CN107500249B - Comprehensive utilization method of acid-etched glass slag - Google Patents
Comprehensive utilization method of acid-etched glass slag Download PDFInfo
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- CN107500249B CN107500249B CN201710829879.4A CN201710829879A CN107500249B CN 107500249 B CN107500249 B CN 107500249B CN 201710829879 A CN201710829879 A CN 201710829879A CN 107500249 B CN107500249 B CN 107500249B
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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
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/10—Compounds containing silicon, fluorine, and other elements
- C01B33/103—Fluosilicic acid; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
- C01F7/743—Preparation from silicoaluminious materials, e.g. clays or bauxite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention provides a method for comprehensively utilizing acid-etched glass slag, which comprises the following steps: (1) heating the acid etching glass slag, evaporating the fluorine-containing acid liquid on the surface of the acid etching glass slag, and absorbing the fluorine-containing acid liquid into the fluorine-containing acid liquid by using water; (2) placing the dried glass slag and concentrated sulfuric acid in a reactor, adopting indirect heating, condensing the gas generated by the reaction to obtain anhydrous hydrogen fluoride, and absorbing the uncondensed gas by using water; outputting the material slag; (3) putting the material residues into the process water for dissolving; the dissolved solution is aluminum sulfate solution, and aluminum sulfate solid products can be prepared by concentration; and carrying out solid-liquid separation on undissolved solids to obtain a finished product of strontium sulfate or/and calcium sulfate. The invention recovers fluorine in the glass slag generated in the glass thinning process to prepare anhydrous hydrogen fluoride and fluosilicic acid, and prepares aluminum and strontium into aluminum sulfate and strontium sulfate with economic value, thereby not only solving the problem of treatment of the glass slag as hazardous waste, but also obtaining products with higher economic value, and being suitable for industrialized popularization and application.
Description
Technical Field
The invention relates to the field of waste treatment in a glass thinning process, in particular to comprehensive utilization of acid-etched glass slag.
Background
Electronic equipment is developing towards the direction of lightness and thinness all the time, so that in the production process of a glass display screen of mobile equipment or handheld equipment, a glass thinning procedure is adopted, and the thickness of the glass of the display screen meets the process requirement in a chemical corrosion mode; a certain amount of precipitates will be produced during the thinning process, which is referred to in the glass thinning industry as glass cullet.
The glass components used for preparing the display screen all contain SiO2、Al2O3、B2O3At the same time, MgO, CaO, SrO, etc. are added to adjust the characteristics of the glass. At present, hydrofluoric acid is adopted as a main thinning chemical in the glass thinning industry, the main component of glass slag generated in the thinning process is aluminum fluoride, and a small amount of strontium fluoride and calcium fluoride are contained (silicon and fluorine form fluorosilicic acid solution, and boron and fluorine form fluoroboric acid)A solution). Along with the process of thinning, the glass slag is gradually increased, and when the content of the glass slag in the thinning liquid reaches a certain amount, the glass slag must be filtered and discharged out of a thinning system, otherwise, the thinning efficiency and quality of the glass are seriously influenced.
The glass slag is a hazardous waste due to its characteristics. Glass thinning enterprises generally entrust units with hazardous waste treatment qualification to carry out harmless treatment, and the treatment cost reaches 5500 yuan/ton; and in glass thinning enterprises, the glass slag is mixed with the wastewater in the production process and then treated with lime in a harmless way, and the treatment cost reaches 2000 yuan/ton. Whatever treatment mode is adopted, fluorine-containing substances in the glass slag are converted into calcium fluoride sludge; the method wastes the fluorine resource and the aluminum resource which are in short supply, wastes a large amount of lime and brings burden to environmental management.
In view of this, the process of treating the waste such as the glass slag to obtain a product with higher economic value is very important.
Disclosure of Invention
The invention provides a method for comprehensively utilizing acid-etched glass slag, which solves the problems of high glass slag treatment cost and waste of fluorine and aluminum resources in glass thinning in the prior art.
