CN1329319C - Treatment of chemical waste - Google Patents
Treatment of chemical waste Download PDFInfo
- Publication number
- CN1329319C CN1329319C CNB2004800021407A CN200480002140A CN1329319C CN 1329319 C CN1329319 C CN 1329319C CN B2004800021407 A CNB2004800021407 A CN B2004800021407A CN 200480002140 A CN200480002140 A CN 200480002140A CN 1329319 C CN1329319 C CN 1329319C
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- Prior art keywords
- ionic
- ion
- water
- unit
- waste gas
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
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- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
A method for the treatment of gaseous chemical waste is provided. The water is continuously circulated through an essentially closed loop that incorporates a gas scrubbing unit and an ion absorption unit. The ion absorption unit comprises a water permeable ion absorbing means. The exhaust gas or a reaction product thereof is then fed to the gas scrubbing unit for dissolution in the circulating water thereby to form an aqueous solution containing ionic species derived from the exhaust gas. The circulating water is continuously brought into contact with the ion absorbing means in the ion absorption unit whilst an electrical potential is applied across the thickness of the ion absorbing means. A more concentrated aqueous solution of the ionic species is then removed from the ion absorbing means. A quantity of water corresponding to the quantity of aqueous solution of the ionic species removed from the ion absorption unit is continuously added to the closed loop.
Description
The present invention relates to deleterious and/or, relate more specifically to treatment of waste gas from various chemical processes to the processing of environmental risk or deleterious material.
Usually, chemical process industry produces a large amount of by product and refuse, and wherein many is environmental hazards, and it must be neutralized and destroy as the necessary part of ultimate disposal.Oil and natural gas processing industry, for example, the great amount of investment in the design of facilities and equipment is especially in order to prevent or to make a large amount of harmful organic substances that are discharged in the environment minimized.For example, microelectronics and semiconductor devices process industry be for before waste gas is discharged into atmosphere, washing or comprise the exhaust flow of inorganics usually and similarly invest from chemical process is unitary with other method processing.The compound and halogen-containing, sulphur, phosphorus and the nitrogen compound that contain heavy metal may be deleterious especially, and their removal is the theme of a considerable amount of technical study and many legislationss of environmental protection.
In many situations, even the dilute solution of this objectionable impurities or suspension can not discharge legally.For example, the legal boundary of moisture HF discharging is the low 3ppm that reaches.Yet traditional washing and other absorption systems produce a large amount of HF that is not only continuously, also have other aqueous acids such as HCl, HNO
3And H
2SO
4In order to control acid concentration, therefore the discharging of this aqueous acids comprises the use of a large amount of fresh waters.For example, by the closed loop washing system that absorbs HF in the waste gas, during with the recirculation rate running of 25l/min, for keep in the recycled water fluorinion concentration one acceptable low-level on, will consume about 6l/min fresh water usually.This emission concentration can under this situation, need effectively further dilution and processing up to 4000ppm.
Ion exchange technique provides a kind of and has caught and the final alternative route of handling many poisonous and other Hazardous substancess.Yet many ion-exchange materials do not have enough selectivity for real validity.In addition, load the ionic ion-exchange material that is hunted down must regenerate by backwash, this brings the more use of the chemical substance of being potentially dangerous property again.
More recently progress is in the deionized technology of electrochemistry that is called described in the European patent NO.0680932.In brief, this technology comprises being used in combination of electrochemical cell and ionic absorption material, and wherein, the ion of being caught on the absorbing material is transported by this material under the effect of electric field that is applied and washing out the liquid zone appearance and be removed at this.As if this processing has good efficiency, but only is used for making the electrochemistry deionizer of single-pass (singlepass) in the described in the text solution.
The invention provides a kind of method, it can remove negatively charged ion and/or cationic substance continuously in the aqueous solution circulating in the closed loop system, and need not the regeneration of separate medium or the new life of other chemistry or physics, the closed loop system is carried above for example comprises the unitary system of gas scrubbing.
First aspect the invention provides the method for handling the gaseous chemical waste, and it comprises step:
Make water wash the unit and comprise that the unitary base closed loop of ionic absorption of the ionic absorption device of porous circulates continuously by contained gas;
With waste gas or its reaction product input gas scrubbing unit and in recirculated water, dissolve, comprise the aqueous solution from the ionic species of waste gas with formation;
When the thickness direction at the ionic absorption device applies electromotive force, recirculated water is contacted with ionic absorption device in the ionic absorption unit, and from the ionic absorption unit, remove the aqueous solution of more spissated described ionic species; With
Corresponding to from the quantity of the aqueous solution of the removed ionic species in ionic absorption unit a certain amount of water of adding in the described closed loop continuously.
