CN111153387A - Method and equipment for recovering fluorine-containing waste liquid of acid-washed coal - Google Patents
Method and equipment for recovering fluorine-containing waste liquid of acid-washed coal Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000002699 waste material Substances 0.000 title claims abstract description 48
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 44
- 239000011737 fluorine Substances 0.000 title claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 93
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000002253 acid Substances 0.000 claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000010703 silicon Substances 0.000 claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 43
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 42
- 238000011084 recovery Methods 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
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- 230000008025 crystallization Effects 0.000 claims abstract description 16
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- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 10
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- 239000000543 intermediate Substances 0.000 claims description 41
- 238000005406 washing Methods 0.000 claims description 16
- 239000002351 wastewater Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005554 pickling Methods 0.000 abstract description 15
- 238000003912 environmental pollution Methods 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
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- 238000005516 engineering process Methods 0.000 description 18
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- 239000013078 crystal Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
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- 239000000446 fuel Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 238000004364 calculation method Methods 0.000 description 3
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002864 coal component Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 239000003502 gasoline Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical group F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
- C01B7/193—Preparation from silicon tetrafluoride, fluosilicic acid or fluosilicates
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Treating Waste Gases (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a method and equipment for recovering fluorine-containing waste liquid of acid-washed coal, wherein the method comprises the following steps: carrying out concentrated crystallization on the fluorine-containing waste liquid, and then filtering to obtain mixed acid liquid and a crystallized solid; reacting the crystalline solid with concentrated sulfuric acid to obtain hydrogen fluoride gas, sulfate and a silicon-containing intermediate; sulfate is output as a byproduct; the silicon-containing intermediate is absorbed and reacted by the mixed acid solution, the concentration of the mixed acid solution is improved, and silicon dioxide precipitate is obtained; after the silicon dioxide is separated, adding concentrated sulfuric acid for reaction to obtain hydrogen fluoride gas and dilute sulfuric acid; the silica is output as a byproduct. The invention solves the problem of recycling the fluorine-containing waste liquid in the coal pickling process, reduces the environmental pollution, reduces the production cost of pickled coal and increases the economic added value. The recovery rate of the hydrofluoric acid can reach more than 98 percent.
Description
Technical Field
The invention relates to the field of clean coal waste recycling, in particular to a method and equipment for recovering fluorine-containing waste liquid of acid-washed coal.
Background
Clean coal technology (clean coal technology) is a generic term for new technologies for coal processing, combustion, conversion, and pollution control that aim to reduce pollution and increase efficiency. In order to reduce the environmental pollution caused by direct coal burning, the development and application of clean coal technology are very important for all countries in the world. China is a big coal-burning country, more than 70% of energy depends on coal, and the technology for vigorously developing clean coal has more important significance. The clean coal technology comprises two aspects, namely a direct coal burning clean technology and a technology for converting coal into clean fuel.
(1) A process for cleaning coal by direct burning includes such steps as cleaning ① before burning, washing, physically separating coal, chemically separating coal and desulfurizing by bacteria, shaping coal by adding lime as sulfur fixating agent to reduce sulfur dioxide and smoke, saving coal, preparing water-coal slurry from high-quality low-ash raw coal, replacing clean combustion technique in petroleum ② burning, fluidized-bed burning and advanced burner, fluidized-bed boiling-bed, bubbling-bed and circulating-bed, and features low discharge of nitrogen oxides, low discharge of sulfur dioxide, comprehensive utilization of slag, burning of poor coal, high smoke-dust removal efficiency, high dust-removing efficiency and high dust-removing efficiency.
(2) ① coal gasification technology, including normal pressure gasification and pressurized gasification, under normal pressure or pressurized conditions, the coal gas is generated by reaction of gasification agents (air, oxygen and steam) and coal, the main components of the coal gas are combustible gases such as carbon monoxide, hydrogen, methane and the like, air and steam are used as gasification agents, the calorific value of the coal gas is low, oxygen is used as gasification agents, the calorific value of the coal gas is high, the coal gas can be desulfurized and denitrified in gasification, ash and slag are removed, therefore, the coal gas is clean fuel, ② coal liquefaction technology is a liquid fuel, two indirect liquefaction and direct liquefaction are adopted, coal gasification is firstly carried out, then the coal gas is liquefied, such as coal is prepared into methanol, the coal can replace gasoline, the application is already existed in China, direct liquefaction is that the coal is directly hydrogenated to convert the coal into the liquid fuel, or residual oil and the coal are mixed into oil coal slurry to react to generate liquid fuel, ③ coal gasification cycle power generation technology is developed jointly, direct current is used for generating electricity by a gas turbine, high-temperature waste gas boiler is discharged, and the whole coal-fired coal power generation technology is developed when the high-power generation efficiency is developed.
