CN109019984A - A kind of method and system recycling efficient resource from glass thinning acid pickle - Google Patents
A kind of method and system recycling efficient resource from glass thinning acid pickle Download PDFInfo
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- CN109019984A CN109019984A CN201811067396.6A CN201811067396A CN109019984A CN 109019984 A CN109019984 A CN 109019984A CN 201811067396 A CN201811067396 A CN 201811067396A CN 109019984 A CN109019984 A CN 109019984A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Abstract
The present invention relates to a kind of from glass thinning acid pickle recycles the method and system of efficient resource, and the method includes: step 1: potassium fluoride solution being added in acid pickle, generates potassium fluosilicate and hydrofluoric acid;Step 2: being separated by solid-liquid separation, and mix acid liquor and potassium fluosilicate solids are obtained;The mix acid liquor returns to primary producing line;Step 3: potassium hydroxide solution reaction will be added in potassium fluosilicate solids and generate silica solid and potassium fluoride solution;Step 4: will be separated by solid-liquid separation, and obtain potassium fluoride solution and silica solid object, clean silica solid object, obtain silica product, and cleaning solution and potassium fluoride solution are mixed to get potassium fluoride mixed liquor;Step 5: heating concentration potassium fluoride mixed liquor obtains potassium fluoride product.The present invention effectively increases the rate of recovery of hydrofluoric acid, so that fluorine resource is all utilized effectively;Zero-emission is realized, harmless treatment that it goes without doing, cost is greatly reduced.
Description
Technical field
The present invention relates to offal treatment fields in glass thinning, particularly relate to one kind and recycle from glass thinning acid pickle
The method and system of efficient resource.
Background technique
Electronic equipment develops towards lightening direction always, so in the glass display screen of mobile device or handheld device
In production process, there are one of glass thinning process, the mix acid liquor mixed using hydrofluoric acid with other inorganic acids, by display screen glass
Glass makes up to the thickness of technique requirement by chemical attack mode;With the progress of thinning process, be thinned acid solution component with it is dense
Degree constantly variation, must just be replaced after thinned acid solution component reaches certain numerical value with concentration, otherwise will seriously affect glass
The thinned efficiency and quality of glass.Therefore a large amount of fluorine-containing spent acid will be generated in thinning process.
The fluohydric acid content of these fluorine-containing spent acid generally in 2~105%wt, the content of other inorganic acids generally 5~
25%wt, the fluosilicic acid content that thinning process generates is generally in 5~35%wt.Since fluorine-containing spent acid belongs to danger wastes, root
According to the current law of China, danger wastes need qualified unit to carry out special treatment, or produce useless unit in oneself work
In-situ processing is carried out in factory, makes general waste.Glass thinning enterprise generally entrusts the list with dangerous waste processing qualification
Position carries out harmless treatment, and processing cost reaches 4500~7500 yuan/ton;Ye You glass thinning enterprise is by fluorine-containing spent acid and produces
Harmless treatment is carried out with lime after waste water mixing in the process, processing cost also reaches 2000 yuan/ton or so.No matter use
Fluorine-containing material in fluorine-containing spent acid is changed into calcium fluoride sludge by which kind of processing mode;This method wastes fluorine in short supply
Resource, while a large amount of lime is also wasted, also burden is brought to environmental improvement.Energy-saving, development low-carbon warp is advocated in the whole world
The epoch of Ji explore the common recognition that new production technology and technique have become insider.If using advanced technology and technique,
These fluorine utilizations of resources are got up, the fluorine product produced high added value, have the market demand can not only be greatly lowered fluorine-containing
Waste acid treatment cost, the national policy for also meeting very much comprehensive utilization of resources and developing a circular economy.So how to integrate circulation
The technology for recycling fluorine-containing spent acid increasingly draws attention.
