CN1191996C - Method for utilizing sulfuric acid/peroxide liquid mixture - Google Patents
Method for utilizing sulfuric acid/peroxide liquid mixture Download PDFInfo
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- CN1191996C CN1191996C CNB981258948A CN98125894A CN1191996C CN 1191996 C CN1191996 C CN 1191996C CN B981258948 A CNB981258948 A CN B981258948A CN 98125894 A CN98125894 A CN 98125894A CN 1191996 C CN1191996 C CN 1191996C
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Abstract
The present invention develops a technique of utilizing a sulfuric acid/peroxide liquid mixture, for example, its waste liquid material, so that the waste liquid can be re-utilized and effectively applied to obviate the problem resulting from disposal. To this end, the present invention provides a method for utilizing a sulfuric acid/peroxide liquid mixture, for example, its waste liquid, in which peroxide in the sulfuric acid/peroxide liquid mixture is decomposed to render it possible to utilize the liquid mixture as sulfuric acid.
Description
Technical field
The present invention relates to a kind of method of utilizing sulfuric acid and peroxide liquid mixture.More particularly, the present invention relates to a kind of its advantage is the method for utilizing sulfuric acid and peroxide liquid mixture that exhausted sulfuric acid and peroxide liquid mixture are reused.
Background technology
So far in most of semiconductor fabrication processes, still use the washing fluid of the mixture of a large amount of sulfuric acid and superoxide as semiconductor chip, or they are with the form of sulfuric acid/aqueous hydrogen peroxide solution, or with the form of sulfuric acid/ozone mixed solution.
This sulfuric acid and peroxide liquid mixture are that a kind of typically being mainly used in peeled off the photoresists on the semiconductor chip or removed the especially washing fluid of heavy metal particles of metallic particles.The usage quantity of this mixed solution is than other washing fluid, and is much bigger as the usage quantity of ammonia/aqueous hydrogen peroxide solution, hydrochloric acid/aqueous hydrogen peroxide solution or rare fluoric acid.
This has just caused using the back to produce a large amount of waste liquids.The waste liquid of this mixed solution following point can occur when disposing:
(i), will produce a large amount of heat (relevant) with the vitriolic hydration heat if these waste liquids are mixed with water;
(ii) stayed peroxy acid (permonosulphuric acid) with strong oxidation capacity; With
(iii) stayed aqueous hydrogen peroxide solution, the result of impact or poly-doped impurity makes it be easy to produce violent foam (foam that oxygen produces).
Because the problem that the pressure due to above-mentioned heat release and the foaming sharply rises and brings, or, be difficult to transport these waste liquids, and directly they be cleaned into sulfuric acid because the possibility of the structure deteriorate due to the oxidation is considered safety or day-to-day operation.Therefore,,, neutralize with alkali such as slaked lime then, then flocculate, at last as discharge of wastewater with inorganic flocculating agent and polymeric flocculant with a large amount of water dilutions and cooling waste liquid according to convention.
Owing to used a large amount of water or chemical reagent such as flocculation agents that are initial sulfuric acid and peroxide liquid mixture tens to hundred times, thereby increased processing costs, i.e. equipment or maintenance cost, and chemical reagent or sludge disposal costs.If waste liquid is handled like this, the waste discharge amount is increased.
Up to now, people think except outflow emits as waste water with sulfur waste acid and peroxide liquid mixture always, the possibility of not reusing.
Summary of the invention
As mentioned above, sulfur waste acid and peroxide liquid mixture locate to be equipped with many shortcomings, the inventor attempts to develop a kind of technology of utilizing this waste liquid and the solution problem relevant with the waste liquid disposal effectively again.In research process, the inventor has finished the present invention, and its purpose is to develop a kind of technology of utilizing sulfuric acid and peroxide liquid mixture such as its waste liquid, and a kind of method of utilizing this waste liquid and solution and waste liquid to dispose relevant problem is provided.
The invention provides a kind of method of utilizing sulfuric acid and peroxide liquid mixture, this method is included in decompose hydroperoxide in sulfuric acid and the peroxide liquid mixture, thereby this mixed solution is used as sulfuric acid.
