CN115403056A - Comprehensive utilization method of by-products fluosilicic acid, dilute ammonia water and sodium sulfate - Google Patents
Comprehensive utilization method of by-products fluosilicic acid, dilute ammonia water and sodium sulfate Download PDFInfo
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- CN115403056A CN115403056A CN202211173162.6A CN202211173162A CN115403056A CN 115403056 A CN115403056 A CN 115403056A CN 202211173162 A CN202211173162 A CN 202211173162A CN 115403056 A CN115403056 A CN 115403056A
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- ammonia water
- sodium sulfate
- fluosilicic acid
- dilute ammonia
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 70
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 70
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 70
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 235000011114 ammonium hydroxide Nutrition 0.000 title claims abstract description 61
- 239000006227 byproduct Substances 0.000 title claims abstract description 61
- 239000002253 acid Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000000243 solution Substances 0.000 claims abstract description 58
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000001914 filtration Methods 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 33
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 28
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 27
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 27
- 229940034610 toothpaste Drugs 0.000 claims abstract description 26
- 239000000606 toothpaste Substances 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000012065 filter cake Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000012045 crude solution Substances 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000002686 phosphate fertilizer Substances 0.000 abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 5
- 159000000002 lithium salts Chemical class 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000005915 ammonolysis reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 229910052629 lepidolite Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/02—Fluorides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- 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
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/186—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof from or via fluosilicic acid or salts thereof by a wet process
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
-
- 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
- C01P2006/19—Oil-absorption capacity, e.g. DBP values
-
- 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
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- 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
-
- 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
- C01P2006/90—Other properties not specified above
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a comprehensive utilization method of by-products of fluosilicic acid, dilute ammonia water and sodium sulfate, which comprises the following steps: a. adding activated carbon into the byproduct diluted ammonia water to adsorb organic oil impurities, stirring for reaction, and filtering to obtain an ammonia water filtrate; b. adding the byproduct fluosilicic acid into the ammonia water filtrate, stirring for reaction, filtering and washing to obtain a silicon dioxide filter cake and an ammonium fluoride solution, and drying the silicon dioxide filter cake to obtain silicon dioxide for toothpaste; wherein the RDA of the silica for toothpaste is less than or equal to 90; c. adding alkali liquor to adjust the pH value of the by-product sodium sulfate crude solution to 10-11, stirring for reaction, filtering to remove metal impurity precipitate, and obtaining sodium sulfate refined solution; d. and c, mixing and stirring the ammonium fluoride solution obtained in the step b and the sodium sulfate refined solution obtained in the step c, reacting at the temperature of 50-80 ℃, and filtering and washing to obtain the silicon-free sodium fluoride. The invention realizes the effective recycling of the by-products of fluosilicic acid, dilute ammonia water and sodium sulfate, and solves the environmental protection problem in the phosphate fertilizer industry and the lithium salt industry.
Description
Technical Field
The invention relates to chemical waste treatment, in particular to a comprehensive utilization method of by-products of fluosilicic acid, dilute ammonia water and sodium sulfate.
Background
Can produce a large amount of fluosilicic acid and weak ammonia water in the phosphorus fertilizer production process, at present, phosphorus fertilizer by-product fluosilicic acid mainly used produces sodium fluosilicate, sells as the raw materials for producing sodium fluoride in the sodium fluoride factory. However, a large amount of carbon dioxide is generated in the process of preparing sodium fluoride from sodium fluosilicate, and is influenced by the policy of national carbon neutralization and carbon peak reaching, and in addition, the silicon content in the sodium fluoride product prepared by the sodium fluosilicate method is high, the product market competitiveness is not strong, the process is gradually eliminated, so that the demand of downstream sodium fluoride enterprises for sodium fluosilicate is insufficient, a large amount of fluosilicic acid in phosphate fertilizer enterprises cannot be effectively utilized, not only is the fluorine resource seriously wasted, but also the environment is polluted. Meanwhile, the concentration of the byproduct diluted ammonia water in the ammonia synthesis process in the phosphate fertilizer industry is only 10-20%, and the product cannot be effectively utilized as industrial-grade ammonia water due to the organic oil impurities. At present, except a small amount of tail gas of sulfuric acid is absorbed by phosphate fertilizer enterprises, most of the rest of tail gas of sulfuric acid cannot be directly utilized and is sent to a phosphogypsum slag warehouse, and a small amount of phosphorus in the phosphogypsum slag warehouse is adopted to neutralize ammonia in dilute ammonia water, so that ammonia resources are wasted, and the environment is polluted to a certain extent.