In a preferred embodiment, the ionic absorption device can comprise the water permeable layer of ionic absorption material, make a surface contact of the layer of ionic absorption material in the homo-ion absorptive unit of continuous round-robin water, and through the aqueous solution of the more spissated ionic species of another surface removal of this layer.
In another preferred embodiment, the ionic absorption device can comprise the water permeable zone of ionic absorption material.
In another preferred embodiment, continuously with waste gas or its reaction product supply gas washing unit.
In another preferred embodiment, off and on waste gas or its reaction product supply gas washing unit.
In another preferred embodiment, waste gas or its reaction product comprise HF and ionic species is F
-
In another preferred embodiment, waste gas or its reaction product comprise HCl and ionic species is Cl
-
In another preferred embodiment, waste gas or its reaction product comprise oxynitride and ionic species is NO
3 -
In another preferred embodiment, waste gas or its reaction product comprise oxysulfide and ionic species is SO
4 2-
In another preferred embodiment, waste gas or its reaction product comprise phosphorous oxides and ionic species is PO
4 3-
Second aspect, the present invention also provides and implements the employed device of this kind method, comprising:
Base closed looped cycle system, its contained gas washing unit and ionic absorption unit, described ionic absorption unit comprise the ionic absorption device of porous and the device that electromotive force can be applied along the thickness direction of ionic absorption device;
Pump makes water circulate continuously along closed loop;
Waste gas or its reaction product enter the unitary inlet of gas scrubbing;
Water enters the inlet of closed loop circulation; With
Be used for outlet from the spissated aqueous solution of the unitary ionic species of ionic absorption.
Device also can comprise one or more heat exchangers and/or strainer, wet cyclone and allied equipment in closed loop circulation, to remove the solid matter of any particulate/suspension from circulation fluid.
In a preferred embodiment, the ionic absorption device can comprise the water permeable layer of ion-exchange material.
In another preferred embodiment, the ionic absorption device can comprise the water permeable zone of ionic absorption material.
Waste gas is the gaseous effluent or any by product of product process for processing, need be to the safe handling of carrying out of itself or its component.If waste gas or its related component are to exist with the form that is adapted in the water dissolving and is fit to be undertaken by method of the present invention subsequent disposal, then perhaps the first pre-treatment of waste gas there is no need.For example: when waste gas bag phosphorated oxide compound itself, the gas scrubbing unit can effectively dissolve the oxide compound of these phosphorus to produce aqueous phosphoric acid salt and/or phosphite.
Perhaps, the material that comprises insoluble in water when waste gas is hydrofluoric ether or CFC for example, uses burner, plasma reactor or other reaction members so that these water-fast materials are converted into water-soluble form with being necessary.Hydrofluoric ether for example, can be converted into HF by this way, and HF is dissolved in the water easily to generate hydrofluoric acid in the gas scrubbing unit.
The ionic absorption material can be caught the ion of expectation, ion-exchange material preferably, and the ion exchange resin that exists with particle or bead form for example, or other can provide the material of following medium:
The infiltrative medium of solution;
Ionic absorption medium (to remove negatively charged ion or positively charged ion);
Ionic conduction medium, the electric field and ionic that passes through to be applied can move into independently in the solution.
The particle or the bead of resin preferably exist with adhesive form, and they are not mobile or loose in other words, but in the structure that is limited in being scheduled to.For example, particle or bead are bonded together or are fixed between the layer of grid or film, so that be permeable for containing the ionic aqueous solution with tackiness agent.For example, the ionic absorption material the layer the electromotive force that thickness direction applied be used to order about captive ion by ionic absorption material one or other electrode movements towards applying electromotive force.Electromotive force can be produced by pair of electrodes, and electrode is arranged and forms electrolytic cell or be aligned to any alternative form, for example the form of electrophoresis battery.
Found to use method and apparatus of the present invention, can make in the negatively charged ion and/or the cationic continuous separation of the closed loop circulation that for example is used for gas scrubbing effectively, need not any regeneration or regularly replace the ionic absorption device.The efficient of method and apparatus depends on ionic absorption device and a kind of ion that will catch or the character of different kinds of ions, the concentration of a kind of ion or different kinds of ions and other factors in the solution, as flow rate and electromotive force, but primary index, the The ion extraction rate of every passage reach 98% and can realize.