Because in sulfuric acid and peroxide liquid mixture, superoxide is decomposed, and the mixed solution that obtains can be used as sulfuric acid and uses, if with the above-mentioned waste liquid of this technical finesse, can utilize the waste liquid of sulfuric acid and peroxide liquid mixture effectively again.So not only effectively utilized this waste liquid, disposed relevant problem but also solved with waste liquid.The present invention provides a kind of effective treatment technology for the waste liquid of sulfuric acid and peroxide liquid mixture, wherein sulfuric acid and superoxide are remaining as a component, if wish waste liquid is used as sulfuric acid, the present invention can also be as a kind of method of utilizing sulfuric acid and peroxide liquid mixture, is applied in the miscellany processing of sulfuric acid except that sulfur waste acid and peroxide liquid mixture and superoxide.
The present invention finishes according to the following data that the contriver obtains.That is, in order to address the above problem, the inventor has carried out insistent research, therefore find, to sulfuric acid and peroxide liquid mixture adding decomposition accelerating agent such as nitric acid the time, this waste liquid can be as the black sulfuric acid utilization, and for example this waste liquid is the waste liquid that produces in the semiconductor production process.This discovery causes having finished the present invention.
According to the present invention, a kind of new method of utilizing sulfuric acid and peroxide liquid mixture is provided, therefore sulfur waste acid and peroxide liquid mixture might be used as sulfuric acid now.Consequently this waste liquid need not to dispose and just can use, thereby has effectively utilized resource, reduces refuse such as discharged waste water.In addition, adopt the present invention, need not to reduce vitriolic concentration in the waste liquid, just decompose hydroperoxide fully.The product that generates can be used as the properties-correcting agent of all cpds such as polymkeric substance, as sulphonating agent or hydrolytic accelerating agent.Decompose hydroperoxide resulting decomposition liquid can be used as the modifying agent of waste resin material, these refuses can be transformed into the high added value material thus, by reducing the refuse amount, effectively utilizes natural resources, the environment of preserving our planet.
Embodiment
Describe content of the present invention below with reference to most preferred embodiment, these embodiment just are used for illustration purpose, can not limit protection scope of the present invention.
The present invention is by decompose hydroperoxide in sulfuric acid and peroxide liquid mixture, with sulfuric acid and peroxide liquid mixture as the sulfuric acid utilization, and found the approach that utilizes sulfuric acid and superoxide mixed waste liquor most effectively, acid of these sulfur wastes and peroxide liquid mixture are that each use field from sulfuric acid and peroxide liquid mixture obtains, and have avoided disposing the variety of issue that these waste liquids bring thus.
According to the present invention, sulfuric acid and peroxide liquid mixture contain vitriolic concentration and are not less than 70wt%, preferably are not less than 80wt%.This be because, if sulfuric acid concentration is lower than 70wt%, even the decomposition accelerating agent that adds as hereinafter will describe also is difficult for making peroxide breakdown.
Use field to sulfuric acid and peroxide liquid mixture is not particularly limited.Usually, sulfuric acid and peroxide liquid mixture are preferably from various cleaning processes.For example, sulfuric acid and peroxide liquid mixture preferably electronic applications wash the washing fluid of various elements or product, especially preferably being used for semiconductor production process peels off the washing lotion of resist or is used as various scavenging solutions, because the vitriolic concentration that is used for the sulfuric acid of semiconductor production process and peroxide liquid mixture is often more than or equal to 70wt%.
Superoxide in sulfuric acid and peroxide liquid mixture can be hydrogen peroxide, ozone and peroxy acid (permonosulphuric acid).Should be noted that common peroxosulphuric is by injecting aqueous hydrogen peroxide solution or ozone gas generation in sulfuric acid.
Concentration to superoxide in sulfuric acid and the peroxide liquid mixture is not particularly limited.Usually, this concentration is preferably 0.001ppm-20wt%, is more preferably 0.01ppm-10wt%.If in mixed solution, except sulfuric acid and superoxide, also contain various ingredients, as water, mineral acid, tensio-active agent or decomposition stablizer, do not have any specific question yet.The total content of these the 3rd components preferably is no more than 30wt%, because these the 3rd components contents are high more, and the decomposition of easy more obstruction superoxide in mixed solution.
When superoxide decomposed in sulfuric acid and peroxide liquid mixture, there is no particular limitation to temperature.If decomposition temperature will not have specific question in 0 ℃-180 ℃ scope, the said temperature scope is the use temperature of sulfuric acid and peroxide liquid mixture normally.Usually, the temperature of mixed solution is high more when decomposing, and the decomposition rate of superoxide or lather quickness are fast more.
