches resource rational utilization, increases Business Economic Benefit.The present invention fully recycles the fluorine resource in composite fertilizer's production process, produces high-quality floride-free composite fertilizer, reduction or the elimination harm to soil.Compare the present invention with existing production technique and have following beneficial effect:
1, the present invention is raw material with the fluosilicic acid as byproduct in phosphoric acid by wet process and sodium (potassium) vitriol or chlorate rich and easy to get, and is with low cost, and a set of equipment can be produced Sodium Silicofluoride, two kinds of products of potassium silicofluoride simultaneously.
2, compare with traditional method, the present invention is by regulating the mol ratio of silicofluoric acid and sodium sulfate (potassium) or sodium-chlor (potassium), allow potassium silicofluoride keep excessive or complete reaction in reaction process, reduce salt concn in reaction soln, temperature is more easily controlled and is helped crystal size to increase.
3, silicofluoric acid utilization ratio of the present invention reaches as high as more than 99%.
4, reaction by-product sulfuric acid of the present invention can directly reclaim the raw material of doing the preparation phosphoric acid by wet process, and hydrochloric acid is directly as commodity selling.
5, method operation of the present invention is simple and direct, reduce production costs, and also simple to operate, the utilization ratio of raw material is high, substantially there is no three waste discharge, finally reaches the purpose of energy-saving and emission-reduction.
Description of drawings
Fig. 1 is that the present invention is take chlorate as the raw material process schema.
Fig. 2 is that the present invention is take vitriol as the raw material process schema.
Embodiment
The present invention will be further described below by specific embodiment, but be not limited to this.
SiF in embodiment in phosphoric acid by wet process
4With HF gas, be derived from the water-soluble fertile project in base, Shandong Kingenta Bio-engineering Stock Co., Ltd. Guizhou; Reaction crystalizer is conventional equipment, and Chengdu Cheng De chemical science and technology limited liability company is on sale.
Embodiment 1
Water absorbs the SiF in phosphoric acid by wet process
4Making mass percentage concentration with HF gas is 15% silicate fluoride solution, getting 2000 kilograms of mass percent concentrations and be 15% silicate fluoride solution adds in reaction crystalizer, and according to silicofluoric acid: the mol ratio of the sodium sulfate ratio of 1.0: 0.8 slowly adds the sodium sulfate solid while stirring, 50 ℃ of stirring reactions had a large amount of Sodium Silicofluoride crystallizations after 1.5 hours; After reaction finishes, stop stirring, sedimentation half an hour, through centrifugal solid and filtrate; The rear 100 ℃ of dryings of solid water washing 3 hours obtain 313 kilograms of Sodium Silicofluorides; Filtrate is the sulphuric acid soln of massfraction 23%, and it is 90% rear direct raw material as the preparation phosphoric acid by wet process that sulphuric acid soln is concentrated into massfraction.
Embodiment 2
As described in Example 1, difference is according to silicofluoric acid: the mol ratio of the vitriolate of tartar ratio of 1.0: 0.9 adds 2000 kilograms of mass percent concentrations in reaction crystalizer be 15% silicate fluoride solution and vitriolate of tartar solid, 60 ℃ of stirring reactions had a large amount of potassium silicofluoride crystallizations after 1 hour; After reaction finishes, stop stirring, sedimentation half an hour, through centrifugal solid and filtrate; The rear 120 ℃ of dryings of solid water washing 1 hour obtain 412 kilograms of potassium silicofluorides, and filtrate is the sulphuric acid soln of massfraction 31%, and it is 98% rear direct raw material as the preparation phosphoric acid by wet process that sulphuric acid soln is concentrated into massfraction.
Embodiment 3
Water absorbs the SiF in phosphoric acid by wet process
4Making mass percentage concentration with HF gas is 20% silicate fluoride solution, adding 2400 kilograms of mass percent concentrations in reaction crystalizer is 20% silicate fluoride solution, and according to silicofluoric acid: the mol ratio of the sodium-chlor ratio of 1.0: 1.8 slowly adds solid sodium chloride while stirring, 70 ℃ of stirring reactions had a large amount of Sodium Silicofluoride crystallizations after 0.5 hour; After reaction finishes, through centrifugal solid and filtrate; The rear 110 ℃ of dryings of solid water washing 2 hours obtain 565 kilograms of Sodium Silicofluorides, and filtrate is the hydrochloric acid soln of massfraction 28%, and hydrochloric acid soln is directly as commodity selling.
Embodiment 4
Water absorbs the SiF in phosphoric acid by wet process
4Making mass percentage concentration with HF gas is 20% silicate fluoride solution, adding 2400 kilograms of mass percent concentrations in reaction crystalizer is 25% silicate fluoride solution, and according to silicofluoric acid: the mol ratio of the Repone K ratio of 1.0: 1.8 slowly adds solid Repone K while stirring, 70 ℃ of stirring reactions had a large amount of potassium silicofluoride crystallizations after 0.5 hour; After reaction finishes, through centrifugal solid and filtrate; The rear 100 ℃ of dryings of solid water washing 3 hours obtain 687 kilograms of potassium silicofluorides, and filtrate is the hydrochloric acid soln of massfraction 33%, and hydrochloric acid soln is directly as commodity selling.