The lithium salt industry produces large amounts of sodium sulfate solution when sulfuric acid process is used to treat lepidolite. If the sodium sulfate solid is recovered by evaporation concentration, the operation cost is high, the economic benefit is poor, meanwhile, the sodium sulfate market is seriously saturated, and the product is lost, so that a large amount of sodium sulfate is accumulated and becomes waste. If the waste water is not directly discharged, the high-salinity waste water can cause serious pollution to the environment.
Therefore, it is necessary to design a method for comprehensively utilizing the by-product fluosilicic acid, dilute ammonia water and sodium sulfate, which can solve the above problems.
Disclosure of Invention
The invention aims to provide a method for comprehensively utilizing by-products of fluosilicic acid, dilute ammonia water and sodium sulfate.
The technical scheme for realizing the purpose of the invention is as follows: a comprehensive utilization method of by-products of fluosilicic acid, dilute ammonia water and sodium sulfate comprises the following steps: a. adding activated carbon into the byproduct dilute ammonia water to adsorb organic oil impurities, stirring for reaction for 25-35 min, and filtering to obtain an ammonia water filtrate.
Further, the mass concentration of the byproduct dilute ammonia water is 10-20%, preferably 15-20%.
Furthermore, the activated carbon is columnar activated carbon, has a good adsorption effect, is not easy to break, and avoids pollution caused by the activated carbon mixed into a solution.
Specifically, the adding proportion of the activated carbon is 1-5% of the mass of the dilute ammonia water. Preferably 3% -5%. The usage amount of the active carbon is increased as much as possible to remove organic oil impurities in the by-product dilute ammonia water.
b. Adding a byproduct, namely fluosilicic acid, into the ammonia water filtrate, stirring for reaction, filtering and washing to obtain a silicon dioxide filter cake and an ammonium fluoride solution, and drying the silicon dioxide filter cake to obtain silicon dioxide for toothpaste; wherein the RDA (friction value) of the silica for toothpaste is less than or equal to 90.
Specifically, the molar ratio of the by-product fluosilicic acid to ammonia in the ammonia water filtrate is 1.0.
The concentration of the by-product fluosilicic acid is 11-18%, preferably 14-15%.
When the by-product fluosilicic acid is added, the ammonia water filtrate is kept alkaline. Under alkaline conditions, precipitated silica has a porous structure, a larger specific surface area and a lower friction value.
Specifically, the reaction time is 25 to 35 minutes under stirring.
Specifically, the drying conditions are as follows: the temperature is 100 ℃ and the time is 2h.
c. Adding alkali liquor to adjust the pH value of the by-product sodium sulfate crude solution to 10-11, stirring to react for 25-35 minutes, and filtering to remove metallic impurities such as calcium, magnesium, aluminum and the like, thereby obtaining sodium sulfate refined solution.
Specifically, the mass concentration of the byproduct sodium sulfate crude solution is 10-30%, and preferably 20-30%.
Further, the alkali liquor is at least one of sodium hydroxide solution and sodium carbonate solution. The sodium hydroxide solution and the sodium carbonate solution are adopted for neutralization, so that other impurities are not easy to dope, the activity is high, the double decomposition reaction can be fully performed, and the metal impurities are precipitated.
d. And (3) mixing and stirring the ammonium fluoride solution obtained in the step (2) and the sodium sulfate refined solution obtained in the step (3), reacting at the temperature of 50-80 ℃, and filtering and washing to obtain the silicon-free sodium fluoride.