Among the technical measures adopted by the direct coal-burning cleaning technology, there is a purification processing technology before combustion, namely coal dressing. As a source and a foundation of clean coal technology, coal dressing has a very important position and function in national economic development and is highly concerned internationally.
Especially, some inferior coals output in coal mining have low combustion value and many harmful substances, cannot be directly combusted, can only be stacked, and cause serious environmental pollution. The successful development and application of the middling quality improving and utilizing technology can certainly improve the recovery rate of clean coal components in middling resources, can promote the progress of the coal preparation technology in China, improve the utilization rate of the coal resources, and simultaneously effectively relieve the environmental pollution condition from the source and protect the ecological environment.
In the coal upgrading and utilizing process in coking, in the process of preparing activated carbon from coal and in the process of preparing a carbon source from inferior coal, an acid pickling process is carried out, namely: removing silicon dioxide and oxide in coal by using fluoric acid liquid. This process produces a waste acid solution containing fluorine. If the fluorine-containing waste acid liquor can not be recycled, the pickling cost is very high; even if the waste acid cannot be treated, the pickling process cannot be performed. If advanced technology and process are adopted, the waste acid containing fluorine is well treated, and the fluorine resource in the waste acid is recycled, which is an important content of coal cleaning work. The method not only can greatly reduce the coal pickling cost, but also is very in line with the national policies of comprehensive utilization of resources and development of circular economy.
Disclosure of Invention
The invention provides a method and equipment for recovering fluorine-containing waste liquid of acid-washed coal, which solve the problem of treatment of the fluorine-containing waste liquid generated in the process of acid-washed coal in the prior art.
The technical scheme of the invention is realized as follows:
a method for recovering fluorine-containing waste liquid of acid-washed coal comprises the following steps:
concentrating and crystallizing the fluorine-containing waste liquid, and then filtering to obtain mixed acid liquid and crystallized solid;
reacting the crystalline solid with concentrated sulfuric acid to obtain hydrogen fluoride gas, sulfate and a silicon-containing intermediate; sulfate is output as a byproduct;
the silicon-containing intermediate is absorbed and reacted by the mixed acid solution, the concentration of the mixed acid solution is improved, and silicon dioxide precipitate is obtained; after the silicon dioxide is separated, adding concentrated sulfuric acid for reaction to obtain hydrogen fluoride gas and dilute sulfuric acid; the silica is output as a byproduct.
In some embodiments, one part of the mixed acid liquid is returned to the acid washing coal process flow, and the other part of the mixed acid liquid is used for absorption and reaction of the silicon-containing intermediate.
In some embodiments, the hydrogen fluoride gas is converted to hydrofluoric acid via condensation for reuse in a coal pickling process or for export as a product.
In some embodiments, the dilute sulfuric acid is concentrated to obtain concentrated sulfuric acid and wastewater; concentrated sulfuric acid is used in the previous step; the wastewater returns to the coal acid washing process flow.
In some embodiments, the sulfate is dissolved in hot water, filtered, evaporated and concentrated, subjected to adiabatic flash evaporation, and cooled to obtain aluminum sulfate;
and adding caustic soda or soda ash into the aluminum sulfate to obtain aluminum hydroxide and sodium sulfate. As a preferable technical scheme, in the concentration and crystallization step, the temperature of the tower bottom is 110-120 ℃, the temperature of the tower top is 85-110 ℃, and the pressure of the tower top is 0.04-0.12 MPa.
As a preferable technical scheme, the reaction temperature of the crystalline solid and concentrated sulfuric acid is controlled at 350 ℃, the reaction temperature is controlled at normal pressure, and the reaction time is controlled to be 2-8 hours. Continuous process equipment is preferred.
