CN102001707B - Method for recycling chromic acid in electroplating waste water - Google Patents
Method for recycling chromic acid in electroplating waste water Download PDFInfo
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- CN102001707B CN102001707B CN201010608303A CN201010608303A CN102001707B CN 102001707 B CN102001707 B CN 102001707B CN 201010608303 A CN201010608303 A CN 201010608303A CN 201010608303 A CN201010608303 A CN 201010608303A CN 102001707 B CN102001707 B CN 102001707B
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- chromic anhydride
- chromic acid
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- 239000002351 wastewater Substances 0.000 title claims abstract description 34
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- 150000001768 cations Chemical class 0.000 claims description 14
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- 239000000126 substance Substances 0.000 claims description 9
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Abstract
The invention discloses a method for recycling chromic acid in electroplating waste water. A complete set of method which can be used for directly and efficiently recycling chromic acid from electroplating cleaning solution and obtaining chromic acid crystals is designed by making use of technical means such as ion exchange, atomization, evaporation, extraction, crystallization, separation and the like and comprehensively utilizing experiences obtained in practice and a method obtained by researches and experiments. Problems existing in the conventional recycling treatment technical method are solved by the method and chromic acid in electroplating waste water is recycled directly by the complete set of method so as to obtain a chromic anhydride raw material. Chromic acid in electroplating chromium-containing waste water is recycled fully by a complete set of device and is taken as an industrial raw material, so that a waste material is recycled, the environment is protected, resources are saved and remarkable economic, social and environmental benefits are achieved. The method is an important innovation for clean production, environmental protection and resource utilization technology.
Description
Technical field
The invention belongs to the heavy metal recycling technical field in the waste water, be specifically related to the chromic anhydride recycling technology in a kind of electroplating wastewater.
Background technology
Heavy metal in the electroplating wastewater; Particularly the toxicity of chromic acid is maximum, is one of environmental carcinogen of generally acknowledging (Schmieman E A, Petersen J N; Yong e D R; Et al.Bacterial Reduction of chromium [J] .Appl BiochemBiotechnol, 1997, (63-65): 855.).It destroys the metabolism of organism, is a kind of protein condenses agent, and the protein in the blood is precipitated; Suction contains the dust of chromic acid, can cause respiratory inflammation; Drink and contain chromic acid waste water, will cause diseases such as anaemia, ephritis, neuritis; Chromic acid also has pungency to skin, can make its ulcer.Long-term absorption can cause diseases such as body sarcoma, squamous cell carcinoma, gland cancer.Simultaneously, chromic acid is again an important resource, is to use to be worth high industrial raw materials, and chromic acid is in field widespread uses such as machinery, electronics, chemical industry, light textile, plating, metallurgy, pigment.How to reclaim the electroplating wastewater chromic acid, turn waste into wealth, realize the regeneration of resource and effectively utilization, be the problem that expert and manufacturing enterprise are constantly explored always.
But up to now, also do not find a cover complete and effective method, can economic recovery electroplating wastewater in chromic acid, make it become industrial raw materials and utilized fully.Although for a long time; Some successful relatively treatment processs have appearred; Like biological process, membrane separation process, electroosmose process, exchange resin method, photocatalytic method etc.; Because all there is particular problem separately in these methods in practice, so the main stream approach of handling for waste electroplating liquor containing chromium at present still is the harmless treatment of chemical precipitation and mud.This present situation is at " the recovery technology of chromium in waste electroplating liquor containing chromium and the precipitating sludge thereof " (" Guangdong chemical industry "; 2009 the 7th phases), " recovery of chrome plating waste liquor and utilization " (" electroplating and finish "; In September, 2004) and the concrete argumentation of different angles all arranged in " treatment technology of waste electroplating liquor containing chromium and the utilization of resources " articles such as (" Jiangsu chemical industry ", April calendar year 2001).
To these problems; The contriver of present method; In April, 2010; 200920039808.5) etc. (patent No.: 200810235197.1) (patent No.: (application number: invention 201010156033.7), these inventions have realized the recycle and the zero release of electroplating wastewater, have also accomplished the high efficiente callback utilization of most of heavy metal in the electroplating wastewater to have accomplished " method of electroplating washing water online classification cycle of treatment utilization " on the basis of item patent with " electroplating metals ion recovery apparatus set in the scavenging solution " " reclaiming the method for cupric ion in the copper plating cleaning fluid "; But because the attribute of chromic acid is special, aforesaid method is to its not enough economical and effective.
