CN106430993A - Acid pickling method for glasses and acid pickling device - Google Patents
Acid pickling method for glasses and acid pickling device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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Abstract
The invention discloses an acid pickling method for glasses and an acid pickling device. The method comprises the steps of adopting pre-treating liquor containing hydrofluoric acid and vitriol to conduct acid pickling on the glasses, filtering the glass acid pickling waste after the acid pickling to obtain a first filter liquor, then adding sodium salt into the first filter liquor, and conducting reaction between the sodium salt and fluosilicic acid to generate sodium fluosilicate. Through a method of sodium salt eliminating fluorine, the fluosilicic acid and vitriol in the first filter liquor are separated in an oriented mode, thus respective treatments and recycle of the vitriol and the fluosilicic acid are achieved, the recycled vitriol can be used as the pre-treating liquor to continue to conduct acid pickling on the glasses, and thus waste of resources is avoided and treatment cost is reduced.
Description
Technical field
The present invention relates to glass treatment technical field, especially relate to a kind of glass acid washing method and acid dip pickle.
Background technology
With the high speed development of electron trade display device, in order to meet user to light, thin product demand, generally require
Using acid solutions such as Fluohydric acid. and sulphuric acid, with photoelectric glass, pickling processes are carried out to flat faced display.Fluohydric acid. and glass surface
Silicon dioxde reaction produce hexafluosilicic acid, therefore process after produce glass pickle liquor in mainly contain sulphuric acid, hexafluosilicic acid with
And some glass impurities.The easy decomposing property of hexafluosilicic acid is unstable, and hexafluosilicic acid be respectively provided with stronger acidity with sulphuric acid, therefore from
Will be larger with hexafluosilicic acid separating difficulty for sulphuric acid in glass pickle liquor.In pretreatment process the effect of sulphuric acid be mainly cleaning and
There is provided the environment of concentrated sulphuric acid, consumption is less, in the waste liquid of discharge after pickling processes typically still there be the mass percentage concentration of sulphuric acid
50%～60%.Glass pickle liquor after pickling processes mainly has following three kinds of processing modes at present：1) committee is outer disposes waste liquid,
2000 yuan/ton of processing cost ＞, high cost, causes huge waste；2) to be located using the method for limestone or lime cream neutralization
Reason waste liquid, taking limestone neutralization as a example, processes one ton of glass pickle liquor and probably need to consume about 1 ton of limestone, and produce about 5.5
The waste residue of ton and 6 tons of waste water, affect environment, waste substantial amounts of sulphuric acid resource, and can produce huge waste landfills expense
And wastewater treatment takes；3) disposed waste liquid using membrane filtration osmosis, osmosis treatment effeciency is low, be not suitable for large-scale industry
Produce.Above-mentioned several glass acid washing method cost is all higher.
Content of the invention
Based on this it is necessary to provide a kind of glass acid washing method that can reduce processing cost and acid dip pickle.
A kind of glass acid washing method, comprises the steps：
Pickling is carried out to glass using the pretreatment liquid containing Fluohydric acid. and sulphuric acid, obtains glass pickling after pickling and give up
Liquid, contains sulphuric acid, hexafluosilicic acid and solid impurity in described glass pickle liquor；
The first filtrate is obtained after described glass pickle liquor is filtered；
Add sodium salt in described first filtrate, filter after fully reacting, obtain prodan precipitation and the second filtrate,
Wherein, the mol ratio of the sodium ion in described sodium salt and the described hexafluosilicic acid in described first filtrate is 1～4:1；And
The mass percentage concentration of sulphuric acid in described second filtrate evaporation and concentration to described second filtrate is 60%～80%,
Obtain retrieval of sulfuric acid liquid；
Described retrieval of sulfuric acid liquid is added in described pretreatment liquid pickling is carried out to glass.
In one embodiment, described sodium salt is at least one in sodium sulfate, sodium chloride, sodium carbonate and sodium nitrate.
In one embodiment, by the percent mass of sulphuric acid in described second filtrate evaporation and concentration to described second filtrate
Concentration is in 60%～80% operation, and described evaporation and concentration is carried out under vacuum, and the vacuum of described evaporation and concentration is
0.06Mpa～0.1Mpa, the temperature of described evaporation and concentration is 60 DEG C～80 DEG C.