CN105753211A, discloses in a kind of solar battery sheet or glass thinning production spent acid fluorine recovery method and is
System utilizes sylvite or sodium salt, recycles potassium fluosilicate or sodium fluorosilicate product.Sodium salt used by the technology and sylvite and spent acid
In fluosilicic acid reaction when produce new acid pickle, in second step will consumption calcium salt or calcium hydroxide, make increased costs;Such as
Fruit is producing spent acid factory treatment in situ, since these factories are all without sale prodan or potassium fluosilicate qualification, the fluorine of output
Sodium metasilicate or potassium fluosilicate still become dangerous waste product;If outward transport is handled, most of processing enterprises for having qualification can only be according to
Innoxious processing mode processing, still cannot sell prodan or potassium fluosilicate product.Therefore, the patented technology not only at
A possibility that this is higher, and since qualification limits, practical application is smaller.
Application publication number: 107540234 A of CN, denomination of invention: a kind of glass thinning system is discharged without spent acid without glass dregs
Method, comprising: the acid pickle after glass thinning is reacted with potassium hydroxide solution;It is separated by solid-liquid separation, is precipitated and filtrate;It will
Above-mentioned filtrate is configured to the mix acid liquor that HF content is 10~25%wt, HCl content is 5~15%wt, reuse;By above-mentioned solid
It is reacted with calcium salt soln and/or calcium hydroxide suspension;Coagulant and/or flocculant are added after the reaction was completed, makes in liquid phase
Precipitation of solid material, using separation of solid and liquid.In the invention processing method, spent acid is recycled, save the cost, is reduced useless
The discharge of object is conducive to environmental protection, realizes recycling for spent acid, is also convenient for automation continuous operation.It does not need individually
Spent acid is handled, the processing cost of dangerous waste object is greatly reduced.But coagulant and/or flocculation is added in method after the reaction was completed
Agent makes the precipitation of solid material in liquid phase, using obtained after separation of solid and liquid can sewage effluent and sludge, have certain danger to environment
Evil does not reach no waste discharge, and whole not high to the recovery utilization rate of resource.
Summary of the invention
The present invention provides a kind of from glass thinning acid pickle recycles the method and system of efficient resource, solves existing
The problems such as there are waste discharge and insufficient resource recyclings in glass thinning spent acid liquor treating process.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A method of recycling efficient resource from glass thinning acid pickle characterized by comprising
Step 1: being added potassium fluoride solution in acid pickle, and the fluosilicic acid in the acid pickle and fluorination nak response generate
Potassium fluosilicate and hydrofluoric acid;
Step 2: the material after step 1 is reacted is separated by solid-liquid separation, and it is mixed less than 0.1-1% to obtain fluosilicic acid content
Acid is closed, while obtaining potassium fluosilicate solids;The mix acid liquor returns to primary producing line as recycling acid solution;
Step 3: potassium hydroxide solution reaction is added in potassium fluosilicate solids and generates silica solid and potassium fluoride
Solution;
Step 4: the material after step 3 is reacted is separated by solid-liquid separation, and obtains potassium fluoride solution and silica solid
Object cleans silica solid object, obtains silica product, cleaning solution is mixed to get potassium fluoride with potassium fluoride solution and mixes
Liquid;
Step 5: heating concentration potassium fluoride mixed liquor reaches a certain concentration rear portion and returns to step 1, and remainder is dry
Constipation crystalline substance is as potassium fluoride product.
The method as a preferred technical solution, further include:
Sulfuric acid: being added remaining potassium fluoride mixed liquor in step 5, produce hydrofluoric acid and potassium sulfate mixed liquor by step 6,
Hydrofluoric acid and potassium sulfate mixed liquor are heated to 60~130 DEG C, the evolution of hydrofluoric acid vapor obtains liquid HF acid after condensation, can
It is mixed with the recycling acid solution of step 2, returns to primary producing line;Potassium sulfate solution is obtained simultaneously;
Step 7: continuing to heat concentrated vitriol potassium solution and crystallize is potassium sulfate crystal;Dry potassium sulfate crystal, obtains sulphur
Sour potassium product.
The reaction temperature of the step 1 is controlled at 10~90 DEG C as a preferred technical solution,;Pressure control 0.1~
0.3MPa。
Fluosilicic acid molar ratio is 2 in the potassium fluoride and acid pickle being added in the step 1 as a preferred technical solution:
1。
The molar ratio of the potassium hydroxide and potassium fluosilicate that are added in the step 3 as a preferred technical solution, is 4:1.