Summary of the invention
The objective of the invention is: according to the particular attribute of chromic acid; Problem to existing recycling technological method existence; The method that experience that obtains in the integrated use engineering practice and research experiment draw; Create a cover complete efficiently, can directly from electroplate scavenging solution, reclaim chromic acid, obtain chromic acid crystalline method.
The present invention at first adopts ion exchange technique according to the chemical property of chromic acid in the waste water, and chromic acid is taken out from waste water, obtains chromic acid solution; Behind chromic acid solution preheating homogeneous, atomize, supercharging realizes that through trellis system vapor-liquid separation obtains the chromic acid liquid concentrator; Adopt physics method crystalline forming again, obtain the chromic acid crystal through solid-liquid separation at last, subsequent use as industrial raw materials.Realize that the concrete technical measures of foregoing invention purpose are following:
A kind of method that reclaims the chromic acid in the electroplating wastewater is characterized in that comprising the steps:
A) to after the even matter of electrodeposited chromium Cleaning Wastewater, remove by filter suspended substance earlier, again through the resin cation(R.C.) device; Other metallic impurity of filtering; Resin cation(R.C.) sees through liquid and gets into the resin anion(R.A) device, absorption chromate wherein, and the elutriant entering of resin anion(R.A) is taken off the sodium post and is taken off the sodium processing;
B) the sodium liquid that takes off that steps A is obtained is heated to 50～70 ℃, adopts nozzle with solution atomization then, and under pressure, makes atomized soln see through the grid vapor-liquid separation that circulates, and obtains liquid concentrator;
C) with liquid concentrator crystallization under the effect of crystallization auxiliary, separate out chromic anhydride;
D) from crystal solution, isolate the chromic anhydride crystal.
Each step of the present invention below is detailed:
(A) chromic acid is collected: after the even matter of electrodeposited chromium Cleaning Wastewater; Filter earlier, impurity such as filtering suspended substance are through the resin cation(R.C.) device; Other metallic impurity of filtering (being other outer metals of dechromisation); Get into resin anion(R.A) absorption again and obtain chromate, take off sodium through resin cation(R.C.) then and handle, obtain the chromic acid that content is 30-60g/L.
Wherein resin cation(R.C.) is selected the strong acid type gel resin for use, and said resin anion(R.A) is selected macropore weak base type resin for use, and the said sodium post that takes off adopts H
+The type resin cation(R.C.).Resin cation(R.C.) device, resin anion(R.A) device and take off the sodium post and all can adopt one or more; Between the device of each same type, and can adopt parallel with one another between the dissimilar devices or/and placed in-line mode of connection.After resin anion(R.A) absorption was saturated, employing contained 50-100g/L NaOH solution and carries out wash-out, obtains containing Na
2CrO
4Elutriant; Said concentration of taking off chromic acid in the sodium liquid is 30-60g/L.
Resin cation(R.C.) with take off the sulphuric acid soln regeneration that sodium post functional quality concentration is 5%-10%, the waste liquid that produces during regeneration can be delivered to the acidic and alkaline waste water treatment system and handle.
(B) solution concentration: through H
+After the type resin cation(R.C.) takes off sodium; At this moment every liter of content of the chromic acid in the solution restrains 60 grams 30; Rare chromic acid is sent into the solution collection box by recycle pump with the 80-120L/h volumetric flow rate; By heating tube it is heated to 50-70 degree (middle temperature), carry out solution atomization through recycle pump and nozzle system again.Mist of chromic acid has the advantages that proportion is big and be easy to condense, and the chromic acid droplet of different-grain diameter is when being suspended in the flowing air; Run foul of each other and be condensed into bigger particle, through blower fan the liquid supercharging of atomizing is maintained the 150-300 handkerchief simultaneously, make atomized liquid see through the trellis system that tortuous close clearance is the 5-10 millimeter; Thereby the chance that has improved collision is condensed more easily; Lighter steam is from the grid escaping slot, the enrichment on grid of denseer solution, and return heating; The vapor-liquid separation that circulates obtains the liquid concentrator that chromic acid concentration is 250～400g/L.