As a preferred technical scheme, the conditions of absorbing and reacting the silicon-containing intermediate after mixing with the mixed acid solution and adding concentrated sulfuric acid for reaction are as follows: the reaction time is 0.1-2 hours at the normal pressure and the temperature of 40-100 ℃. Continuous process equipment is preferred.
The silicon-containing intermediate is silicon tetrafluoride; products from the reaction of crystalline solids with concentrated sulfuric acid, and products from the reaction of mixed acid liquors with sulfuric acid, may also be added commercially.
An apparatus for recovering fluorine-containing waste liquid from acid washing coal, comprising:
the concentration and crystallization device is used for treating the fluorine-containing waste liquid and comprises a crystallized solid discharge port, a mixed acid liquid first discharge port and a mixed acid liquid second discharge port;
the hydrogen fluoride recovery device is used for treating crystalline solids and is arranged at a crystalline solid discharge port of the concentrated crystallization device, and the hydrogen fluoride recovery device comprises a first concentrated sulfuric acid inlet, a silicon-containing intermediate discharge port, a first hydrogen fluoride discharge port and a sulfate discharge port; and
the silicon-containing intermediate recovery device is used for treating a silicon-containing intermediate and is arranged at a silicon-containing intermediate discharge port of the hydrogen fluoride recovery device, and the silicon-containing intermediate treatment device comprises a mixed acid liquid inlet and a silicon dioxide discharge port.
Further, the acid mixing reactor is further included and comprises a second mixed acid liquid adding port, a second concentrated sulfuric acid adding port, a second hydrogen fluoride discharging port and a dilute sulfuric acid discharging port.
Further, the first hydrogen fluoride discharge port and the second hydrogen fluoride discharge port are connected into the acid preparation tank after passing through a condensing device;
and the second discharge hole of the mixed acid liquid is connected into the acid preparation tank through a pipeline.
Further, the device also comprises a sulfuric acid concentration tower which is used for concentrating dilute sulfuric acid and comprises a wastewater discharge port and a concentrated sulfuric acid discharge port; the concentrated sulfuric acid discharge port is respectively communicated with the first concentrated sulfuric acid inlet and the second concentrated sulfuric acid inlet.
Advantageous effects
(1) The invention solves the problem of environmental pollution and waste recycling of the acid-washed coal, reduces the environmental pollution, increases the material recycling, reduces the production cost and increases the economic added value.
(2) The scheme of the invention can improve the recovery rate of hydrofluoric acid to more than 98 percent, and hardly causes environmental pollution.
(3) The invention realizes the regeneration and the cyclic utilization of the auxiliary agent and water resources and provides technical support for the utilization of the acid-washed coal.
(4) The scheme of the invention changes the waste which is difficult to treat into the material which can generate economic value, promotes the development and progress of the industry and promotes the upgrading and updating of the coal industry.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive exercise.
FIG. 1: example 1 schematic diagram of an apparatus for recovering a fluorine-containing waste liquid of acid-washed coal.
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 invention mainly solves the technical problem of how to treat the fluorine-containing waste liquid generated in the existing coal pickling process. The prior treatment method is mainly a chemical adsorption method, but the method has the highest recovery rate of only 75 percent for the auxiliary agent and is accompanied with the problems of waste of fluorine resources and pollution to the environment. In order to better solve the problem of environmental pollution of waste acid liquor and improve the recovery rate of the auxiliary agent, the inventor adopts a brand-new visual angle and provides a technical route different from the prior art, so that the recovery rate of hydrofluoric acid reaches more than 98 percent, fluorine resources are utilized to the maximum extent, the output of byproducts is realized, the economic value is increased, the environmental pollution is reduced, and the regeneration and the cyclic utilization of the auxiliary agent and water resources are realized.
The fluorine-containing waste acid liquor used in the following examples is from the process of coal pickling, and the rest of the raw materials can be purchased from the market.
