CN1047368C - Electroplating waste water compound purifying agent and preparing process - Google Patents
Electroplating waste water compound purifying agent and preparing process Download PDFInfo
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- CN1047368C CN1047368C CN 94119658 CN94119658A CN1047368C CN 1047368 C CN1047368 C CN 1047368C CN 94119658 CN94119658 CN 94119658 CN 94119658 A CN94119658 A CN 94119658A CN 1047368 C CN1047368 C CN 1047368C
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- purifying agent
- waste water
- compound purifying
- electroplating waste
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- Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract
The present invention relates to a compound purifying agent used for treating electroplating waste water with chromium, a preparing process and a use process thereof. The compound purifying agent is composed of 40% to 60% (weight percentage as following) of ferroferric oxide, 5% to 20% of active aluminum oxide and 20% to 50% of iron scurf; the materials are weighed according to proportions; wet mixing is carried out on the ferroferric oxide and the active aluminum oxide; the ferroferric oxide and the active aluminum oxide are dewatered at the temperature of 300 DEG C to 800 DEG C and are calcined for 5 to 15 hours at the temperature of 850 DEG C to 1100 DEG C; after pulverized, the ferroferric oxide and the active aluminum oxide are uniformly mixed with the iron scurf. The use process comprises: after treated by the compound purifying agent, electroplating waste water with chromium is purified. The compound purifying agent has the advantages of high efficiency of removing heavy metal ions, multiple functions, low price and no secondary pollution.
Description
The present invention relates to handle and contain scavenging agent and the method for making that heavy metal compound waste water is used, handle composite purifying agent and method for making thereof that electroplating wastewater of chromium is used more precisely.
The waste water that electroplating industry gave off contains contents of many kinds of heavy metal ion such as chromium, copper, nickel, zinc.
If not adding, this waste water handles directly discharging, meeting havoc ecotope; Especially sexavalent chrome toxicity is very big, and it enters, and skin, kidney, blood and the nervus centralis to the people can both cause very big infringement behind the human body, thus very strict to the emission standard that contains chromic waste water, its chromium content must 0.5 milligram/below the liter.
The treatment process of chromate waste water has ion exchange method, iron filings internal electrolysis, the ferrite method of purification, the chemical reduction precipitator method etc.
Ion exchange method is that spent ion exchange resin is as scavenging agent.This method is easy to make electroplating wastewater to reach emission standard, also can obtain water quality preferably, but this processing method more complicated, the ion exchange resin life cycle is short, need carry out manipulation of regeneration through common acid, alkali, and cause secondary pollution, and running expense is also high.
The iron filings internal electrolysis is to adopt industrial waste iron filing as scavenging agent the compound of the metal ion generation indissoluble in the waste water to be separated out, and reaches the purpose of purification after filtration.This method technology is simple, and scavenging material is cheap, but this method with useless industrial iron filings as scavenging agent, iron filings are very easy to harden in the process of purifying liquid waste, and form channel and wall effect, have reduced treatment effect widely.Therefore need clear up and change iron filings continually and equipment is overhauled.As untimely replacing iron filings even cause the iron filings that harden and its container to become one to make equipment scrapping.
Though its treatment effect of the ferrite method of purification is better, when being to use this material processing, need be with steam heating to 90 ℃, energy consumption is higher.In operational process, add alkali, quickened the corrosion of equipment, the working cost height.Ferrite and iron filings are easy to harden equally.
The chemical reduction precipitator method are to add a certain amount of reductive agent in waste water, make high volence metal ion for example hexavalent chromium be reduced into the trivalent chromium metal ion, add the purpose that oxyhydroxide that alkali generates indissoluble reaches precipitate and separate then, make waste water reach purification standard.The main drawback of this method is to consume a large amount of alkali, has increased the expense of purifying liquid waste.Used in addition equipment is many, complicated operation.If mismanagement can cause the run, drip, leak of waste water, alkali lye, acid solution again, environment is polluted.