In one embodiment, in described glass pickle liquor, the mass percentage concentration of sulphuric acid is 50%～60%, fluorine
The mass percentage concentration of silicic acid is 2%～5%.
In one embodiment, after obtaining the operation of the first filtrate after described glass pickle liquor being filtered, also wrap
Include the operation of the content of hexafluosilicic acid recording in described first filtrate using sodium hydroxide titration, concrete titration operation is as follows：
Take a certain amount of first filtrate, add enough saturation KCl solution to obtain mixed solution, be subsequently adding soda acid instruction
Agent, with the NaOH solution titration of the first concentration, to mixed solution be in stable blueness and 15s does not fade for terminal, record first
The NaOH solution consumption of concentration；
Described mixed solution after first time is titrated is heated to when two or three bubbles are emerged immediately with the second concentration
It is stable blueness that NaOH solution is titrated to mixed solution, and 15s does not fade, the NaOH solution consumption of record the second concentration；
The concentration of the NaOH solution of the concentration of the NaOH solution according to the first concentration and consumption and the second concentration and use
Hexafluosilicic acid in amount described first filtrate of calculating and the content of sulphuric acid.
In one embodiment, also include adding the operation of sulfuric acid solution in the described retrieval of sulfuric acid liquid obtaining, mend
Plus described sulfuric acid solution in sulphuric acid mass percentage concentration be 60%～80%.
A kind of glass acid dip pickle, including glass pickler, spent acid groove, the first defecator, sodium salt delivery device,
Two defecators and evaporation concentration device；
Described glass pickler is used for glass is carried out pickling, the inlet of described spent acid groove and glass pickler
Liquid outlet is connected by pipeline, and described spent acid groove is used for collecting the glass pickle liquor producing in described glass pickler, institute
State glass pickle liquor and include sulphuric acid, hexafluosilicic acid and solid impurity；
The inlet of described first defecator is connected by pipeline with the liquid outlet of described spent acid groove, described first filtration
Device obtains the first filtrate after filtering described glass pickle liquor, described first filtrate includes sulphuric acid and hexafluosilicic acid；
The inlet of described sodium salt delivery device is connected by pipeline with the liquid outlet of described first defecator, and described
One filtrate and described sodium salt react in described sodium salt delivery device and obtain mixed serum, wherein, described sodium salt and described first
The mol ratio of the described hexafluosilicic acid in filtrate is 1～4:1；
The inlet of described second defecator is connected by pipeline with the liquid outlet of described sodium salt delivery device, and described
Two defecators obtain prodan precipitation and the second filtrate after filtering described mixed serum；
The inlet of described evaporation concentration device is connected by pipeline with the liquid outlet of described second defecator, described steaming
Send out enrichment facility by the mass percentage concentration of described second filtrate evaporation and concentration to sulphuric acid in described second filtrate be 60%～
80%, obtain retrieval of sulfuric acid liquid, the liquid outlet of described evaporation concentration device passes through pipe with the inlet of described glass pickler
Road connects.
In one embodiment, also include acid solution supplementing device, described acid solution supplementing device is set with described glass pickling
Standby inlet is connected by pipeline.
In one embodiment, when described evaporation concentration device is used for evaporation and concentration, the vacuum of evaporation and concentration is
0.06Mpa～0.1Mpa, the temperature of evaporation and concentration is 60 DEG C～80 DEG C.
In one embodiment, described first defecator and described second defecator are centrifugal filter device.
