CN110155956A - Fluoride Waste acid treating device and its processing method - Google Patents
Fluoride Waste acid treating device and its processing method Download PDFInfo
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- CN110155956A CN110155956A CN201910314836.1A CN201910314836A CN110155956A CN 110155956 A CN110155956 A CN 110155956A CN 201910314836 A CN201910314836 A CN 201910314836A CN 110155956 A CN110155956 A CN 110155956A
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- 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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/765—Multi-stage SO3-conversion
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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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses fluoride Waste acid treating device and its processing methods, including surge tank, underground tank, pyrolysis furnace, purification power scrubbing tower and Absorption of Fluoride tower, the surge tank is connected to underground tank by pipeline, the underground tank is connected to pyrolysis furnace by pipeline, the pyrolysis furnace is connected to purification power scrubbing tower by pipeline, and the purification power scrubbing tower is connected by pipeline；One side bottom of Absorption of Fluoride tower offers smoke inlet, another side bottom of Absorption of Fluoride tower offers waterglass outlet, waterglass outlet top offers waterglass entrance, the purification power scrubbing tower is connected to smoke inlet by pipeline, the waterglass outlet connects waterglass absorption cycle slot by pipeline, and the waterglass absorption cycle slot is located at the waterglass spray equipment in Absorption of Fluoride tower by the connection of waterglass entrance.The present invention solves equipment corrosion, and catalyst poisoning can produce process level sulfuric acid by-product fluosilicic acid sodium, reduce costs.
Description
Technical field
The present invention relates to waste acid treatment technical field more particularly to fluoride Waste acid treating device and its processing methods.
Background technique
Waste Sulfuric Acid processing mainly has Waste Sulfuric Acid concentration, Pintsch process, chemical oxidation, extraction, crystallization, production chemical fertilizer and neutralization
The techniques such as processing.Each enterprise is generally according to the purposes of sulfuric acid after Waste Sulfuric Acid amount, sulfur waste acid concentration, impurity component and content, processing
Etc. taking different treatment process, it is sometimes desirable to which several techniques are used cooperatively.In these methods, only neutralisation treatment method cannot be again
Raw sulfuric acid.Handling Waste Sulfuric Acid is mainly the impurity removed in Waste Sulfuric Acid, while to sulfuric acid enrichment, waste acid treatment technique generally passes through
Alkali neutralization discharge is concentrated by evaporation utilization and cracking SO2 relieving haperacidity, and fluoride spent acid is generally useless using traditional calcine technology processing
Fluosulfonic acid, the nitration mixture that calcining tail gas uses water to absorb production are sold outside as commodity；Using the useless fluorine chlorination of traditional alkaline hydrolysis process
Antimony obtains antimony oxide as commodity and sells outside；It is reacted using hydrochloric acid with carbide slag and generates CaCL2 solution, then is anti-with Waste Sulfuric Acid
Gypsum should be made, HCl recovery reuses；Fluorination catalyst production uses the precipitation method；Boiler oil is done using the molecular sieve of failure
Carry out burning harmless treatment；Waste active carbon does fuel treatment, and processing cost is high, and investment is big.
If the SO2 gas that fluoride spent acid is produced using spent acid cracking technology through 1050 DEG C of pyrolysis furnace or more Pintsch process
Fluoride ion 1000ppm or so in body, corrosion of the hydrofluoric acid containing to cleaning equipment in purification and washing diluted acid purify incomplete contains
Fluorine ion SO2 gas enters dry suction, conversion system equally causes the burn into vanadium pentoxide catalyst of equipment to be poisoned, Wo Menfa
A kind of bright fluoride spent acid cracks relieving haperacidity new process, solves the poisoning of above equipment burn into vanadium pentoxide catalyst.It produces
Process level sulfuric acid by-product fluosilicic acid sodium.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is proposition fluoride Waste acid treating device and its processing method, joined waterglass, to gas harmful in furnace gas
Body fluoride is absorbed, and the speed for accelerating reaction improves the efficiency of reaction, and produces process level sulfuric acid by-product fluorine
Sodium metasilicate reduces the cost of production.