Chinese patent literature CN1032328A CN1046513 CN1087879A has reported the purifying method of electroplating wastewater, and used scavenging agent all is scavenging agents that solid adds liquid, needs more acid or alkali, has the weak point of above-mentioned certain methods equally.For example the used scavenging agent of Chinese patent literature CN1087879A be mixed with exactly weight percentage for containing the 2-90% iron powder or/and iron filings, 1-97% concentrated hydrochloric acid (containing hydrogenchloride 36%), 1-80% water, 0-3% wood charcoal powder, 0-10% boiler ash sediment and 0-1% zinc powder.
Purpose of the present invention just is to develop and overcomes in the prior art a kind of novel electroplating waste water compound purifying agent that removes heavy metal ion scavenging agent shortcomings such as dechromising, make this composite purifying agent have the high efficiency heavy metal ion ability such as dechromise of removing, long service life has multiple function again.
Another object of the present invention is the processing method that works out the above-mentioned composite purifying agent of preparation.
A kind of electroplating waste water compound purifying agent of the present invention is by the Z 250 of 40-60% weight percentage, the activated alumina of 5-20% weight percentage, and the iron filings of 20-50% weight percentage are formed.
Heavy metal ion in composite purifying agent of the present invention and the acid waste water is carried out inhomogeneous reaction, makes heavy metal ion generate the oxyhydroxide and the ferriferous oxide of solid phase indissoluble.Owing to contain iron filings in composite purifying agent, electrolytic effect in having has the adsorbing activated alumina of catalysis owing to contain, and produces effects such as catalysis absorption under the effect of activated alumina.Owing to contain Z 250 in the composite purifying agent, and Z 250 is made up of ferric oxide and ferric oxide, can produce redoxomorphism.Though in composite purifying agent of the present invention, contain iron filings, can prevent to resemble the phenomenon that hardens of simple ferrite and simple iron filings.Therefore constituted a kind of composite purifying agent of novel multifunctional.With the hexavalent chromium is example.Hexavalent chromium generates trivalent chromic ion under the effect of ferrous ion, trivalent chromic ion can generate chromium hydroxide precipitation with hydroxide radical again, ferric iron also can generate ferric hydroxide precipitate, ironic hydroxide can resolve into ferriferous oxide (FeOOH) again, and ferriferous oxide can generate FeOOHFe (OH) with ferrous hydroxide again
2, FeOOHFe (OH)
2Generate Fe with FeOOH
2O
3And water.
The preparation method of a kind of electroplating waste water compound purifying agent of the present invention, press the Z 250 of electroplating waste water compound purifying agent 40-60% weight percentage, the activated alumina of 5-20% weight percentage, the composition proportioning of the iron filings of 20-50% weight percentage is carried out weighing; Z 250 is ground to form≤adding water with the powdered activated alumina behind 0.5 millimeter the coccoid carries out wet mixing; The wet mixing thing of Z 250 and activated alumina is carried out processed under 300-800 ℃ of temperature make this mixture to doing; The mixture that Z 250 and activated alumina are done in 850-1100 ℃ carry out calcination processing 5-15 hour after, be broken into the block powder of 0.5-10 millimeter, to remove the bar of the husky iron filings pulverizing growth 2-20 millimeter of handling and mix through oil removing, make composite purifying agent of the present invention with the blocky-shaped particle material of the above-mentioned 0.5-10 of being broken into millimeter.
Four used oxygen three-irons grind to form≤0.5 millimeter meal, and again to grind to form 0.2-0.5 millimeter powdery object for well.The iron scale that said Z 250 gets off with steel rolling is that scale oxide is advisable.Its low price is again utilization of waste material.The granularity of used active oxidation aluminum feedstock is the 0.2-1 millimeter.The wet mixing thing of Z 250 and activated alumina carries out processed in 300-800 ℃, again to carry out processed in 300-500, carries out being advisable in calcination processing 5-15 hour in 850-950 ℃ again.
