CN102491487A - Depth processing method of cyanogen-containing waste water - Google Patents
Depth processing method of cyanogen-containing waste water Download PDFInfo
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- CN102491487A CN102491487A CN2011103876644A CN201110387664A CN102491487A CN 102491487 A CN102491487 A CN 102491487A CN 2011103876644 A CN2011103876644 A CN 2011103876644A CN 201110387664 A CN201110387664 A CN 201110387664A CN 102491487 A CN102491487 A CN 102491487A
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- exchange resin
- anionite
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- cyanide
- hypochlorite
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Abstract
The invention discloses a depth processing method of cyanogen-containing waste water. The method comprises the following step of treating the cyanogen-containing waste water with chlorine oxidizing agent generating hypochlorite and anion exchange resin. The method is specifically one of the following modes: 1. mixing well the cyanogen-containing waste water and the chlorine oxidizing agent generating hypochlorite and treating the mixture with the anion exchange resin; 2. treating the cyanogen-containing waste water with anion exchange resin loaded with hypochlorite. The method needs no equalizing tank, oxidation reaction tank or filtering treatment, greatly saves sewage treatment place and effectively treats total cyanide in the cyanogen-containing waste water to realize stable and standard reached discharge and satisfy industrial water quality in municipal sewage regeneration and utilization.
Description
Technical field
The invention belongs to the environment-friendly engineering technical field, be specifically related to the deep treatment method of cyanide wastewater.
Background technology
Cyanide wastewater is meant the waste water that contains various prussiates.In industrial production; Industries such as the wet method of gold and silver is extracted, the production of man-made fiber, coking, synthetic ammonia, plating, gas prodn all can relate to uses prussiate or by-product prussiate; Thereby can discharge the cyanide wastewater of some amount in production process; But, very big difference is arranged all between the composition of each cyanide wastewater and the content because industry is different to be specifically related to technology different.
Prussiate can be divided into two kinds of simple prussiate and complex cyanides in the water.Simple prussiate comprises the salt (alkali metal cyanide) of basic metal (sodium, potassium, ammonium) and the salt (metal cyanides) of other metal.In the aqueous solution of alkali metal cyanide, cyanic acid is generally with CN
-Exist with the form of HCN molecule, the two ratio depends on the pH size.And in other metal-cyanide solution, the form of the complex anion of various metal-prussiates that cyanic acid then possibly not wait with stability exists.No matter alkali metal cyanide or other metal cyanides all belong to highly toxic substance; Toxicity to organism is mainly reflected in and can combines with ferricytochrome oxidase; Generate cyanocytochromeoxidase and make it to lose the effect of transmitting oxygen, and then cause that histanoxia suffocates.Therefore, the discharging meeting polluted drinking water source and the farmland of cyanide wastewater threaten the life securities of people, animal, fish, and the havoc eubiosis must be handled in strictness, make that prussiate reaches the requirement that national environmental protection department stipulates in the outer draining.
The existing processing of China for trade effluent; Generally handle through biochemical A/O technology; Waste water is after biochemical treatment, and conventional pollutent such as COD, ammonia nitrogen all can be realized qualified discharge with comparalive ease in the water outlet, but if contain prussiate; Because the prussiate component is complicated, the prussiate in the water outlet is difficult to can't stably reaching standard.Other treatment processs, as, advanced oxidation processes etc. (Fenton, common oxychlorination method, ozone oxidation etc.) all need stop more of a specified duration and reaction times; And, also lack the space of transformation and newly-increased reaction tank for some sewage work that has moved.Less to the advanced treatment process of prussiate in the waste water at present; Chinese invention patent CN101514063A discloses the method that a kind of in-depth coking wastewater and biochemical tail water is handled; This method after equalizing tank uses alkaline matter adjusting pH to be 9～12, adds coking chemical waste water biochemical tail water elder generation high-efficient oxidant and carries out oxide treatment, and mixed solution is through precipitate and separate 0.5～1.5h; Filtrating is carried out the resin absorption processing afterwards, and the COD of waste water can be reduced to below the 100mg/L by 200mg/L.But, the removal of prussiate in this technology and the not mentioned waste water, and equalizing tank need be set in the treatment step carry out pH regulator and oxidizing reaction, reaction back supernatant liquid still needs filtration treatment.In the case, demand developing Treatment of Cyanide-containing Wastewater technology with strong points urgently.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the prior art after biochemical treatment, to be difficult to stably reaching standard for cyanide wastewater; Reaction tank need be set separately; Treatment time is long; Defectives such as site requirements height provide a kind of advanced waste treatment method that can effectively remove the prussiate in the cyanide wastewater and realize the stably reaching standard discharging.