Fluoride Waste acid treating device according to an embodiment of the present invention and its processing method, fluoride waste acid treatment dress
It sets, including surge tank, underground tank, pyrolysis furnace, purification power scrubbing tower and Absorption of Fluoride tower, the surge tank are connected by pipeline
Logical underground tank, the underground tank are connected to pyrolysis furnace by pipeline, and the pyrolysis furnace is connected to purification power scrubbing tower, institute by pipeline
Purification power scrubbing tower is stated to connect by pipeline；
One side bottom of Absorption of Fluoride tower offers smoke inlet, and another side bottom of Absorption of Fluoride tower opens up
There is waterglass outlet, waterglass outlet top offers waterglass entrance, and the purification power scrubbing tower is connected by pipeline
Logical smoke inlet, the waterglass outlet connect waterglass absorption cycle slot by pipeline, and the waterglass absorption cycle slot is logical
Cross the waterglass spray equipment that the connection of waterglass entrance is located in Absorption of Fluoride tower.
In some embodiments of the invention, the Absorption of Fluoride top of tower offers exhanst gas outlet.
In other embodiments of the invention, the waterglass absorption cycle slot side is connected to hydrogen peroxide storage box, institute
It states the waterglass absorption cycle slot other side and is fixedly connected with prodan and remove filter press.
In other embodiments of the invention, the surge tank quantity is set as 1-6.
In other embodiments of the invention, processing method are as follows:
S1: fluoride spent acid enters surge tank, and buffering pot bottom goes out liquid, enters underground tank by filter screen, using
It is vertical to be pumped into atomizing lance, atomization, which is come into full contact with, with compressed air enters pyrolysis furnace；
S2: the cracking fluorine-containing furnace gas of outlet of still through cooler is cooled to predetermined temperature, subsequently into purification dynamic wave scrubbing tower,
Predetermined temperature or less is cooled the temperature into Absorption of Fluoride tower；
S3: fluoride is sprayed by waterglass spray equipment through metering pump positioned at the waterglass of waterglass absorption cycle slot and is inhaled
It receives in tower, the flue gas containing hydrogen fluoride gas chemically reacts generation by the waterglass that waterglass spray equipment sprays into absorption tower
Prodan and water；
S4: it is discharged by the furnace gas that Absorption of Fluoride tower removes fluoride from exhanst gas outlet.
In other embodiments of the invention, the fluoride spent acid is useless fluosulfonic acid, fluorine antimony chloride, tetrafluoro second
Alkene, heptafluoro-propane.
Beneficial effect in the present invention is: joined waterglass, absorbs to pernicious gas fluoride in furnace gas, accelerates
The speed of reaction improves the efficiency of reaction, and produces process level sulfuric acid by-product fluosilicic acid sodium, reduce production at
This.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the structural schematic diagram of fluoride Waste acid treating device proposed by the present invention；
Fig. 2 is the flow chart of fluoride waste acid treatment method proposed by the present invention.
In figure: 1- surge tank, 2- underground tank, 3- pyrolysis furnace, 4- purify power scrubbing tower, 5- exhanst gas outlet, 6- waterglass
Spray equipment, 7- Absorption of Fluoride tower, 8- prodan go filter press, 9- waterglass absorption cycle slot, the storage of 10- hydrogen peroxide
Case, 11- metering pump, 12- pipeline, 13- waterglass entrance, 14- smoke inlet, the outlet of 15- waterglass.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.
Examples of the embodiments are shown in the accompanying drawings, and in which the same or similar labels are throughly indicated identical or classes
As element or element with the same or similar functions.The embodiments described below with reference to the accompanying drawings are exemplary, purport
It is being used to explain the present invention, and is being not considered as limiting the invention.
In the description of the present invention, it is to be understood that, term " center ", " longitudinal direction ", " transverse direction ", " length ", " width ",
" thickness ", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom" "inner", "outside", " up time
The orientation or positional relationship of the instructions such as needle ", " counterclockwise ", " axial direction ", " radial direction ", " circumferential direction " be orientation based on the figure or
Positional relationship is merely for convenience of description of the present invention and simplification of the description, rather than the device or element of indication or suggestion meaning must
There must be specific orientation, be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include one or more of the features.In the description of the present invention, the meaning of " plurality " is two or more,
Unless otherwise specifically defined.