The usage of scavenging agent of the present invention is to contain the Z 250 of 40-60% weight percentage, the activated alumina of 5-20% weight percentage, the composite purifying agent that the iron filings of 20-50% weight percentage are formed joins and purifies (for example in the vertical reaction tower) in the reaction vessel, the height of this composite purifying agent pack into for purifying the high 3/4-4/5 of reaction vessel, with PH is the electroplating wastewater to be clean of 3-6.5, the suitable flow of all knowing with those skilled in the art adds from the vertical input tube of reaction vessel, behind the composite purifying agent layer, flow out from the bottom output tube that purifies reaction vessel, be discharged in the clean water basin, the PH that purifies waste water that is discharged is 7-8.
The PH of the electroplating wastewater to be clean in the purification reaction vessel that is entered is 3-6.5, is that 4-6 is good with its PH again.
Electroplating waste water compound purifying agent of the present invention has the high-level efficiency of removing heavy metal ion such as chromium in the electroplating wastewater, (water of electroplating wastewater after composite purifying agent is handled that contains 100 milligrams/liter of sexavalent chrome contains sexavalent chrome less than 0.05-0.5 milligram/liter) long service life, multiple function with physical-chemical reactions such as catalytic oxidation-reduction adsorption-flocculations, in use do not need to add the precipitate reduction agent, more do not need to add acid and add alkali, in same device, just can reach the purpose that a step purifies.Eliminate the shortcoming that iron filings, ferrite harden and often change, also eliminated the pollution that ion exchange method is brought with acid, alkali regeneration.Electroplating waste water compound purifying agent of the present invention cheap also can be used for the purification of other heavy metal ions in wastewater.
The preparation method of electroplating waste water compound purifying agent of the present invention is simple, and raw material is easy to get and is inexpensive.The method that purifies electroplating wastewater is simple, and required equipment is also simple, does not produce secondary pollution.
With following embodiment electroplating waste water compound purifying agent of the present invention and method for making thereof are further described; to help understanding to the present invention and advantage thereof; and not as the qualification to protection scope of the present invention, protection scope of the present invention is decided by claim.
Embodiment 1
The electroplating waste water compound purifying agent of present embodiment is by the scale oxide (being Z 250) of 55% weight percentage, the activated alumina of 15% weight percentage, and the iron filings of 30% weight percentage are formed.
Z 250 is ground to form the coccoid of 0.2-0.5 millimeter, add water with the active oxidation aluminium powder of 0.2-1 mm particle size and carry out wet mixing, its wet mixing thing carries out processed to doing under 400 ± 10 ℃ temperature, the mixture that to do through the Z 250 of processed and activated alumina was in 900 ± 10 ℃ temperature lower calcination 10 hours, obtain the blocky sintered compact of sintering, then blocky sintered compact is broken into the blocky-shaped particle of 0.5-10 millimeter.Go husky iron filings to be crushed to the bar of 2-10 millimeter and the above-mentioned blocky-shaped particle that is broken into the 0.5-10 millimeter de-oiling, mix.
The composite purifying agent of above-mentioned electroplating wastewater is packed in the vertical reaction tower, the height of this composite purifying agent of packing into is 3/4 of a vertical reaction tower, 2.8 meters of tower heights (tower height is 2.2 meters-3.8 meters usually), the electroplating wastewater of chromium of pending PH5.2 ± 0.2 is entered from cat head, go out to purify from tower bottom flow, the flow that the chromate waste water of pending PH5.2 ± 0.2 enters cat head is 50 liters/minute (is generally 17 liters/minute-250 liters/minute), and its PH to be clean contains Cr in 5.2 ± 0.2 electroplating wastewater of chromium
+ aBe 100 milligrams/liter, Cu
2+Be 100 milligrams/liter, Ni
2+30 milligrams/liter, Zn
2+30 milligrams/liter, through Cr in the water after the composite purifying agent processing
+ aContent be 0.06 milligram/liter, Cu
2+Be 0.2 milligram/liter (generally less than 0.10-1.0 milligram/liter between), Ni
2+0.6 milligram/liter (generally less than 0.5-1.0 milligram/liter between), Zn
2+1.1 milligram/liter (being generally less than between 1.0-5 milligram/liter), chromic content also meets the emission standard of country in the outflow water after the purification.The PH of the outflow water after the purification is 7.2 ± 0.2.