Be preferably in one or more materials that add in sulfuric acid and the peroxide liquid mixture in nitric acid, nitrosonitric acid, nitrogen peroxide, nitrate or the hydrochloric acid, as the decomposition accelerating agent of its superoxide.Compound concentrations that these also are not used or that be used is not particularly limited.From effectively utilizing the angle of natural resources, preferably select the exhausted compound for use.Same reason, any waste liquid of above-mentioned decomposition accelerating agent that is used for the semiconductor chip scavenging solution of semiconductor fabrication processes preferably all is used as the decomposition accelerating agent of the inventive method.Can determine the addition of decomposition accelerating agent in suitable sulfuric acid and the peroxide liquid mixture, this depends on the kind of superoxide or the temperature of concentration or liquid.Usually, the addition of decomposition accelerating agent in mixed solution is preferably 0.001ppm-10wt%, is more preferably 0.01ppm-5wt%.When adding decomposition accelerating agent, if the stirring abundance of mixed solution, decomposition accelerating agent can disperse well, can increase the addition of decomposition rate or minimizing decomposition accelerating agent thus.
When using this mixed solution, above-mentioned decomposition reaction can occur, wash in the molten device as semiconductor chip in semiconductor fabrication processes, or in an equipment that is exclusively used in decomposition reaction.Because will generate a large amount of gases in existing decomposition reaction usually mainly is oxygen, produced decomposition heat, reduce decomposition heat whipping appts and/or refrigerating unit so preferably be provided with, perhaps take suitable measure, as compression-resistant structure or the pressure release pipeline is set, prevent because the liquid level that the gas bubbling causes raises or pressure raises.
In order to decompose effectively, preferably under stirring condition, inject the decomposition accelerating agent drop to mixed solution.Usually decomposition reaction has very high speed of response, therefore, if disposable injection decomposition accelerating agent will be difficult to control and bubble or thermopositive reaction.
Adopt above-mentioned treatment process, can finish the decomposition of superoxide in sulfuric acid and peroxide liquid mixture in a short period of time, the liquid after feasible the processing can be used as sulfuric acid and reuses.For example, the liquid after the processing can be used as strong acid or sulphonating agent is reused.For example, the sulfuric acid that obtains from sulfuric acid and peroxide liquid mixture can be used as the sulphonating agent of macromolecular compound in this way, perhaps is used for the hydrolysis reaction of macromolecular compound.
Very a spot of decomposition accelerating agent just has Decomposition, and therefore the sulfuric acid in sulfuric acid and peroxide liquid mixture is reduced hardly.After decomposing like this, when purifying treatment liquid, obviously improve regeneration efficiency, made the sulfuric acid of generation be convenient to be regenerated as the vitriol oil, reduced cost simultaneously.
In addition, can be from the treatment solution of decomposition course with decomposing state as sulfuric acid.For example, the treatment solution of decomposing state also can be as the sulphonating agent of all cpds, be used as unsaturated compound that contains aromatic substance, halogen, alcohol or the sulphonating agent that contains the anhydride group compound, especially the sulphonating agent that can be used as the alkyl organic compound is perhaps as the hydrolytic accelerating agent of all cpds.More particularly, the liquid after the processing can be used for synthetic (ABS) of alkylbenzene sulfonate.Above-claimed cpd can be used as the dispersion agent of multiple material, i.e. tensio-active agent, or as static inhibitor.
Treatment solution can also gather sulfonic acid styrene esters and its sodium salt with polystyrene reactant production, they can be used as various dispersion agents, for example, dispersion agent as cement or coal slurry, as heat-resisting thermoplastic resin, as static inhibitor as paper, resin or fiber, as the flocculation agent of disposing of sewage, or as paste or ion exchange resin.Treatment solution can also be produced lignosulfonic acid and salt thereof with lignin reaction, and it can be used as the dispersion agent of cement effectively.Treatment solution can also the hydrolysis ABS resin, the vinyl cyanide group in SAN resin or the PAN resin, and the hydrolysate that obtains with modification is used as moisture-absorption resin.
Compound before compound after handling with the treatment solution of decomposing state such as organic compound can be to use or use after compound, i.e. refuse.From effectively utilizing the viewpoint of natural resources, preferably use refuse as starting material.For example, preferably the exhausted plastics waste material is used as former parent material.