Further, in the ammonium fluoride solution and the sodium sulfate refined solution, the molar ratio of ammonium fluoride to sodium sulfate is 2:1.
Furthermore, the reaction feeding adopts two raw material opposite feeding modes, and the reaction temperature is preferably 60-70 ℃. The adding mode is that the ammonium fluoride solution and the sodium sulfate refined solution are added simultaneously and completely. The mode of adding is adopted, which is beneficial to the growth of sodium fluoride crystal particles, increases the particle size of sodium fluoride products and is beneficial to the filtration and washing of the products.
By adopting the technical scheme, the invention at least has the following beneficial effects: (1) The invention takes the by-product fluosilicic acid and the diluted ammonia water in the phosphate fertilizer industry and the by-product sodium sulfate in the lithium salt industry as raw materials to prepare qualified sodium fluoride without silicon and a silica product for toothpaste, realizes the effective recycling of the by-product fluosilicic acid, the diluted ammonia water and the sodium sulfate, and solves the environmental protection problem in the phosphate fertilizer industry and the lithium salt industry. (2) The RDA friction value of the prepared silica for the toothpaste is less than 90, is obviously lower than the upper limit 250 of the RDA of the silica for the toothpaste, is lower than the average value 150 of the RDA of the existing silica for the toothpaste, meets the standard of 80-150 of the friction value of the silica for the high-quality toothpaste, and has better product quality. (3) The silicon-free sodium fluoride prepared by the invention has the silicon dioxide content of less than or equal to 0.1 percent, the product quality far exceeds that of the existing sodium fluosilicate method preparation process, the product quality is higher, and the market application prospect is better. (4) The production process of the invention does not generate carbon dioxide gas, does not generate carbon emission, and is more environment-friendly. (5) The invention adopts raw material byproduct resources, has lower production cost and obvious economic benefit.
Detailed Description
A large amount of fluosilicic acid and diluted ammonia water can be produced in the production process of the phosphate fertilizer, the concentration of the diluted ammonia water of the byproduct in the ammonia synthesis process in the phosphate fertilizer industry is low, organic oil impurities are contained, a good treatment means is lacked, the treatment cost is high, and the utilization rate is low.
The lithium salt industry produces large amounts of sodium sulfate solution when treating lepidolite via a sulfuric acid process. If the sodium sulfate solid is recovered by evaporation concentration, the operation cost is high, the economic benefit is poor, and meanwhile, the sodium sulfate market is seriously saturated, so that a large amount of sodium sulfate is accumulated due to product lost and becomes waste. If the waste water is not treated and directly discharged, the high-salinity waste water can cause serious pollution to the environment.
Silica for toothpaste is used as an abrasive in toothpaste to remove dirt from the surface of teeth. At present, concentrated sulfuric acid and sodium silicate are mainly adopted for precipitation reaction, and then the silicon dioxide is obtained through high-pressure pulping, curing and drying. Although the method is simple and easy to operate, the prepared silicon dioxide has the problems of high friction value, high viscosity, poor stability and the like, and meanwhile, the production cost is high and the economic benefit of the product is poor.
Therefore, in order to solve the above problems, the present application provides a method for comprehensively utilizing by-products, namely fluosilicic acid, dilute ammonia water and sodium sulfate, comprising the following steps:
a. adding activated carbon into the byproduct diluted ammonia water to adsorb organic oil impurities, stirring for reaction for 25-35 min, and filtering to obtain ammonia water filtrate.
b. Adding the byproduct fluosilicic acid into the ammonia water filtrate, stirring for reaction, filtering and washing to obtain a silicon dioxide filter cake and an ammonium fluoride solution, and drying the silicon dioxide filter cake. The traditional preparation of silica from sodium silicate and sulfuric acid is in an acidic environment. The application adds fluosilicic acid into ammonia water filtrate, and the silicon dioxide precipitates and separates out and is in an alkaline environment. Under alkaline conditions, the precipitated silica has a porous structure, the specific surface area is larger, and the friction value of the obtained silica is lower.