Because high like this extraction yield is as F
-, SO
4 2-And NO3
-The removal of acidic anionic will have significant effect to the work-ing life of improving the equipment (as pump, instrument, valve and dividing plate) in the recycle system.
Method of the present invention is suitable for a variety of anionic species, negatively charged ion such as vitriol, sulphite, nitrate, nitrite, phosphoric acid salt, phosphite and halogenide (being fluorochemical, muriate, bromide and iodide), effective to cationic substance equally, particularly metal, more especially heavy metal.
Yet the present invention has unique suitability to fluorochemical, and is that fluorochemical produces as the by product for semi-conductor industry and owing to following dissolving in the gas scrubbing unit to produce those of hydrofluoric acid aqueous solution.
Find unexpectedly that the ion of desorb no longer enters continuous flow from the aqueous solution, for example the water cycle stream on the surface by the ionic absorption material.Though usually the gas scrubbing operation is based on realizing continuously, the acid content that enters the gas of washer can be change with can usually not exist fully.This just means that the content of fluoride ion by the water of ionic absorption material surface is to change relatively.Under the influence of the electromotive force that is applied, the ion that is hunted down is transported from the ionic absorption material surface, and such fact prevents that these ions from dissolving in the water once more.This shows great advance on ionic absorption efficient.
In contrast to the embodiment of the closed loop gas scrubbing system that provides above, this system produces the fresh water that runs on the moisture HF that recirculation rate is 25l/min and consume about 6l/min, and the similar system that comprises feature of the present invention has demonstrated in initial test can realize nearly 30 times reduce of fresh water requirement.
Only present invention is described by embodiment with reference to the accompanying drawings below, wherein:
Fig. 1 is the synoptic diagram of existing known closed loop recycle gas treatment unit;
Fig. 2 is the synoptic diagram according to closed loop recycle gas treatment unit of the present invention;
Fig. 3 is the synoptic diagram that can be used for the embodiment of the electrochemical cell in the device shown in Figure 2; With
Fig. 4 is the synoptic diagram that can be used for another embodiment of the electrochemical cell in the device shown in Figure 2;
Reference drawing has shown in Fig. 1 for the synoptic diagram from traditional air processing unit of the waste gas of semiconductor devices manufacturing works.Waste gas can comprise many different materials, comprises the compound of halogen-containing, phosphorus, silicon and boron.Waste gas or its pre-reaction product, with regard to fluorochemicals, for example HF enters gas scrubbing unit 3 by pipeline 4, contacts closely with the water that enters by pipeline 2 at this.The closed loop circulation 1 of pipeline 2 component parts, system comprises pump 5, is used for along the pump circulation and the pipeline 6 of the water of loop, and whereby, aqueous HF can discharge from system, and pipeline 7, and whereby, the fresh water of respective amount can enter into loop.The recycle system 1 also can comprise one or more other traditional element, for example strainer, wet cyclone, heat exchanger, instrument, scale and valve.Gas scrubbing unit 3 may comprise filler, dividing plate, cyclonic separator and/or similar installation, by optimizing contact promotion dissolving of gas at aqueous liquid of liquid/gas surface; This washing technology is that the present technique field is known, need not independent description here.
In an embodiment of traditional operation, comprise 2,000sccm C
2F
6The waste gas of 200slpm be converted into HF (12,000sccm HF) with stoichiometric relation, it enters gas scrubbing unit 3 by pipeline 4, and contacts by the water that pipeline 2 enters with speed 25l/m, and is dissolved in this water.HF up to 400ppm can be dissolved in the aqueous fluid usually in this way, although concentration up to the HF of 4000ppm can be by higher input air-flow and prolong fluid re-circulation and realize.Typically, undissolved gas is discharged into atmosphere from washer.Fresh water is added into loop with speed 6l/min by pipeline 7, and aqueous acid is extracted by pipeline 6 with corresponding speed.The HF content of the acid of being extracted depends on the gas input, and will bring serious handling problem.