Above-mentioned processing can make superoxide effectively decompose in exhausted sulfuric acid and superoxide waste mixed solution, is convenient to reclaim high-concentration sulfuric acid thus.The sulfuric acid that reclaims not only can be used for himself and purifies as black sulfuric acid, but also can be used as all cpds, as the sulphonating agent or the hydrolytic accelerating agent of various organic compound.
In conventional practice, need to add a large amount of water and chemical reagent processing sulfuric acid and peroxide liquid mixture, produce a large amount of refuses thus the most at last.And can reduce the amount of these refuses now significantly.In addition, the mixed solution that goes out of use up to now can also change into high value-added product.In addition, the plastics waste material that goes out of use up to now can also be converted into high value added product equally.
It can be seen from the above, adopts technical scheme of the present invention can save or reclaim resource, reduces the refuse amount, the environment of preserving our planet thus.
Describe content of the present invention with reference to several preferred embodiments below, these embodiment only are used to illustrate the present invention, and can not limit protection scope of the present invention.In embodiment 1 and 2, the decomposition situation of superoxide in sulfuric acid and peroxide liquid mixture waste liquid described.Similarly, in embodiment 3-9, the particular instance of utilizing sulfuric acid and peroxide liquid mixture degradation production has been described with comparative example.In the following example, the decomposition of superoxide in sulfuric acid and peroxide liquid mixture described, with and the utilization of degradation production, following sulfuric acid and superoxide waste mixed solution (a) and (b) be used for estimating:
(a) before the oxide film of semiconductor fabrication processes forms (preliminary step), (the initial mixing volume ratio is H to be used as the sulfuric acid of pretreated scavenging solution and the waste liquid of peroxide liquid mixture
2SO
4/ H
2O=5: 1, the temperature of use is 80 ℃, in use, has added a spot of aqueous hydrogen peroxide solution); And
(b), be used as and peel off the sulfuric acid of resist liquid and the waste liquid of peroxide liquid mixture (blast ozone gas in the vitriol oil, the temperature of use is 110 ℃) at peel off (preliminary step) in the resist step of semiconductor fabrication processes.
The starting point concentration of sulfuric acid and aqueous hydrogen peroxide solution is respectively 96wt% and 30wt%.
Embodiment 1
5 liters of waste liquids (a) are injected in the reactor that has agitator and refrigerating unit, and it is cooled to water temperature.Under agitation, Dropwise 5 drips the nitrosonitric acid waste liquid in waste liquid, and every weight approximately is 0.2 gram, and this nitrosonitric acid waste liquid peels off liquid as the resist of metal interconnected step in the semiconductor fabrication processes.From dripping nitric acid, occurred because the foam that peroxide breakdown produces and in 2 minutes, having disappeared again immediately greatly.Analysis is in decomposition reaction front and back, the residual content of aqueous hydrogen peroxide solution in the waste liquid.Discovery approximately is that the residual content of 1wt% is reduced to less than and equals 10ppm after decomposition.By the vitriolic concentration in the decomposition resulting decomposition liquid is 82wt%.The sulfuric acid that obtains after the purification can be used as industrial sulphuric acid again.
Embodiment 2
Under 110 ℃ temperature, drip the sulfuric acid of 7 10wt% in 20 liters of waste liquids (b) in being contained in the semiconductor chip rinse bath, every weight approximately is 0.3 gram, in the above-mentioned semi-conductor rinse bath recursive filter is housed, similar to the situation of embodiment 1, from dripping the position of nitric acid, occurred because the foam that peroxide breakdown produces.This foam disappeared in about 1 minute.Before and after decomposition reaction, in this waste liquid, drip resist solution.As for the solution before decomposing, after injecting resist solution, whole solution has become light yellow, and within about 3 minutes, it is transparent as before that solution becomes once more.And the solution after decomposing will be kept light yellow.Its reason is to have finished the decomposition of superoxide in waste liquid.By the vitriolic concentration in the decomposition resulting decomposition liquid is 90wt%.The same with embodiment 1, the sulfuric acid after the purification can be used as industrial sulphuric acid again.
Embodiment 3
In 5 gram embodiment 1, in the resulting decomposed solution (sulfuric acid concentration is 82wt%), add 0.2 gram refuse (ABS resin) of 8mm magnetictape cartridge protecting sheet ash color part, under 80 ℃ temperature, reacted 60 minutes then.After reaction finishes, reclaim solid product, and water washes, till acid does not have.The dry jel products that generate are 2 hours under 80 ℃.The black solid material that obtains is respectively about 100 times and about 50 times of himself weight to the wettability power of pure water and simulation urine.