The temperature of the step 3 is controlled in room temperature~90 DEG C as a preferred technical solution,;Pressure is normal pressure.
The reaction temperature of the step 6 is controlled in room temperature~120 DEG C as a preferred technical solution,;Pressure be normal pressure~
0.3MPa。
The cleaning silica solid object is that a point level Four is washed as a preferred technical solution, is first washed with third
Tank liquor cleaning product in slot, cleaning solution and potassium fluoride solution are mixed to get potassium fluoride mixed liquor;Again in the second sink
Tank liquor cleaning product, cleaning solution are squeezed into third sink, and then with the tank liquor cleaning product in the first sink, cleaning solution is beaten
Enter in the second sink, finally use clear water cleaning product, cleaning solution squeezes into the first sink.At least contain in acid pickle of the invention
There are hydrofluoric acid (2~15%wt) and fluosilicic acid (5~35%wt) and hydrochloric acid (or sulfuric acid or nitric acid) (5~25%wt).
The system that present invention provides a kind of from glass thinning acid pickle recycles efficient resource, including by pipeline according to
The first reaction kettle, potassium fluosilicate solid-liquid separating machine, the second reaction kettle, silica seperator and the potassium fluoride concentration of secondary connection
Kettle, the potassium fluosilicate solid-liquid separating machine connect accurate filter, and the silica seperator connection silica is washed
Slot is washed, the potassium fluoride concentration kettle connects potassium fluoride dryer.
The system that the present invention provides another to recycle efficient resource from glass thinning acid pickle, including pass through pipeline
Sequentially connected first reaction kettle, potassium fluosilicate solid-liquid separating machine, the second reaction kettle, silica seperator, potassium fluoride concentration
Kettle, third reaction kettle, hydrofluoric acid distillation still, potassium sulfate crystallization kettle, potassium sulfate solid-liquid separating machine and potassium sulfate dryer, it is described
Potassium fluosilicate solid-liquid separating machine connects filter, and the silica seperator connects silica sink, the fluorine
Change potassium concentration kettle and connect potassium fluoride dryer, the hydrofluoric acid distillation still connects hydrofluoric acid condenser.
Beneficial effects of the present invention:
1, fluosilicic acid is removed with potassium fluoride, increases the rate of recovery of hydrofluoric acid.
2, potassium fluosilicate is hydrolyzed with potassium hydroxide, is converted into potassium fluoride and silica, fluorine resource all obtains effective benefit
With.
3, the hydrochloric acid or sulfuric acid or nitric acid etc. contained in former spent acid, is all recycled in step 2.
4, spent acid realizes zero-emission, and harmless treatment that it goes without doing, cost is greatly reduced.
5, spent acid does not do harmless treatment, without mud discharging.
6, potassium hydroxide, sulfuric acid can be waste materials, all use waste material in full process stream journey, and produce industrial production
Product greatly improve the utilization rate of waste resource.
Detailed description of the invention
In order to illustrate more clearly of technical solution of the present invention, attached drawing needed in the embodiment will be made simply
It introduces.
Fig. 1 is the structural block diagram of one embodiment of the present of invention;
Fig. 2 is the structural block diagram of another embodiment of the invention.
Specific embodiment
Below in conjunction with attached drawing of the present invention, technical solution of the present invention is clearly and completely described, it is clear that retouched
The content stated is only one embodiment of the invention, instead of all the embodiments.Based on the embodiments of the present invention, this field
Those of ordinary skill's every other embodiment obtained without making creative work, belongs to protection of the present invention
Range.
Embodiment 1
As shown in Figure 1, a kind of system that efficient resource is recycled from glass thinning acid pickle, including successively connected by pipeline
The first reaction kettle, potassium fluosilicate solid-liquid separating machine, the second reaction kettle, silica seperator and the potassium fluoride concentration kettle connect, institute
The potassium fluosilicate solid-liquid separating machine connection filter stated, the silica seperator connects silica sink, described
Potassium fluoride concentration kettle connect potassium fluoride dryer.