The deep treatment method of cyanide wastewater of the present invention comprises the steps: that the chlorine with cyanide wastewater multiparity hypochlorite is that oxygenant and anion-exchange resin treatment get final product, and is specially any of following manner:
Mode one: with the chlorine of cyanide wastewater and parity chlorate anions is the oxygenant uniform mixing, gets final product through anion-exchange resin treatment afterwards; Mode two: the anion-exchange resin treatment of cyanide wastewater through the overload hypochlorite got final product.
Among the present invention, described cyanide wastewater is the conventional said cyanide wastewater in this area, and referring generally to be designated as total cyanide content is 0.5mg/L～100mg/L; The COD value is 50mg/L～1000mg/L, and BOD is 30mg/L～1000mg/L, colourity 50～200; Also can be the coking chemical waste water biochemical tail water; Preferable index is total cyanide content 0.5mg/L～5mg/L, and the COD value is 50mg/L～500mg/L, and BOD is 30mg/L～300mg/L; Colourity 80～150; Preferred here process object embodies the present invention especially and can the waste water after handling be risen to the reuse water category from the qualified discharge waste water category that still contains total cyanide for the treatment effect of total cyanide, has realized the leap of cyanide containing wastewater treatment process on matter.
Among the present invention, the chlorine of described parity chlorate anions is that oxygenant is that this area routine is used, is generally in the aqueous solution and can discharges ClO
-, or the medicament of HClO, one or more that preferable is in Youxiaolin, Losantin, liquid chlorine and the dioxide peroxide.Wherein, liquid chlorine and dioxide peroxide effectively group itself is not hypochlorite, but can produce hypochlorite after its hydrolysis.
Among the present invention; Described anionite-exchange resin is the conventional use in this area; Phenylethylene resin series or acrylic resin all can; Preferable is strongly basic anion exchange resin; Better is D293 macroporous strong basic quaternary ammonium I type anionite-exchange resin, D202 macroporous strong basic quaternary ammonium II type anionite-exchange resin, D201 macroporous strong basic quaternary ammonium I type anionite-exchange resin, D261 macropore highly basic Zeo-karb, the equal hole of JK206 strong basic type anion-exchange resin, the equal hole of JK204 highly basic gel-type anionite-exchange resin, HZ202 highly basic gel-type anionite-exchange resin, 201 * 2 strong-basicity styrene series anion exchange resins, 201 * semi-finals basicity styrene series anion exchange resin, 201 * 7 strong-basicity styrene series anion exchange resins, or 201 * Final 8 basicity styrene series anion exchange resin, commercially available getting.
When deep treatment method employing mode a period of time of cyanide wastewater, actual conditions is preferably following:
Wherein, when the chlorine of described cyanide wastewater and parity chlorate anions was the oxygenant uniform mixing, the chlorine of described parity chlorate anions was that the consumption of oxygenant is that oxygenant produces ClO with chlorine
-Amount is counted CN in the cyanide wastewater
-1～5 mole of amount doubly, better is 2.5 moles of doubly amounts.
Wherein, When the chlorine of described cyanide wastewater and parity chlorate anions is the oxygenant uniform mixing; Anionite-exchange resin to the treatment of cyanide waste water amount generally with waste water in total cyanide relevant, those skilled in the art know all according to concentration of cyanide in the waste water and suitably adjust that the present invention is in the ordinary course of things; Anionite-exchange resin to treatment of cyanide waste water amount volume ratio preferable be 1: 300～1: 1000, better is 1: 500.Behind the described anion-exchange resin treatment waste water, can more not renew resin, can reuse after the regeneration.
When the deep treatment method of cyanide wastewater adopted mode two, actual conditions was preferably following:
Wherein, The anionite-exchange resin of described load hypochlorite can be loaded to anionite-exchange resin with hypochlorite through this area ordinary method and obtain; Preferable comprises the steps: that the chlorine with the parity chlorate anions is that aqueous oxidizing agent solution stream passes through anionite-exchange resin, gets final product.
Wherein, the chlorine of described parity chlorate anions be the concentration of aqueous oxidizing agent solution preferable for ClO
-Meter mass percent 10%～30%.
Wherein, what the theoretical exchange capacity ratio of the hypochlorite charge capacity of described anionite-exchange resin and anionite-exchange resin was preferable is 1: 1～1: 3, and better is 1: 2, and the unit of theoretical exchange capacity is mmol/mL.
Wherein, the chlorine of described parity chlorate anions be the load flow velocity of aqueous oxidizing agent solution and anionite-exchange resin preferable be 0.1m
3/ h～0.5m
3/ h, what load temperature was preferable is 15 ℃-40 ℃ of room temperature conditions.
