CN102560517A - Comprehensive utilization method for waste hydrochloric acid containing zinc - Google Patents
Comprehensive utilization method for waste hydrochloric acid containing zinc Download PDFInfo
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- CN102560517A CN102560517A CN2012100439503A CN201210043950A CN102560517A CN 102560517 A CN102560517 A CN 102560517A CN 2012100439503 A CN2012100439503 A CN 2012100439503A CN 201210043950 A CN201210043950 A CN 201210043950A CN 102560517 A CN102560517 A CN 102560517A
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Abstract
The invention discloses a comprehensive utilization method for waste hydrochloric acid containing zinc, and belongs to the technical field of comprehensive utilization of waste acid containing the zinc. The method comprises the steps of: (A), removing suspended matter in waste hydrochloric acid washing liquor for zinc castings by means of sand filtration; (B), passing through a static bed absorption tower filled with strong-base anion exchange resin and provided with a heat preservation jacket at the operating temperature of 0-40DEG C and the working flow of 1.0-3.0 BV/h; (C), adding technical hydrochloric acid, and returning to the production processes to be the hydrochloric acid washing liquor for the zinc casting for recycling after the HCL (hydrogen chloride) concentration is increased to 8mol/L; and (D), eluting zinc complex anions exchanged on the strong-base anion exchange resin to produce aqueous solution containing zinc chloride, and taking the aqueous solution as a soldering flux by-product for use. In the method, hydrogen ions are effectively separated from zinc ions by using the anion exchange resin; the waste hydrochloric acid washing liquor for the zinc casting realizes zero release; the hydrochloric acid can be recycled completely; and the resin regeneration solution can be used for preparing the soldering flux, thereby achieving the purposes of separating, purification and recycling of the waste hydrochloric acid washing liquor for the zinc casting.
Description
Technical field
The present invention relates to contain the method for comprehensive utilization technical field of zinc spent acid, in the industry production processes such as iron and steel, metallurgy, machinery, electric, plating in the abraum salt pickle solution of zinc casting, the isolation of purified of hydrochloric acid and zine ion and recoverying and utilizing method.
Background technology
Industries such as iron and steel, metallurgy, machinery, electric, plating use zinc casting as starting material in a large number.These zinc castings are used and are gone to toward utilizing concentrated hydrochloric acid to flood and rinsing.The HCl concentration of this abraum salt pickle solution is 4-8 mol/L, and zinc ion content is 500-2000mg/L.With the engineering investigation, the improvement of zinc casting abraum salt pickle is mainly adopted the method for alkali lye neutralization, precipitation both at home and abroad according to the literature.The shortcoming of this terms of settlement is: not only wasted useful hydrochloric acid and zinc chloride resource, and increased the neutralizing treatment expense, significantly increased the salts contg in enterprise's waste discharge simultaneously, directly caused the lifting significantly of subsequent wastewater treatment cost.
Contain in the acid of zinc abraum salt and contain positively charged hydrogen ion and zine ion, as general knowledge, general Study personnel can use Zeo-karb that both are separated.But it is all very high to contain in the acid of zinc abraum salt hydrogen ion and zinc ion concentration, only relies on Zeo-karb to be difficult to realize effective separation.Literature search shows, for zinc casting abraum salt pickle solution middle and high concentration zine ion and concentrated hydrochloric acid, adopts strongly basic anion exchange resin to carry out isolation of purified and recoverying and utilizing method, does not see bibliographical information.
Summary of the invention
The technical problem that invention will solve
It is low to the present invention is directed to the ubiquitous zinc casting abraum salt of industry pickle solution recovery utilization rates such as iron and steel, metallurgy, machinery, electric, plating, and the high deficiency of processing costs, and a kind of method of comprehensive utilization that contains the acid of zinc abraum salt is provided.