Above-mentioned glass acid washing method, carries out pickling, pickling using the pretreatment liquid containing Fluohydric acid. and sulphuric acid to glass
Glass pickle liquor afterwards obtains the first filtrate after filtering, then adds sodium salt, wherein, sodium in sodium salt in the first filtrate
The mol ratio of the hexafluosilicic acid in ion and the first filtrate is 1～4:1.Sodium salt and hexafluosilicic acid react and can produce prodan, pass through
Sodium salt goes the method orientation of fluorine to separate the hexafluosilicic acid in the first filtrate with sulphuric acid, and the prodan of generation is further used as producing
The raw material of glass etc., realizes the recycling to hexafluosilicic acid.Sodium salt is filtrated to get the second filtrate after reacting with the first filtrate, enters one
The mass percentage concentration of sulphuric acid in the second filtrate evaporation and concentration to the second filtrate is 60%～80% by step, obtains retrieval of sulfuric acid
Liquid, during retrieval of sulfuric acid liquid can return to operate for glass pickling processes, thus realizing the reuse of sulphuric acid again, above-mentioned pickling side
Sulphuric acid and hexafluosilicic acid are processed recycling by method respectively, and the sulphuric acid of recovery can continue to carry out pickling to glass as pretreatment liquid,
Substantially do not produce waste water and dregs etc. in pickling, it is to avoid the waste of resource, reduce processing cost.
Above-mentioned glass acid dip pickle, structure is simple, can process back the acid in glass pickle liquor and hexafluosilicic acid respectively
Receive and utilize, the sulphuric acid of recovery can continue to carry out pickling to glass as pretreatment liquid, does not substantially produce waste water and dregs etc. in pickling,
Avoid the waste of resource, reduce processing cost.
Brief description
Fig. 1 is the flow chart of the glass acid washing method of an embodiment；
Fig. 2 is the structural representation of the glass acid dip pickle of an embodiment.
Specific embodiment
Mainly in combination with drawings and the specific embodiments, further details of theory is made to glass acid washing method and acid dip pickle below
Bright.
The glass acid washing method of an embodiment as shown in Figure 1, comprises the steps S110～S150.
S110, pickling is carried out to glass using the pretreatment liquid containing Fluohydric acid. and sulphuric acid, after pickling, obtain Hyaluronic Acid
Wash waste liquid.
Specifically, glass pickle liquor includes sulphuric acid, hexafluosilicic acid and solid impurity.
Glass pickling processes (also referred to as glass pre-treatment), typically adopt containing acid solutions such as Fluohydric acid. and sulphuric acid to flat board
Display photoelectric glass carries out pickling processes, and Fluohydric acid. produces hexafluosilicic acid with glass surface silicon dioxde reaction, thus etching
Thinning glass or the out-of-flatness eliminating glass surface, the effect of sulphuric acid is mainly the environment cleaning and providing concentrated sulphuric acid.Through surveying
Fixed, mainly contain the solid impurities such as sulphuric acid, hexafluosilicic acid and some chipss of glass in the glass pickle liquor producing after pickling.
Specifically, in glass pickle liquor, the mass percentage concentration of sulphuric acid is 50%～60%, the percent mass of hexafluosilicic acid
Concentration is 2%～5%.The mass percentage concentration of solid impurity is 1%～10%.
Herein, to refer to that the percentage ratio of the quality accounting for complete soln with the quality of solute to represent dense for mass percentage concentration
Degree.
S120, by the glass obtaining in S110 pickle liquor filter after obtain the first filtrate.
Glass pickle liquor is filtered, removes solid impurity, you can obtain the first filtrate including sulphuric acid and hexafluosilicic acid.
Specifically, the method for filtration can have centrifugal filtration, filter pressing or sucking filtration etc..
In present embodiment, after glass pickle liquor being filtered by the way of centrifugal filtration, obtain the first filtrate.Centrifugation
Filter efficiency is high, the rate of filtration fast it is adaptable to industrialized production.
In S130, the first filtrate obtaining in S120 add sodium salt, after reaction filter, obtain prodan precipitation and
Second filtrate.
Wherein, the mol ratio of the hexafluosilicic acid in the sodium ion in sodium salt and the first filtrate is 1～4:1.
First filtrate includes sulphuric acid and hexafluosilicic acid, and after adding sodium salt, sodium salt can react generation hexafluosilicic acid with hexafluosilicic acid
Sodium precipitates, and is oriented by the method that sodium salt removes fluorine and separates the hexafluosilicic acid in the first filtrate with sulphuric acid.
