CN102011130A - Regeneration method of aqueous rust remover - Google Patents
Regeneration method of aqueous rust remover Download PDFInfo
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- CN102011130A CN102011130A CN2010102743778A CN201010274377A CN102011130A CN 102011130 A CN102011130 A CN 102011130A CN 2010102743778 A CN2010102743778 A CN 2010102743778A CN 201010274377 A CN201010274377 A CN 201010274377A CN 102011130 A CN102011130 A CN 102011130A
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Abstract
The present invention provides a novel regeneration method of an aqueous rust remover which comprises aliphatic low thiol. The regeneration method of the aqueous rust remover which comprises aliphatic low thiol is characterized by comprising the following steps: (a) a step 1 of generating the deposit comprising copper through adding acid into the aqueous rust remover after copper rust elimination, (b) a step 2 for removing the deposit through solid liquid separation, and (c) a step 3 of adjusting the pH value of the liquid obtained through eliminating the deposit. The regeneration method is also characterized by comprising the following steps: (A) a step 1 of dividing the aqueous rust remover after steel rust elimination through adding an organic solvent comprising acid phosphate and mixing, and extracting steel component in the organic phase; and (B) a step 2 of eliminating the organic phase.
Description
Technical field
The present invention relates to renovation process the water-based rust remover that is used to eliminate rust (being also referred to as " waste liquid ").
Background technology
In the past, known have a water-based rust remover that contains as effective constituent with the aliphatics low-grade thioalcohol.Above-mentioned water-based rust remover can be used for removing in the patina (patent documentation 1) of object being treated surface formation or the purposes of iron tin (Sn) rust (patent documentation 2).Then, the waste liquid dilution liquid phase part after using is discarded, the mud of solid phase part is buried processing after burning simultaneously.
From the raising of in recent years environmental protection consciousness with save the requirement of resource, wish to make it to regenerate as the water-based rust remover from above-mentioned water-based rust remover separating metal.If such regeneration becomes possibility, be high efficiency then reusing aspect the water-based rust remover, simultaneously, to reclaim connection metal be significant can effectively utilizing.
Therewith relatively, as the technology that reclaims the metal ingredient that contains in the waste liquid, in patent documentation 3, disclose by adding alkali and the method for separating metal in the waste liquid after the metal rust is handled.When in the regeneration of the water-based rust remover that contains the aliphatics low-grade thioalcohol, using this method, except the separation difficulty of the unreacted and the effective constituent of react, when interpolation alkali owing to neutralization heat causes exothermic reaction, in operation with danger.Also produce and generate block (outstanding absurd creature matter agglutinative block), be difficult to generate the precipitation of copper, the problem of operating efficiency difference.Therefore, it is inadequate using the method for record in the patent documentation 3.
Patent documentation 1: Japanese kokai publication hei 1-263286 communique
Patent documentation 2: Japanese kokai publication hei 1-168883 communique
Patent documentation 3: Japanese kokai publication sho 64-11928 communique
Summary of the invention
The object of the present invention is to provide the novel renovation process of the water-based rust remover that contains the aliphatics low-grade thioalcohol.
The inventor furthers investigate to achieve these goals and repeatedly, found that, by add special component in the waste liquid of the water-based rust remover that contains the aliphatics low-grade thioalcohol, removes the metal ingredient in the waste liquid, the water-based of can regenerating rust remover.
That is, the present invention relates to the renovation process of following water-based rust remover.
1. renovation process that contains the water-based rust remover of aliphatics low-grade thioalcohol, be characterised in that, comprise: (a) add acid by the water-based rust remover after being used for removing patina, generation contains the sedimentary operation 1 of copper, (b) remove above-mentioned sedimentary operation 2 and (c) will be adjusted into 6～9 operation 3 by solid-liquid separation by the pH that removes the liquid that above-mentioned precipitation obtains.
2. in the above-mentioned operation 1, by add acid in above-mentioned water-based rust remover, making pH is above-mentioned item 1 described renovation process 5 below.
3. above-mentioned water-based rust remover contains tensio-active agent, in the above-mentioned operation 3, to be replaced into the water-based rust remover that is used to remove before the patina by 10～40 weight % that remove the liquid that above-mentioned precipitation obtains, afterwards pH will be adjusted into 6～9 above-mentioned 1 described renovation process.