Wherein, The chlorine of described parity chlorate anions is the time of aqueous oxidizing agent solution and anionite-exchange resin load to confirm that according to the theoretical exchange capacity and the load flow velocity of hypochlorite charge capacity, anionite-exchange resin those skilled in the art all know according to above-mentioned known conditions calculating and confirm.For example, the exchange capacity of 201 * 2 strong-basicity styrene series anion exchange resins is 4mmol/mL, and setting charge capacity is 50% of exchange capacity, according to above-mentioned, and 1m
3Resin need 0.42m
330% chlorine bleach liquor of volume (density 1.18, total 496.27kg) is at 0.5m
3/ h flow velocity needs down to accomplish load through about 50min.
Wherein, Described cyanide wastewater is when the anion-exchange resin treatment of overload hypochlorite; To the treatment of cyanide waste water amount generally with waste water in total cyanide relevant, those skilled in the art know all according to concentration of cyanide in the waste water and suitably adjust that the present invention is in the ordinary course of things; The anionite-exchange resin of load hypochlorite to treatment of cyanide waste water amount volume ratio preferable be 1: 300～1: 700, better is 1: 500.Behind the anion-exchange resin treatment waste water of described load hypochlorite, can more not renew resin, can reuse after the regeneration.
Among the present invention; The anion-exchange resin treatment of described anion-exchange resin treatment or described load hypochlorite is this area routine operation; This handles condition mode one and all is suitable for mode two; This condition generally comprises treatment temp and the unit time is handled the water yield, and preferable condition is: 10 ℃～40 ℃ of temperature, the water yield 2m of unit time unit volume plastic resin treatment
3/ (m
3H)～20m
3/ (m
3H).
Among the present invention; The liquid air speed of the anion-exchange resin treatment of described anion-exchange resin treatment or described load hypochlorite does not need special qualification; Generally confirm to get final product according to concrete cyanide wastewater and anion-exchange resin treatment ability; As long as the water outlet after handling is up to standard, liquid air speed is the bigger the better.
Among the present invention, the anionite-exchange resin of described load hypochlorite generally carried out pre-treatment according to this area routine operation to described anionite-exchange resin before preparation using before perhaps.The pre-treatment of described anionite-exchange resin is this area routine operation; The general deionized water that uses earlier soaks; Get final product with after the NaOH solution soaking again; Preferable comprising the steps: doubly measured anionite-exchange resin after deionized water soaks more than the 24h with 4～10 volumes, more than the NaOH solution soaking 2h of the mass percentage concentration 2%～10% that anionite-exchange resin is doubly measured with 4～10 volumes again, gets final product.
Among the present invention; The anionite-exchange resin of described anionite-exchange resin or described load hypochlorite is after Treatment of Cyanide-containing Wastewater reaches capacity; Also can obtain regeneration according to this area conventional processing; Preferable can handle as follows, washes 1h～3h with the aqueous solution that contains mass percent 10%～25%NaCl and mass percent 1%～5%NaOH as washing fluid, gets final product.Wherein, washing the elutriant that obtains places accident pool to get final product by this area routine.What the speed of described flushing was preferable is with 0.1m
3/ (m
3H)～2.0m
3/ (m
3H), unit is for per hour washing every m
3The rinsing liq product of resin.The temperature of described flushing is that this area is conventional, and room temperature condition all can for 15 ℃-40 ℃.
Agents useful for same of the present invention and raw material are all commercially available to be got.
On the basis that meets this area general knowledge, the optimum condition of each above-mentioned technical characterictic can arbitrary combination obtain preferred embodiments of the present invention among the present invention.
Positive progressive effect of the present invention is:
(1) the deep treatment method Treatment of Cyanide-containing Wastewater of cyanide wastewater of the present invention; Do not need equalizing tank and oxidizing reaction pond fully; Need not to filter and go to handle, the chlorine of cyanide wastewater and parity chlorate anions is that oxygenant need not mix (if can utilize the existed building facility certainly, can in the pond, mix) separately in the pond yet; Be that oxygenant is put in the transport pipe of cyanide wastewater and just can be realized mixing directly, greatly practiced thrift the WWT place the chlorine of parity chlorate anions.
(2) the deep treatment method reagent of cyanide wastewater of the present invention is simple and easy to, and the continuous working period is long, and the resin iterative regenerable uses, and greatly reduces processing cost;
(3) deep treatment method of cyanide wastewater of the present invention is simple to operate, and treatment effect is good, can realize the stably reaching standard discharging for a long time; Satisfy national composite wastewater first discharge standard GB8978-1996, total cyanide content≤0.5mg/L mg/L, COD≤100mg/L; BOD≤30mg/L, colourity≤50 are under the prerequisite that realizes qualified discharge; Even can satisfy the reuse water water quality standard SL368-2006 of urban sewage reutilization, COD≤60mg/L, BOD≤10mg/L; Colourity≤30, the total cyanide content of handling the back water outlet satisfies＜0.3mg/L, and other contamination indexs in the waste water such as indexs such as COD, ammonia nitrogen continue to reduce after the present invention handles simultaneously.