Technical scheme
For achieving the above object, technical scheme provided by the invention is:
A kind of method of comprehensive utilization that contains the acid of zinc abraum salt of the present invention the steps include:
(A), be 4-8 mol/L with HCl concentration, zinc ion content is that the zinc casting abraum salt pickle solution of 500-2000mg/L is removed suspended substance through sand filtration;
(B), the zinc casting abraum salt pickle solution after step (A) is handled; Service temperature be 0-40 ℃ with working flow be under the condition of 1.0-3.0BV/h through being filled with strongly basic anion exchange resin and having the ADSORPTION IN A FIXED BED tower of insulation jacket, HCl concentration is 4-8mol/L, zinc ion concentration≤100mg/L in the effluent after the processing;
(C), the effluent after step (B) handled adds technical hydrochloric acid, enrichment HCl concentration is returned production process to 8mol/L, recycle as the zinc casting hydrochloric acid lotion;
(D), with zero(ppm) water or deionized water as regenerator; Regenerator passes through resin bed; The zinc complex anion of exchange on strongly basic anion exchange resin in the step (B) eluted, form the aqueous solution that contains zinc chloride, can directly use as the soldering flux sub product; The service temperature of regenerative process is 5-40 ℃, and working flow is 0.5-2.0BV/h.
Further, in the step (B), strongly basic anion exchange resin is to be skeleton with vinylbenzene-divinyl interpolymer, and specific surface area is 27-500 m
2/ g, the exchange capacity that contains Trimethylamine 99, triethylamine, Tributylamine, pyrimidyl, pyridyl, pyranyl, dimethyl propanol amine, methyldiethanolamine or dioctyl thanomin group is the resin of 0.5-4.5mmol/g.
Further, the strongly basic anion exchange resin in the step (B) is D201, or 201 * 4, or 201 * 7; Or 202 * II, or D296, or NDA900, or NDA96; Or NDA1106, or the NDA1107 resin, or Amberlite IRA-900; Or Amberlite IRA-96, or Amberlite IRA-400, or Duolite A-101D resin.
The present invention contains the comprehensive utilization of zinc abraum salt acid can adopt double-column in series absorption zinc, single tower regeneration operation process.I, II, three resin towers of III promptly are set, and with I, the series connection of II tower, the I tower is as the one-level adsorption tower earlier, and the II tower is as the secondary absorption tower.After the I tower removes zincification, switch to II, the series connection of III tower, the II tower is as the one-level adsorption tower, and the III tower is as the secondary absorption tower.Simultaneously, the I tower carries out reverse regeneration.So circular flow does not stop to contain the fractionation by adsorption processing of zinc abraum salt pickle solution yet when adsorption tower is regenerated, effect is even more ideal.
Principle of the present invention:Contain in the acid of zinc abraum salt and contain positively charged hydrogen ion and zine ion, as general knowledge, general Study personnel can use Zeo-karb that both are separated.But it is all very high to contain in the acid of zinc abraum salt hydrogen ion and zinc ion concentration, only relies on Zeo-karb to be difficult to realize effective separation.The ingenious utilization of the present invention; Under the high-concentration chlorine ion condition; Zine ion will exist with electronegative zinc chloride complex anion form, this characteristic, and the hydrogen ion that utilizes anionite-exchange resin will contain in the acid of zinc abraum salt effectively separates with zine ion; Thereby reach purpose, realized the complete recycle of hydrochloric acid zinc casting abraum salt pickle solution isolation of purified and recycling.It is 4-8 mol/L that the comprehensive utilization that the present invention contains zinc abraum salt acid can make concentration of hydrochloric acid; Zinc ion content is the zinc casting abraum salt pickle solution of 500-2000mg/L; After treatment, zinc ion concentration is less than 100mg/L, and can require further to reduce zinc ion concentration according to reuse; The HCl concentration of the effluent after the processing is 4-8mol/L, can add industrial concentrated hydrochloric acid enrichment HCl concentration and to 8mol/L, return production process, recycles as the zinc casting hydrochloric acid lotion; The concentration of zine ion is high in the resin elution regenerated liquid, can be used as the soldering flux sub product and uses.