Embodiment 4
Under the condition identical, be used as that resulting decomposed liquid (sulfuric acid concentration is 90wt%) reacts among raw-material transparent styrene-acrylonitrile (SAN) resin and the embodiment 2 with embodiment 3.The transparent solid material that obtains is respectively about 150 times and about 70 times of himself weight to the wettability power of pure water and simulation urine.
Comparative example 3 ' (comparative example of embodiment 3)
Use sulfuric acid and peroxide liquid mixture (a).That is to say, use the waste liquid that does not decompose through oxide compound.In addition, under the condition identical, carry out this reaction with embodiment 3.In this case, with remaining superoxide the resin refuse is decomposed fully, but waste resin material can not be transformed into hygroscopicity resin.
Comparative example 4 ' (comparative example of embodiment 4)
Use sulfuric acid and peroxide liquid mixture (b).That is to say, use the waste liquid that does not decompose through oxide compound.In addition, under the condition identical, carry out this reaction with embodiment 4.In this case, the same with comparative example 3 ', useless SAN resin material can not be transformed into hygroscopicity resin.
Embodiment 5
Be dissolved in 1, polystyrene (the Mw=ca.280 of 2-ethylene dichloride, 000) in, adds resulting decomposed liquid (vitriolic concentration is 82wt%) and diacetyl oxide (mol ratio 1: 1: 2) among the embodiment 1, under 60 ℃ temperature, carried out thermal response 5 hours.After reaction finishes, reaction product is poured in the hot water, wash and redeposition.The throw out that obtains is dried to the Sulfonated polystyrene (SPS) of 10mol%.Regulate the sulfonation ratio by changing the vitriolic additional proportion that is reclaimed.The sulfonated polystyrene (SPS) that obtains is dissolved in the tetrahydrofuran (THF).The aqueous sodium hydroxide solution of the sulfonic group equimolar amount in the solution that obtains in adding and the sulfonated polystyrene (SPS).Reclaim resulting solution, and be dried to sulfonated polystyrene sodium (SPS-Na).Compare with the raw-material second-order transition temperature of polystyrene (about 100 ℃), the second-order transition temperature (Tg) of the sulfonated polystyrene sodium (SPS-Na) of generation has improved about 40 ℃.That is to say that through this processing, polystyrene can present thermotolerance.
Embodiment 6
Except adopting CD-ROM drive shell refuse (polystyrene-poly phenylene ether blending of polymers; Contain carbon black) in addition, all the other use the mode identical with embodiment 5 to handle.Compare with initial vitrifying of wastes transition temperature, the second-order transition temperature (Tg) that generates resin has improved about 30 ℃.
Comparative example 6 ' (comparative example of embodiment 6)
Here use sulfuric acid/ozone mixed solution.In addition, under the condition identical, carry out this reaction with embodiment 6.In this case, in the sulfonation reaction process, expansible vinylbenzene refuse decomposes fully.
Embodiment 7
To inject embodiment 2 resulting decomposed liquid with the polystyrene bead of 5% divinylbenzene crosslink, under 80 ℃ temperature, carry out 15 hours sulfonation reaction.After reaction finishes,, obtain Zeo-karb with big water gaging flushing sulfonated products.
Embodiment 8
Resulting decomposed liquid, 8 gram polystyrene (Mw=10,000) and 8 gram naphthalenes among the embodiment 1 of 18 grams are mixed, under 150 ℃ temperature, reacted 5 hours then.Reactant is cooled to 90 ℃, and adds 10 gram water.Under the condition that drips 7 grams, 37% formalin, the reactant that obtains was reacted 5 hours under 100 ℃ temperature.After reaction, in reaction system, add the aqueous sodium hydroxide solution of 30 gram water and 10 grams 48%.The product that obtains was stirred 30 minutes down at 80 ℃, add 5 gram calcium hydroxides then and stirred 1 hour.The final product that obtains after filtering can be used as cement dewatering agent or coal water slurry dispersing agent.