4. renovation process that contains the water-based rust remover of aliphatics low-grade thioalcohol, be characterised in that, comprise: (A) add organic solvent and the stirring that contains acid phosphoric acid ester by the water-based rust remover after being used for removing iron rust, be divided into organic phase and water, and in above-mentioned organic phase, extract the operation 1 of ferrous components and (B) remove the operation 2 of above-mentioned organic phase.
5. acid phosphoric acid ester is above-mentioned 4 described renovation process of phosphate monoester.
6. phosphate monoester is above-mentioned 5 described renovation process of 2-ethylhexyl phosphonic acid-2-(ethyl hexyl) ester.
7. above-mentioned 6 described renovation process that also contain the 2-ethylhexyl phosphoric acid in the organic solvent.
8. above-mentioned 7 described renovation process that contain 2-ethylhexyl phosphonic acid-2-(ethyl hexyl) ester and 2-ethylhexyl phosphoric acid in the organic solvent with 5: 1～1: 1 mol ratio.
9. in the above-mentioned operation 1, the pH of above-mentioned water-based rust remover is adjusted into 4.5～8.0 after, above-mentioned 4 described renovation process that add above-mentioned organic solvent and stir.
10. repeat above-mentioned 4 described renovation process of above-mentioned operation 1 and above-mentioned operation 2 for many times.
Below, describe the renovation process of water-based rust remover of the present invention in detail.
Aliphatics low-grade thioalcohol as the water-based rust remover effective constituent of using among the present invention, for example, can enumerate Thiovanic acid derivatives such as ammonium mercaptoacetate, Thioglycolic acid sodium salt, Thiovanic acid monoethanolamine, Thiovanic acid diethanolamine, Thiovanic acid trolamine, sulfydryl malic acid derivatives such as sulfydryl oxysuccinic acid monoethanolamine, sulfydryl oxysuccinic acid diethanolamine, sulfydryl oxysuccinic acid trolamine, thiolactic acid etc.These aliphatics low-grade thioalcohols play a role as the effective constituent that is used to remove processed patina or iron rust.
The pH of above-mentioned water-based rust remover is generally 6.0～9.0, is preferably 7.5～8.5, most preferably is 8.0～8.5.
Can contain tensio-active agent in the above-mentioned water-based rust remover.As tensio-active agent, can enumerate nonionic class tensio-active agent, cationic tensio-active agent, anionic species tensio-active agent, amphoterics etc.Wherein, preferred nonionic class tensio-active agent.
As the example of nonionic class tensio-active agent, can enumerate polyoxyalkylenes lauryl ether, fluorine class, polyoxyethylene polyoxypropylene block copolymer, special ether, higher fatty acid alkylolamide of the polyoxyalkylenes alkyl oxide, polyoxyethylene lauryl ether etc. of Voranol EP 2001 etc. etc.
The content of the tensio-active agent that contains in the above-mentioned water-based rust remover is preferably 0.05～10 weight %, more preferably 0.05～5 weight %, most preferably 0.05～1 weight %.
In the above-mentioned water-based rust remover,, as required, can contain spices in order to relax the stink of aliphatics low-grade thioalcohol.In addition, also can contain tinting material.When containing tinting material, assurance becomes easily corresponding to the variable color degree of the water-based rust remover of usage degree, and become easy the period that identification is suitable for manipulation of regeneration.
Below, illustrate that (1) remove the renovation process that the waste liquid after the iron rust is removed in the renovation process of the waste liquid after the patina and (2).
Be used to remove the renovation process of patina waste liquid (contained waste liquid) afterwards
Utilizing the patina of above-mentioned water-based rust remover to remove processing can carry out according to known method.Particularly, by effect as the aliphatics low-grade thioalcohol of water-based rust remover main component, (thio group of aliphatics low-grade thioalcohol itself is oxidized for the metal oxide (copper oxide) of reduction conduct rust and metal hydroxides (copper oxyhydroxide), form disulfide linkage (disulfide bond)), finally form metal complex and be removed.
Example more specifically below is described.As above-mentioned aliphatics low-grade thioalcohol be ammonium mercaptoacetate, the composition that forms rust is cupric oxide (I) and (II) time, for example, according to following chemical reaction, patina is removed.