(C) extractive crystallization: use recycle pump that concentration 250～400g/L liquid concentrator is sent into crystallizer tank, make its crystallization under the effect of crystallization auxiliary form chromic anhydride.Wherein crystallization auxiliary is that mass concentration is the sulfuric acid of 40%-60%.
(D) brilliant liquid separates: adopt solid-liquid separating machine directly the chromic anhydride crystallization to be separated from crystallization solution, for example adopt the solid-liquid separating machine among CN2762865 or the CN200957322 can reach separating effect preferably.The present invention also provides a kind of mode of many moving plates solid-liquid separation, adopts many moving plates solid-liquid separating machine that the chromic anhydride crystal is separated from crystal solution; Many moving plates solid-liquid separating machine has the moving plate that has the transmission shaft that filters guide groove and be located at said transmission shaft periphery.After crystal solution gets into and filters guide groove; Brilliant liquid separation function is to cooperate completion jointly through having the transmission shaft and the moving plate that filter guide groove; When reducing motor promotes the transmission shaft rotation, be located at transmission shaft peripheral moving plate and moving plate and relatively move, owing between moving plate and moving plate minim gap is arranged; Water leaches from the lamination gap that relatively moves, and realizes concentrating fast.Along with the rotation of transmission shaft is constantly moved, the space of filtering in the guide groove is constantly dwindled through spissated chromic anhydride forward, interior pressure strengthens gradually, promotes down the crystal solution squeeze to be increased at the transmission shaft continuous operation, and the discharge that is squeezed of the moisture in the chromic anhydride is many more.The chromic anhydride solid content is constantly raise, be delivered to discharge port by transmission shaft at last.
Be designed with riser in solution reserve tank upper end, when the crystal solution liquid level is higher, be back to crystallizer tank from riser.Reducing motor uses buncher, and power range is: 0.8-1.5 kilowatt.The liquid that produces after brilliant liquid separates also can be delivered to the acidic and alkaline waste water treatment system and handle.
Evident characteristic of the present invention: the distinctive toxicity according to chromic acid is bigger; Have attributes such as strongly-acid and corrodibility; To the problem that existing recycling technological method exists, technique means such as creationary utilization IX, atomizing, evaporation, extraction, crystallization, separation, the comprehensive experience of acquisition in the practice and the method that research experiment draws used; One cover of design is complete efficiently, can be directly from electroplate scavenging solution, reclaim chromic acid, obtains chromic acid crystalline method.Relatively have following beneficial effect with prior art:
1, the present invention reclaims the chromic acid that technique means such as IX, atomizing, evaporation, extraction, crystallization, separation creatively apply to electroplating wastewater; Overcome the problem that existing recycling technological method exists; With the complete method of a cover; Directly reclaim the chromic acid in the electroplating wastewater, obtain the chromic anhydride starting material.This is that prior art can't be accomplished.
2, the grid of the present invention's original creation separates method of evaporating and many moving plates solid-liquid separating method, and is simple, is convenient to realize having better practicality, constituted a complete recovery technology scheme with each unit of the present invention.
3, the middle temperature liquid vapour stripping technique and the normal temperature physical crystal forming technique of the present invention's employing, processing efficiency is high, and energy consumption is low, because auxiliary agent recycles, has practiced thrift the material consumption in the recycling process simultaneously.
4, the present invention is through a whole set of device; Reclaim the chromic acid in the waste electroplating liquor containing chromium fully, make it become industrial raw materials, turn waste into wealth; Both protected environment; Having practiced thrift resource again, had tangible economy and social environment benefit, is the great innovation of cleaner production, environment protection and utilization of resources technology.
Description of drawings
Fig. 1 is a schematic flow sheet of the present invention.
Fig. 2 is that chromic acid is collected the frock synoptic diagram.
101-rinsing tank, 102-rinse water collection box, 103-topping-up pump, 104-accurate filter; 105-acid case, 106-topping-up pump, 107, the 108-cationic exchange coloum; 109,1010, the 1011-anion-exchange column, 1012-takes off the sodium post, the 1013-topping-up pump; 1014-alkali case, 1015-take off sodium liquid collection box, 1016-topping-up pump.
Fig. 3 is a solution concentration frock synoptic diagram.
The 201-heating tube, 202-solution bin, 203-grid, 204-vapor pipe, the outlet of 205-dope, 206-atomizing mouth, 207-blower fan, 208-recycle pump.