Specifically, after obtaining the operation of the first filtrate after glass pickle liquor being filtered, also include adopting sodium hydroxide
Hexafluosilicic acid in titration measuring first filtrate and the content of sulphuric acid.Can be with the first filtrate of measured amounts, using two steps
The method of titration titrates to the hexafluosilicic acid in the first filtrate and sulphuric acid.Concrete titration operation comprise the steps S210～
S230.
S210, take a certain amount of first filtrate, add enough saturation KCl solution to obtain mixed solution, be subsequently adding acid
Neutralization indicator, with the NaOH solution titration of the first concentration, to mixed solution be in stable blueness and 15s does not fade for terminal, note
Record the NaOH solution consumption of the first concentration.
Specifically, acid-base indicator can be bromine Herba thymi vulgariss fragrant indigo plant indicator.Enough saturation KCl solution refer to enough to
H in first filtrate2SiF6The amount of the KCl solution of reaction.
The NaOH solution of the first concentration can be certain density NaOH standard solution, for example, can be 1.0mol/L's
NaOH solution.
S220, by first time titrate after mixed solution be heated to when two or three bubbles are emerged immediately with the second concentration
It is stable blueness that NaOH solution is titrated to mixed solution, and 15s does not fade, the NaOH solution consumption of record the second concentration.
Specifically, the mixed solution after can titrating first time is placed in heating on electromagnetic oven.The NaOH solution of the second concentration
Can be certain density NaOH standard solution, for example, can be the NaOH solution of 0.1mol/L.
The concentration of the NaOH solution of S230, the concentration according to the NaOH solution of the first concentration and consumption and the second concentration with
And the content of the hexafluosilicic acid in consumption calculating the first filtrate and sulphuric acid.
Specifically, the following reaction equation of inclusion in titrating twice：
①2KCl+H2SiF6=K2SiF6+2HCl
2. NaOH+HCl=NaCl+H2O
③2NaOH+H2SO4=Na2SO4+2H2O
④K2SiF6+3H2O=2KF+4HF+H2SiO3
5. HF+NaOH=NaF+H2O
Specifically, the computing formula of hexafluosilicic acid and sulphuric acid is as follows：
In formula (1) and formula (2),
ω(H2SiF6) represent H2SiF6Mass percentage concentration；
ω(H2SO4) represent H2SO4Mass percentage concentration；
C1Represent the concentration of the NaOH solution of the first concentration, mol/L；
C2Represent the concentration of the NaOH solution of the second concentration, mol/L；
V1Represent the NaOH solution consumption of the first concentration, mL；
V2Represent the NaOH solution consumption of the second concentration, mL；
M represents the quality of the first filtrate that mensure is taken, g；
K1 represents the hexafluosilicic acid quality suitable with 1.0mol sodium hydroxide, 36.02g/mol；
K2 represents the hexafluosilicic acid quality suitable with 1.0mol sodium hydroxide, 49.04g/mol.
In one embodiment, the concrete operations of titration are as follows, provide analytical reagent bromine Herba thymi vulgariss fragrant indigo plant indicator,
1.0mol/L NaOH solution, 0.1mol/L NaOH solution and saturation KCl solution.
Take the first filtrate 3g, be accurate to 0.01g, the first filtrate is placed in 250mL conical flask, add 35mL～40mL to satisfy
With KCl solution, add 10 bromine Herba thymi vulgariss fragrant indigo plant indicator in conical flask, with the NaOH solution titration of 1.0mol/L, extremely become
Stable blueness and 15s do not fade for terminal, the consumption (body of the record NaOH (NaOH of 1.0mol/L) of the first concentration used
Long-pending V1), the mixed liquor after first time is titrated is placed in heating on electromagnetic oven, uses immediately when emerging to there being two or three bubbles
The NaOH solution titration of 0.1mol/L is stable blueness to terminal, and 15s does not fade, and records the NaOH of now the second concentration
The volume of the consumption of (NaOH of 0.1mol/L) is V2.According to V1、V2HF, H in the first filtrate can be calculated2SiF6And Na+
Content.
By two step drop reactions, the first filtrate component can be measured, accurately determine in the first filtrate hexafluosilicic acid with
And the content of sulphuric acid, thus judge to need the amount of the sodium salt of addition, it is to avoid reaction is insufficient or introduces relatively in the second filtrate
Many other impurity.