Beneficial effect
Adopt technical scheme provided by the invention, compare, have following unusual effect with existing known technology:
(1) a kind of method of comprehensive utilization that contains the acid of zinc abraum salt of the present invention; The hydrogen ion that utilizes anionite-exchange resin will contain in the acid of zinc abraum salt effectively separates with zine ion; Zinc casting abraum salt pickle solution is realized zero release; Hydrochloric acid recycle fully, resin regeneration liquid can be used for disposing soldering flux, thereby reaches the purpose to zinc casting abraum salt pickle solution isolation of purified and recycling;
(2) a kind of method of comprehensive utilization that contains the acid of zinc abraum salt of the present invention; Ingenious being utilized under the high-concentration chlorine ion condition; Zine ion exists with electronegative zinc chloride complex anion form; The hydrogen ion that utilizes anionite-exchange resin will contain in the acid of zinc abraum salt effectively separates with zine ion, and this resin physical strength height, life-span length, absorption and regenerability are good, can steady in a long-termly use;
(3) the present invention compares neutralization of the prior art, intermediate processing, and is simple to operate, and device simple has been cut down the neutralizing treatment expense, significantly reduces the salts contg of enterprises comprehensive waste water, economical environment-protective subsequent treatment cost significantly, and economic benefit is obvious.
Embodiment
For further understanding content of the present invention, the present invention is done further description below in conjunction with embodiment.
Embodiment 1
The NDA900 resin is packed into, and (among the Φ 12 * 160mm), wherein the NDA900 resin is provided by Yongtai, Jiangsu Environmental Protection Technology Co., Ltd the glass resin post of being with insulation jacket, is skeleton with vinylbenzene-divinyl interpolymer, and specific surface area is 38 m with 10mL (about 7 grams)
2/ g, the quaternary amines of being with is a Trimethylamine 99, exchange capacity is 3.8mmol/g.The 450mL zinc casting abraum salt pickle solution of production plant discharging, HCl concentration is about 4.5mol/L, and zinc ion content is about 500mg/L; Filter back following current downwards through above-mentioned resin column, flow is 1.0 BV/h, and temperature is 25 ℃; Effluent after the processing, HCl concentration is about 4.5mol/L, and the about concentration of zine ion is 50mg/L; Can add industrial concentrated hydrochloric acid enrichment HCl concentration and to 8mol/L, return production process, recycle as the zinc casting hydrochloric acid lotion; Get into resin column with the 20mL deionized water as the downward following current of NDA900 resin regeneration agent, the regenerative process service temperature is 25 ℃, and the regenerator flow is 0.5BV/h; The eluting rate of zine ion about 100%; Just begun effusive 10mL wash-out regenerated liquid, included zine ion 20000mg/L, can be used as the soldering flux sub product and use; The effusive 10mL lower concentration wash-out regenerated liquid in back can overlap the resin regeneration agent that is used for the back, to form the high density regenerated liquid.Adopt the inventive method, the zine ion recovery utilization rate is about 90%, and the hydrochloric acid recovery utilization rate is compared neutralizing treatment mode in the past greater than 95%, and processing cost can be saved about 520 yuan of/ton abraum salt acid.
Embodiment 2
The NDA900 resin is packed into, and (among the Φ 25 * 250mm), wherein the NDA900 resin is provided by Yongtai, Jiangsu Environmental Protection Technology Co., Ltd the glass resin post of being with insulation jacket, is skeleton with vinylbenzene-divinyl interpolymer, and specific surface area is 38 m with 100 mL (about 72 grams)
2/ g, the quaternary amines of being with is a Trimethylamine 99, exchange capacity is 3.8mmol/g.3500 mL zinc casting abraum salt pickle solutions of production plant discharging, HCl concentration is about 6 mol/L, and zinc ion content is about 1000 mg/L; Through filtering, following current downwards is through above-mentioned resin column, and flow is 1.5 BV/h; Temperature is 0 ℃, the effluent after the processing, and HCl concentration is about 6 mol/L; The about concentration of zine ion is 70 mg/L, can add industrial concentrated hydrochloric acid enrichment HCl concentration and to 8mol/L, return production process, recycles as the zinc casting hydrochloric acid lotion; Get into resin column with 150 mL deionized waters as the downward following current of NDA900 resin regeneration agent, the regenerative process service temperature is 15 ℃, and the regenerator flow is 1BV/h; The eluting rate of zine ion about 100%; Just begun effusive 100 mL wash-out regenerated liquids, included zine ion 28000 mg/L, can be used as the soldering flux sub product and use; The effusive 50 mL lower concentration wash-out regenerated liquids in back can overlap the resin regeneration agent that is used for the back, to form the high density regenerated liquid.Adopt the inventive method, the zine ion recovery utilization rate is about 93%, and the hydrochloric acid recovery utilization rate is compared neutralizing treatment mode in the past greater than 95%, and processing cost can be saved about 720 yuan of/ton abraum salt acid.