4HS-CH
2COONH
3+2Cu
2O+H
2O→4HS-CH
2COOCu+4NH
4OH+O
2
Carried out removing patina contained waste liquid afterwards, can directly supply with renovation process of the present invention, but preferably remove the insoluble compositions such as tinsel of sneaking into inevitably by solid-liquid separation in advance.The method of the insoluble composition of solid-liquid separation is not limited, can enumerate leave standstill and reclaim supernatant liquor method, supply with centrifugation and isolating method, the method handled by filtration etc.Use when filtering, can use appropriate filters and methods such as natural filtration, filtration under diminished pressure, pressure filtration, centrifuging, vacuum filtration.Preferred filtration under diminished pressure.
The renovation process of contained waste liquid of the present invention comprises (a) and adds acid by the above-mentioned water-based rust remover (contained waste liquid) after being used for removing patina, generation contains the sedimentary operation 1 of copper, (b) remove above-mentioned sedimentary operation 2 by solid-liquid separation and (c) will be adjusted into above-mentioned 1～3 operation of 6～9 operation 3 by the pH that removes the liquid that above-mentioned precipitation obtains.Below, each operation is described.
About operation 1
As the acid of adding in the operation 1, can enumerate sulfuric acid, hydrochloric acid, nitric acid, formic acid, oxalic acid, acetate etc.If consider the industrial cost aspect, then preferably sulfuric acid, hydrochloric acid, nitric acid etc., if consider copper precipitation formation efficiency and add secure context when handling, more preferably sulfuric acid then.
The addition of above-mentioned acid generates then no problemly as long as acid and copper component react the precipitation that makes abundant amount, but more preferably can make the sedimentary amount of whole copper components.The amount of acid can suitably be adjusted according to the kind and the concentration of acid.
If from the viewpoint of pH, have change according to the kind of acid, but preference is as being adjusted into the method below the pH5.The pH below 4 more preferably.By the adjustment of this pH, can make all copper component precipitations in fact, remove copper component from waste liquid.
The copper that generates in this operation precipitates, and can enumerate the compound of aliphatics low-grade thioalcohol and copper, for example, can enumerate Thiovanic acid copper etc.
About operation 2
The sedimentary method of solid-liquid separation is not particularly limited, can be set forth in the method that leaves standstill liquid after the processing of operation 1, utilize centrifugation to supply with to handle and carry out isolating method, by filtering method that operation handles etc.If for leaving standstill the method for liquid after handling, then, leave standstill more than 1 minute preferably by after adding acid precipitation being produced.More preferably more than 5 minutes, most preferably more than 30 minutes.Such leave standstill processing after, get supernatant liquor by branch, can precipitation separation.
Use when filtering operation, use appropriate filters, can select methods such as natural filtration, filtration under diminished pressure, pressure filtration, centrifuging, vacuum filtration.Preferred filtration under diminished pressure.The example of strainer can suitably be selected to use from trevira, nylon 6 fiber, polypropylene fibre, Saran, acrylic fibre etc.
The copper component that contains in the precipitation of removing by using known method of refining such as reduction refining method, wet type purifying method, can carry out refining as new metal source after reclaiming, and utilizes again.
About operation 3
The pH that adjusts in the operation 3 is the operation that is used to return the pH before the water-based rust remover uses, and is to make pH get back to the operation of an alkaline side.In this operation, preferably use ammoniacal liquor, sodium hydroxide, potassium hydroxide, lime carbonate etc. to adjust pH, more preferably use the ammoniacal liquor adjustment.Here, the pH of adjustment is preferably 6.0～9.0, and more preferably 8.0～8.5.
In the operation 3, before pH being adjusted into 6.0～9.0 operation, can comprise to be the operation that is used to remove the water-based rust remover (being new water-based rust remover) before the patina by removing a part of liquid displacement that above-mentioned precipitation obtains.Metathetical water-based rust remover is preferably 10～40 weight % when removing liquid that above-mentioned precipitation obtains as 100 weight %, more preferably 20～30 weight %.This operation is followed and is made water-based rust remover repeated regeneration, has the effect of accumulating in the water-based rust remover of salt (hydrochloride, nitrate, vitriol etc.) after regeneration that prevents from the acid of adding in the comfortable above-mentioned operation 1.Also have the effects of composition arbitrarily such as tensio-active agent that contain in the precipitation that is removed in the additional process 2.