Example 1
Referring to FIG. 1: an apparatus 1 for recovering fluorine-containing waste liquid from acid washing coal, comprising: a concentration crystallization apparatus 10, a hydrogen fluoride recovery apparatus 20, and a silicon-containing intermediate recovery apparatus 50. The concentration and crystallization device 10 is used for treating fluorine-containing waste liquid generated in the coal pickling process and comprises a crystallized solid discharge port 101, a mixed acid liquid first discharge port 102 and a mixed acid liquid second discharge port 103. The hydrogen fluoride recovery device 20 is configured to treat the above-mentioned crystalline solid, and is disposed at the crystalline solid discharge port 101 of the concentration crystallization device 10, and the hydrogen fluoride recovery device 20 includes a first concentrated sulfuric acid inlet 201, and further includes a silicon-containing intermediate discharge port 202, a first hydrogen fluoride discharge port 203, and a sulfate discharge port 204. The silicon-containing intermediate recovery device 50 is configured to treat a silicon-containing intermediate, and is disposed at the silicon-containing intermediate discharge port 202 of the hydrogen fluoride recovery device 20, and the silicon-containing intermediate treatment device 50 includes a mixed acid liquid inlet 501 and a silicon dioxide discharge port 502 connected to the first mixed acid liquid discharge port 102.
For better treatment effect, the apparatus 1 may further include a mixed acid reactor 60, which includes a second mixed acid liquid inlet 601, a second concentrated sulfuric acid inlet 602, a second hydrogen fluoride outlet 603, and a dilute sulfuric acid outlet 604 connected to the silicon-containing intermediate recovery device 50. The first hydrogen fluoride discharge port 203 and the second hydrogen fluoride discharge port 603 pass through the condensing device 30 and then are connected into the acid preparation tank 40. The second mixed acid liquid outlet 103 is connected into the acid preparing tank 40 through a pipeline.
In order to recycle resources, improve economic benefits and reduce environmental pollution, the equipment further comprises a sulfuric acid concentration tower 70 for concentrating dilute sulfuric acid, which comprises a wastewater discharge port 701 and a concentrated sulfuric acid discharge port 702. The concentrated sulfuric acid discharge port 702 is respectively communicated with the first concentrated sulfuric acid inlet port 201 and the second concentrated sulfuric acid inlet port 602.
Example 2
Obtaining fluorine-containing waste liquid of an acid coal washing process flow of an enterprise: 12 percent of hydrofluoric acid, 28 percent of fluosilicic acid, 8 percent of fluoroaluminate and 4.061 tons of hydrofluoric acid.
A method for recovering fluorine-containing waste liquid of acid-washed coal comprises the following steps:
(1) continuously adding 4.061 tons of fluorine-containing waste liquid into a concentration crystallization device 10; the temperature of a tower kettle of a 10 concentration crystallization device is controlled to be 110 ℃, the temperature of a tower top is controlled to be 85 ℃, and the pressure of the tower top is controlled to be 0.04 MPa. Then 1.405 tons of soluble salt crystals and 2.656 tons of mixed acid liquor are obtained after cooling, filtering and separating. 1.4 tons of mixed acid liquor is used in the step (3), and 1.256 tons of residual mixed acid liquor are returned to the acid-washing coal process flow.
(2) 1.405 tons of soluble salt crystals and 2.51 tons of 98 percent concentrated sulfuric acid are added into a hydrogen fluoride recovery device 20, the temperature is kept at 90 ℃, the pressure is normal, the material retention time is 8 hours, and 1.75 tons of sulfate and a plurality of hydrogen fluoride gases and silicon-containing intermediate gases are obtained after reaction. The hydrogen fluoride gas is introduced into a condenser 30, condensed and recovered to 1.46 tons of 50 percent hydrofluoric acid, and returned to an acid preparation tank 40 of the coal pickling process flow.
(3) Introducing the silicon-containing intermediate gas in the step (2) into a silicon-containing intermediate recovery device 50, introducing 1.4 tons of mixed acid liquid in the step (1) into the silicon-containing intermediate recovery device 50, and reacting the silicon-containing intermediate with the mixed acid liquid to generate silicon dioxide precipitate; the silica was separated and washed to obtain 56kg (water content: about 50%) of a wet silica product. Adding 2.5 tons of mixed acid liquid and 98 percent concentrated sulfuric acid into a mixed acid reactor 60, reacting at the temperature of 40 ℃ under normal pressure for about 2 hours to obtain 1.01 tons of 50 percent hydrofluoric acid and 3.86 tons of dilute sulfuric acid; the hydrofluoric acid is returned to the acid preparation tank 40 of the coal pickling process flow. The silica is output as a byproduct.
