CN1277759C - System and process of treating fluorhydric acid - Google Patents
System and process of treating fluorhydric acid Download PDFInfo
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- CN1277759C CN1277759C CN 200410006602 CN200410006602A CN1277759C CN 1277759 C CN1277759 C CN 1277759C CN 200410006602 CN200410006602 CN 200410006602 CN 200410006602 A CN200410006602 A CN 200410006602A CN 1277759 C CN1277759 C CN 1277759C
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- hydrofluoric acid
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- acid waste
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Abstract
The present invention relates to a hydrofluoric acid treatment system. The present invention comprises a pre-treatment trough and a reaction trough, wherein the pre-treatment trough is used for treating partial hydrofluoric acid waste liquid so that the first part of hydrofluoric acid waste liquid reacts with excessive calcium salt to form first waste liquid; the reaction trough is used for treating the second part of hydrofluoric acid waste liquid and the first waste liquid to form second waste liquid so as to generate waste material which can be discharged and buried.
Description
Technical field that the present invention belongs to
The invention relates to a kind of Waste Water Treatment and method, and, be to speed hydrofluoric acid treatment speed and amount of reagent that minimizing is added in stage hydrogen fluoride trealment mode especially in regard to a kind of hydrofluoric acid treatment System and method for.
Prior art
Hydrogen fluoride (HF) is gas under high-temperature pressure, and water-soluble back is a kind of strong acid, is called hydrofluoric acid (anhydrous hydrogen fluoride, fluorohydric acid, anhydrous hydrofluoric acid).Hydrofluoric acid is very good to the effect of removing oxide compound, so can be used in many industries, as in the semi-conductor industry with hydrofluoric acid as in clean-out system, the glass etching industry with hydrofluoric acid as in etching reagent, the Iron And Steel Industry with hydrofluoric acid as in surface derusting agent, the petrochemical industry with hydrofluoric acid as in catalyzer, the cleaning service industry with hydrofluoric acid as dirt corrosion clean-out system or outside Wall Cleaning agent, even all contain hydrofluoric acid in the used in the family rust remover.Yet the characteristic of hydrofluoric acid intensive corrodibility and fat-solubility, make it very easily permeate human body, combine with intravital calcium, magnesium ion, corrode bone and muscle, and not only skin contact has injury, even enter human body by respiratory tract and also can produce suitable danger, all must just can not cause the harm of human body and the pollution of environment so contain the waste water of hydrofluoric acid through handling.
The most of calcium salt precipitation method that uses of semi-conductor industry is handled hydrofluoric acid at present, and wherein calcium salt can be calcium hydroxide (Ca (OH)
2), calcium sulfate (CaSO
4) or calcium chloride (CaCl
2) etc., hydrofluoric acid and calcium salt form Calcium Fluoride (Fluorspan) (CaF
2) and precipitate, and Calcium Fluoride (Fluorspan) is a kind of compound of nontoxic and high stability, thus can directly be buried in the sanitary landfill field, and remaining hydrofluoric acid concentration is if, can discharge when following less than the legal quantity discharged of 15ppm.
The synoptic diagram of known hydrogen fluoride trealment system comprises a reactive tank 10, a coagulation tank 20, a collection surface 30, a purification tank 40, a sludge sump 50, a plurality of fluorinion concentration meter 60 and a plurality of pH meters 70 as shown in Figure 1.At first hydrofluoric acid waste liquid Q enters reactive tank 10, under fluorinion concentration fixed situation, the settling rate of Calcium Fluoride (Fluorspan) is influenced by calcium ion concn and potential of hydrogen mainly, so add calcium chloride C and sodium hydroxide N according to fluorinion concentration meter 60 and pH meter 70, and react completely for making, the calcium chloride C that is added is generally in right amount, and the interpolation of sodium hydroxide N is for whole waste liquid environment being under the alkaline condition, being beneficial to the formation of Calcium Fluoride (Fluorspan); But along with the reduction of fluorinion concentration, the reaction times will be longer, so can add calcium chloride C again one time at next step usually, be called hydrofluoric two-part and handle.