Embodiment
Mode through embodiment further specifies the present invention below, but does not therefore limit the present invention among the described scope of embodiments.
Among the following embodiment, the detection method of total cyanide, COD, BOD and colourity is all carried out by national standard: the total cyanide examination criteria is the mensuration GB/T 7486-1987 of prussiate; The COD examination criteria is that hydrochemistry oxygen requirement dichromate titration is measured GB/T 11914-1989; The BOD examination criteria is measured (BOD5) GB/T 7488-1987 for dilution of water quality five-day BOD and inoculation method; The colorimetric detection standard is the mensuration GB/T 11903-1989 of water quality colourity.
Embodiment 1
1, resin pre-treatment:
Get 0.2m
3201 * 4 type anionite-exchange resin add 0.8m
3Deionized water soaks 24h, and then places 1m
3Mass concentration 2%NaOH solution soaking 6h, transfer resin to OH
-Type.
2, the anionite-exchange resin of preparation load hypochlorite:
With commercially available active chlorine concentrations is 10% chlorine bleach liquor, at 15 ℃ and 0.1m
3Through being filled with the ADSORPTION IN A FIXED BED post of 201 * 4 type anionite-exchange resin, load time is 2h under the condition of/h load flow velocity, and hypochlorite is loaded on the resin; The theoretical exchange capacity ratio of the hypochlorite charge capacity of anionite-exchange resin and anionite-exchange resin is 1: 3, and the Youxiaolin consumption is that oxygenant produces ClO with chlorine
-Amount is counted CN in the cyanide wastewater
-1 mole of amount doubly.
3, the advanced treatment of cyanide wastewater
With total cyanogen concentration is 0.5mg/L, and the COD value is 100mg/L～300mg/L, and BOD is 90mg/L～300mg/L, and the biochemical treatment water outlet of the coking chemical waste water of colourity 80～150 is at 20 ℃ and 4m
3/ (m
3H) under the condition, through the fixed bed of anion exchange resin adsorption column of above-mentioned load hypochlorite; Carry out 10,20,30,60,120 in reaction respectively, during 240min sampling analysis is carried out in water outlet, total cyanide content is respectively 0.01,0.01,0.01,0.01 in the water outlet, 0.01mg/L, and prussiate is almost removed fully.Behind the device continuous service 40h, the total cyanide content in the water outlet is 0.05mg/L, and clearance reaches 90.0%, satisfies the reuse water water quality standard SL368-2006 of urban sewage reutilization, COD≤50mg/L, BOD≤10mg/L, colourity≤30.
4, resin regeneration:
Under normal temperature condition, adopt the mixing solutions of 10%NaCl+1%NaOH the ADSORPTION IN A FIXED BED post that anionite-exchange resin is housed to be washed regeneration as desorbing agent, the speed of control wash-down water is 2m
3/ (m
3H), flush time is 3h, makes polymeric adsorbent obtain regeneration, and the desorption efficiency of 201 * 4 type ion exchange resin is 94.2%, and the elutriant that washes gets into accident pool.
Embodiment 2
1, resin pre-treatment
Get 0.75m
3201 * 7 type ion exchange resin add 3.0m
3Deionized water soaks 24h, and then places 3.75m
3The NaOH solution soaking 4h of mass percent 6% transfers resin to OH
-Type.
2, the anionite-exchange resin of preparation load hypochlorite:
The ClO 2 solution of preparation 20% is at 30 ℃ and 0.3m
3Through being filled with the ADSORPTION IN A FIXED BED post of 201 * 7 type anionite-exchange resin, load time is 1.5h under the condition of/h load flow velocity, and hypochlorite is loaded on the resin; The theoretical exchange capacity ratio of the hypochlorite charge capacity of anionite-exchange resin and anionite-exchange resin is 1: 2, and the chlorine of parity chlorate anions is that the consumption of oxygenant is that oxygenant produces ClO with chlorine
-Amount is counted CN in the cyanide wastewater
-2.5 moles of amounts doubly.
3, the advanced treatment of cyanide wastewater
With total cyanogen concentration is 2.8mg/L, and the COD value is 50mg/L～500mg/L, and BOD is 30mg/L～300mg/L, and the biochemical treatment water outlet of the coking chemical waste water of colourity 80～150 is at 25 ℃ and 12m
3/ (m
3H) under the condition, through the fixed bed of anion exchange resin adsorption column of above-mentioned load hypochlorite; Carry out 10,30,60,120 in reaction respectively, during 240min sampling analysis is carried out in water outlet, total cyanide content is respectively 0.01,0.01,0.02 in the water outlet, 0.02mg/L, and prussiate is almost removed fully.Behind the device continuous service 32h, the total cyanide content of water outlet is 0.12mg/L, and the total cyanide clearance reaches 95.7%, satisfies the reuse water water quality standard SL368-2006 of urban sewage reutilization, COD≤60mg/L, BOD≤10mg/L, colourity≤30.