Concentrating the dilute sulfuric acid in a sulfuric acid concentration tower 70 to obtain concentrated sulfuric acid and wastewater, wherein the concentrated sulfuric acid is used in the step (1); the wastewater returns to the coal acid washing process flow.
According to calculation, in the recovery test, the hydrogen fluoride loss is 24.67kg, the 50% hydrofluoric acid recovery rate is 2.47 tons, and the recovery rate is 97.67%.
Example 3
Obtaining fluorine-containing waste liquid of an acid coal washing process flow of an enterprise: 12 percent of hydrofluoric acid, 28 percent of fluosilicic acid, 8 percent of fluoroaluminate and 4.061 tons of hydrofluoric acid.
A method for recovering fluorine-containing waste liquid of acid-washed coal comprises the following steps:
(1) continuously adding 4.061 tons of fluorine-containing waste liquid into a concentration crystallization device 10; the temperature of a tower kettle of a 10 concentration crystallization device is controlled to be 110 ℃, the temperature of a tower top is controlled to be 85 ℃, and the pressure of the tower top is controlled to be 0.04 MPa. Then 1.405 tons of soluble salt crystals and 2.656 tons of mixed acid liquor are obtained after cooling, filtering and separating. 1.4 tons of mixed acid liquor is used in the step (3), and 1.256 tons of residual mixed acid liquor are returned to the acid-washing coal process flow.
(2) 1.405 tons of soluble salt crystals and 2.51 tons of 98 percent concentrated sulfuric acid are added into a hydrogen fluoride recovery device 20, the temperature is kept at 450 ℃, the pressure is normal, the material retention time is 0.5 hour, and 1.75 tons of sulfate and a plurality of hydrogen fluoride gases and silicon-containing intermediate gases are obtained after reaction. The hydrogen fluoride gas is introduced into a condenser 30, condensed and recycled to be 1.45 tons of 50 percent hydrofluoric acid, and returned to an acid preparation tank 40 of the coal pickling process flow.
(3) Introducing the silicon-containing intermediate gas in the step (2) into a silicon-containing intermediate recovery device 50, introducing 1.4 tons of mixed acid liquid in the step (1) into the silicon-containing intermediate recovery device 50, and reacting the silicon-containing intermediate with the mixed acid liquid to generate silicon dioxide precipitate; the silica was separated and washed to obtain 56kg (water content: about 50%) of a wet silica product. Adding 2.5 tons of mixed acid liquid and 98 percent concentrated sulfuric acid into a mixed acid reactor 60, reacting at the temperature of 60 ℃ under normal pressure, and obtaining 1.02 tons of 50 percent hydrofluoric acid and 3.86 tons of dilute sulfuric acid after about 1.5 hours of reaction time; the hydrofluoric acid is returned to the acid preparation tank 40 of the coal pickling process flow. The silica is output as a byproduct.
Concentrating the dilute sulfuric acid in a sulfuric acid concentration tower 70 to obtain concentrated sulfuric acid and wastewater, wherein the concentrated sulfuric acid is used in the step (1); the wastewater returns to the coal acid washing process flow.
According to calculation, in the recovery test, the loss of the hydrogen fluoride is 18.67kg, the 50% hydrofluoric acid is recovered by 2.47 tons, and the recovery rate is 98.02%.
Example 4
Obtaining fluorine-containing waste liquid of an acid coal washing process flow of an enterprise: 12 percent of hydrofluoric acid, 28 percent of fluosilicic acid, 8 percent of fluoroaluminate and 4.061 tons of hydrofluoric acid.
A method for recovering fluorine-containing waste liquid of acid-washed coal comprises the following steps:
(1) continuously adding 4.061 tons of fluorine-containing waste liquid into a concentration crystallization device 10; the temperature of a tower kettle of a 10 concentration crystallization device is controlled to be 110 ℃, the temperature of a tower top is controlled to be 85 ℃, and the pressure of the tower top is controlled to be 0.04 MPa. Then 1.405 tons of soluble salt crystals and 2.656 tons of mixed acid liquor are obtained after cooling, filtering and separating. 1.4 tons of mixed acid liquor is used in the step (3), and 1.256 tons of residual mixed acid liquor are returned to the acid-washing coal process flow.