The technical scheme of the invention is realized as follows:
a method for comprehensively utilizing acid-etched glass slag comprises the following steps:
(1) drying the glass slag: heating the acid etching glass slag, evaporating the fluorine-containing acid liquid on the surface of the acid etching glass slag, and absorbing the fluorine-containing acid liquid into the fluorine-containing acid liquid by using water;
(2) sulfuric acid reaction: placing the glass slag dried in the step (1) and concentrated sulfuric acid into a reactor, adopting indirect heating, controlling the reaction temperature to be 120-600 ℃, condensing the gas generated in the reaction to obtain anhydrous hydrogen fluoride, and absorbing the uncondensed gas into fluosilicic acid by using water; after full reaction, discharging slag in the reactor;
(3) dissolving in water: putting the material slag obtained in the step (2) into process water, and dissolving under stirring; the dissolved solution is aluminum sulfate solution, and aluminum sulfate solid products can be prepared by concentration; and carrying out solid-liquid separation on undissolved solids to obtain a finished product of strontium sulfate or/and calcium sulfate.
As a preferred technical scheme, the process conditions for drying the glass slag in the step (1) are as follows: indirectly heating with hot air at 100-500 deg.C, absorbing acid-containing steam generated by evaporation with water in a spray absorption tower, cooling tail gas during spraying, and controlling the temperature of gas discharged into atmosphere to be lower than 50 deg.C; discharging the fluorine-containing acid solution after the concentration of the fluorine-containing acid in the spray solution reaches a process value to obtain the fluorine-containing acid solution; and returning the fluorine-containing acid to the glass thinning process flow. More preferably, the heating temperature is 350-450 ℃; the initial spraying liquid is process water, and the fluorine-containing acid is recycled before the concentration of the fluorine-containing acid reaches the process concentration.
Preferably, the concentrated sulfuric acid in the step (2) includes one or a combination of more of 92-98% sulfuric acid, 105% sulfuric acid, and waste sulfuric acid with a concentration of 90% or more.
As a preferable technical scheme, the reaction temperature in the step (2) is 250-400 ℃, and the reaction residence time is controlled to be 20-600 minutes. More preferably, the reaction residence time is controlled to 180 to 420 minutes
As a preferred technical scheme, the reaction gas in the step (2) is cooled by concentrated sulfuric acid spraying, then condensed and rectified to obtain an anhydrous hydrogen fluoride product, and the non-condensable gas in the reaction gas is absorbed by water to obtain a fluosilicic acid solution.
As a preferable technical scheme, the water dissolving temperature in the step (3) is controlled to be between room temperature and 120 ℃.
Preferably, the acid-etched glass slag in the step (1) is solid waste generated after the glass material reacts with hydrofluoric acid.
As a preferable technical scheme, the acid etching glass slag in the step (1) is derived from a display glass panel thinning process; the acid etching glass slag at least contains fluoride salt of aluminum, strontium and calcium.
Advantageous effects
(1) The invention recovers fluorine in the glass slag generated in the glass thinning process to prepare anhydrous hydrogen fluoride and fluosilicic acid, and prepares aluminum and strontium into aluminum sulfate and strontium sulfate with economic value, thereby not only solving the problem of treatment of the glass slag as hazardous waste, but also obtaining products with higher economic value, and being suitable for industrialized popularization and application.
(2) The invention has the advantages of short treatment process flow, simple conditions, no need of complex equipment, less investment and high return rate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The materials used in the following examples are commercially available and may be conveniently purchased from commercial sources.
The method for comprehensively utilizing the acid-etched glass slag in the following embodiments comprises the steps of (1) heating at 100-500 ℃, and (2) controlling the reaction temperature at 120-600 ℃ and the reaction residence time at 20-600 minutes. These values are all able to achieve the object of the invention. And will not be described in detail.