Then the hydrofluoric acid solution Q with treated mistake in the reactive tank 10 introduces in the coagulation tank 20, add calcium chloride C and sodium hydroxide N according to fluorinion concentration meter 60 and pH meter 70 equally, it is more complete that fluoride ion removing is got, and adding POLY ALUMINIUM CHLORIDE (Poly Aluminium Chloride, abbreviation PAC) P1 is as coagulating agent, make the Calcium Fluoride (Fluorspan) of molecule condense into the colloid of larger particles, be beneficial to precipitation.
Then this waste liquid is introduced collection surface 30, add polymkeric substance flocculation agent P2 and make the colloid precipitation; Afterwards waste liquid is introduced purification tank 40 to filter, the waste liquid that leaches is measured through fluorinion concentration meter 60 and can be discharged when being lower than legal emission standard, and remaining mud then enters sludge sump 50 as burying preparation.
But utilize this method to handle tiny, the difficult precipitation of the formed colloid of hydrofluoric acid waste liquid, shorten, need add the more POLY ALUMINIUM CHLORIDE of volume for making the bulk treatment time; And more complete for the fluorion reaction that makes lower concentration, need to add a large amount of calcium chloride; Amount of reagent is increased, not only do not meet cost benefit, sludge quantity also can increase simultaneously, does not also meet environmental benefit.
Summary of the invention
In view of this, the purpose of this invention is to provide a kind of treatment system and method for hydrofluoric acid, speed hydrofluoric acid treatment speed, reduce amount of reagent and sludge quantity by stage hydrogen fluoride trealment mode.
For achieving the above object, the invention provides a kind of treatment system of hydrofluoric acid, comprising: a pre-treatment groove, in order to handle first part's hydrofluoric acid waste liquid, make the reaction of this first part's hydrofluoric acid waste liquid and excessive calcium salt, form first waste liquid; And a reactive tank, in order to handle second section hydrofluoric acid waste liquid and above-mentioned first waste liquid, form second waste liquid, to produce a kind of waste that discharges and bury.
For achieving the above object, the invention provides a kind of treatment process of hydrofluoric acid, comprising: first part's hydrofluoric acid waste liquid is placed the pre-treatment groove, and add excessive calcium salt, form first waste liquid; And second section hydrofluoric acid waste liquid and above-mentioned first waste liquid placed a reactive tank, form second waste liquid, to produce a kind of waste that discharges and bury.
The simple declaration of accompanying drawing
Fig. 1 is in order to illustrate the synoptic diagram of known hydrofluoric acid treatment system;
Fig. 2 is the synoptic diagram in order to the hydrofluoric acid treatment system of the explanation embodiment of the invention.
Nomenclature
10,120～reactive tank, 20～coagulation tank
30,130～collection surface, 40,140～purification tank
50,150～sludge sump, 60,160～fluorinion concentration meter
70,170～pH meter, 100～scale tank
110～pre-treatment groove C～calcium chloride
N～sodium hydroxide P1～many aluminum oxide
P2～polymkeric substance Q～feed liquor amount
X～feed liquor ratio
Embodiment
For above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, hereinafter the spy enumerates preferred embodiment, and conjunction with figs., is described in detail below:
Fig. 2 is a hydrofluoric acid treatment system diagram of the present invention, includes a scale tank 100, a pre-treatment groove 110, a reactive tank 120, a collection surface 130, a purification tank 140, a sludge sump 150 and a plurality of fluorinion concentration meter 160 and one or more pH meters 170.