(2) 1.405 tons of soluble salt crystals and 2.51 tons of 98 percent concentrated sulfuric acid are added into a hydrogen fluoride recovery device 20, the temperature is kept at 240 ℃, the pressure is normal, the material retention time is 3 hours, and 1.75 tons of sulfate and a plurality of hydrogen fluoride gases and silicon-containing intermediate gases are obtained after reaction. The hydrogen fluoride gas is introduced into a condenser 30, condensed and recovered to 1.46 tons of 50 percent hydrofluoric acid, and returned to an acid preparation tank 40 of the coal pickling process flow.
(3) Introducing the silicon-containing intermediate gas in the step (2) into a silicon-containing intermediate recovery device 50, introducing 1.4 tons of mixed acid liquid in the step (1) into the silicon-containing intermediate recovery device 50, and reacting the silicon-containing intermediate with the mixed acid liquid to generate silicon dioxide precipitate; the silica was separated and washed to obtain 56kg (water content: about 50%) of a wet silica product. Adding 2.5 tons of mixed acid liquid and 98 percent concentrated sulfuric acid into a mixed acid reactor 60, reacting at the temperature of 80 ℃ under normal pressure, and obtaining 1.01 tons of 50 percent hydrofluoric acid and 3.87 tons of dilute sulfuric acid after about 0.5 hour of reaction time; the hydrofluoric acid is returned to the acid preparation tank 40 of the coal pickling process flow. The silica is output as a byproduct.
Concentrating the dilute sulfuric acid in a sulfuric acid concentration tower 70 to obtain concentrated sulfuric acid and wastewater, wherein the concentrated sulfuric acid is used in the step (1); the wastewater returns to the coal acid washing process flow.
According to calculation, in the recovery test, the loss of the hydrogen fluoride is 28.37kg, the 50% hydrofluoric acid is recovered by 2.47 tons, and the recovery rate is 96.97%.
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 (10)
1. The method for recovering the fluorine-containing waste liquid of the acid-washed coal is characterized by comprising the following steps:
concentrating and crystallizing the fluorine-containing waste liquid, and then filtering to obtain mixed acid liquid and crystallized solid;
reacting the crystalline solid with concentrated sulfuric acid to obtain hydrogen fluoride gas, sulfate and a silicon-containing intermediate; sulfate is output as a byproduct;
the silicon-containing intermediate is absorbed and reacted by the mixed acid solution, the concentration of the mixed acid solution is improved, and silicon dioxide precipitate is obtained; after the silicon dioxide is separated, adding concentrated sulfuric acid for reaction to obtain hydrogen fluoride gas and dilute sulfuric acid; the silica is output as a byproduct.
2. The method for recovering the fluorine-containing waste liquid of acid-washed coal according to claim 1, wherein one part of the mixed acid liquid is returned to the process flow of acid-washed coal, and the other part of the mixed acid liquid is used for absorption and reaction of silicon-containing intermediates.
3. The method for recovering the fluorine-containing waste liquid of acid-washed coal according to claim 1, wherein the hydrogen fluoride gas is condensed and converted into hydrofluoric acid, and the hydrofluoric acid is recycled in the process flow of acid-washed coal or output as a product.
4. The method for recovering the fluorine-containing waste liquid of the acid-washed coal according to claim 1, wherein the dilute sulfuric acid is concentrated to obtain concentrated sulfuric acid and waste water; concentrated sulfuric acid is used in the previous step; the wastewater returns to the coal acid washing process flow.
5. The method for recovering fluorine-containing waste liquid from acid-washed coal as claimed in claim 1, wherein in the step of concentration and crystallization, the temperature of the bottom of the column is 110-150 ℃, the temperature of the top of the column is 85-120 ℃, and the pressure of the top of the column is 0.04-0.12 MPa.
6. The method for recovering fluorine-containing waste liquid of acid-washed coal according to claim 1, wherein the reaction temperature of the crystalline solid and the concentrated sulfuric acid is controlled to be 90-450 ℃, the reaction time is 0.5-8 hours under normal pressure.