The reaction formula is as follows: h 2 SiF 6 +2NH 3 ·H 2 O＝(NH 4 ) 2 SiF 6 +2H 2 O
(NH 4 ) 2 SiF 6 +4NH 3 ·H 2 O＝6NH 4 F+SiO 2 ↓+2H 2 O
c. Adding alkali liquor to adjust the pH value of the by-product sodium sulfate crude solution to 10-11, stirring to react for 25-35 minutes, and filtering to remove metallic impurities such as calcium, magnesium, aluminum and the like, thereby obtaining sodium sulfate refined solution.
d. And (3) mixing and stirring the ammonium fluoride solution obtained in the step (2) and the sodium sulfate refined solution obtained in the step (3), and filtering and washing to obtain the sodium fluoride without silicon.
The reaction formula is as follows: 2NH 4 F+Na 2 SO 4 ＝2NaF↓+(NH 4 ) 2 SO 4
(example 1)
The embodiment comprises the following steps:
step 1: activated carbon adsorption: adding 11g of columnar activated carbon into 1122g of 10 mass percent by-product dilute ammonia water for adsorbing organic oil impurities, stirring for reacting for 25 minutes, and filtering to obtain an ammonia water filtrate.
Step 2: ammonolysis: step 1: adding 1309g of ammonia water filtrate into a byproduct fluosilicic acid with the mass concentration of 11%, stirring for reaction for 25 minutes, filtering and washing to obtain a silicon dioxide filter cake and an ammonium fluoride solution, and drying the silicon dioxide filter cake at 100 ℃ for 2 hours to obtain silicon dioxide for toothpaste;
and step 3: removing impurities by sodium sulfate: 4260g of a 10% by-product sodium sulfate crude solution, adding an alkali liquor, wherein the alkali liquor is at least one of sodium hydroxide and sodium carbonate, adjusting the pH value to 10-11, stirring for reacting for 25 minutes, and filtering to remove metallic impurities such as calcium, magnesium, aluminum and the like, thereby obtaining a sodium sulfate refined solution.
And 4, step 4: and (3) synthesizing sodium fluoride: and (3) carrying out mixing reaction on the ammonium fluoride solution obtained in the step (2) and the sodium sulfate refined solution obtained in the step (3), carrying out stirring reaction for 25 minutes at the reaction temperature of 50 ℃ by adopting a counter-addition mode, and filtering and washing to obtain the silicon-free sodium fluoride, wherein the molar ratio of ammonium fluoride to sodium sulfate in the ammonium fluoride solution and the sodium sulfate refined solution is 2:1.
The properties of the silica for toothpaste prepared in this example are shown in Table 1.
The properties of the sodium fluoride without silicon prepared in this example are shown in Table 2.
(example 2)
Step 1: activated carbon adsorption: adding 22g of columnar activated carbon into 748g of dilute ammonia water with the mass concentration of 15% as a byproduct to adsorb organic oil impurities, stirring for reaction for 30 minutes, and filtering to obtain an ammonia water filtrate.
Step 2: ammonolysis: adding 1028g of ammonia water filtrate obtained in the step 1 into 14 mass percent by-product fluosilicic acid, stirring for reaction for 30 minutes, filtering and washing to obtain a silicon dioxide filter cake and an ammonium fluoride solution, and drying the silicon dioxide filter cake at 100 ℃ for 2 hours to obtain silicon dioxide for toothpaste;
and step 3: removing impurities by sodium sulfate: adding alkali liquor into 2130g of 20 mass percent by-product sodium sulfate crude solution, adjusting the pH of the alkali liquor to 10-11 by selecting at least one of sodium hydroxide and sodium carbonate, stirring and reacting for 30 minutes, and filtering to remove metallic impurities such as calcium, magnesium, aluminum and the like and precipitate to obtain sodium sulfate refined solution.