At first the hydrofluoric acid waste liquid is introduced in the above-mentioned scale tank 100, record a Q unit volume, and record the concentration of fluorion by fluorinion concentration meter 160, this concentration is multiplied by measured Q unit volume, can learn the amount of whole calcium chloride that the hydrofluoric acid waste liquid of this Q unit volume is required; Hydrofluoric acid waste liquid with XQ (X is a per-cent) unit volume enters in the above-mentioned pre-treatment groove 110 again, and the hydrofluoric acid waste liquid of remaining (1-X) Q ((1-X) is per-cent) unit volume enters in the above-mentioned reactive tank 120.Wherein X is preferably 10%～20%, and in this embodiment, X is 15%.
Then in the hydrofluoric acid waste liquid of the 15%Q of pre-treatment groove 110 unit volume, add the required whole calcium chloride C of Q unit volume of hydrogen fluoric acid waste liquid, the reaction of the calcium chloride C that this is excessive and hydrofluoric acid forms the Calcium Fluoride (Fluorspan) particle, and the waste liquid in the treatment trough 110 enters in the reactive tank 120 before this again.
Because the fluorion of the hydrofluoric acid waste liquid of 15%Q unit volume forms the Calcium Fluoride (Fluorspan) particle with calcium chloride C in pre-treatment groove 110, so in reactive tank, can be with the Calcium Fluoride (Fluorspan) particle of this formation as crystal seed; And the fluorion of the former hydrofluoric acid waste liquid that is stored in 15%Q unit volume in the reactive tank 120 and excessive calcium ion form Calcium Fluoride (Fluorspan) in above-mentioned plane of crystal, form the bigger Calcium Fluoride (Fluorspan) particle of particle, so not only fluorion can be separated out as long as add a calcium chloride, and the Calcium Fluoride (Fluorspan) particle of being separated out is also bigger, so settling rate is very fast, the coagulating agent of calcium chloride and follow-up interpolation and the add-on of flocculation agent are reduced.In addition, in reactive tank 120, add simultaneously sodium hydroxide N, make the fluorine of hydrofluoric acid waste liquid be easier to formal solution by hydrofluoric acid, increase the speed of reaction of fluorion and calcium ion from coming out.In addition, add POLY ALUMINIUM CHLORIDE (PolyAluminium Chloride is called for short PAC) P1 again in reactive tank 120,, make Calcium Fluoride (Fluorspan) form the particle of bigger colloidal, be beneficial to precipitation as coagulating agent.Afterwards, whole waste liquids in the reactive tank 120 are entered in the collection surface 130.
In this collection surface 130, add polymer P 2 as flocculation agent, this polymer P 2 can be anion-polyacrylamide (anionic polyacrylamide), anionic Poly Dimethyl Diallyl Ammonium Chloride (cationic poly dimethyl dially ammonium chloride) or non-ionic polyacrylamide (nonionic polyacrylamide), make the Calcium Fluoride (Fluorspan) precipitation of colloidal, again this waste liquid is entered in the above-mentioned purification tank 140.
Waste liquid in the purification tank 140 is filtered, wherein the mud that is produced enters in the sludge sump 150, bury after the processing such as compressed, and remaining waste liquid is measured through fluorinion concentration meter 160 and can be discharged when its fluorinion concentrations such as its concentration are lower than legal emission standard 15ppm.
After real-world operation, find, hydrofluoric acid treatment of the present invention system can make more than the fast twice of treatment time of hydrofluoric acid, the add-on of calcium chloride can reduce 20%～50%, the add-on of POLY ALUMINIUM CHLORIDE and polymkeric substance also can reduce 10%～20%, sludge quantity also reduces, and only need one group of calcium chloride charging machine, lacked a charging machine than known way.
Though the present invention discloses preferred embodiment as above; right its is not in order to restriction the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; can carry out some and change and modification, so protection scope of the present invention is worked as with being as the criterion that claims were defined.