The regenerated liquid of the contained waste liquid that obtains by operation 1～3 described method of the present invention, as long as contained copper component is fully removed, then use regenerated liquid remove patina the time no problem, at this moment, residual rate as the aliphatics low-grade thioalcohol of main component is preferably more than the 70 weight %, more preferably more than the 80 weight %, most preferably be more than the 90 weight %.
In the above-mentioned contained waste liquid, except copper compound, allow to contain more than one metal or this metal ion in zinc, lead, cobalt, nickel, chromium, titanium, iron, strontium, magnesium, tin, selenium, gold, platinum, beryllium, lithium, boron, phosphorus, zirconium, niobium, tantalum, molybdenum, vanadium, palladium, indium, cadmium, antimony and the barium of being selected from of the trace that do not become obstacle in removing patina when regenerated liquid utilized once more.As an example, when the copper component that contains in the contained waste liquid was 0.5 weight %, the total amount of above-mentioned other metal ingredient was preferably below the 0.2 weight %.
Be used to remove the renovation process of iron rust waste liquid (iron content waste liquid) afterwards
Utilizing the iron rust of above-mentioned water-based rust remover to remove processing can carry out according to known method.Particularly, by effect as the aliphatics low-grade thioalcohol of water-based rust remover main component, (sulfydryl of aliphatics low-grade thioalcohol itself is oxidized for the metal oxide (ferriferous oxide) of reduction conduct rust and metal hydroxides (iron hydroxide), form disulfide linkage (disulfide bond)), finally form metal complex and be removed.
Example more specifically below is described.As above-mentioned aliphatics low-grade thioalcohol be ammonium mercaptoacetate, the composition that forms rust is ferric oxide (II) and (III) time, for example, according to following chemical reaction, iron rust is removed.
4HS-CH
2COONH
3+2FeO+4H
2O→2Fe(HSCH
2COO)
2+4NH
4OH+O
2
Having carried out the tinsel of sneaking into inevitably in the liquid (iron content waste liquid) after the processing of liquid that iron rust removes processing etc. by aforesaid method does not need composition, removes by solid-liquid separation in advance, residual liquid phase can be supplied with renovation process of the present invention.Solid-liquid separation can similarly be implemented with the regeneration of contained waste liquid.
The renovation process that contains the iron rust waste liquid of the present invention comprises (A) and adds organic solvent and the stirring that contains acid phosphoric acid ester by the above-mentioned rust remover after being used for removing iron rust (iron content waste liquid), be divided into organic phase and water, and in above-mentioned organic phase, extract the operation 1 of ferrous components and (B) remove the operation 2 of above-mentioned organic phase.Below, each operation is described.
About operation 1
The acid phosphoric acid ester that uses in the operation 1 can be any one of monoesters or diester, but preferably uses monoesters.As the example of concrete acid phosphatase monoesters, can enumerate 2-ethylhexyl phosphonic acid-2-(ethyl hexyl) ester (PC-88A) etc., as the example of acid phosphatase diester, can enumerate di-(2-ethylhexyl)phosphoric acid ester (D2EHPA) etc.
The method that is divided into organic phase and water in this operation is to mix organic solvent and the iron content waste liquid that contains above-mentioned acid phosphoric acid ester, leaves standstill after the stirring, is separated into the operation of organic phase and water.For example, can enumerate 10～15 minutes churning time.By this operation,, therefore, extract to organic phase owing to can in containing the organic solvent of acid phosphoric acid ester, stably exist at the ferrous components that aqueous phase comprises.
The acid phosphoric acid ester that uses in the operation 1 is in order to make it to be separated into water and organic phase, with the organic solvent diluting of necessity.Here, organic solvent is not particularly limited, and can enumerate kerosene, toluene, dimethylbenzene, benzene etc.Preferred kerosene.In addition, the concentration of the acid phosphoric acid ester that contains in the organic solvent is preferably 1～50 weight %, and more preferably 10～30 weight % are more preferably 14～16 weight %.
In the operation 1, pH is adjusted into 4.5～8.0, the extraction efficiency of ferrous components is improved by in the iron content waste liquid, adding acid in advance.For efficient is further risen, preferably be adjusted into 5.5～7.5 pH in advance, most preferably be 6.0～7.5 scope.Here, in the adjustment of pH, can use the various acid of in the renovation process of above-mentioned contained waste liquid, enumerating.Identical acid when acid can be used and regenerate with contained waste liquid.