4, polymeric adsorbent regeneration
Under 20 ℃ of conditions of normal temperature, adopt the mixing solutions of 18%NaCl+3%NaOH the ADSORPTION IN A FIXED BED post that anionite-exchange resin is housed to be washed regeneration as desorbing agent, the speed of control wash-down water is 0.1m
3/ (m
3H), flush time is 1h, makes polymeric adsorbent obtain regeneration, and the resolution factor of 201 * 7 type ion exchange resin is 92.8%, and the elutriant that washes gets into accident pool.
Embodiment 3
1, resin pre-treatment
Get 0.5m
3201 * 2 type ion exchange resin add 2m
3Deionized water soaks 24h, and then places 3m
3The NaOH solution soaking 3h of mass percent 10% transfers resin to OH
-Type.
2, the advanced treatment of cyanide wastewater
Oxygenant mixes with the biochemical treatment water outlet: be that the chlorine bleach liquor of mass percent 30% is under 35 ℃ of conditions and 5m with commercially available active chlorine concentrations
3Total cyanogen concentration is 2.8mg/L, and the COD value is 50mg/L～500mg/L, and BOD is 30mg/L～300mg/L, and the biochemical treatment water outlet of the coking chemical waste water of colourity 80～150 mixes, and makes that active chlorine concentrations is 60mg/L in the mixing solutions.
With the waste water after the mixing in the step 2 at 35 ℃ and 10m
3/ (m
3H) under the condition through being filled with the ADSORPTION IN A FIXED BED post of 201 * 2 type ion exchange resin; Carry out 10,20,30,60,120 in reaction respectively, during 240min sampling analysis is carried out in water outlet, total cyanide content is respectively 0.01,0.01,0.02,0.02 in the water outlet, 0.03mg/L, and prussiate is almost removed fully.Behind the device continuous service 48h, the total cyanide content in the water outlet is 0.26mg/L, and clearance reaches 90.7%, satisfies the reuse water water quality standard SL368-2006 of urban sewage reutilization, COD≤60mg/L, BOD≤10mg/L, colourity≤30.
3, polymeric adsorbent regeneration
Under 25 ℃ of conditions of normal temperature, adopt the mixing solutions of 25%NaCl+5%NaOH the ADSORPTION IN A FIXED BED post that anionite-exchange resin is housed to be washed regeneration as desorbing agent, the speed of control wash-down water is 2m
3/ (m
3H), flush time is 2h, makes polymeric adsorbent obtain regeneration, and the desorption efficiency of 201 * 2 type ion exchange resin is 93.0%, and the elutriant that washes gets into accident pool.
Embodiment 4
1, resin pre-treatment:
Get 1.1m
3201 * 8 type anionite-exchange resin add 4.4m
3Deionized water soaks 24h, and then places 11m
3The NaOH solution soaking 2h of mass percent 10% transfers resin to OH
-Type.
2, the anionite-exchange resin of preparation load hypochlorite:
With commercially available active chlorine concentrations is 30% chlorine bleach liquor, at 40 ℃ and 0.5m
3Through being filled with the ADSORPTION IN A FIXED BED post of 201 * 8 type anionite-exchange resin, load time is 1h under the condition of/h load flow velocity, and hypochlorite is loaded on the resin; The theoretical exchange capacity ratio of the hypochlorite charge capacity of anionite-exchange resin and anionite-exchange resin is 1: 1, and the chlorine of parity chlorate anions is that the consumption of oxygenant is that oxygenant produces ClO with chlorine
-Amount is counted CN in the cyanide wastewater
-5 moles of amounts doubly.
3, the advanced treatment of cyanide wastewater
With total cyanogen concentration is 5.0mg/L, and the COD value is 50mg/L～500mg/L, and BOD is 30mg/L～300mg/L, and the biochemical treatment water outlet of the coking chemical waste water of colourity 80～150 is at 40 ℃ and 20m
3/ (m
3H) under the condition, through the fixed bed of anion exchange resin adsorption column of above-mentioned load hypochlorite; Carry out 10,20,30,60,120 in reaction respectively, during 240min sampling analysis is carried out in water outlet, total cyanide content is respectively 0.01,0.02,0.02,0.05 in the water outlet, 0.08mg/L, and prussiate is almost removed fully.Behind the device continuous service 40h, the total cyanide content in the water outlet is 0.25mg/L, and clearance reaches 95.0%, satisfies the reuse water water quality standard SL368-2006 of urban sewage reutilization, COD≤60mg/L, BOD≤10mg/L, colourity≤30.