A method of recycling efficient resource from glass thinning acid pickle, comprising:
Step 1: acid pickle and potassium fluoride solution are added in the first reaction kettle;Fluosilicic acid and fluorine in the acid pickle
Change nak response, generate potassium fluosilicate and hydrofluoric acid, reaction temperature is controlled at 10~90 DEG C;Pressure controls 0.1~0.3MPa, fluorination
Fluosilicic acid molar ratio is 2:1 in potassium and waste liquid;
Step 2: the material after reaction is separated by solid-liquid separation by potassium fluosilicate solid-liquid separating machine, and the liquid after separation exists
Secondary filter is carried out by filter, obtains the mix acid liquor and potassium fluosilicate solids of fluosilicic acid content 0.1-1%;It is described mixed
Conjunction acid solution, which matches to postpone by thinning acid solution make-up tank, returns to primary producing line as recycling acid solution;
Step 3: being added potassium fluosilicate solids in the second reaction kettle and potassium hydroxide solution reaction generates silica
Solid and potassium fluoride solution, be added potassium hydroxide and potassium fluosilicate and molar ratio be 4:1, temperature is controlled in room temperature~90 DEG C;
Pressure is normal pressure;
Step 4: the material after reaction is separated by solid-liquid separation by silica seperator, obtains potassium fluoride solution, two
Silica solids object, silica solid object are cleaned by silica sink, obtain silica product, cleaning solution
Potassium fluoride mixed liquor is mixed to get with potassium fluoride solution;
Step 5: potassium fluoride concentration kettle heat concentration potassium fluoride mixed liquor, then pass sequentially through potassium fluoride concentration kettle and
Potassium fluoride dryer condensing crystallizing and drying obtain potassium fluoride product.
Cleaning silica solid object is that a point level Four is washed, and first with the cleaning solution cleaning product in third sink slot, is washed
It washs liquid and potassium fluoride solution is mixed to get potassium fluoride mixed liquor;Cleaning solution uses the cleaning solution cleaning product in the second sink again,
Cleaning solution is squeezed into third sink slot, and then with the cleaning solution cleaning product in the first sink, cleaning solution is squeezed into second and washed
It washs in slot slot, finally uses clear water cleaning product, cleaning solution squeezes into the first sink.
Spent acid the liquid mixture wherein hydrofluoric acid 4.7%, fluosilicic acid 9.6%, hydrochloric acid of certain glass thinning workshop discharge
14.2%, potassium fluoride purity used is 99%, potassium hydroxide solution concentration is 40%.Potassium hydroxide solution is glass thinning technique
Spent lye in process, sulfuric acid used are industrial waste sulfuric acid.
Specific experiment: taking 500kg spent acid liquid mixture with after the fully reacting of 39kg potassium fluoride, (reaction temperature is room temperature, pressure
Power is 0.1MPa), it is separated by solid-liquid separation (equipment used is plate and frame filter press), obtained mix acid liquor 466kg, sediment
73kg, fluosilicic acid content 0.5% in mix acid liquor.
The hydrofluoric acid solution of 65%wt and the hydrochloric acid solution of 36%wt are added in mix acid liquor, being configured to HF content is
25%wt, HCl content are the mix acid liquor that 15%wt, H2SiF6 content are 0.5%wt, and the mix acid liquor is by heat exchange, temperature
Control is at 40~55 DEG C;Mix acid liquor is back to use glass thinning system later, be used for glass thinning, be thinned rate be 18 microns/
Minute, product reaches requirement.
Sediment is added in 186KG potassium hydroxide solution and is reacted, reaction condition is normal temperature and pressure, to its fully reacting
After be separated by solid-liquid separation, obtain sediment 33.3KG and separating liquid 225.7KG.Titanium dioxide will be obtained after sediment undergoes washing, drying
Silicon 20KG.Separating liquid heating is concentrated to get potassium fluoride product 115.4KG.Potassium fluoride not reuse in the present embodiment, but it is complete
Portion becomes potassium fluoride product.Concentration of the general reuse in 35-50%).