Example 1
Glass frits used in this example: the glass slag discharged from a certain glass thinning workshop is reduced by 56.50 percent, and the solid content is 43.50 percent (wherein the aluminum fluoride is 28.00 percent, the magnesium fluoride is 0.17 percent, the calcium fluoride is 5.71 percent, the strontium fluoride is 9.09 percent, and the other is 0.53 percent); the mother liquor in the glass slag filtering process comprises the following components: HF-10%, H2SiF610 percent to 10 percent, HCl to 5 percent, soluble salt to 0.93 percent and the rest is process water.
A method for comprehensively utilizing acid-etched glass slag comprises the following steps:
step S1: drying the glass slag
Starting a tail gas absorption system and a heating system of the rotary kiln, controlling the rotary kiln to rotate at 1rpm, taking 500kg of fluorgypsum, putting the fluorgypsum into the rotary kiln by using a screw, immediately feeding 2000kg of wet glass residue into the rotary kiln, and then using the wet glass residue to carry out dryingCleaning 500kg of fluorgypsum spiral, controlling the hot air temperature of the rotary kiln to be 500 ℃, outputting the mixed material from the tail of the kiln, naturally cooling, and packaging into ton bags for later use. The furnace end dry tail gas is absorbed by tap water to obtain 2000kg of recovered fluorine-containing acid (HF-5.6%, H)2SiF6——5.65％、HCl——2.8％)。
Step S2: digestion of glass slag
Starting a tail gas absorption system and a heating system of a rotary kiln, controlling the rotating speed of the rotary kiln to be 1.5rpm, taking 1000kg of fluorgypsum, putting the fluorgypsum into the rotary kiln by using a screw, immediately feeding 1275kg of dried glass slag/fluorgypsum mixture and 1275kg (mixed acid of 98 percent sulfuric acid and fuming sulfuric acid, namely 100 percent sulfuric acid prepared by 98 percent sulfuric acid and fuming sulfuric acid) into the rotary kiln, cleaning the screw by using 500kg of fluorgypsum, controlling the hot air temperature of the rotary kiln to be 500 ℃, outputting reaction material slag from a furnace tail, naturally cooling, and sampling and analyzing (the content of calcium sulfate is 65.61 percent, the content of aluminum sulfate is 27.72 percent and the content of strontium sulfate is 6.46. The reaction gas at the furnace end is absorbed by tap water to obtain 2520kg of hydrofluoric acid (HF-10.20%, H)2SO4——0.09％)。
Step S3: treatment of reaction slag
To 0.5M3Adding 350Kg of tap water into a reaction kettle with a stirrer, taking 100Kg of reaction slag at the furnace tail, starting stirring, adding the reaction slag into the reaction kettle, starting a jacket electric heater after the feeding is finished, starting timing and keeping the temperature for 2 hours when the temperature of the suspension reaches 110 ℃, and filtering to obtain 269Kg of mother liquor (the concentration of aluminum sulfate is 7.33%); the filter cake was washed 5 times with tap water and sampled for analysis and the filter cake composition was as follows (dry basis): 89.98 percent of calcium sulfate and 9.04 percent of strontium sulfate.
Note: the fluorgypsum is added to protect the reaction rotary furnace, and the method is adopted to protect the reaction rotary furnace when the normal fluorite-sulfuric acid method is used for producing hydrofluoric acid.
Example 2
Glass frits used in this example: the glass slag discharged from a certain glass thinning workshop is reduced by 56.50 percent, and the solid content is 43.50 percent (wherein the aluminum fluoride is 28.00 percent, the magnesium fluoride is 0.17 percent, the calcium fluoride is 5.71 percent, the strontium fluoride is 9.09 percent, and the other is 0.53 percent); glassThe mother liquor in the slag filtration process comprises the following components: HF-10%, H2SiF610 percent to 10 percent, HCl to 5 percent, soluble salt to 0.93 percent and the rest is process water.