Embodiment 5
As described in Example 3, difference is that to add 3000 kilograms of mass percent concentrations in reaction crystalizer be 10% silicate fluoride solution, and slowly add while stirring solid sodium chloride according to the mol ratio ratio of 1.0: 2.0 of silicofluoric acid and sodium-chlor, 55 ℃ of stirring reactions 1.5 hours have a large amount of Sodium Silicofluoride crystallizations; After reaction finishes, through centrifugal solid and filtrate; The rear 120 ℃ of dryings of solid water washing 1 hour obtain 392 kilograms of Sodium Silicofluorides, and filtrate is the hydrochloric acid soln of massfraction 16%, and hydrochloric acid soln is directly as commodity selling.
Embodiment 6
As described in Example 2, difference is that to add 3000 kilograms of mass percent concentrations in reaction crystalizer be 30% silicate fluoride solution, and slowly add while stirring the vitriolate of tartar solid according to the mol ratio ratio of 1.0: 1.0 of silicofluoric acid and vitriolate of tartar, 65 ℃ of stirring reactions 2 hours have a large amount of potassium silicofluoride crystallizations; After reaction finishes, through centrifugal solid and filtrate; The rear 120 ℃ of dryings of solid water washing 2 hours obtain 1371 kilograms of potassium silicofluorides, and filtrate is the sulphuric acid soln of massfraction 66%, and it is 93% rear direct raw material as the preparation phosphoric acid by wet process that sulphuric acid soln is concentrated into massfraction.
Claims (3)
1. a comprehensive utilization of resources method that reclaims fluorine from phosphoric acid by wet process, is characterized in that, comprises the following steps:
(1) with the SiF of the generation in phosphoric acid by wet process
4Absorb with HF gas water, make mass percentage concentration and be 10% ~ 35% silicate fluoride solution;
(2) solid sodium sulfate, solid sulphuric acid potassium, solid sodium chloride or the solid Repone K silicate fluoride solution with step (1) is mixed, 30 ~ 80 ℃ of stirring reactions 0.1 ~ 2 hour get mixture;
When solid was sodium sulfate or vitriolate of tartar, silicofluoric acid: the mol ratio of sodium sulfate or vitriolate of tartar was 1.0: (0.8 ~ 1.0); Perhaps, when solid was sodium-chlor or Repone K, silicofluoric acid: the mol ratio of sodium-chlor or Repone K was 1: (1.6 ~ 2.0);
(3) with the centrifugation of step (2) gained mixture, get solid and filtrate; Solid obtained Sodium Silicofluoride or potassium silicofluoride crystal in 1 ~ 3 hour through water washing, 100 ~ 120 ℃ of dryings.
2. the comprehensive utilization of resources method that reclaims fluorine from phosphoric acid by wet process according to claim 1, is characterized in that, the described temperature of reaction of step (2) is 40 ~ 70 ℃.
3. the comprehensive utilization of resources method that reclaims fluorine from phosphoric acid by wet process according to claim 1, is characterized in that, step (3) also comprises to be processed and recycle described filtrate, and step is as follows:
When the solid of step (2) was sodium sulfate or vitriolate of tartar, it was 90 ~ 98% that filtrate is concentrated into the sulfuric acid massfraction, gets the vitriol oil, and the vitriol oil is used for preparing phosphoric acid with Rock Phosphate (72Min BPL) reaction wet method;
Perhaps, when the solid of step (2) was sodium-chlor or Repone K, in filtrate, the mass concentration of hydrogenchloride was 15 ~ 33%.Directly sell as hydrochloric acid.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211068A (en) * | 2014-09-18 | 2014-12-17 | 福建省漳平展鹏化工有限公司 | Preparation method of large granular potassium fluosilicate |
| CN105110536A (en) * | 2015-08-19 | 2015-12-02 | 石家庄工大化工设备有限公司 | Recycling method for high-salinity wastewater containing sodium chloride and sodium sulfate |
| CN105174270A (en) * | 2015-10-15 | 2015-12-23 | 湖南有色氟化学科技发展有限公司 | Technology for preparing sodium fluorosilicate through fluoride-containing wastewater |
| CN105439150A (en) * | 2015-11-30 | 2016-03-30 | 洛阳绿仁环保设备有限公司 | Method for preparing sodium fluosilicate by adopting potassium feldspar decomposed gas absorption liquid |
| CN107381578A (en) * | 2017-07-17 | 2017-11-24 | 贵州川恒化工股份有限公司 | The method that defluorination residues purification prepares prodan |