In the present invention unless specifically defined or limited otherwise, term " installation ", " connected ", " connection ", " fixation " etc.
Term shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integral；It can be mechanical connect
It connects, is also possible to be electrically connected；It can be directly connected, can also can be in two elements indirectly connected through an intermediary
The interaction relationship of the connection in portion or two elements.It for the ordinary skill in the art, can be according to specific feelings
Condition understands the concrete meaning of above-mentioned term in the present invention.
Referring to Fig.1-2, fluoride Waste acid treating device and its processing method, fluoride Waste acid treating device, including
Surge tank 1, underground tank 2, pyrolysis furnace 3, purification power scrubbing tower 4 and Absorption of Fluoride tower 7, the surge tank 1 pass through pipeline 12
It is connected to underground tank 2, the underground tank 2 is connected to pyrolysis furnace 3 by pipeline 12, and the pyrolysis furnace 3 is dynamic by the connection purification of pipeline 12
Power scrubbing tower 4, the purification power scrubbing tower 4 are connected by pipeline 12；
7 one side bottom of Absorption of Fluoride tower offers smoke inlet 14, another side bottom of the Absorption of Fluoride tower 7
Waterglass outlet 15 is offered, 15 top of waterglass outlet offers waterglass entrance 13, the purification power scrubbing tower 4
It is connected to smoke inlet 14 by pipeline 12, the waterglass outlet 15 connects waterglass absorption cycle slot 9 by pipeline 12, described
Waterglass absorption cycle slot 9 is located at the waterglass spray equipment 6 in Absorption of Fluoride tower 7, institute by the connection of waterglass entrance 13
It states and offers exhanst gas outlet 5 at the top of Absorption of Fluoride tower 7,9 side of waterglass absorption cycle slot is connected to hydrogen peroxide storage box
10,9 other side of waterglass absorption cycle slot is fixedly connected with prodan and removes filter press 8, and 1 quantity of surge tank is set as
1-6；
Its processing method are as follows:
S1: fluoride spent acid enters surge tank 1, and 1 bottom of surge tank goes out liquid, enters underground tank 2 by filter screen, then pass through
Cross it is vertical be pumped into atomizing lance, with compressed air come into full contact with atomization enter pyrolysis furnace 3；
S2: pyrolysis furnace 3 exports fluorine-containing furnace gas and is cooled to predetermined temperature through cooler, subsequently into purification dynamic wave scrubbing
Tower cools the temperature to predetermined temperature or less into Absorption of Fluoride tower 7；
S3: the waterglass positioned at waterglass absorption cycle slot 9 sprays into fluorination by waterglass spray equipment 6 through metering pump 11
In object absorption tower 7, the waterglass that the flue gas containing hydrogen fluoride gas is sprayed by waterglass spray equipment 6 chemistry in absorption tower is anti-
Prodan and water should be generated；
S4: it is discharged by the furnace gas that Absorption of Fluoride tower 7 removes fluoride from exhanst gas outlet 5.
In other embodiments of the invention, the fluoride spent acid is useless fluosulfonic acid, fluorine antimony chloride, tetrafluoro second
Alkene, heptafluoro-propane.
Embodiment one:
Fluoride spent acid (useless fluosulfonic acid, fluorine antimony chloride, tetrafluoroethene, heptafluoro-propane) enters surge tank 1, surge tank 1
Setting two, 1 bottom of surge tank goes out liquid, enters underground tank 2 by filter screen, atomizing lance is pumped into using vertical, with pressure
Contracting air comes into full contact with atomization and enters pyrolysis furnace 3, while for device in Gas with by preheater, temperature reaches 400 in pyrolysis furnace 3
DEG C or more air full combustion generate high temperature so that low-concentration sulfuric acid is split completely at a high temperature of up to 1000~1100 DEG C
It solves, the sulphur in low-concentration sulfuric acid all becomes SO2.It is 9% that low-concentration sulfuric acid pyrolysis furnace 3, which exports furnace gas SO2 concentration, and cracking is anti-
It answers:
H2SO4→H2O+SO3；SO3→SO2+(1/2)O2；
HSO3F→HF+SO3；SO3→SO2+(1/2)O2；
The 1050 DEG C of fluorine-containing furnace gases in outlet of pyrolysis furnace 3 are cooled to 400 DEG C through cooler will be warm into purification dynamic wave scrubbing tower
Degree is down to 60 DEG C or less into Absorption of Fluoride tower 7, and Absorption of Fluoride tower 7 is to increase in original purification system dynamic wave scrubbing tower
Absorption of Fluoride tower 7 absorbs pernicious gas fluoride in furnace gas, and the waterglass positioned at waterglass absorption cycle slot 9 is through counting
Amount pump 11 is sprayed into Absorption of Fluoride tower 7 by waterglass spray equipment 6, and the flue gas containing hydrogen fluoride gas is sprayed by waterglass
The waterglass that device 6 sprays into chemically reacts in absorption tower generates prodan and water, reaction process:
SiO2+HF→H2SiF6+H2O；
Relieving haperacidity system is being sent into after demisting by the furnace gas (absorptivity is greater than 95%) that Absorption of Fluoride tower 7 removes fluoride
System, the prodan liquid for absorbing generation settle down by filter press filtering, dry take-away through flocculant, filter down
Water returns to purification system and uses.