With reference now to Fig. 2,, shown in system be according to of the present invention, broadly similar is in shown in Fig. 1, wherein, closed loop 1 comprises gas scrubbing unit 3 and pump 5, yet, in this case, also comprised an acid in the loop and removed unit 8.Suitable acid is removed unitary embodiment and is described in greater detail below, but shown in test, can from the 400-500ppm HF that imports continuously with 25slpm, produce 0.1-0.2l/min (about 2001/ day) the 0.7-1.2M HF aqueous solution, and provide the continuous liq output of 10-30ppm HF.As a result, enter the unitary aqueous liquid of gas scrubbing and comprise still less dissolved HF, make that therefore the HF in the gas scrubbing unit absorbs more effective.Equally, with comparing so far, in the circulating liquid in the loop HF concentration can maintain one more low-level, therefore work-ing life of having improved equipment.In addition, the reduction of resultant is 0.7-1.2M hydrofluoric acid in this case, itself also is useful, and therefore it is not handled can bring problem.
Forward Fig. 3 of figure now to, show the embodiment of an electrochemical cell in the closed loop that is suitable for comprising device shown in Figure 2 into, be used for separating HF from recycle acid solution.This battery is closely similar, as above for referencial use with described in the European patent No.0680932 in fact.
In order to remove fluorochemical and nitrate ion in the circulation fluid from the closed loop system, layer 14 can comprise weak anion exchange resin thoroughly.The circulate soln of fluoride and nitrate through enter the mouth 24 and outlet 25 by chamber 12, it is in front surface 16 and counter electrode 26 contacts of battery neutralize ions exchange layer 14.Electromotive force between feeder line 13 (anode) and counter electrode 26 (negative electrode) produces H at feeder line 13
+These H
+Ion interacts and with its activation towards the anionite-exchange resin in counter electrode 26 motion and the layer 14.Fluorochemical in the solution and nitrate ion shift-in layer 14, on this ion is adsorbed to activated ion exchange resin, and rearward face 17 moves under the influence of the gesture that is applied.This can be absorbed more fluorochemical and nitrate ion at front surface 14, and making can be from by removing these ions the battery 10 round-robin aqueous solution continuously.Also infiltrate through layer 14 from the water of solution, flow to rear surface 17, at this, itself and captive fluorochemical and nitrate ion are brought together, and are removed by wash-out hole 19 with the form of hydrofluoric acid/aqueous nitric acid.
Fig. 4 illustrates another embodiment of electrochemical cell, and it can comprise in the closed loop of device shown in Figure 2 into.Electrochemical cell 30 shown in Figure 4 comprises electrode assemblie 36 and electrode assemblie 31, and its separated district 32 separates, and the disengaging zone comprises the inlet 33 and the outlet 35 of the aqueous solution.Electrode assemblie 36 and 31 and the common solution chamber 37 that limit in disengaging zone 32.
Electrode assemblie by suitable ion permeable membrane 41 and 42 and solution chamber separate, permeable membrane makes positively charged ion enter cathode compartment 34, negatively charged ion enters anolyte compartment 40.Anolyte compartment 40 comprises anode 38, and cathode compartment 34 comprises negative electrode 39.
But catholyte through port 43 and 44 enters cathode compartment 34 and therefrom removes, but anolyte through port 45 and 46 enters anolyte compartment 40 and therefrom removes.Solution chamber 37 has filled suitable ion-exchange material, is used for negatively charged ion and cationic absorption.
With regard to the inlet 33 of the aqueous solution in battery and the situations of outlet 35 by chamber 37 of fluorochemical or other negatively charged ion such as nitrate, these ions are adsorbed on the resin.Electrode 38 and 39 s' electromotive force makes that adsorbed fluorochemical or other negatively charged ion arrives film 41 and enter anolyte compartment 40 by film by ion exchange layer on the resin, forms spissated fluorochemical or other anion solutions in the anolyte compartment.The input aqueous solution of fluorochemical or other negatively charged ion dilutions flows out battery through exporting 35.
Another embodiment of the ion adsorption unit of forming by ion-exchange material, when operation is from regenerated, it crosses the side to discharge as concentrated aqueous solution with the positively charged ion and/or the anion transport of being caught effectively, and when not having other positively charged ions or anionic species and exist, the form of its hydrogen or oxyhydroxide will be regenerated as.This electric regenerant ions crosspoint is known with the ERIX unit.This unit can comprise the ion remaval and the concentration channels of many parallel connections, should be that those skilled in the art is known.