And 4, step 4: and (3) synthesizing sodium fluoride: and (3) carrying out mixing reaction on the ammonium fluoride solution obtained in the step (2) and the sodium sulfate refined solution obtained in the step (3), carrying out stirring reaction for 30 minutes at the reaction temperature of 60 ℃ by adopting a counter-addition mode, and filtering and washing to obtain the silicon-free sodium fluoride, wherein the molar ratio of ammonium fluoride to sodium sulfate in the ammonium fluoride solution and the sodium sulfate refined solution is 2:1.
The properties of the silica for toothpaste prepared in this example are shown in Table 1.
The properties of the sodium fluoride without silicon prepared in this example are shown in Table 2.
(example 3)
The embodiment comprises the following steps:
step 1: adsorbing by activated carbon, adding 37g of columnar activated carbon into 748g of the by-product dilute ammonia water with the mass concentration of 15% to adsorb organic oil impurities, stirring for reaction for 30 minutes, and filtering to obtain an ammonia water filtrate.
And 2, step: ammonolysis, namely adding the ammonia water filtrate obtained in the step 1 into 960g of by-product fluosilicic acid with the mass concentration of 15%, stirring for reaction for 30 minutes, filtering and washing to obtain a silicon dioxide filter cake and an ammonium fluoride solution, and drying the silicon dioxide filter cake for 2 hours at 100 ℃ to obtain silicon dioxide for toothpaste;
and step 3: removing impurities from sodium sulfate, adding alkali liquor into 1420g of 30% by-product crude sodium sulfate solution, adjusting pH to 10-11, stirring for reaction for 30 min, filtering to remove metallic impurities such as calcium, magnesium and aluminum, and precipitating to obtain refined sodium sulfate solution.
And 4, step 4: and (3) synthesizing sodium fluoride, namely mixing the ammonium fluoride solution obtained in the step (2) and the sodium sulfate refined solution obtained in the step (3) for reaction, stirring the mixture at the reaction temperature of 70 ℃ for reaction for 30 minutes in a counter-addition mode, and filtering and washing the mixture to obtain the silicon-free sodium fluoride, wherein the molar ratio of ammonium fluoride to sodium sulfate in the ammonium fluoride solution and the sodium sulfate refined solution is 2:1.
The properties of the silica for toothpaste prepared in this example are shown in Table 1.
The properties of the sodium fluoride without silicon prepared in this example are shown in Table 2.
(example 4)
The embodiment comprises the following steps:
step 1: activated carbon adsorption, namely adding 28g of columnar activated carbon into 561g of 20 mass percent by-product dilute ammonia water to adsorb organic oil impurities, stirring for reaction for 35 minutes, and filtering to obtain an ammonia water filtrate.
Step 2: ammonolysis, namely adding the ammonia water filtrate obtained in the step 1 into 800g of 18 mass percent by-product fluosilicic acid, stirring for reaction for 35 minutes, filtering and washing to obtain a silicon dioxide filter cake and an ammonium fluoride solution, and drying the silicon dioxide filter cake for 2 hours at 100 ℃ to obtain silicon dioxide for toothpaste;
and step 3: removing impurities from sodium sulfate, adding alkali liquor into 1420g of 30% by-product crude sodium sulfate solution, adjusting pH to 10-11, stirring for reaction for 35 min, filtering to remove precipitate of calcium, magnesium, aluminum and other metal impurities, and obtaining refined sodium sulfate solution.
And 4, step 4: and (3) synthesizing sodium fluoride, namely mixing the ammonium fluoride solution obtained in the step (2) and the sodium sulfate refined solution obtained in the step (3) for reaction, stirring the mixture at the reaction temperature of 80 ℃ for reaction for 35 minutes in a counter-addition mode, and filtering and washing the mixture to obtain the silicon-free sodium fluoride, wherein the molar ratio of ammonium fluoride to sodium sulfate in the ammonium fluoride solution and the sodium sulfate refined solution is 2:1.