The extraction degree of ferrous components can be that index is confirmed with the water pH that balances each other after stablizing of water and organic phase.As an example, if the pH of water is 4.8～5.6 scope, can confirm that then roughly the ferrous components more than 60% is extracted by organic phase, if be 5.2～5.4 scope, can confirm that then roughly the ferrous components more than 70% is extracted by organic phase.
In the operation 1, if the acid phosphoric acid ester that contains in organic solution is 2-ethylhexyl phosphonic acid-2-(ethyl hexyl) ester (PC-88A), then by and with 2-ethylhexyl phosphoric acid (EAP), can shorten the extraction efficiency of consumed time and raising ferrous components in the extraction of ferrous components.At this moment, the mol ratio of PC-88A: EAP is preferably set to 5: 1～1: 1 scope.In renovation process of the present invention,, can more effectively remove de-iron by repeating above-mentioned operation 1 and operation 2.
The above-mentioned iron content waste liquid that is used for removing after the iron rust, except iron cpd, allow to contain more than one metal or this metal ion in the zinc, lead, cobalt, nickel, chromium, titanium, copper, strontium and the magnesium that are selected from trace that does not become obstacle in removing iron rust when regenerated liquid utilized once more.For example, if the ferrous components that comprises in the iron content waste liquid is 0.15% o'clock, then the total amount of above-mentioned other metal ingredient is preferably below the 0.06 weight %.
The effect of invention
By renovation process of the present invention, the waste liquid after the water-based rust remover that can regenerate cancels so far abandons processing uses is supplied with and is utilized.
Description of drawings
Fig. 1 is the figure that is illustrated in the result of the influence of pH in the precipitation of copper and the residual sulphur constituent concentration.
Fig. 2 is that 0.5mol/cm is used in expression
3Result's the figure of the waste liquid solvent extraction of iron ions of PC-88A after handle.
Fig. 3 is the figure that the result of PC-88A and the D2EHPA waste liquid solvent extraction of iron ions after handle is used in expression.
Fig. 4 is expression and with the result's of PC-88A and the EAP waste liquid solvent extraction of iron ions after the processing figure.
Embodiment
Below, expression embodiment specifically describes the present invention.But the present invention is not limited by embodiment.
The waste liquid that removes patina agent and removing rust agent that uses among the following embodiment is the waste liquid with rust remover of 20～25% ammonium mercaptoacetates as rust cleaning effective constituent, 0.05～0.1% tensio-active agent, spices, tinting material.
Embodiment 1 (removing patina regeneration afterwards)
The experimental result 1 of copper spent solution regeneration
In the present embodiment, in the waste liquid after removing patina, the waste liquid that use is dissolved in copper with 0.5 weight % concentration experimentizes.In this waste liquid, drip POV, make pH drop to acidic region and removed by 100%, the complex compound sediment of Thiovanic acid and copper is formed until copper.
From result shown in Figure 1 as can be known, the pH of waste liquid is copper 100% precipitation almost near 5 the time, and the pH of waste liquid is in 4.0～4.5. 100% copper precipitation, effective constituent and copper precipitate component that can separation of supernatant.In addition, the sulphur composition that contains in the Thiovanic acid as rust cleaning effective constituent is residual more than 80% when pH4.
The experimental result 2 of copper spent solution regeneration
Then, in order to confirm in the liquid ingredient of supernatant liquor, to contain the effective constituent of which kind of degree, implement redox titration.After filter paper or strainer filtering supernatant, add 25% ammoniacal liquor, pH is adjusted into 8.0～8.5 after, measure the residual quantity of Thiovanic acid by the redox titration of using iodine.Result as shown in table 1 as can be known, the new liquid phase ratio with removing before the patina contains the effective constituent more than 90% in regenerated liquid.The water-based rust remover that contains these effective constituents etc. as can be known can utilize fully again.
[table 1]
| ? | The amount of ammonium mercaptoacetate (g/ml) among the 1ml |
| New liquid | 0.30? |
| Regenerated liquid | 0.27? |
Embodiment 2 (removing iron rust regeneration afterwards)
To the iron content waste liquid, form the Fe be higher than with the compound stability of water-based removing rust agent
2+Complex compound is removed by it is extracted in organic phase.