Fig. 4 is an extractive crystallization frock synoptic diagram.
301-crystallizer tank, 302-crystallization auxiliary, the 303-return line of filtrating, 304-topping-up pump, 305-filtrate collecting tank.
Fig. 5 is that brilliant liquid separates the frock synoptic diagram.
The 401-refluxing opening of filtrating, 402-riser, 403-solution conveyor tube, 404-solution reserve tank, 405-feed-pipe, 406-stator, 407-moving plate, 408-transmission shaft, 409-reducing motor, 4010-filtrate collection case, 4011-discharge port.
Embodiment
Below in conjunction with accompanying drawing and embodiment content of the present invention is further specified.The present invention is not limited to present embodiment, and model adopts and is equal to replacement or the formed technical scheme of equivalence replacement, all belongs to the present invention's scope required for protection.
Below be that example specifies to reclaim a kind of chromic acid of electroplating in the Cleaning Wastewater, its main-process stream is as shown in Figure 1.
A, chromic acid are collected: Fig. 2 is seen in technical process, the water quality staple characteristic before present embodiment is handled: nickel ion＜5mg/L; Suspended substance＜80mg/L; Sexavalent chrome 80-130mg/L; Its treatment process is to use the topping-up pump (103) of pressure range 0.2～1Mpa that poaching wastewater is sent into accurate filter (104), cation-adsorption post (107,108), negatively charged ion adsorption column (109,1010,1011) processing; The present embodiment accurate filter is selected the pp filter core less than 1um for use; Zeo-karb selects for use strong acid type gel resin, negative resin to select macropore weak base type resin for use; Present method is carried out single collection entering rinse water collection boxs (102) earlier and is sent into impurity such as accurate filter filtration suspended substance by topping-up pump (103), gets into metallic impurity in sun bed (107) absorbed Ni ion rinse water again.The work side by side of sun bed (107) and sun bed (108).Contain the chromium poaching wastewater and be introduced into sun bed (107), when sun bed (107) was saturated, sun bed (107) quit work and regenerates.At this moment poaching wastewater gets into sun bed (108), sun bed (108) work.When sun bed (108) was saturated, sun bed (108) quit work and regenerates.At this moment waste water gets into sun bed (107), goes round and begins again.When the liquid that sees through of sun bed gets into cloudy bed with absorption chromic acid and dichromic acid, cloudy bed (109,1010,1011) but can the parallel connection tandem working.When cloudy bed (109) the Zhiyang bed (1010) of connect when hastening towards saturation, escape out the moon bed in reuse water to prevent dichromate ion and chromate.Contain the chromium poaching wastewater when saturated and directly get into cloudy bed (1010) when cloudy bed (109) is complete, at this moment cloudy bed (109) regenerative elution liquid gets into and takes off the sodium post and take off sodium.Cloudy bed (1010) works on, and cloudy bed (1010) the Zhiyin bed (1011) of connect when hastening towards saturation is escaped out the moon bed in reuse water to prevent dichromate ion and chromate.Cloudy bed (1011) is connected serially to the good cloudy bed (109) of having regenerated when hastening towards saturation again, and non-stop run goes round and begins again.Be that the sulphuric acid soln of 5%-10% is squeezed into (107, the 108) drip washing of sun bed by topping-up pump (106) with the mass concentration in the acid tank (105) when sun bed is saturated, leacheate enters the acidic and alkaline waste water pond and handles.By topping-up pump (1013) alkali case (1014) 50-100g/L NaOH solution is squeezed into (109,1010, the 1011) drip washing of cloudy bed when cloudy bed is saturated.Carry out because lessivation was divided into for two steps, at first OH-is with the Cr that adsorbs on the resin
2O
7 -2Turn to CrO
4 -2, OH then
-Replace CrO on the resin
4 -2, the chromium in the regenerated liquid that drip washing obtains is Na
2CrO
4, must be transformed into H through IX
2Cr
2O
7Just can be recovered.Take off sodium post (1012) and adopt H
+The cationic exchange of type generates H
2Cr
2O
7Sodium liquid collection box (1015) is taken off in entering.B, solution concentration: Fig. 3 is seen in technical process; Solution by topping-up pump (1016) will take off in the sodium liquid collection box (1015) is squeezed into solution bin (202); By heating tube (201) it is heated to 60 degree, recycle pump (208) work at this moment atomizes to solution through nozzle; Blower fan (207) work simultaneously; Liquid supercharging to atomizing maintains the 150-300 handkerchief, makes liquid see through the grid that tortuous close clearance is the 5-10 millimeter (203), because steam is lighter; Escape from the grid slit to vapor pipe (204) and discharge, rise to the cohesion of grid crotch from the grid wall and drip that to get back to solution bin (202) from dope outlet (205) be 300～350 to restrain until solution concentration to every liter of content and dense solution is heavier.