Embodiment 2
As shown in Fig. 2, a kind of system that efficient resource is recycled from glass thinning acid pickle, including successively connected by pipeline
The first reaction kettle, potassium fluosilicate solid-liquid separating machine, the second reaction kettle, the silica seperator, potassium fluoride concentration kettle, third connect
Reaction kettle, hydrofluoric acid distillation still, potassium sulfate crystallization kettle, potassium sulfate solid-liquid separating machine and potassium sulfate dryer, the fluosilicic acid
Potassium solid-liquid separating machine connects filter, and the silica seperator connects silica sink, and the potassium fluoride is dense
Contracting kettle connects potassium fluoride dryer, and the hydrofluoric acid distillation still connects hydrofluoric acid condenser.
A method of recycling efficient resource from glass thinning acid pickle, comprising:
Step 1: acid pickle and potassium fluoride solution are added in the first reaction kettle;Fluosilicic acid and fluorine in the acid pickle
Change nak response, generate potassium fluosilicate and hydrofluoric acid, reaction temperature is controlled at 10~90 DEG C;Pressure controls 0.1~0.3MPa, fluorination
Fluosilicic acid molar ratio is 2:1 in potassium and waste liquid;
Step 2: the material after reaction is separated by solid-liquid separation by potassium fluosilicate solid-liquid separating machine, and the liquid after separation exists
Secondary filter is carried out by filter, obtains the mix acid liquor and potassium fluosilicate solids of fluosilicic acid content 0.1-1%;It is described mixed
Conjunction acid solution, which matches to postpone by thinning acid solution make-up tank, returns to primary producing line as recycling acid solution;
Step 3: being added potassium fluosilicate solids in the second reaction kettle and potassium hydroxide solution reaction generates silica
Solid and potassium fluoride solution, be added potassium hydroxide and potassium fluosilicate and molar ratio be 4:1, temperature is controlled in room temperature~90 DEG C;
Pressure is normal pressure;
Step 4: the material after reaction is separated by solid-liquid separation by silica seperator, obtains potassium fluoride solution, two
Silica solids object, silica solid object are cleaned by silica sink, obtain silica product, cleaning solution
Potassium fluoride mixed liquor is mixed to get with potassium fluoride solution;
Step 5: concentration potassium fluoride mixed liquor is heated in potassium fluoride concentration kettle, reaches a certain concentration rear portion and returns to step
In rapid one;
Step 6: remaining potassium fluoride mixed liquor is added to third reaction kettle in step 5, and sulfuric acid is then added, and produces hydrogen
Fluoric acid and potassium sulfate mixed liquor, heat hydrofluoric acid and potassium sulfate mixed liquor to 60~130 DEG C in hydrofluoric acid distillation still, hydrofluoric acid
Vapor evolution, hydrofluoric acid vapor obtain liquid HF acid after condensing by hydrofluoric acid condenser, can be with the recycling of step 2
Acid solution mixing, returns to primary producing line, obtains potassium sulfate solution, answers temperature control in room temperature~120 DEG C;Pressure be normal pressure~
0.3MPa;
Step 7: continue to heat potassium sulfate solution crystallization in potassium sulfate crystallization kettle to be potassium sulfate crystal, pass through potassium sulfate
The isolated potassium sulfate crystal of solid-liquid separating machine;Then by obtaining potassium sulfate according to potassium sulfate drier potassium sulfate crystal
Product.
Cleaning silica solid object is that a point level Four is washed, and first with the cleaning solution cleaning product in third sink slot, is washed
It washs liquid and potassium fluoride solution is mixed to get potassium fluoride mixed liquor;Cleaning solution uses the cleaning solution cleaning product in the second sink again,
Cleaning solution is squeezed into third sink slot, and then with the cleaning solution cleaning product in the first sink, cleaning solution is squeezed into second and washed
It washs in slot slot, finally uses clear water cleaning product, cleaning solution squeezes into the first sink.
Spent acid the liquid mixture wherein hydrofluoric acid 4.7%, fluosilicic acid 9.6%, hydrochloric acid of certain glass thinning workshop discharge
14.2%, potassium fluoride purity used is 99%, potassium hydroxide solution concentration is 40%.Potassium hydroxide solution is glass thinning technique
Spent lye in process, sulfuric acid used are industrial waste sulfuric acid.