Specifically, sodium salt is filtered after being reacted with the first filtrate and can get prodan precipitation and the second filtrate.Filter
Method can have centrifugal filtration, filter pressing or sucking filtration etc..In present embodiment, by sodium salt and first by the way of centrifugal filtration
The reacted serosity of filtrate obtains prodan precipitation and the second filtrate after filtering.Centrifugal filtration efficiency high, the rate of filtration is fast,
It is applied to industrialized production.The prodan obtaining can be further used as producing the raw material of glass etc., realizes to hexafluosilicic acid
Recycle.
Specifically, sodium salt can be at least one in sodium sulfate, sodium chloride, sodium carbonate and sodium nitrate.Sodium salt can be with
The form of solid adds in the first filtrate it is also possible to add as a solution in the first filtrate.
The mol ratio of the hexafluosilicic acid in the sodium ion in sodium salt and the first filtrate is 1～4:1.Further, in sodium salt
The mol ratio of the hexafluosilicic acid in sodium ion and the first filtrate is 1.5～2.5:1.Further, the sodium ion in sodium salt and
The mol ratio of the hexafluosilicic acid in one filtrate is 2:1.
In present embodiment, sodium salt is that the mol ratio of the hexafluosilicic acid in sodium sulfate, the sodium sulfate of addition and the first filtrate is
1:1, that is, the mol ratio of the hexafluosilicic acid in the sodium ion in sodium salt and the first filtrate is 2:1.Using sodium sulfate as sodium salt, sulphuric acid
Sodium generates prodan precipitation and sulphuric acid, thus not introducing new impurity in the second filtrate, side with hexafluosilicic acid after reacting
The operation of the recovery sulphuric acid continuing after an action of the bowels.
S140, the mass percentage concentration of sulphuric acid in the obtain in S130 second filtrate evaporation and concentration to the second filtrate is
60%～80%, obtain retrieval of sulfuric acid liquid.
Specifically, can evaporation and concentration under vacuum.Vacuum condition generally refers to actual pressure and is less than atmospheric pressure
Condition.Under vacuum condition, evaporation and concentration is conducive to improving evaporation rate, is suitable for the industrialized production of reality.
In present embodiment, by the mass percentage concentration of sulphuric acid in the second filtrate evaporation and concentration to the second filtrate be 60%～
In 80% operation, the vacuum of evaporation and concentration is 0.06Mpa～0.1Mpa, and the temperature of evaporation and concentration is 60 DEG C～80 DEG C.Very
Reciprocal of duty cycle is that manometric gauge pressure is shown as -0.06Mpa～-0.1Mpa for 0.06Mpa～0.1Mpa, is equivalent to residing for evaporation and concentration
Environment in actual pressure be less than atmospheric pressure condition 0.06Mpa～0.1Mpa.
S150, will the retrieval of sulfuric acid that obtain in S140 liquid add S110 in pretreatment liquid in pickling is carried out to glass.
The retrieval of sulfuric acid liquid obtaining can be directly returned as pretreatment liquid in the operation of glass pickling processes, thus realizing
The reuse of sulphuric acid.
Specifically, after obtaining retrieval of sulfuric acid liquid, also include adding the operation of sulfuric acid solution in the retrieval of sulfuric acid liquid obtaining,
In the sulfuric acid solution added, the mass percentage concentration of sulphuric acid is 60%～80%.Add the sulphuric acid that sulfuric acid solution can be outsourcing.
The mass percentage concentration of the retrieval of sulfuric acid molten sulfur acid obtaining after evaporation and concentration typically also can reach 60%～80%, in the mistake reclaiming
Inevitably cause the waste of some sulphuric acid in journey, by adding sulfuric acid solution, retrieval of sulfuric acid liquid with add sulfuric acid solution
Mixing, so that iteration process operation is uninterrupted in can return to operate for glass pickling processes.Can be according to the demand of actual cleaning
Determine the amount of the sulfuric acid solution added.