The experimental result 1 of iron spent solution regeneration
At pH is that 7.7 water-based is removed in the patina agent and dissolved in the waste liquid of copper with 0.117% concentration, adds hydrochloric acid, pH is set in 6 near after, with the PC-88A of kerosene dilution with 1: 1 (10cm of volume ratio
3: 10cm
3) mix and stirring, processing is separated.After this, take out water, add PC-88A kerosene diluent, repeat mixing, stir process.Result as shown in Figure 2 increases Fe along with extracting operation
2+Extraction yield increase, extract for 1 time be operating as extract for 71.5%, 2 time be operating as 84.9%, the 4th extracts and is operating as 94.6% extraction yield.On the other hand, the sulphur concentration in the aqueous solution behind the regenerative operation extracts operation for 1 time and only reduces and extract that operation only reduces 2.3%, the 4th is extracted operation and only reduced 6.5% for 1.2%, 2 time.Therefore, most of as can be known effective constituent (ammonium mercaptoacetate) is residual in solution.
The experimental result 2 of iron spent solution regeneration
In order to confirm to contain the effective constituent of which kind of degree, implement redox titration at isolating aqueous phase.In table 2, conclude its result.As can be known from the results of Table 2, the new liquid phase ratio with removing before the iron rust contains the effective constituent more than 70% in regenerated liquid.The water-based rust remover that contains effective constituent of being reproduced like this etc. as can be known can utilize fully again.
[table 2]
| ? | The amount of ammonium mercaptoacetate (g/ml) among the 1ml |
| New liquid | 0.30? |
| Regenerated liquid | 0.21? |
The experimental result 3 of iron spent solution regeneration
To containing the waste liquid that pH is adjusted into 7.5 iron, use 2-ethylhexyl phosphonic acid-2-(ethyl hexyl) ester (PC-88A), carry out the extraction of iron.As a comparative example, use the di-(2-ethylhexyl)phosphoric acid ester (D2EHPA) of the phosphoric acid ester different, carry out the extraction of iron with PC-88A.Ecbatic in Fig. 3.
PC-88A can reclaim iron from waste liquid with the ratio that is higher than D2EHPA about 80% as can be known.
The experimental result 4 of iron spent solution regeneration
And, carry out the extraction of iron with 2-ethylhexyl phosphonic acid-2-(ethyl hexyl) ester (PC-88A) and 2-ethylhexyl phosphoric acid (EAP).In experiment, use PC-88A is only arranged, with the mixture of 5: 1 mixed in molar ratio PC-88A and EAP with the experiment of the mixture of 1: 1 mixed in molar ratio PC-88A and EAP.Ecbatic in Fig. 4.Fig. 4 represents to use multiple extraction agent to extract the measurement result of the starting time of Fe.Wherein, 0.5mol/dm is used in zero expression
3The result of PC88-A, △ represent and use 0.5mol/dm
3PC88-A and 0.1mol/dm
3The result of 2-ethylhexyl phosphoric acid, represent and use 0.5mol/dm
3PC88-A and 0.5mol/dm
3The result of 2-ethylhexyl phosphoric acid.
By using the solution that mixes PC-88A and EAP, the extraction efficiency ratio of iron further improves when using PC-88A separately as can be known.
Claims (10)
1. the renovation process of a water-based rust remover, this water-based rust remover contains the aliphatics low-grade thioalcohol, it is characterized in that, comprising:
(a) add acid by the water-based rust remover after being used for removing patina, generate the sedimentary operation 1 that contains copper,
(b) by solid-liquid separation remove described sedimentary operation 2 and
(c) will be adjusted into 6～9 operation 3 by the pH that removes the liquid that described precipitation obtains.
2. renovation process as claimed in claim 1 is characterized in that:
In the described operation 1, by add acid in described water-based rust remover, making pH is below 5.
3. renovation process as claimed in claim 1 is characterized in that:
Described water-based rust remover contains tensio-active agent, in the described operation 3, will be replaced into the water-based rust remover that is used to remove before the patina by 10～40 weight % that remove the liquid that described precipitation obtains, and afterwards pH is adjusted into 6～9.