Embodiment 3
The glass resin post (among the Φ 12 * 160mm) that 10 mL (about 7.5 gram) Amberlite IRA-96 resin is packed into and is with insulation jacket; Wherein Amberlite IRA-96 resin is provided by DOW company; With vinylbenzene-divinyl interpolymer is skeleton, and specific surface area is 122 m
2/ g, the quaternary amines of being with is a triethylamine, exchange capacity is 2.8mmol/g.440 mL zinc casting abraum salt pickle solutions of production plant discharging, HCl concentration is about 5 mol/L, and zinc ion content is about 2000 mg/L; Through filtering, following current downwards is through above-mentioned resin column, and flow is 1.0 BV/h; Temperature is 0 ℃, the effluent after the processing, and HCl concentration is about 5 mol/L; The about concentration of zine ion is 90mg/L, can add industrial concentrated hydrochloric acid enrichment HCl concentration and to 8mol/L, return production process, recycles as the zinc casting hydrochloric acid lotion; Get into resin column with 25 mL deionized waters as the downward following current of Amberlite IRA-96 resin regeneration agent, the regenerative process service temperature is 20 ℃, and the regenerator flow is 0.75 BV/h; The eluting rate of zine ion about 100%; Just begun effusive 10 mL wash-out regenerated liquids, included zine ion 44000mg/L, can be used as the soldering flux sub product and use; The effusive 15 mL lower concentration wash-out regenerated liquids in back can overlap the resin regeneration agent that is used for the back, to form the high density regenerated liquid.Adopt the inventive method, the zine ion recovery utilization rate is about 95%, and the hydrochloric acid recovery utilization rate is compared neutralizing treatment mode in the past greater than 95%, and processing cost can be saved about 560 yuan of/ton abraum salt acid.
Embodiment 4
The D201 resin is packed into, and (among the Φ 60 * 300mm), wherein the D201 resin is provided by Yongtai, Jiangsu Environmental Protection Technology Co., Ltd the glass resin post of being with insulation jacket, is skeleton with vinylbenzene-divinyl interpolymer, and specific surface area is 28 m with 1 L (about 700 grams)
2/ g, the quaternary amines of being with is a triethylamine, exchange capacity is 4.2mmol/g.24 L zinc casting abraum salt pickle solutions of production plant discharging, HCl concentration is about 8 mol/L, and zinc ion content is about 2000mg/L; Through filtering, following current downwards is through above-mentioned resin column, and flow is 2BV/h; Temperature is 10 ℃, the effluent after the processing, and HCl concentration is about 8 mol/L; The about concentration of zine ion is 50 mg/L, can directly return production process, recycles as the zinc casting hydrochloric acid lotion; Get into resin column with 1.5 L zero(ppm) water as the downward following current of D201 resin regeneration agent, the regenerative process service temperature is 40 ℃, and the regenerator flow is 1 BV/h; The eluting rate of zine ion about 100%; Just begun effusive 0.8 L wash-out regenerated liquid, included zine ion 31000 mg/L, can be used as the soldering flux sub product and use; The effusive 0.7 L lower concentration wash-out regenerated liquid in back can overlap the resin regeneration agent that is used for the back, to form the high density regenerated liquid.Adopt the inventive method, the zine ion recovery utilization rate is about 97%, and the hydrochloric acid recovery utilization rate is compared neutralizing treatment mode in the past greater than 95%, and processing cost can be saved about 770 yuan of/ton abraum salt acid.