In the glass pickle liquor obtaining after glass cleaning, the mass percentage concentration of sulphuric acid still has 50%～60%, and content is relatively
Height, directly discharge will result in huge waste.But because the sulphuric acid that mass percentage concentration is 50%～60% is dense with percent mass
Spend hexafluosilicic acid boiling point for 2%～5% relatively, and be all strong acid, traditional method will both separate more difficult, one
As be all the waste causing resource using direct neutralisation of sulphuric acid.And adopt above-mentioned glass acid washing method, the side of fluorine is gone to by sodium salt
Legal separate to by the hexafluosilicic acid in the first filtrate with sulphuric acid.Sodium salt obtain after reacting with the first filtrate prodan precipitation and
Second filtrate, prodan is further used as producing the raw material of glass etc., realizes the recycling to hexafluosilicic acid.Further by
In two filtrate evaporation and concentration to the second filtrate, the mass percentage concentration of sulphuric acid is 60%～80%, obtains retrieval of sulfuric acid liquid, sulphuric acid
During recovered liquid can return to operate for glass pickling processes, thus realizing the reuse of sulphuric acid again.Sulphuric acid is with hexafluosilicic acid respectively
Process and recycle, substantially do not produce waste water and dregs etc. in pickling, it is to avoid the waste of resource, reduce processing cost.
Additionally, the present invention provides a kind of glass acid dip pickle.Refer to Fig. 2, corresponding for above-mentioned glass acid washing method
The glass acid dip pickle 10 of one embodiment is provided, including glass pickler 20, spent acid groove 100, the first defecator 200,
Sodium salt delivery device 300, the second defecator 400 and evaporation concentration device 500.
Glass pickler 20 is used for carrying out pickling to glass.The inlet of spent acid groove 100 and glass pickler 20
Liquid outlet is connected by pipeline, and spent acid groove 100 is used for collecting the glass pickle liquor producing in glass pickler 20, Hyaluronic Acid
Wash waste liquid and include sulphuric acid, hexafluosilicic acid and solid impurity.The inlet of the first defecator 200 goes out liquid with spent acid groove 100
Mouth is connected by pipeline, and the first defecator 200 obtains the first filtrate by after the filtration of glass pickle liquor, and the first filtrate includes
Sulphuric acid and hexafluosilicic acid.The inlet of sodium salt delivery device 300 is connected by pipeline with the liquid outlet of the first defecator 200,
First filtrate and sodium salt react and obtain mixed serum, wherein, the sodium ion in sodium salt and the first filtrate in sodium salt delivery device
In hexafluosilicic acid mol ratio be 1～4:1.The inlet of the second defecator 400 is led to the liquid outlet of sodium salt delivery device 300
Piping connects, and the second defecator 400 obtains prodan precipitation and the second filtrate after filtering mixed serum.Evaporation is dense
The inlet of compression apparatus 500 is connected by pipeline with the liquid outlet of the second defecator 400, and evaporation concentration device 400 is by second
Filtrate evaporation and concentration is 60%～80% to the mass percentage concentration of sulphuric acid in the second filtrate, obtains retrieval of sulfuric acid liquid.Evaporation is dense
The liquid outlet of compression apparatus 500 is connected by pipeline with the inlet of glass pickler 20.Thus from evaporation concentration device 500
The retrieval of sulfuric acid liquid flowing out can flow directly into and carry out glass pickling in glass pickler 20, and the circulating repetition realizing sulphuric acid makes
With.
Further, this glass acid dip pickle 10 also includes acid solution supplementing device 600, acid solution supplementing device 600 and glass
The inlet of pickler 20 is connected by pipeline.The percent mass of the retrieval of sulfuric acid molten sulfur acid that evaporation concentration device 500 flows out
Concentration typically also can reach 60%～80%, inevitably causes the waste of some sulphuric acid, pass through during reclaiming
Acid solution supplementing device 600, retrieval of sulfuric acid liquid mixes with adding sulfuric acid solution, in can return to operate for glass pickling processes, makes
Obtain iteration process operation uninterrupted.
Specifically, the first defecator 200 and the second defecator 400 can for centrifugal filter device, filter-pressing device or
Suction filtration device.In present embodiment, the first defecator 200 and the second defecator 400 are centrifugal filter device.