Present embodiment adopts the asynchronous blower fan of low-noise outer rotor (207), and power is 1.1KW, recycle pump (208) applying pressure scope 0.2～1Mpa.Grid (203) material is PVC
C, extractive crystallization: Fig. 4 is seen in technical process; Its treatment process of present embodiment is through filtrating return line (303) liquid concentrator to be sent into crystallizer tank (301) by recycle pump (208); Because crystallization auxiliary (302) constituent concentration is the sulfuric acid of 40%-60%; Liquid concentrator gets into back solubleness to be reduced, and chromic anhydride is separated out, and at this moment uses topping-up pump (304) that crystal solution is sent into the moving plate solid-liquid separating machine.Filtrate collecting tank (305) uses when reclaiming filtrating after brilliant liquid separates as secondary crystal, and crystallizer tank (301) is used alternatingly as secondary filtrating accumulator tank and secondary crystal groove (305).
Crystallizer tank (301) filtrate collecting tank (305) material that present embodiment adopts is PVC, and topping-up pump (304) material is PVDF, and pressure is 0.2～1Mpa.
D, brilliant liquid separate: adopt solid-liquid separating machine to isolate crystal, also can adopt flow process shown in Figure 5 to separate, by topping-up pump (304) crystal solution is sent into solution reserve tank (404), send into the filtration guide groove through feed-pipe (405) and carry out brilliant liquid separation.Brilliant liquid separation function by moving plate stay (406), moving plate (407) with have the common cooperation completion of the transmission shaft (408) that filters guide groove; When reducing motor (409) promotes the transmission shaft rotation; Being located at the peripheral moving plate of transmission shaft relatively moves; Water leaches from the lamination gap that relatively moves, and realizes concentrating fast.The spissated chromic anhydride of process is along with the rotation of transmission shaft is constantly moved forward; The volume that filters guide groove constantly shrinks; The interior pressure gradually strengthens; Under the transmission shaft continuous operation promoted, the moisture in the chromic anhydride was squeezed and enters filtrate collection case (4010), flowed into filtrate collecting tank (305) through filtrating refluxing opening (401).Simultaneously, the chromic anhydride solid content constantly raises, and is delivered to discharge port (4011) by transmission shaft at last.
When the crystal solution liquid level is higher, be back to crystallizer tank (301) from riser (403).Solution reserve tank (404) material PVC, moving plate stay (406), moving plate (407) and transmission shaft (408) they are SUS316L, and filtrate collection case (4010) is PVC, and step-down gear power is: 1 kilowatt, it is adjustable that rotating speed changes speed at PM 30-120.
Filtrating behind the collection fractional crystallization is returned the acidic and alkaline waste water treatment system and is handled.
Monitor the chromium content in each sepn process, the recovery that records final chromium adopts many moving plates solid-liquid separating method the recovery of chromium to be increased to more than 99% more than 98%, near 100%, and obtains the higher chromic anhydride crystal of purity.
Claims (6)
1. a method that reclaims the chromic anhydride in the electroplating wastewater is characterized in that comprising the steps:
A) to after the even matter of electrodeposited chromium Cleaning Wastewater, remove by filter suspended substance earlier, again through the resin cation(R.C.) device; Other metallic impurity of filtering; Resin cation(R.C.) sees through liquid and gets into the resin anion(R.A) device, absorption chromate wherein, and the elutriant entering of resin anion(R.A) is taken off the sodium post and is taken off the sodium processing; Said resin cation(R.C.) device, resin anion(R.A) device or take off the sodium post and all adopt one or more; Said resin cation(R.C.) is selected the strong acid type gel resin for use, and said resin anion(R.A) is selected macropore weak base type resin for use, and the said sodium post that takes off adopts H+ type resin cation(R.C.);
B) the sodium liquid that takes off that steps A is obtained is heated to 50～70 ℃, adopts nozzle with solution atomization then, and under pressure, makes atomized soln see through the grid vapor-liquid separation that circulates, and obtains liquid concentrator;
C) with liquid concentrator crystallization under the effect of crystallization auxiliary, separate out chromic anhydride;
D) from crystal solution, isolate the chromic anhydride crystal.