Claims (15)
1. handle the method for gaseous chemical waste, it comprises step:
Make water wash the unit and comprise that the unitary base closed loop of ionic absorption of the ionic absorption device of porous circulates continuously by contained gas;
With waste gas or its reaction product input gas scrubbing unit and in recirculated water, dissolve, comprise the aqueous solution from the ionic species of waste gas with formation;
When the thickness direction at the ionic absorption device applies electromotive force, recirculated water is contacted with ionic absorption device in the ionic absorption unit, and from the ionic absorption unit, remove the aqueous solution of more spissated described ionic species; With
Corresponding to from the quantity of the aqueous solution of the removed ionic species in ionic absorption unit a certain amount of water of adding in the described closed loop continuously.
2. according to the process of claim 1 wherein, described ionic absorption device comprises the water permeable layer of ion-exchange material.
3. according to the method for claim 2, wherein, make a surface contact of the layer of the ion-exchange material in the homo-ion absorptive unit of continuous round-robin water, and through the aqueous solution of the more spissated ionic species of another surface removal of this layer.
4. according to the process of claim 1 wherein, described ionic absorption device comprises the water permeable zone of ion-exchange material.
5. according to the method for arbitrary aforesaid claim, wherein, continuously waste gas or its reaction product supply gas are washed the unit.
6. according to the method for arbitrary claim of claim 1-4, wherein, off and on waste gas or its reaction product supply gas washing unit.
7. according to the method for arbitrary claim of claim 1-4, wherein, waste gas or its reaction product comprise HF and ionic species is F
-
8. according to the method for arbitrary claim of claim 1-4, wherein, waste gas or its reaction product comprise HCl and ionic species is Cl
-
9. according to the method for arbitrary claim of claim 1-4, wherein, waste gas or its reaction product comprise oxynitride and ionic species is NO
3 -
10. according to the method for arbitrary claim of claim 1-4, wherein, waste gas or its reaction product comprise oxysulfide and ionic species is SO
4 2-
11. according to the method for arbitrary claim of claim 1-4, wherein, waste gas or its reaction product comprise phosphorous oxides and ionic species is PO
4 3-
12. be used to implement the device of the method for claim 1, comprise:
Base closed looped cycle system, its contained gas washing unit and ionic absorption unit, described ionic absorption unit comprise the ionic absorption device of porous and the device that electromotive force can be applied along the thickness direction of ionic absorption device;
Pump makes water circulate continuously along closed loop;
Waste gas or its reaction product enter the unitary inlet of gas scrubbing;
Water enters the inlet of closed loop circulation; With
Be used for outlet from the spissated aqueous solution of the unitary ionic species of ionic absorption.
13. according to the device of claim 12, wherein, described ionic absorption device comprises the water permeable layer of ion-exchange material.
14. according to the device of claim 12, wherein, described ionic absorption device comprises the water permeable zone of ion-exchange material.
15. the device according to arbitrary claim of claim 12-14 wherein, also comprises one or more heat exchangers, strainer and/or wet cyclone in closed loop circulation.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0300793.7 | 2003-01-14 | ||
| GB0300793A GB0300793D0 (en) | 2003-01-14 | 2003-01-14 | Treatment of chemical waste |
| GB0321579.5 | 2003-09-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1735566A CN1735566A (en) | 2006-02-15 |
| CN1329319C true CN1329319C (en) | 2007-08-01 |
Family
ID=9951113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800021407A Expired - Fee Related CN1329319C (en) | 2003-01-14 | 2004-01-12 | Treatment of chemical waste |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1329319C (en) |
| GB (1) | GB0300793D0 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0680932A2 (en) * | 1994-05-06 | 1995-11-08 | United Kingdom Atomic Energy Authority | Electrochemical deionisation |
| EP0967003A1 (en) * | 1998-06-23 | 1999-12-29 | Takuma Co., Ltd. | Process and system for exhaust gas treatment |
-
2003
- 2003-01-14 GB GB0300793A patent/GB0300793D0/en not_active Ceased
-
2004
- 2004-01-12 CN CNB2004800021407A patent/CN1329319C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0680932A2 (en) * | 1994-05-06 | 1995-11-08 | United Kingdom Atomic Energy Authority | Electrochemical deionisation |
| EP0967003A1 (en) * | 1998-06-23 | 1999-12-29 | Takuma Co., Ltd. | Process and system for exhaust gas treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1735566A (en) | 2006-02-15 |
| GB0300793D0 (en) | 2003-02-12 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: EDWARDS CO., LTD. Free format text: FORMER OWNER: THE BOC GROUP PLC Effective date: 20071214 |
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Granted publication date: 20070801 Termination date: 20110112 |