Specific experiment: taking 500kg spent acid liquid mixture with after the fully reacting of 39kg potassium fluoride, (reaction temperature is room temperature, pressure
Power is 0.1MPa), it is separated by solid-liquid separation (equipment used is plate and frame filter press), obtained mix acid liquor 466kg, sediment
73kg。
Fluosilicic acid content 0.4% in mix acid liquor.The hydrofluoric acid solution and 36%wt of 65%wt are added in mix acid liquor
Hydrochloric acid solution, it is the mixed acid that 15%wt, H2SiF6 content are 0.5%wt that be configured to HF content, which be 25%wt, HCl content,
Liquid, the mix acid liquor are controlled by heat exchange, temperature at 40~55 DEG C;Mix acid liquor is back to use glass thinning system later, is used for
Glass thinning, it is 18 [mus that rate, which is thinned, and product reaches requirement.
Sediment is added in 186KG potassium hydroxide solution and is reacted, reaction condition is normal temperature and pressure, to its fully reacting
After be separated by solid-liquid separation, obtain sediment 33.3KG and separating liquid 225.7KG.Titanium dioxide will be obtained after sediment undergoes washing, drying
Silicon 20KG.Separating liquid heating is concentrated to get 40% potassium fluoride solution, reflux 97.5kg40% potassium fluoride solution to the first step is used
In progress next group acid pickle processing.Concentration of the general reuse in 35-50%.
Then sulfuric acid 64.5kg is added in remaining potassium fluoride solution (sulfuric acid concentration is made into concentration with 98 acid and 105 acid-mixeds and approaches
100% sulfuric acid), hydrofluoric acid and potassium sulfate mixed liquor are produced, hydrofluoric acid and potassium sulfate mixing are heated in hydrofluoric acid distillation still
For liquid to 100 DEG C, hydrofluoric acid vapor evolution, hydrofluoric acid vapor obtains 26.3kg hydrofluoric acid after condensing by hydrofluoric acid condenser
Liquid mixes with the recycling acid solution of step 2, returns to primary producing line, obtain potassium sulfate solution, answers temperature control at 100 DEG C;Pressure
Power is 0.3MPa;
Continue to heat potassium sulfate solution crystallization in potassium sulfate crystallization kettle to be potassium sulfate crystal, be separated by solid-liquid separation by potassium sulfate
The isolated potassium sulfate crystal of machine;Then by obtaining the production of 114.8kg potassium sulfate according to potassium sulfate drier potassium sulfate crystal
Product.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method for recycling efficient resource from glass thinning acid pickle characterized by comprising
Step 1: being added potassium fluoride solution in acid pickle, and the fluosilicic acid in the acid pickle and fluorination nak response generate fluorine silicon
Sour potassium and hydrofluoric acid;
Step 2: the material after step 1 is reacted is separated by solid-liquid separation, and obtains the mixing that fluosilicic acid content is less than 0.1-1%
Acid, while obtaining potassium fluosilicate solids;The mix acid liquor returns to primary producing line as recycling acid solution;
Step 3: being added potassium hydroxide solution reaction generation silica solid in potassium fluosilicate solids and potassium fluoride is molten
Liquid;
Step 4: the material after step 3 is reacted is separated by solid-liquid separation, and obtains potassium fluoride solution and silica solid object, clearly
Silica solid object is washed, silica product is obtained, cleaning solution and potassium fluoride solution are mixed to get potassium fluoride mixed liquor;
Step 5: heating concentration potassium fluoride mixed liquor reaches a certain concentration rear portion and returns to step 1, the dry knot of remainder
Crystalline substance is used as potassium fluoride product.
2. a kind of method for recycling efficient resource from glass thinning acid pickle according to claim 1, it is characterised in that:
The method further include:
Sulfuric acid: being added remaining potassium fluoride mixed liquor in step 5 by step 6, produces hydrofluoric acid and potassium sulfate mixed liquor, heating
To 60~130 DEG C, the evolution of hydrofluoric acid vapor obtains liquid HF acid after condensation, can be with step for hydrofluoric acid and potassium sulfate mixed liquor
Rapid two recycling acid solution mixing, returns to primary producing line;Potassium sulfate solution is obtained simultaneously;
Step 7: continuing to heat concentrated vitriol potassium solution and crystallize is potassium sulfate crystal;Dry potassium sulfate crystal, obtains potassium sulfate
Product.