4, resin regeneration:
Under normal temperature condition, adopt the mixing solutions of 25%NaCl+5%NaOH the ADSORPTION IN A FIXED BED post that anionite-exchange resin is housed to be washed regeneration as desorbing agent, the speed of control wash-down water is 1m
3/ (m
3H), flush time is 1h, makes polymeric adsorbent obtain regeneration, and the desorption efficiency of 201 * 4 type ion exchange resin is 91.2%, and the elutriant that washes gets into accident pool.
Embodiment 5
1, resin pre-treatment:
Get 0.3m
3D293 macroporous strong basic quaternary ammonium I type anionite-exchange resin adds 3m
3Deionized water soaks 30h, and then places 3m
3Mass concentration 5%NaOH solution soaking 4h transfers resin to OH
-Type.
2, the anionite-exchange resin of preparation load hypochlorite:
With commercially available active chlorine concentrations is 10% calcium hypochlorite solution, at 30 ℃ and 0.2m
3Through being filled with the ADSORPTION IN A FIXED BED post of D293 macroporous strong basic quaternary ammonium I type anionite-exchange resin, load time is 1h under the condition of/h load flow velocity, and hypochlorite is loaded on the resin; The theoretical exchange capacity ratio of the hypochlorite charge capacity of anionite-exchange resin and anionite-exchange resin is 1: 2, and the chlorine of parity chlorate anions is that the consumption of oxygenant is that oxygenant produces ClO with chlorine
-Amount is counted CN in the cyanide wastewater
-2.5 moles of amounts doubly.
3, the advanced treatment of cyanide wastewater
With total cyanogen concentration is 2.4mg/L, and the COD value is 50mg/L～500mg/L, and BOD is 30mg/L～300mg/L, and the biochemical treatment water outlet of the coking chemical waste water of colourity 80～150 is at 10 ℃ and 6m
3/ (m
3H) under the condition, through the fixed bed of anion exchange resin adsorption column of above-mentioned load hypochlorite; Carry out 10,20,30,60,120 in reaction respectively, during 240min sampling analysis is carried out in water outlet, total cyanide content is respectively 0.01,0.01,0.01,0.01 in the water outlet, 0.01mg/L, and prussiate is almost removed fully.Behind the device continuous service 40h, the total cyanide content in the water outlet is 0.15mg/L, and clearance reaches 90.0%, satisfies the reuse water water quality standard SL368-2006 of urban sewage reutilization, COD≤60mg/L, BOD≤10mg/L, colourity≤30.
4, resin regeneration:
Under normal temperature condition, adopt the mixing solutions of 18%NaCl+2%NaOH the ADSORPTION IN A FIXED BED post that anionite-exchange resin is housed to be washed regeneration as desorbing agent, the speed of control wash-down water is 1.5m
3/ (m
3H), flush time is 1.5h, makes polymeric adsorbent obtain regeneration, and the desorption efficiency of D293 macroporous strong basic quaternary ammonium I type anionite-exchange resin is 94.2%, and the elutriant that washes gets into accident pool.
Embodiment 6
1, resin pre-treatment
Get 0.15m
3The equal hole of JK206 strong basic type anion-exchange resin adds 0.9m
3Deionized water soaks 28h, and then places 0.9m
3The NaOH solution soaking 4h of mass percent 6% transfers resin to OH
-Type.
2, the anionite-exchange resin of preparation load hypochlorite:
The ClO 2 solution of preparation 15% is at 25 ℃ and 0.1m
3Through being filled with the ADSORPTION IN A FIXED BED post of the equal hole of JK206 strong basic type anion-exchange resin, load time is 1.5h under the condition of/h load flow velocity, and hypochlorite is loaded on the resin; The theoretical exchange capacity ratio of the hypochlorite charge capacity of anionite-exchange resin and anionite-exchange resin is 1: 2, and the chlorine of parity chlorate anions is that the consumption of oxygenant is that oxygenant produces ClO with chlorine
-Amount is counted CN in the cyanide wastewater
-2.5 moles of amounts doubly.