Embodiment 5
10 L (about 7000 gram) D201 resin is packed in the resin column (Φ 0.25 * 1 m) of being with insulation jacket, and wherein the D201 resin is provided by Yongtai, Jiangsu Environmental Protection Technology Co., Ltd, is skeleton with vinylbenzene-divinyl interpolymer, and specific surface area is 28 m
2/ g, the quaternary amines of being with is a triethylamine, exchange capacity is 4.2mmol/g.355 L zinc casting abraum salt pickle solutions of production plant discharging, HCl concentration is about 6.5 mol/L, and zinc ion content is about 1200 mg/L; Through filtering, following current downwards is through above-mentioned resin column, and flow is 1.0 BV/h; Temperature is 25 ℃, the effluent after the processing, and HCl concentration is about 6.5mol/L; The about concentration of zine ion is 90mg/L, can add industrial concentrated hydrochloric acid enrichment HCl concentration and to 8mol/L, return production process, recycles as the zinc casting hydrochloric acid lotion; Get into resin column with 16 L deionized waters as the downward following current of D201 resin regeneration agent, the regenerative process service temperature is 5 ℃, and the regenerator flow is 0.7 BV/h; The eluting rate of zine ion about 100%; Just begun effusive 6 L wash-out regenerated liquids, included zine ion 59000mg/L, can be used as the soldering flux sub product and use; The effusive 10 L lower concentration wash-out regenerated liquids in back can overlap the resin regeneration agent that is used for the back, to form the high density regenerated liquid.Adopt the inventive method, the zine ion recovery utilization rate is about 90%, and the hydrochloric acid recovery utilization rate is compared neutralizing treatment mode in the past greater than 95%, and processing cost can be saved about 580 yuan of/ton abraum salt acid.
Embodiment 6
The NDA900 resin is packed into, and (among the Φ 12 * 160mm), wherein the NDA900 resin is provided by Yongtai, Jiangsu Environmental Protection Technology Co., Ltd the glass resin post of being with insulation jacket, is skeleton with vinylbenzene-divinyl interpolymer, and specific surface area is 38 m with 10mL (about 7 grams)
2/ g, the quaternary amines of being with is a Trimethylamine 99, exchange capacity is 3.8mmol/g.The 550mL zinc casting abraum salt pickle solution of production plant discharging, HCl concentration is about 5 mol/L, and zinc ion content is about 500mg/L; Through filtering, following current downwards is through above-mentioned resin column, and flow is 3.0 BV/h; Temperature is 15 ℃, the effluent after the processing, and HCl concentration is about 5 mol/L; The about concentration of zine ion is 60mg/L, can add industrial concentrated hydrochloric acid enrichment HCl concentration and to 8mol/L, return production process, recycles as the zinc casting hydrochloric acid lotion; Get into resin column with 25 mL deionized waters as the downward following current of NDA900 resin regeneration agent, the regenerative process service temperature is 15 ℃, and the regenerator flow is 1.5BV/h; The eluting rate of zine ion about 100%; Just begun effusive 15mL wash-out regenerated liquid, included zine ion 15000mg/L, can be used as the soldering flux sub product and use; The effusive 10mL lower concentration wash-out regenerated liquid in back can overlap the resin regeneration agent that is used for the back, to form the high density regenerated liquid.Adopt the inventive method, the zine ion recovery utilization rate is about 88%, and the hydrochloric acid recovery utilization rate is compared neutralizing treatment mode in the past greater than 95%, and processing cost can be saved about 550 yuan of/ton abraum salt acid.
Embodiment 7
The D201 resin is packed into, and (among the Φ 12 * 160mm), wherein the D201 resin is provided by Yongtai, Jiangsu Environmental Protection Technology Co., Ltd the glass resin post of being with insulation jacket, is skeleton with vinylbenzene-divinyl interpolymer, and specific surface area is 28 m with 10 mL (about 7 grams)
2/ g, the quaternary amines of being with is a triethylamine, exchange capacity is 4.2mmol/g.The 250mL zinc casting abraum salt pickle solution of production plant discharging, HCl concentration is about 5.5 mol/L, and zinc ion content is about 1000mg/L; Through filtering, following current downwards is through above-mentioned resin column, and flow is 2.5BV/h; Temperature is 40 ℃, the effluent after the processing, and HCl concentration is about 5.5mol/L; The about concentration of zine ion is 50mg/L, can add industrial concentrated hydrochloric acid enrichment HCl concentration and to 8mol/L, return production process, recycles as the zinc casting hydrochloric acid lotion; Get into resin column with the 18mL deionized water as the downward following current of D201 resin regeneration agent, the regenerative process service temperature is 20 ℃, and the regenerator flow is 2.0 BV/h; The eluting rate of zine ion about 100%; Just begun effusive 12mL wash-out regenerated liquid, included zine ion 19000mg/L, can be used as the soldering flux sub product and use; The effusive 6 mL lower concentration wash-out regenerated liquids in back can overlap the resin regeneration agent that is used for the back, to form the high density regenerated liquid.Adopt the inventive method, the zine ion recovery utilization rate is about 95%, and the hydrochloric acid recovery utilization rate is compared neutralizing treatment mode in the past greater than 95%, and processing cost can be saved about 580 yuan of/ton abraum salt acid.