A method for comprehensively utilizing acid-etched glass slag comprises the following steps:
step S1: drying the glass slag
Starting a rotary kiln tail gas absorption system and a heating system, controlling the rotary kiln to rotate at 1rpm, taking 500kg of fluorgypsum, putting the fluorgypsum into the rotary kiln by using a screw, immediately feeding 2000kg of wet glass residue into the rotary kiln, cleaning the screw by using 500kg of fluorgypsum, indirectly heating by using hot air, controlling the hot air temperature of the rotary kiln to be 150 ℃, outputting the mixed material from the tail of the rotary kiln, naturally cooling, and packaging into ton bags for later use. The furnace end dry tail gas is absorbed by a spray tower absorption tower, the spray liquid is tap water, the temperature of the spray liquid is reduced by a graphite heat exchanger in the spraying process, the temperature of the spray liquid is controlled to be lower than 50 ℃, and 2050kg of recovered fluorine-containing acid (HF-5.35%, H2SiF 6-5.45%, HCl-2.84%) is obtained.
Step S2: digestion of glass slag
Starting a tail gas absorption system and a heating system of a rotary kiln, controlling the rotating speed of the rotary kiln to be 1.5rpm, taking 1000Kg of fluorgypsum, putting the fluorgypsum into the rotary kiln by using a screw, immediately feeding a dried glass slag/fluorgypsum mixture and 1285Kg (using 90% of mixed acid of waste acid and fuming sulfuric acid) into the rotary kiln, cleaning the screw by using 500Kg of fluorgypsum, controlling the hot air temperature of the rotary kiln to be 600 ℃, outputting reaction material slag from the tail of the rotary kiln, naturally cooling, and sampling and analyzing (the content of calcium sulfate is 65.63%, the content of aluminum sulfate is 27.71% and the content of strontium sulfate is 6.45%). The furnace end reaction gas is sprayed and cooled by concentrated sulfuric acid, and then condensed and rectified to obtain 2512kg of hydrogen fluoride (HF-10.14%, H)2SO4——0.08％)。
Step S3: treatment of reaction slag
To 0.5M3350Kg of tap water is put into a reaction kettle with a stirrer, 100Kg of furnace tail reaction material slag is taken, the stirring is started, the reaction material slag is put into the reaction kettle, after the feeding is finished, a jacket electric heater is started, when the temperature of the suspension liquid reaches 110 ℃, the timing is started and the heat preservation is carried out2h, filtering to obtain 267kg of mother liquor (the concentration of aluminum sulfate is 7.32%); the filter cake was washed 5 times with tap water and sampled for analysis and the filter cake composition was as follows (dry basis): 89.96 percent of calcium sulfate and 9.03 percent of strontium sulfate.
Note: the fluorgypsum is added to protect the reaction rotary furnace, and the method is adopted to protect the reaction rotary furnace when the normal fluorite-sulfuric acid method is used for producing hydrofluoric acid.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A method for comprehensively utilizing acid-etched glass slag comprises the following steps:
(1) drying the glass slag: heating the acid etching glass slag, evaporating the fluorine-containing acid liquid on the surface of the acid etching glass slag, and absorbing the fluorine-containing acid liquid into the fluorine-containing acid liquid by using water; the acid-etched glass slag is solid waste generated after the reaction of a glass material and hydrofluoric acid;
(2) sulfuric acid reaction: placing the glass slag dried in the step (1) and concentrated sulfuric acid into a reactor, adopting indirect heating, controlling the reaction temperature to be 120-600 ℃, condensing the gas generated in the reaction to obtain anhydrous hydrogen fluoride, and absorbing the uncondensed gas into fluosilicic acid by using water; after full reaction, discharging slag in the reactor;
(3) dissolving in water: putting the material slag obtained in the step (2) into process water, and dissolving under stirring; the dissolved solution is aluminum sulfate solution, and aluminum sulfate solid products are prepared by concentration; and carrying out solid-liquid separation on undissolved solids to obtain a finished product of strontium sulfate or/and calcium sulfate.