Embodiment two:
Fluoride spent acid (useless fluosulfonic acid, fluorine antimony chloride, tetrafluoroethene, heptafluoro-propane) enters surge tank 1, surge tank 1
Setting four, 1 bottom of surge tank goes out liquid, enters underground tank 2 by filter screen, atomizing lance is pumped into using vertical, with pressure
Contracting air comes into full contact with atomization and enters pyrolysis furnace 3, while for device in Gas with by preheater, temperature reaches 450 in pyrolysis furnace 3
DEG C or more air full combustion generate high temperature so that low-concentration sulfuric acid is split completely at a high temperature of up to 1050~1150 DEG C
It solves, the sulphur in low-concentration sulfuric acid all becomes SO2.It is 8% that low-concentration sulfuric acid pyrolysis furnace 3, which exports furnace gas SO2 concentration, and cracking is anti-
It answers:
H2SO4→H2O+SO3；SO3→SO2+(1/2)O2；
HSO3F→HF+SO3；SO3→SO2+(1/2)O2；
The 1100 DEG C of fluorine-containing furnace gases in outlet of pyrolysis furnace 3 are cooled to 450 DEG C through cooler will be warm into purification dynamic wave scrubbing tower
Degree is down to 65 DEG C or less into Absorption of Fluoride tower 7, and Absorption of Fluoride tower 7 is to increase in original purification system dynamic wave scrubbing tower
Absorption of Fluoride tower 7 absorbs pernicious gas fluoride in furnace gas, and the waterglass positioned at waterglass absorption cycle slot 9 is through counting
Amount pump 11 is sprayed into Absorption of Fluoride tower 7 by waterglass spray equipment 6, and the flue gas containing hydrogen fluoride gas is sprayed by waterglass
The waterglass that device 6 sprays into chemically reacts in absorption tower generates prodan and water, reaction process:
SiO2+HF→H2SiF6+H2O；
Relieving haperacidity system is being sent into after demisting by the furnace gas (absorptivity is greater than 96%) that Absorption of Fluoride tower 7 removes fluoride
System, the prodan liquid for absorbing generation settle down by filter press filtering, dry take-away through flocculant, filter down
Water returns to purification system and uses.
Present invention adds waterglass, absorb to pernicious gas fluoride in furnace gas, the speed for accelerating reaction mentions
The high efficiency of reaction, and process level sulfuric acid by-product fluosilicic acid sodium is produced, reduce the cost of production.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
Centainly refer to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
One or more embodiment or examples in can be combined in any suitable manner.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. fluoride Waste acid treating device, it is characterised in that: including surge tank, underground tank, pyrolysis furnace, purification power scrubbing tower
With Absorption of Fluoride tower, the surge tank is connected to underground tank by pipeline, and the underground tank is connected to pyrolysis furnace by pipeline, described
Pyrolysis furnace is connected to purification power scrubbing tower by pipeline, and the purification power scrubbing tower is connected by pipeline；
One side bottom of Absorption of Fluoride tower offers smoke inlet, and another side bottom of Absorption of Fluoride tower offers water
Glass exit, waterglass outlet top offer waterglass entrance, and the purification power scrubbing tower is connected to cigarette by pipeline
Gas entrance, the waterglass outlet connect waterglass absorption cycle slot by pipeline, and the waterglass absorption cycle slot passes through water
Glass inlet port connection is located at the waterglass spray equipment in Absorption of Fluoride tower.