Removal rate of heavy metal after the processing is between 96-99.9.Effusive water quality of purifying waste water reaches national specified discharge standard fully.It is that the experiment operation result that 24 tons attachments of a bicycle factory carried out 2 years shows that the index of the water quality after the purification all reaches national specified discharge standard that this composite purifying agent is used for day output, and the water quality after handling has reached the water quality standard of reuse.Experiment shows uses composite purifying agent of the present invention to handle electroplating wastewater, and the composite purifying agent consumption is few, consumes for a short time, and the life-span is long, does not produce and hardens.After reactant was adsorbed on the composite purifying agent, the water pressurization after the available processes was washed, and removes settling, makes scavenging agent obtain regeneration, continue to use, so the life-span is long again.Adopt composite purifying agent of the present invention, need not any other chemical reagent, do not produce again and harden, reduced the expense of operation significantly.
Claims (6)
1. an electroplating waste water compound purifying agent is characterized in that, by the Z 250 of 40-60% weight percentage, and the activated alumina of 5-20% weight percentage, the iron filings of 20-50% weight percentage are formed.
2. the preparation method of an electroplating waste water compound purifying agent is characterized in that,
(1) press the Z 250 of electroplating waste water compound purifying agent 40-60% weight percentage, the activated alumina of 5-20% weight percentage, the composition proportioning of the iron filings of 20-50% weight percentage is carried out weighing;
(2) Z 250 is ground to form≤adding water with the powdered activated alumina behind 0.5 millimeter the coccoid carries out wet mixing;
(3) the wet mixing thing of Z 250 and activated alumina being carried out processed under 300-800 ℃ temperature makes this mixture to doing;
(4) mixture that Z 250 and activated alumina are done in 850-1100 ℃ carry out calcination processing 5-15 hour after, be broken into the blocky-shaped particle material of 0.5-10 millimeter;
(5) will remove the bar of the husky iron filings pulverizing growth 2-20 millimeter of handling and mix through oil removing with the blocky-shaped particle material of the above-mentioned 0.5-10 of being broken into millimeter.
3. the preparation method of an electroplating waste water compound purifying agent according to claim 2 is characterized in that, Z 250 grinds to form 0.2-0.5 millimeter coccoid, and said Z 250 is a scale oxide.
4. the preparation method of an electroplating waste water compound purifying agent according to claim 2 is characterized in that, the granularity of activated alumina is the 0.2-1 millimeter.
5. the preparation method of an electroplating waste water compound purifying agent according to claim 2 is characterized in that, carries out processed in 300-500 ℃.
6. the preparation method of an electroplating waste water compound purifying agent according to claim 2 is characterized in that, carries out calcination processing 5-15 hour in 850-950 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94119658 CN1047368C (en) | 1994-12-16 | 1994-12-16 | Electroplating waste water compound purifying agent and preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94119658 CN1047368C (en) | 1994-12-16 | 1994-12-16 | Electroplating waste water compound purifying agent and preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1124719A CN1124719A (en) | 1996-06-19 |
| CN1047368C true CN1047368C (en) | 1999-12-15 |
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ID=5039316
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94119658 Expired - Fee Related CN1047368C (en) | 1994-12-16 | 1994-12-16 | Electroplating waste water compound purifying agent and preparing process |
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| Country | Link |
|---|---|
| CN (1) | CN1047368C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2006332710B2 (en) * | 2005-12-29 | 2012-07-12 | Micronose Technologies, Inc. | Methods and compositions for removal of arsenic and heavy metals from water |
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1994
- 1994-12-16 CN CN 94119658 patent/CN1047368C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1124719A (en) | 1996-06-19 |
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