Embodiment 9
70 gram hexanaphthenes are being housed and are maintaining in 50 ℃ of reactors under the temperature, in about 60 minutes time, drip among the 12 gram embodiment 1 resulting decomposed liq simultaneously and under heating condition in 68 gram hexanaphthenes dissolving expansible vinylbenzene waste materials resulting solution.Then with temperature maintenance at 50 ± 2 ℃, make the reaction carried out 1 hour.Carrying out along with reaction generated the pulpous state product in reaction solution.Under agitation, aqueous sodium hydroxide solution is added in the reaction system gradually, to neutralize.Under heating, distill the solvent hexanaphthene in the reaction system then.With sodium hydroxide the pH value of remaining aqueous solution finally is adjusted to 8, produces the polymer electrolyte aqueous solution of 10wt%.The water-soluble macromolecule electrolyte that so obtains can be used as polymeric flocculant, or the dewatering agent of sewage work's sewage or waste water.
Claims (9)
1, a kind of utilization comprises the vitriolic method that contains in the waste liquid mixture of sulfuric acid and superoxide, and this method comprises:
One or more be selected from nitric acid, nitrosonitric acid, nitrogen peroxide, nitrate compound and hydrochloric acid decomposition accelerating agent in the presence of decompose described superoxide decomposition step.
2, utilize the vitriolic method that contains in the waste liquid mixture according to claim 1, wherein in sulfuric acid and the peroxide liquid mixture vitriolic concentration more than or equal to 70wt%.
3, according to the method for utilizing sulfuric acid and peroxide liquid mixture of claim 1, wherein the superoxide in sulfuric acid and peroxide liquid mixture is one or more in hydrogen peroxide, ozone or the peroxosulphuric.
4, the vitriolic method that contains in the waste liquid mixture according to utilizing of claim 1, wherein said decomposition accelerating agent derives from described waste material.
5, according to the method for utilizing sulfuric acid and peroxide liquid mixture of claim 1, wherein sulfuric acid and peroxide liquid mixture are the waste liquids from semiconductor fabrication processes.
6, according to the method for utilizing sulfuric acid and peroxide liquid mixture of claim 5, wherein with one or more the decomposition accelerating agents in nitric acid, nitrosonitric acid, nitrogen peroxide, nitrate compound or the hydrochloric acid as superoxide in sulfuric acid and peroxide liquid mixture.
7, according to the method for utilizing sulfuric acid and peroxide liquid mixture of claim 1, wherein the sulfuric acid that will obtain from sulfuric acid and peroxide liquid mixture is as sulphonating agent.
8,, wherein will be used for the sulfonation reaction and/or the hydrolysis reaction of macromolecular compound from the sulfuric acid that sulfuric acid and peroxide liquid mixture obtain according to the method for utilizing sulfuric acid and peroxide liquid mixture of claim 1.
9, the method for utilizing sulfuric acid and peroxide liquid mixture according to Claim 8, wherein said macromolecular compound is the exhausted Plastic wastes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB981258948A CN1191996C (en) | 1997-12-01 | 1998-12-01 | Method for utilizing sulfuric acid/peroxide liquid mixture |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33015897A JP3551734B2 (en) | 1997-12-01 | 1997-12-01 | How to use sulfuric acid / peroxide mixture |
| JP330158/97 | 1997-12-01 | ||
| JP330158/1997 | 1997-12-01 | ||
| CNB981258948A CN1191996C (en) | 1997-12-01 | 1998-12-01 | Method for utilizing sulfuric acid/peroxide liquid mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1223971A CN1223971A (en) | 1999-07-28 |
| CN1191996C true CN1191996C (en) | 2005-03-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB981258948A Expired - Lifetime CN1191996C (en) | 1997-12-01 | 1998-12-01 | Method for utilizing sulfuric acid/peroxide liquid mixture |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI562957B (en) * | 2013-11-01 | 2016-12-21 | Yu Ming Chia | Methoh of the decomposition of hydrogen peroxide included in sulfuric acid |
| US9278860B2 (en) | 2014-07-22 | 2016-03-08 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method and apparatus for recycling waste sulfuric acid |
| TWI646055B (en) * | 2017-11-27 | 2019-01-01 | 陳世雄 | Method and apparatus for decomposition of hydrogen peroxide in waste acid solution by liquid catalyst coupled with photocatalytic reaction |
| JP7219088B2 (en) * | 2018-12-28 | 2023-02-07 | 関東化学株式会社 | Method for decomposing hydrogen peroxide and apparatus for use in said method |
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1998
- 1998-12-01 CN CNB981258948A patent/CN1191996C/en not_active Expired - Lifetime
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