3, the advanced treatment of cyanide wastewater
With total cyanogen concentration is 2.0mg/L, and the COD value is 50mg/L～500mg/L, and BOD is 30mg/L～300mg/L, and the biochemical treatment water outlet of the coking chemical waste water of colourity 80～150 is at 25 ℃ and 2m
3/ (m
3H) under the condition, through the fixed bed of anion exchange resin adsorption column of above-mentioned load hypochlorite; Carry out 10,30,60,120 in reaction respectively, during 240min sampling analysis is carried out in water outlet, total cyanide content is respectively 0.01,0.01,0.02 in the water outlet, 0.02mg/L, and prussiate is almost removed fully.Behind the device continuous service 32h, the total cyanide content of water outlet is 0.12mg/L, and the total cyanide clearance reaches 94.0%, satisfies the reuse water water quality standard SL368-2006 of urban sewage reutilization, COD≤60mg/L, BOD≤10mg/L, colourity≤30.
4, polymeric adsorbent regeneration
Under 20 ℃ of conditions of normal temperature, adopt the mixing solutions of 20%NaCl+3%NaOH the ADSORPTION IN A FIXED BED post that anionite-exchange resin is housed to be washed regeneration as desorbing agent, the speed of control wash-down water is 0.5m
3/ (m
3H), flush time is 1h, makes polymeric adsorbent obtain regeneration, and the resolution factor of the equal hole of JK206 strong basic type anion-exchange resin is 92.8%, and the elutriant that washes gets into accident pool.
Embodiment 7
1, resin pre-treatment
Get 0.5m
3HZ202 highly basic gel-type anionite-exchange resin adds 2m
3Deionized water soaks 24h, and then places 2m
3The NaOH solution soaking 3h of mass percent 8% transfers resin to OH
-Type.
2, the advanced treatment of cyanide wastewater
Oxygenant mixes with the biochemical treatment water outlet: be that the chlorine bleach liquor of mass percent 10% is under 35 ℃ of conditions and 5m with commercially available active chlorine concentrations
3Total cyanogen concentration is 2.8mg/L, and the COD value is 50mg/L～500mg/L, and BOD is 30mg/L～300mg/L, and the biochemical treatment water outlet of the coking chemical waste water of colourity 80～150 mixes, and makes that active chlorine concentrations is 60mg/L in the mixing solutions.
With the waste water after the mixing in the step 2 at 35 ℃ and 10m
3/ (m
3H) under the condition through being filled with the ADSORPTION IN A FIXED BED post of HZ202 highly basic gel-type anionite-exchange resin; Carry out 10,20,30,60,120 in reaction respectively, during 240min sampling analysis is carried out in water outlet, total cyanide content is respectively 0.01,0.01,0.02,0.02 in the water outlet, 0.03mg/L, and prussiate is almost removed fully.Behind the device continuous service 48h, the total cyanide content in the water outlet is 0.26mg/L, and clearance reaches 90.7%, satisfies the reuse water water quality standard SL368-2006 of urban sewage reutilization, COD≤60mg/L, BOD≤10mg/L, colourity≤30.
3, polymeric adsorbent regeneration
Under 25 ℃ of conditions of normal temperature, adopt the mixing solutions of 20%NaCl+3%NaOH the ADSORPTION IN A FIXED BED post that anionite-exchange resin is housed to be washed regeneration as desorbing agent, the speed of control wash-down water is 0.8m
3/ (m
3H), flush time is 2h, makes polymeric adsorbent obtain regeneration, and the desorption efficiency of HZ202 highly basic gel-type anionite-exchange resin is 93.0%, and the elutriant that washes gets into accident pool.
Claims (10)
1. the deep treatment method of a cyanide wastewater is characterized in that, it comprises the steps: that the chlorine with cyanide wastewater multiparity hypochlorite is that oxygenant and anion-exchange resin treatment get final product, and is specially any of following manner:
Mode one: with the chlorine of cyanide wastewater and parity chlorate anions is the oxygenant uniform mixing, gets final product through anion-exchange resin treatment afterwards; Mode two: the anion-exchange resin treatment of cyanide wastewater through the overload hypochlorite got final product.
2. deep treatment method as claimed in claim 1 is characterized in that, described cyanide wastewater index is: total cyanide content is 0.5mg/L～100mg/L; The COD value is 50mg/L～1000mg/L, and BOD is 30mg/L～1000mg/L, colourity 50～200; Preferable index is total cyanide content 0.5mg/L～5mg/L; The COD value is 50mg/L～500mg/L, and BOD is 30mg/L～300mg/L, colourity 80～150.
3. deep treatment method as claimed in claim 1 is characterized in that, the chlorine of described parity chlorate anions is that oxygenant is one or more in Youxiaolin, Losantin, liquid chlorine and the dioxide peroxide.