Specifically, when evaporation concentration device 500 is used for evaporation and concentration, the vacuum in evaporation concentration device 500 is
0.06Mpa～0.1Mpa, the temperature of evaporation and concentration is 60 DEG C～80 DEG C.
Hexafluosilicic acid in glass pickle liquor can be separated by above-mentioned glass acid dip pickle 10 with sulphuric acid.Realize to hexafluosilicic acid
And the recycling of sulphuric acid, the sulphuric acid of recovery can continue to carry out pickling to glass as pretreatment liquid, realizes cycle pickling behaviour
Make, substantially do not produce waste water and dregs etc. in pickling, it is to avoid the waste of resource, reduce processing cost.
It is specific embodiment below.
Embodiment 1
Pickling is carried out to glass using the pretreatment liquid containing Fluohydric acid. and sulphuric acid, obtains glass pickling after pickling and give up
Liquid.After measured, in this glass pickle liquor, the mass percentage concentration of sulphuric acid is 55%, and the mass percentage concentration of hexafluosilicic acid is
3%, the mass percentage concentration of solid impurity is 5%.Remove solid impurity after glass pickle liquor is filtered, obtain the first filter
Liquid.Add metabisulfite solution in the first filtrate, filter after reaction, obtain prodan precipitation and the second filtrate, wherein, sulfur
The mol ratio of the hexafluosilicic acid in sour sodium and the first filtrate is 1:1.Second filtrate is 0.06Mpa～0.1Mpa in vacuum, temperature
The mass percentage concentration spent for evaporation and concentration under conditions of 60 DEG C～80 DEG C to sulphuric acid in the second filtrate is 70%, obtains sulphuric acid and returns
Receive liquid.Add the sulfuric acid solution that mass percentage concentration is 60%～80% in retrieval of sulfuric acid liquid, the sulphuric acid mixing being recycled
Liquid, sulfuric acid mixture liquid adds in pretreatment liquid in the operation of glass pickling processes.After measured with the sulfuric acid mixture liquid of this recovery
The glass processing is no significant with the glass propertiess (surface roughness and thickness etc.) of the sulfuric acid treatment of outsourcing of same volume
Difference, illustrates that the sulphuric acid that this glass acid washing method reclaims is circularly used for the pickling processes of glass, realizes the repetition profit of resource
With reduces cost.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, some deformation can also be made and improve, these broadly fall into the guarantor of the present invention
Shield scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of glass acid washing method is it is characterised in that comprise the steps：
Pickling is carried out to glass using the pretreatment liquid containing Fluohydric acid. and sulphuric acid, after pickling, obtains glass pickle liquor, institute
State and in glass pickle liquor, contain sulphuric acid, hexafluosilicic acid and solid impurity；
The first filtrate is obtained after described glass pickle liquor is filtered；
Add sodium salt in described first filtrate, filter after fully reacting, obtain prodan precipitation and the second filtrate, its
In, the mol ratio of the sodium ion in described sodium salt and the described hexafluosilicic acid in described first filtrate is 1～4:1；And
The mass percentage concentration of sulphuric acid in described second filtrate evaporation and concentration to described second filtrate is 60%～80%, obtains
Retrieval of sulfuric acid liquid；
Described retrieval of sulfuric acid liquid is added in described pretreatment liquid pickling is carried out to glass.
2. glass acid washing method according to claim 1 is it is characterised in that described sodium salt is sodium sulfate, sodium chloride, carbonic acid
At least one in sodium and sodium nitrate.
3. glass acid washing method according to claim 1 is it is characterised in that by described second filtrate evaporation and concentration to described
In second filtrate, the mass percentage concentration of sulphuric acid is in 60%～80% operation, and described evaporation and concentration is entered under vacuum
OK, the vacuum of described evaporation and concentration is 0.06Mpa～0.1Mpa, and the temperature of described evaporation and concentration is 60 DEG C～80 DEG C.
4. glass acid washing method according to claim 1 is it is characterised in that in described glass pickle liquor, the matter of sulphuric acid
Amount percentage concentration is 50%～60%, and the mass percentage concentration of hexafluosilicic acid is 2%～5%.