| CN107827113A (en) * | 2017-11-29 | 2018-03-23 | 湖北祥云(集团)化工股份有限公司 | In a kind of industrial monoammonium phosphate and slurry in fluorine recovery method |
| CN109647137A (en) * | 2019-01-04 | 2019-04-19 | 襄阳泽东化工集团有限公司 | A kind of fluorine absorption system for phosphoric acid by wet process |
| CN112320820A (en) * | 2020-10-27 | 2021-02-05 | 贵州省化工研究院 | Method for producing high-purity sodium fluoride by utilizing fluosilicic acid in phosphoric acid |
| CN114345106A (en) * | 2021-12-30 | 2022-04-15 | 湖北瓮福蓝天化工有限公司 | Method and system for removing chlorine element in anhydrous hydrogen fluoride production process |
| CN115385341A (en) * | 2022-09-27 | 2022-11-25 | 江西拓泓新材料有限公司 | Method for preparing potassium fluosilicate by recovering acid wastewater from tantalum-niobium hydrometallurgy |
| CN118005021A (en) * | 2024-02-22 | 2024-05-10 | 鑫时基(江苏南京)企业管理咨询服务有限责任公司 | Method for preparing fluorosilicate from fluorine-containing waste liquid of acid washing process |
| WO2024197510A1 (en) * | 2023-03-27 | 2024-10-03 | 广东邦普循环科技有限公司 | Method for preparing sodium fluorosilicate by using fluorosilicic acid which is by-product of wet-process phosphoric acid, and device therefor |
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| CN104211068B (en) * | 2014-09-18 | 2015-11-11 | 福建省漳平展鹏化工有限公司 | A kind of preparation method of macrobead potassium silicofluoride |
| CN104211068A (en) * | 2014-09-18 | 2014-12-17 | 福建省漳平展鹏化工有限公司 | Preparation method of large granular potassium fluosilicate |
| CN105110536A (en) * | 2015-08-19 | 2015-12-02 | 石家庄工大化工设备有限公司 | Recycling method for high-salinity wastewater containing sodium chloride and sodium sulfate |
| CN107902823A (en) * | 2015-08-19 | 2018-04-13 | 石家庄工大化工设备有限公司 | The recovery and treatment method of the high-salt wastewater of sodium chloride-containing and sodium sulphate |
| CN105174270A (en) * | 2015-10-15 | 2015-12-23 | 湖南有色氟化学科技发展有限公司 | Technology for preparing sodium fluorosilicate through fluoride-containing wastewater |
| CN105439150A (en) * | 2015-11-30 | 2016-03-30 | 洛阳绿仁环保设备有限公司 | Method for preparing sodium fluosilicate by adopting potassium feldspar decomposed gas absorption liquid |
| CN107381578A (en) * | 2017-07-17 | 2017-11-24 | 贵州川恒化工股份有限公司 | The method that defluorination residues purification prepares prodan |
| CN107827113B (en) * | 2017-11-29 | 2020-05-15 | 湖北祥云(集团)化工股份有限公司 | Method for recovering fluorine in industrial monoammonium phosphate neutralized slag slurry |
| CN107827113A (en) * | 2017-11-29 | 2018-03-23 | 湖北祥云(集团)化工股份有限公司 | In a kind of industrial monoammonium phosphate and slurry in fluorine recovery method |
| CN109647137A (en) * | 2019-01-04 | 2019-04-19 | 襄阳泽东化工集团有限公司 | A kind of fluorine absorption system for phosphoric acid by wet process |
| CN109647137B (en) * | 2019-01-04 | 2021-08-10 | 襄阳泽东化工集团有限公司 | Fluorine absorption system for wet-process phosphoric acid |
| CN112320820A (en) * | 2020-10-27 | 2021-02-05 | 贵州省化工研究院 | Method for producing high-purity sodium fluoride by utilizing fluosilicic acid in phosphoric acid |
| CN114345106A (en) * | 2021-12-30 | 2022-04-15 | 湖北瓮福蓝天化工有限公司 | Method and system for removing chlorine element in anhydrous hydrogen fluoride production process |
| CN114345106B (en) * | 2021-12-30 | 2023-12-12 | 湖北瓮福蓝天化工有限公司 | Method and system for removing chlorine element in anhydrous hydrogen fluoride production process |
| CN115385341A (en) * | 2022-09-27 | 2022-11-25 | 江西拓泓新材料有限公司 | Method for preparing potassium fluosilicate by recovering acid wastewater from tantalum-niobium hydrometallurgy |
| CN115385341B (en) * | 2022-09-27 | 2024-04-16 | 江西拓泓新材料有限公司 | Method for preparing potassium fluosilicate by recycling acid wastewater generated in tantalum-niobium wet smelting |
| WO2024197510A1 (en) * | 2023-03-27 | 2024-10-03 | 广东邦普循环科技有限公司 | Method for preparing sodium fluorosilicate by using fluorosilicic acid which is by-product of wet-process phosphoric acid, and device therefor |
| CN118005021A (en) * | 2024-02-22 | 2024-05-10 | 鑫时基(江苏南京)企业管理咨询服务有限责任公司 | Method for preparing fluorosilicate from fluorine-containing waste liquid of acid washing process |
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Application publication date: 20130612 |