4. deep treatment method as claimed in claim 1; It is characterized in that; Described anionite-exchange resin is strongly basic anion exchange resin, preferable is D293 macroporous strong basic quaternary ammonium I type anionite-exchange resin, D202 macroporous strong basic quaternary ammonium II type anionite-exchange resin, D201 macroporous strong basic quaternary ammonium I type anionite-exchange resin, D261 macropore highly basic Zeo-karb, the equal hole of JK206 strong basic type anion-exchange resin, the equal hole of JK204 highly basic gel-type anionite-exchange resin, HZ202 highly basic gel-type anionite-exchange resin, 201 * 2 strong-basicity styrene series anion exchange resins, 201 * semi-finals basicity styrene series anion exchange resin, 201 * 7 strong-basicity styrene series anion exchange resins, or 201 * Final 8 basicity styrene series anion exchange resin.
5. deep treatment method as claimed in claim 1 is characterized in that, when the deep treatment method of described cyanide wastewater adopts mode for the moment: the chlorine of described parity chlorate anions is that the consumption of oxygenant is that oxygenant produces ClO with chlorine
-Amount is counted CN in the cyanide wastewater
-1～5 mole of amount doubly, preferable is 2.5 moles of doubly amounts; Described anionite-exchange resin is 1: 300～1: 1000 to treatment of cyanide waste water amount volume ratio, and preferable is 1: 500; When the deep treatment method of described cyanide wastewater adopted mode two: the anionite-exchange resin of described load hypochlorite was 1: 300～1: 700 to treatment of cyanide waste water amount volume ratio, and preferable is 1: 500.
6. deep treatment method as claimed in claim 1; It is characterized in that; When the deep treatment method of described cyanide wastewater adopted mode two: the anionite-exchange resin of described load hypochlorite was made by following method: with the chlorine of parity chlorate anions is that aqueous oxidizing agent solution stream passes through anionite-exchange resin, gets final product.
7. deep treatment method as claimed in claim 6 is characterized in that, the chlorine of described parity chlorate anions is that the concentration of aqueous oxidizing agent solution is with ClO
-Meter mass percent 10%～30%; The theoretical exchange capacity ratio of the hypochlorite charge capacity of described anionite-exchange resin and anionite-exchange resin is 1: 1～1: 3, and preferable is 1: 2, and the unit of theoretical exchange capacity is mmol/mL; The chlorine of described parity chlorate anions is that the load flow velocity of aqueous oxidizing agent solution and anionite-exchange resin is 0.1m
3/ h～0.5m
3/ h, load temperature are 15 ℃-40 ℃ of room temperature conditions.
8. deep treatment method as claimed in claim 1; It is characterized in that; The treatment condition of the anion-exchange resin treatment of the treatment condition of described anion-exchange resin treatment or described load hypochlorite are: 10 ℃～40 ℃ of temperature, the water yield 2m of unit time unit volume plastic resin treatment
3/ (m
3H)～20m
3/ (m
3H).
9. deep treatment method as claimed in claim 1; It is characterized in that; The anionite-exchange resin of described load hypochlorite carried out pre-treatment to described anionite-exchange resin before preparation using before perhaps; Described pre-treatment is to use earlier deionized water to soak, and get final product with after the NaOH solution soaking again, preferable is doubly measure deionized water immersion 24h more than with 4～10 volumes anionite-exchange resin after; More than the NaOH solution soaking 2h of the mass percentage concentration 2%～10% that anionite-exchange resin is doubly measured with 4～10 volumes again, get final product.
10. deep treatment method as claimed in claim 1; It is characterized in that; The anionite-exchange resin of described anionite-exchange resin or described load hypochlorite is after Treatment of Cyanide-containing Wastewater reaches capacity; Also handle regeneration as follows, wash 1h～3h as washing fluid, get final product with the aqueous solution that contains mass percent 10%～25%NaCl and mass percent 1%～5%NaOH; Wherein, the speed of described flushing is with 0.1m
3/ (m
3H)～2.0m
3/ (m
3H), unit is for per hour washing every m
3The rinsing liq product of resin.
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| CN103523964A (en) * | 2013-10-25 | 2014-01-22 | 长春黄金研究院 | O&R (Ozone-Resin) harmless treatment process of cyanogens-containing tailing pulp |
| CN103908954A (en) * | 2014-03-31 | 2014-07-09 | 河南中烟工业有限责任公司 | Resin material for reducing hydrocyanic acid release quantity in smoke as well as preparation method thereof |
| CN111847566A (en) * | 2020-07-23 | 2020-10-30 | 上海乔尼水处理设备工程有限公司 | Method and device for treating high-COD wastewater in electronic industry |
| CN111960527A (en) * | 2020-07-14 | 2020-11-20 | 中原环保知和(郑州)水环境科技有限公司 | ClO (ClO)2Method for deeply treating biochemical tail water of sewage by effervescent tablets |
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| CN111847566A (en) * | 2020-07-23 | 2020-10-30 | 上海乔尼水处理设备工程有限公司 | Method and device for treating high-COD wastewater in electronic industry |
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