Claims (9)
1. hydrofluoric acid treatment system comprises:
One scale tank, in order to the hydrofluoric acid waste liquid is divided into first part's hydrofluoric acid waste liquid and second section hydrofluoric acid waste liquid, wherein the volume of this first part's hydrofluoric acid waste liquid is 10%～20% of a hydrofluoric acid waste liquid volume;
One pre-treatment groove in order to handle above-mentioned first part hydrofluoric acid waste liquid, makes this first part's hydrofluoric acid waste liquid and excessive calcium salt reaction, forms first waste liquid;
One reactive tank in order to handle above-mentioned second section hydrofluoric acid waste liquid and above-mentioned first waste liquid, forms second waste liquid, wherein also is added with sodium hydroxide and a kind of coagulating agent in this reactive tank;
One collection surface in order to handle second waste liquid, reacts itself and a flocculation agent, forms the 3rd waste liquid; And
One purification tank is in order to handle the 3rd waste liquid, to produce a kind of waste that discharges and bury.
2. hydrofluoric acid treatment as claimed in claim 1 system, wherein this scale tank also comprises the fluorinion concentration meter, in order to measure the fluorinion concentration of this hydrofluoric acid waste liquid.
3. hydrofluoric acid treatment as claimed in claim 1 system, wherein this calcium salt is calcium hydroxide, calcium sulfate or calcium chloride.
4. hydrofluoric acid treatment as claimed in claim 1 system, wherein this coagulating agent is a POLY ALUMINIUM CHLORIDE.
5. hydrofluoric acid treatment method comprises:
One hydrofluoric acid waste liquid is placed a scale tank, and measure the volume and the fluorinion concentration of this hydrofluoric acid waste liquid, and this hydrofluoric acid waste liquid is divided into first part's hydrofluoric acid waste liquid and second section hydrofluoric acid waste liquid, and wherein the volume of this first part's hydrofluoric acid waste liquid is 10%～20% of a hydrofluoric acid waste liquid volume;
Above-mentioned first part hydrofluoric acid waste liquid is placed the pre-treatment groove, and add excessive calcium salt, form first waste liquid;
Above-mentioned second section hydrofluoric acid waste liquid and above-mentioned first waste liquid are placed the reactive tank that is added with a sodium hydroxide and a coagulating agent, form second waste liquid;
Above-mentioned second waste liquid is placed collection surface, and add a kind of flocculation agent and react, form the 3rd waste liquid; And
Above-mentioned the 3rd waste liquid is placed purification tank, to produce a kind of waste that discharges and bury.
6. hydrofluoric acid treatment method as claimed in claim 5, wherein this calcium salt is calcium hydroxide, calcium sulfate or calcium chloride.
7. hydrofluoric acid treatment method as claimed in claim 5 also comprises a kind of potential of hydrogen step of measuring this second waste liquid.
8. hydrofluoric acid treatment method as claimed in claim 5, wherein this coagulating agent is a POLY ALUMINIUM CHLORIDE.
9. hydrofluoric acid treatment method as claimed in claim 5 also comprises a step of measuring the potential of hydrogen of this purification tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410006602 CN1277759C (en) | 2004-02-24 | 2004-02-24 | System and process of treating fluorhydric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410006602 CN1277759C (en) | 2004-02-24 | 2004-02-24 | System and process of treating fluorhydric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1559931A CN1559931A (en) | 2005-01-05 |
| CN1277759C true CN1277759C (en) | 2006-10-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410006602 Expired - Fee Related CN1277759C (en) | 2004-02-24 | 2004-02-24 | System and process of treating fluorhydric acid |
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|---|---|---|---|---|
| KR101340161B1 (en) * | 2011-12-15 | 2013-12-10 | 노바테크 (주) | High Concentration Hydrofluoric Acid Waste Liquor treatment Method |
| CN112156631A (en) * | 2020-10-10 | 2021-01-01 | 北京石晶光电科技股份有限公司 | Artificial crystal plate corrosion volatile liquid treatment device |
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Granted publication date: 20061004 Termination date: 20210224 |