2. The method for comprehensively utilizing acid-etched glass slag according to claim 1, wherein the process conditions for drying the glass slag in the step (1) are as follows: indirectly heating with hot air at 100-500 deg.C, absorbing acid-containing steam generated by evaporation with water in a spray absorption tower, cooling tail gas during spraying, and controlling the temperature of gas discharged into atmosphere to be lower than 50 deg.C; discharging the fluorine-containing acid solution after the concentration of the fluorine-containing acid in the spray solution reaches a process value to obtain the fluorine-containing acid solution; and returning the fluorine-containing acid to the glass thinning process flow.
3. The method for comprehensively utilizing the acid-etched glass slag according to claim 2, wherein the heating temperature is 350-450 ℃; the initial spraying liquid is process water, and the fluorine-containing acid is recycled before the concentration of the fluorine-containing acid reaches the process concentration.
4. The method for comprehensively utilizing the acid-etched glass slag according to claim 1, wherein the concentrated sulfuric acid in the step (2) comprises one or a combination of 92-98% of sulfuric acid, 105% of sulfuric acid and waste sulfuric acid with the concentration of 90% or more.
5. The method for comprehensively utilizing the acid-etched glass slag according to claim 1, wherein the reaction temperature in the step (2) is 250-400 ℃, and the reaction residence time is controlled to be 20-600 minutes.
6. The method for comprehensively utilizing acid-etched glass slag according to claim 1, wherein the reaction gas in the step (2) is sprayed and cooled by concentrated sulfuric acid, and then condensed and rectified to obtain an anhydrous hydrogen fluoride product, and the non-condensable gas in the reaction gas is absorbed by water to obtain a fluosilicic acid solution.
7. The method for comprehensively utilizing the acid-etched glass slag according to claim 1, wherein the water dissolution temperature in the step (3) is controlled to be between room temperature and 120 ℃.
8. The method for comprehensively utilizing the acid-etched glass slag according to claim 1, wherein the acid-etched glass slag in the step (1) is obtained from a display glass panel thinning process; the acid etching glass slag at least contains fluoride salt of aluminum, strontium and calcium.
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| CN113860257B (en) * | 2021-11-04 | 2022-04-22 | 浙江容跃环保科技有限公司 | Method and system for regenerating and recycling glass thinning waste acid liquor |
Citations (4)
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| CN102249279A (en) * | 2010-12-21 | 2011-11-23 | 王莉 | Method for using vitriol sludge hydrolyzed filter cake to prepare aluminum sulfate and byproduct calcium sulfate |
| CN102502502A (en) * | 2011-11-08 | 2012-06-20 | 湖南有色郴州氟化学有限公司 | Method for preparing hydrogen fluoride gas from 98% sulphuric acid |
| CN103539127A (en) * | 2013-10-31 | 2014-01-29 | 洛阳氟钾科技有限公司 | Process for decomposing potash feldspars |
| CN104341111A (en) * | 2013-07-26 | 2015-02-11 | 睿志达光电(深圳)有限公司 | Glass etching solution regeneration method and glass etching method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249279A (en) * | 2010-12-21 | 2011-11-23 | 王莉 | Method for using vitriol sludge hydrolyzed filter cake to prepare aluminum sulfate and byproduct calcium sulfate |
| CN102502502A (en) * | 2011-11-08 | 2012-06-20 | 湖南有色郴州氟化学有限公司 | Method for preparing hydrogen fluoride gas from 98% sulphuric acid |
| CN104341111A (en) * | 2013-07-26 | 2015-02-11 | 睿志达光电(深圳)有限公司 | Glass etching solution regeneration method and glass etching method |
| CN103539127A (en) * | 2013-10-31 | 2014-01-29 | 洛阳氟钾科技有限公司 | Process for decomposing potash feldspars |
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