2. the method for the chromic anhydride in the recovery electroplating wastewater according to claim 1, it is characterized in that the absorption of said resin anion(R.A) is saturated after, adopt the NaOH solution that contains 50-100g/L to carry out wash-out, obtain containing Na
2CrO
4Elutriant; Said concentration of taking off chromic acid in the sodium liquid is 30-60g/L.
3. the method for the chromic anhydride in the recovery electroplating wastewater according to claim 1 is characterized in that adopting among the step B blower fan to the atomized soln supercharging, makes it to see through grid.
4. according to the method for the chromic anhydride in claim 1 or the 3 described recovery electroplating wastewaters; It is characterized in that atomized soln is when seeing through grid; Lighter steam is from the grid escaping slot, the enrichment on grid of denseer solution, and return heating; The vapor-liquid separation that circulates obtains the liquid concentrator that chromic acid concentration is 250～400g/L.
5. the method for the chromic anhydride in the recovery electroplating wastewater according to claim 1 is characterized in that said crystallization auxiliary is that mass concentration is the sulfuric acid of 40%-60%.
6. the method for the chromic anhydride in the recovery electroplating wastewater according to claim 1 is characterized in that adopting many moving plates solid-liquid separating machine that the chromic anhydride crystal is separated from crystal solution; Many moving plates solid-liquid separating machine has the moving plate that has the transmission shaft that filters guide groove and be located at said transmission shaft periphery; After crystal solution gets into and filters guide groove; Brilliant liquid separation function is to cooperate completion jointly through having the transmission shaft and the moving plate that filter guide groove; When reducing motor promotes the transmission shaft rotation, be located at transmission shaft peripheral moving plate and moving plate and relatively move, owing between moving plate and moving plate minim gap is arranged; Water leaches from the lamination gap that relatively moves, and realizes concentrating fast; Along with the rotation of transmission shaft is constantly moved, the space of filtering in the guide groove is constantly dwindled through spissated chromic anhydride forward, interior pressure strengthens gradually, promotes down the crystal solution squeeze to be increased at the transmission shaft continuous operation, and the discharge that is squeezed of the moisture in the chromic anhydride is many more; The chromic anhydride solid content is constantly raise, be delivered to discharge port by transmission shaft at last.
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| CN116282163A (en) * | 2021-12-20 | 2023-06-23 | 重庆昌元化工集团有限公司 | Method for improving quality of chromic anhydride |
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| CN101891323B (en) * | 2010-04-27 | 2011-12-07 | 南京源泉环保科技股份有限公司 | Method for classifying, treating and recycling plating washing water on line |
| CN104355365B (en) * | 2014-10-31 | 2016-08-24 | 武汉钢铁(集团)公司 | The processing method of chromate waste water zero release of pollutant |
| CN104709968B (en) * | 2015-03-03 | 2017-09-15 | 重庆青天环保材料有限公司 | A kind of method and apparatus system of electroplating wastewater processing |
| CN105366767B (en) * | 2015-12-10 | 2018-01-12 | 重庆青天环保材料有限公司 | The processing system and processing method of a kind of cyanide-containing electroplating water |
| CN106587260A (en) * | 2016-11-21 | 2017-04-26 | 国佳环境科技湖北连锁有限公司 | Resource utilization process of electroplating wastewater containing chromium |
| CN110540364B (en) * | 2019-09-17 | 2021-10-26 | 济南大学 | Method for performing gelation treatment on sulfate-containing electroplating wastewater and preparing foam glass ceramics from obtained gel and product |
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| CN116282163A (en) * | 2021-12-20 | 2023-06-23 | 重庆昌元化工集团有限公司 | Method for improving quality of chromic anhydride |
| CN116282163B (en) * | 2021-12-20 | 2024-03-22 | 重庆昌元化工集团有限公司 | Method for improving quality of chromic anhydride |
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