7. The method for recovering the fluorine-containing waste liquid of acid-washed coal according to claim 1, wherein after the absorption and reaction of the silicon-containing intermediate and the mixed acid liquid, concentrated sulfuric acid is added for reaction under the following conditions: normal pressure, 40-100 deg.c and reaction time of 0.1-2 hr.
8. The utility model provides an equipment of recovery acid-washed coal fluorine-containing waste liquid which characterized in that includes:
the concentration and crystallization device is used for treating the fluorine-containing waste liquid and comprises a crystallized solid discharge port, a mixed acid liquid first discharge port and a mixed acid liquid second discharge port;
the hydrogen fluoride recovery device is used for treating crystalline solids and is arranged at a crystalline solid discharge port of the concentrated crystallization device, and the hydrogen fluoride recovery device comprises a first concentrated sulfuric acid inlet, a silicon-containing intermediate discharge port, a first hydrogen fluoride discharge port and a sulfate discharge port; and
the silicon-containing intermediate recovery device is used for treating a silicon-containing intermediate and is arranged at a silicon-containing intermediate discharge port of the hydrogen fluoride recovery device, and the silicon-containing intermediate treatment device comprises a mixed acid liquid inlet and a silicon dioxide discharge port.
9. The apparatus for recovering fluorine-containing waste liquid from acid washing coal as claimed in claim 8, further comprising an acid mixing reactor, comprising a second adding port for mixed acid liquid, a second concentrated sulfuric acid adding port, a second hydrogen fluoride discharging port and a dilute sulfuric acid discharging port; the device also comprises a sulfuric acid concentration tower which is used for concentrating dilute sulfuric acid and comprises a wastewater discharge port and a concentrated sulfuric acid discharge port; the concentrated sulfuric acid discharge port is respectively communicated with the first concentrated sulfuric acid inlet and the second concentrated sulfuric acid inlet.
10. The apparatus for recovering fluorine-containing waste liquid of acid-washed coal according to claim 8, wherein the first hydrogen fluoride discharge port and the second hydrogen fluoride discharge port are connected into the acid preparation tank after passing through the condensing device;
and the mixed acid liquid discharge port is connected into the acid preparation tank through a pipeline.
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| CN102951611A (en) * | 2012-12-24 | 2013-03-06 | 贵州省化工研究院 | Method for preparing anhydrous hydrogen fluoride by utilizing fluorine-containing waste liquid or fluorosilicic acid in phosphate fertilizer enterprises |
| CN107188129A (en) * | 2017-07-24 | 2017-09-22 | 衢州市鼎盛化工科技有限公司 | The method that calcium fluoride containing waste material prepares hydrogen fluoride and ocratation |
| CN107601434A (en) * | 2017-11-07 | 2018-01-19 | 衢州市鼎盛化工科技有限公司 | A kind of method and apparatus that hydrogen fluoride is prepared by fluosilicic acid |
| CN211712623U (en) * | 2020-03-03 | 2020-10-20 | 衢州市鼎盛化工科技有限公司 | Equipment for recovering fluorine-containing waste liquid of acid-washed coal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102951611A (en) * | 2012-12-24 | 2013-03-06 | 贵州省化工研究院 | Method for preparing anhydrous hydrogen fluoride by utilizing fluorine-containing waste liquid or fluorosilicic acid in phosphate fertilizer enterprises |
| CN107188129A (en) * | 2017-07-24 | 2017-09-22 | 衢州市鼎盛化工科技有限公司 | The method that calcium fluoride containing waste material prepares hydrogen fluoride and ocratation |
| CN107601434A (en) * | 2017-11-07 | 2018-01-19 | 衢州市鼎盛化工科技有限公司 | A kind of method and apparatus that hydrogen fluoride is prepared by fluosilicic acid |
| CN211712623U (en) * | 2020-03-03 | 2020-10-20 | 衢州市鼎盛化工科技有限公司 | Equipment for recovering fluorine-containing waste liquid of acid-washed coal |
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| CN116462157A (en) * | 2023-04-26 | 2023-07-21 | 西安热工研究院有限公司 | System and method for comprehensively utilizing coal washing waste containing high sulfur content |
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