The properties of the silica for toothpaste prepared in this example are shown in Table 1.
The properties of the sodium fluoride without silicon prepared in this example are shown in Table 2.
As can be seen from Table 1, all indexes of the silica for the toothpaste prepared by the method meet the national standard, the RDA 80-88 numerical value is far superior to the upper limit of the friction value of the toothpaste of 250, the product performance is excellent, and the silica for the toothpaste meets the standard of the silica for the toothpaste.
As can be seen from table 2, the sodium fluoride produced in the present application was excellent in performance, and was all the first grade.
TABLE 1 analysis results of silica products for toothpaste produced according to the present invention
| Item | QB/T 2346—2007 | Example 1 | Example 2 | Example 3 | Example 4 |
| Friction value RDA | - | 85 | 88 | 80 | 83 |
| Silicon dioxide content/%) | ≥96 | 97.1％ | 96.5％ | 97.5％ | 97.2％ |
| Undersize (325 mesh) | ≥98％ | 98.5％ | 98.7％ | 98.1％ | 98.3％ |
| Whiteness degree | ≥96 | 97 | 97 | 97 | 97 |
| 105 ℃ volatile matter | ≤10％ | 9.1％ | 8.5％ | 8.1％ | 9.4％ |
| Loss on ignition at 900 DEG C | ≤8.3％ | 7.2％ | 7.6％ | 6.8％ | 6.5％ |
| pH value | 6.5～8.5 | 7.0 | 7.5 | 7.5 | 7.5 |
| Total salt (NaCl meter) | ≤2％ | 1.1％ | 1.5％ | 0.8％ | 1.4％ |
| Iron content | ≤0.035％ | 0.012％ | 0.021％ | 0.015％ | 0.014％ |
| Oil absorption number | 90～120 | 100 | 110 | 110 | 105 |
TABLE 2 Properties of sodium silicofluoride-free products prepared according to the invention
| Item | YST 517-2009 | Example 1 | Examples2 | Example 3 | Example 4 |
| Particle size (. Mu.m) | - | 85％(>60 mesh) | 90％(>60 mesh) | 95％(>60 mesh) | 95％(>60 mesh) |
| NaF | ≥98％ | 98.1％ | 98.5％ | 98.7％ | 98.5％ |
| SiO 2 | ≤0.5％ | 0.05％ | 0.06％ | 0.06％ | 0.07％ |
| Carbonate salt | ≤0.37％ | 0.25％ | 0.15％ | 0.11％ | 0.17％ |
| Sulfates of sulfuric acid | ≤0.3％ | 0.2％ | 0.21％ | 0.18％ | 0.20％ |
| Acidity of | ≤0.1％ | 0.05％ | 0.05％ | 0.06％ | 0.04％ |
| Insoluble matter in water | ≤0.7％ | 0.22％ | 0.18％ | 0.10％ | 0.23％ |
| H 2 O | ≤0.5％ | 0.21％ | 0.21％ | 0.33％ | 0.23％ |
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A comprehensive utilization method of by-product fluosilicic acid, dilute ammonia water and sodium sulfate is characterized by comprising the following steps:
a. adding activated carbon into the byproduct diluted ammonia water to adsorb organic oil impurities, stirring for reaction, and filtering to obtain an ammonia water filtrate;
b. adding the byproduct fluosilicic acid into the ammonia water filtrate, stirring for reaction, filtering and washing to obtain a silicon dioxide filter cake and an ammonium fluoride solution, and drying the silicon dioxide filter cake to obtain silicon dioxide for toothpaste; wherein the RDA of the silica for toothpaste is less than or equal to 90;
c. adding alkali liquor to adjust the pH value of the by-product sodium sulfate crude solution to 10-11, stirring for reaction, filtering to remove metal impurity precipitate, and obtaining sodium sulfate refined solution;
d. and c, mixing and stirring the ammonium fluoride solution obtained in the step b and the sodium sulfate refined solution obtained in the step c, reacting at the temperature of 50-80 ℃, and filtering and washing to obtain the silicon-free sodium fluoride.