3. a kind of method for recycling efficient resource from glass thinning acid pickle according to claim 1, it is characterised in that:
The reaction temperature of the step 1 is controlled at 10~90 DEG C;Pressure controls 0.1~0.3MPa.
4. a kind of method for recycling efficient resource from glass thinning acid pickle according to claim 1, it is characterised in that:
Fluosilicic acid molar ratio is 2:1 in the potassium fluoride and acid pickle being added in the step 1.
5. a kind of method for recycling efficient resource from glass thinning acid pickle according to claim 1, it is characterised in that:
The molar ratio of the potassium hydroxide and potassium fluosilicate that are added in the step 3 is 4:1.
6. a kind of method for recycling efficient resource from glass thinning acid pickle according to claim 1, it is characterised in that:
The temperature of the step 3 is controlled in room temperature~90 DEG C;Pressure is normal pressure.
7. a kind of method for recycling efficient resource from glass thinning acid pickle according to claim 2, it is characterised in that:
The reaction temperature of the step 6 is controlled in room temperature~120 DEG C;Pressure is normal pressure~0.3MPa.
8. a kind of method for recycling efficient resource from glass thinning acid pickle according to claim 1, it is characterised in that:
The cleaning silica solid object is that a point level Four is washed, first with the tank liquor cleaning product in third sink, cleaning solution with
Potassium fluoride solution is mixed to get potassium fluoride mixed liquor;Again with the tank liquor cleaning product in the second sink, cleaning solution squeezes into third
In sink, then with the tank liquor cleaning product in the first sink, cleaning solution is squeezed into the second sink, is finally washed with clear water
Product is washed, cleaning solution squeezes into the first sink.
9. a kind of system for recycling efficient resource from glass thinning acid pickle as described in claim 1, it is characterised in that: packet
Include by sequentially connected first reaction kettle of pipeline, potassium fluosilicate solid-liquid separating machine, the second reaction kettle, silica seperator and
Potassium fluoride concentration kettle, the potassium fluosilicate solid-liquid separating machine connect accurate filter, the silica seperator connection
Silica sink, the potassium fluoride concentration kettle connect potassium fluoride dryer.
10. a kind of system for recycling efficient resource from glass thinning acid pickle as claimed in claim 2, it is characterised in that:
Including passing through sequentially connected first reaction kettle of pipeline, potassium fluosilicate solid-liquid separating machine, the second reaction kettle, silica separation
Machine, potassium fluoride concentration kettle, third reaction kettle, hydrofluoric acid distillation still, potassium sulfate crystallization kettle, potassium sulfate solid-liquid separating machine and potassium sulfate
Dryer, the potassium fluosilicate solid-liquid separating machine connect accurate filter, and the silica seperator connects titanium dioxide
Silicon sink, the potassium fluoride concentration kettle connect potassium fluoride dryer, the hydrofluoric acid distillation still connection hydrofluoric acid condensation
Device.
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CN110589854A (en) * | 2019-10-24 | 2019-12-20 | 徐小岗 | Method for producing electronic-grade fluoride salt by using fluosilicic acid and fluosilicate |
CN111392732A (en) * | 2020-05-14 | 2020-07-10 | 江西渠成氟化学有限公司 | Treatment process of organic byproduct potassium fluoride and potassium chloride mixture |
CN114933316A (en) * | 2022-05-09 | 2022-08-23 | 盛隆资源再生(无锡)有限公司 | Resourceful treatment method for fluosilicic acid and hydrofluoric acid mixed acid and product thereof |
CN116425168A (en) * | 2023-05-31 | 2023-07-14 | 云南云天化股份有限公司 | Method for preparing potassium fluosilicate and calcium fluoride by utilizing photovoltaic fluorine-containing waste acid |
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CN116425168A (en) * | 2023-05-31 | 2023-07-14 | 云南云天化股份有限公司 | Method for preparing potassium fluosilicate and calcium fluoride by utilizing photovoltaic fluorine-containing waste acid |
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