5. glass acid washing method according to claim 1 is it is characterised in that obtain after filtering described glass pickle liquor
After the operation of the first filtrate, also include recording hexafluosilicic acid and the sulphuric acid in described first filtrate using sodium hydroxide titration
Content operation, concrete titration operation is as follows：
Take a certain amount of first filtrate, add enough saturation KCl solution to obtain mixed solution, be subsequently adding acid-base indicator,
With the NaOH solution titration of the first concentration, to mixed solution be in stable blueness and 15s does not fade for terminal, record the first concentration
NaOH solution consumption；
Described mixed solution after first time is titrated is heated to when two or three bubbles are emerged immediately with the NaOH of the second concentration
It is stable blueness that solution is titrated to mixed solution, and 15s does not fade, the NaOH solution consumption of record the second concentration；
The concentration of the NaOH solution of the concentration of the NaOH solution according to the first concentration and consumption and the second concentration and use gauge
Calculate the content of hexafluosilicic acid in described first filtrate and sulphuric acid.
6. glass acid washing method according to claim 1 is it is characterised in that also include to the described retrieval of sulfuric acid liquid obtaining
In add the operation of sulfuric acid solution, in the described sulfuric acid solution added, the mass percentage concentration of sulphuric acid is 60%～80%.
7. a kind of glass acid dip pickle is it is characterised in that include glass pickler, spent acid groove, the first defecator, sodium salt throwing
Put device, the second defecator and evaporation concentration device；
Described glass pickler is used for glass is carried out pickling, and the inlet of described spent acid groove goes out liquid with glass pickler
Mouth is connected by pipeline, and described spent acid groove is used for collecting the glass pickle liquor producing in described glass pickler, described glass
Glass pickle liquor includes sulphuric acid, hexafluosilicic acid and solid impurity；
The inlet of described first defecator is connected by pipeline with the liquid outlet of described spent acid groove, described first defecator
The first filtrate is obtained, described first filtrate includes sulphuric acid and hexafluosilicic acid after described glass pickle liquor is filtered；
The inlet of described sodium salt delivery device is connected by pipeline with the liquid outlet of described first defecator, described first filter
Liquid and described sodium salt react and obtain mixed serum, wherein, described sodium salt and described first filtrate in described sodium salt delivery device
In described hexafluosilicic acid mol ratio be 1～4:1；
The inlet of described second defecator is connected by pipeline with the liquid outlet of described sodium salt delivery device, described second mistake
Filter device obtains prodan precipitation and the second filtrate after filtering described mixed serum；
The inlet of described evaporation concentration device is connected by pipeline with the liquid outlet of described second defecator, and described evaporation is dense
The mass percentage concentration of sulphuric acid in described second filtrate evaporation and concentration to described second filtrate is 60%～80% by compression apparatus, obtains
To retrieval of sulfuric acid liquid, the liquid outlet of described evaporation concentration device is connected by pipeline with the inlet of described glass pickler.
8. glass acid dip pickle according to claim 7 is it is characterised in that also include acid solution supplementing device, described acid solution
Supplementing device is connected by pipeline with the inlet of described glass pickler.
9. glass acid dip pickle according to claim 7 is it is characterised in that described evaporation concentration device is used for evaporation and concentration
When, the vacuum of evaporation and concentration is 0.06Mpa～0.1Mpa, and the temperature of evaporation and concentration is 60 DEG C～80 DEG C.
10. glass acid dip pickle according to claim 7 is it is characterised in that described first defecator and described second
Defecator is centrifugal filter device.
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| CN201610799543.3A CN106430993A (en) | 2016-08-30 | 2016-08-30 | Acid pickling method for glasses and acid pickling device |
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| CN109694203A (en) * | 2017-10-24 | 2019-04-30 | 天津美泰真空技术有限公司 | A kind of glass thin chemical industry skill pretreatment fluid |
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| CN113292177A (en) * | 2021-05-24 | 2021-08-24 | 安徽诚志显示玻璃有限公司 | Treatment method for high-concentration waste acid glass powder |
| CN115784623A (en) * | 2022-11-18 | 2023-03-14 | 江西沃格光电股份有限公司 | Glass thinning pretreatment liquid, glass thinning method and application thereof |
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