2. The comprehensive utilization method of by-product fluosilicic acid, dilute ammonia water and sodium sulfate according to claim 1, characterized in that: in the step a, the activated carbon is columnar activated carbon, and the addition amount of the activated carbon is 1-5% of the mass of the dilute ammonia water.
3. The comprehensive utilization method of by-product fluosilicic acid, dilute ammonia water and sodium sulfate according to claim 1, characterized in that: the concentration of the byproduct dilute ammonia water is 10-20%; the concentration of the by-product fluosilicic acid is 11-18%.
4. The comprehensive utilization method of by-product fluosilicic acid, dilute ammonia water and sodium sulfate according to claim 3, characterized in that: the concentration of the byproduct dilute ammonia water is 15-20%; the concentration of the by-product fluosilicic acid is 14-15%.
5. The comprehensive utilization method of by-product fluosilicic acid, dilute ammonia water and sodium sulfate according to one of claims 3 or 4, characterized in that: in the step b, the molar ratio of the byproduct fluosilicic acid to ammonia in the ammonia water filtrate is 1.0.
6. The comprehensive utilization method of by-product fluosilicic acid, dilute ammonia water and sodium sulfate according to claim 1, characterized in that: and in the step b, keeping the ammonia water filtrate alkaline when the byproduct fluosilicic acid is added.
7. The comprehensive utilization method of by-product fluosilicic acid, dilute ammonia water and sodium sulfate according to claim 1, characterized in that: in the step c, the alkali liquor is at least one of sodium hydroxide solution and sodium carbonate solution.
8. The comprehensive utilization method of by-product fluosilicic acid, dilute ammonia water and sodium sulfate according to claim 1, characterized in that: in the step d, the molar ratio of ammonium fluoride to sodium sulfate in the ammonium fluoride solution and the sodium sulfate refined solution is 2:1.
9. The comprehensive utilization method of by-product fluosilicic acid, dilute ammonia water and sodium sulfate according to claim 1, characterized in that: in the step d, the reaction charging adopts two raw material adding modes, and the reaction temperature is 60-70 ℃.
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|---|---|---|---|---|
| US2780522A (en) * | 1953-12-17 | 1957-02-05 | Int Minerals & Chem Corp | Production of fluorine compounds |
| GB1062649A (en) * | 1962-09-16 | 1967-03-22 | Chemical & Phosphates Ltd | Process for the production of sodium fluoride |
| SE7411814L (en) * | 1973-09-21 | 1975-03-24 | Bayer Ag | |
| US5165907A (en) * | 1988-04-14 | 1992-11-24 | Imcera Group Inc. | Method of production of high purity silica and ammonium fluoride |
| CN108862323A (en) * | 2018-05-28 | 2018-11-23 | 湖南工业大学 | Sodium fluoride co-producing white carbon black is produced using ammonia nitrogen waste water fluorine silicon resource metaplasia with high salt |
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- 2022-09-26 CN CN202211173162.6A patent/CN115403056A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2780522A (en) * | 1953-12-17 | 1957-02-05 | Int Minerals & Chem Corp | Production of fluorine compounds |
| GB1062649A (en) * | 1962-09-16 | 1967-03-22 | Chemical & Phosphates Ltd | Process for the production of sodium fluoride |
| SE7411814L (en) * | 1973-09-21 | 1975-03-24 | Bayer Ag | |
| US5165907A (en) * | 1988-04-14 | 1992-11-24 | Imcera Group Inc. | Method of production of high purity silica and ammonium fluoride |
| CN108862323A (en) * | 2018-05-28 | 2018-11-23 | 湖南工业大学 | Sodium fluoride co-producing white carbon black is produced using ammonia nitrogen waste water fluorine silicon resource metaplasia with high salt |
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