2. fluoride Waste acid treating device according to claim 1, it is characterised in that: the Absorption of Fluoride top of tower
Offer exhanst gas outlet.
3. fluoride Waste acid treating device according to claim 1, it is characterised in that: the waterglass absorption cycle slot
Side is connected to hydrogen peroxide storage box, and the waterglass absorption cycle slot other side is fixedly connected with prodan and removes filter press.
4. fluoride Waste acid treating device according to claim 1, it is characterised in that: the surge tank quantity is set as
1-6.
5. fluoride waste acid treatment method according to claim 1, it is characterised in that: its processing method are as follows:
S1: fluoride spent acid enters surge tank, and buffering pot bottom goes out liquid, enters underground tank by filter screen, using vertical
It is pumped into atomizing lance, atomization is come into full contact with compressed air and enters pyrolysis furnace；
S2: the cracking fluorine-containing furnace gas of outlet of still is cooled to predetermined temperature through cooler, will be warm subsequently into purification dynamic wave scrubbing tower
Degree is down to predetermined temperature or less into Absorption of Fluoride tower；
S3: the waterglass positioned at waterglass absorption cycle slot sprays into Absorption of Fluoride tower by waterglass spray equipment through metering pump
Interior, the flue gas containing hydrogen fluoride gas chemically reacts in absorption tower by the waterglass that waterglass spray equipment sprays into and generates fluorine silicon
Sour sodium and water；
S4: it is discharged by the furnace gas that Absorption of Fluoride tower removes fluoride from exhanst gas outlet.
6. fluoride waste acid treatment method according to claim 5, it is characterised in that: the fluoride spent acid is useless
Fluosulfonic acid, fluorine antimony chloride, tetrafluoroethene, heptafluoro-propane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910314836.1A CN110155956A (en) | 2019-04-18 | 2019-04-18 | Fluoride Waste acid treating device and its processing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910314836.1A CN110155956A (en) | 2019-04-18 | 2019-04-18 | Fluoride Waste acid treating device and its processing method |
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| CN110155956A true CN110155956A (en) | 2019-08-23 |
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| CN201910314836.1A Pending CN110155956A (en) | 2019-04-18 | 2019-04-18 | Fluoride Waste acid treating device and its processing method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112387096A (en) * | 2020-10-16 | 2021-02-23 | 楚雄滇中有色金属有限责任公司 | Novel method for purifying and recycling arsenic-containing flue gas by using acidic liquid medium |
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| US5324499A (en) * | 1990-11-30 | 1994-06-28 | Chemetics International Co. Ltd. | Fluoride removal from sulphuric acid |
| CN101274210A (en) * | 2007-12-25 | 2008-10-01 | 金川集团有限公司 | Method for removing fluoride in flue gas during smelting |
| CN106315520A (en) * | 2015-06-23 | 2017-01-11 | 中国石油化工股份有限公司 | Waste sulfuric acid cracking technology |
| CN107774112A (en) * | 2017-11-10 | 2018-03-09 | 金堆城钼业股份有限公司 | A kind of defluorination method of high fluorine troilite production sulfuric acid |
| CN107954403A (en) * | 2018-01-08 | 2018-04-24 | 上海乐谦工程科技有限公司 | A kind of resource-conserving spent acid treatment process and device |
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2019
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|---|---|---|---|---|
| US5324499A (en) * | 1990-11-30 | 1994-06-28 | Chemetics International Co. Ltd. | Fluoride removal from sulphuric acid |
| CN101274210A (en) * | 2007-12-25 | 2008-10-01 | 金川集团有限公司 | Method for removing fluoride in flue gas during smelting |
| CN106315520A (en) * | 2015-06-23 | 2017-01-11 | 中国石油化工股份有限公司 | Waste sulfuric acid cracking technology |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112387096A (en) * | 2020-10-16 | 2021-02-23 | 楚雄滇中有色金属有限责任公司 | Novel method for purifying and recycling arsenic-containing flue gas by using acidic liquid medium |
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