4. the renovation process of a water-based rust remover, this water-based rust remover contains the aliphatics low-grade thioalcohol, it is characterized in that, comprising:
(A) add the organic solvent contain acid phosphoric acid ester by the water-based rust remover after being used for removing iron rust and stir, be divided into organic phase and water, and in described organic phase, extract ferrous components operation 1 and
(B) remove the operation 2 of described organic phase.
5. renovation process as claimed in claim 4 is characterized in that:
Acid phosphoric acid ester is a phosphate monoester.
6. renovation process as claimed in claim 5 is characterized in that:
Phosphate monoester is 2-ethylhexyl phosphonic acid-2-(ethyl hexyl) ester.
7. renovation process as claimed in claim 6 is characterized in that:
Also contain the 2-ethylhexyl phosphoric acid in the organic solvent.
8. renovation process as claimed in claim 7 is characterized in that:
Mol ratio with 5: 1～1: 1 in the organic solvent contains 2-ethylhexyl phosphonic acid-2-(ethyl hexyl) ester and 2-ethylhexyl phosphoric acid.
9. renovation process as claimed in claim 4 is characterized in that:
In the described operation 1, the pH of described water-based rust remover is adjusted into 4.5～8.0 after, add described organic solvent and stir.
10. renovation process as claimed in claim 4 is characterized in that:
Repeatedly repeat described operation 1 and described operation 2.
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| CN115261872A (en) * | 2021-04-29 | 2022-11-01 | 上海丽卡环保技术有限公司 | Rust remover for steel parts and preparation method thereof |
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| CN102618736B (en) | 2012-03-31 | 2013-09-04 | 中国科学院长春应用化学研究所 | Extraction separation method of rare-earth element |
| KR101801002B1 (en) * | 2017-06-01 | 2017-11-23 | 이원호 | Derusting Agent Composition and Derusting Method using it |
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| JP2007297662A (en) * | 2006-04-28 | 2007-11-15 | Nittetsu Mining Co Ltd | Method for producing high purity electrolytic copper from ammonia-based copper etching waste liquid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5493672A (en) * | 1977-12-31 | 1979-07-24 | Daihachi Chem Ind | Method of separating rare earth metals each other by solvent extraction |
| JPS59196793A (en) * | 1983-04-20 | 1984-11-08 | Nishimura Watanabe Chiyuushiyutsu Kenkyusho:Kk | Recovery of liquid etchant |
-
2009
- 2009-09-07 JP JP2009205522A patent/JP4540738B1/en not_active Expired - Fee Related
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2010
- 2010-09-07 CN CN201010274377.8A patent/CN102011130B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58131185A (en) * | 1982-01-29 | 1983-08-04 | Kawasaki Steel Corp | Method of extracting metallic ion from aqueous solution |
| JPS59196796A (en) * | 1983-04-19 | 1984-11-08 | Mitsubishi Heavy Ind Ltd | Treatment of liquid waste |
| JPS61250186A (en) * | 1985-04-25 | 1986-11-07 | Neos Co Ltd | Rust remover for copper or copper alloy |
| JPH01168883A (en) * | 1987-12-24 | 1989-07-04 | Sumitomo Chem Co Ltd | Dissolving and removing agent for iron oxide scale |
| JPH01263286A (en) * | 1988-04-14 | 1989-10-19 | Neos Co Ltd | Rust remover for copper |
| JP2001234372A (en) * | 2000-02-25 | 2001-08-31 | Shinko Tokushu Kokan Kk | Scale removing method for stainless steel surface |
| CN1840739A (en) * | 2005-03-04 | 2006-10-04 | 法布罗技术有限公司 | Regeneration of cupric etchants and recovery of copper sulfate |
| JP2007297662A (en) * | 2006-04-28 | 2007-11-15 | Nittetsu Mining Co Ltd | Method for producing high purity electrolytic copper from ammonia-based copper etching waste liquid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108914143A (en) * | 2018-06-21 | 2018-11-30 | 广东优贝精细化工有限公司 | Neutral wheel hub cleaning material and preparation method thereof with colour developing and derusting corrosion protection |
| CN115261872A (en) * | 2021-04-29 | 2022-11-01 | 上海丽卡环保技术有限公司 | Rust remover for steel parts and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4540738B1 (en) | 2010-09-08 |
| JP2011058017A (en) | 2011-03-24 |
| CN102011130B (en) | 2014-11-05 |
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