Embodiment 8
10 L (about 7 gram) D201 resin is packed in the glass resin post (Φ 0.4 * 1.5 m) of being with insulation jacket, and wherein the D201 resin is provided by Yongtai, Jiangsu Environmental Protection Technology Co., Ltd, is skeleton with vinylbenzene-divinyl interpolymer, and specific surface area is 28 m
2/ g, the quaternary amines of being with is a triethylamine, exchange capacity is 4.2mmol/g.345 L zinc casting abraum salt pickle solutions of production plant discharging, HCl concentration is about 5 mol/L, and zinc ion content is about 1300mg/L; Through filtering, following current downwards is through above-mentioned resin column, and flow is 1.3 BV/h; Temperature is 25 ℃, the effluent after the processing, and HCl concentration is about 5 mol/L; The about concentration of zine ion is 70mg/L, can add 30% ~ 33% industrial concentrated hydrochloric acid enrichment HCl concentration and to 8mol/L, return production process, recycles as the zinc casting hydrochloric acid lotion; Get into resin column with 20 L zero(ppm) water as the downward following current of D201 resin regeneration agent, the regenerative process service temperature is 25 ℃, and the regenerator flow is 0.5BV/h; The eluting rate of zine ion about 100%; Just begun effusive 10 L wash-out regenerated liquids, included zine ion 39000mg/L, can be used as the soldering flux sub product and use; The effusive 10 L lower concentration wash-out regenerated liquids in back can overlap the resin regeneration agent that is used for the back, to form the high density regenerated liquid.Adopt the inventive method, the zine ion recovery utilization rate is about 94%, and the hydrochloric acid recovery utilization rate is compared neutralizing treatment mode in the past greater than 95%, and processing cost can be saved about 550 yuan of/ton abraum salt acid.
Embodiment 9
10 L (about 7 gram) D201 resin is packed in the glass resin post (Φ 0.4 * 1.5 m) of being with insulation jacket, and wherein the D201 resin is provided by Yongtai, Jiangsu Environmental Protection Technology Co., Ltd, is skeleton with vinylbenzene-divinyl interpolymer, and specific surface area is 28 m
2/ g, the quaternary amines of being with is a triethylamine, exchange capacity is 4.2mmol/g.350 L zinc casting abraum salt pickle solutions of production plant discharging, HCl concentration is about 4 mol/L, and zinc ion content is about 1200mg/L; Through filtering, following current downwards is through above-mentioned resin column, and flow is 1.3 BV/h; Temperature is 25 ℃, the effluent after the processing, and HCl concentration is about 4 mol/L; The about concentration of zine ion is 70mg/L, can add industrial concentrated hydrochloric acid enrichment HCl concentration and to 8mol/L, return production process, recycles as the zinc casting hydrochloric acid lotion; Get into resin column with 20 L zero(ppm) water as the downward following current of D201 resin regeneration agent, the regenerative process service temperature is 25 ℃, and the regenerator flow is 0.5BV/h; The eluting rate of zine ion about 100%; Just begun effusive 10 L wash-out regenerated liquids, included zine ion 35000mg/L, can be used as the soldering flux sub product and use; The effusive 10 L lower concentration wash-out regenerated liquids in back can overlap the resin regeneration agent that is used for the back, to form the high density regenerated liquid.Adopt the inventive method, the zine ion recovery utilization rate is about 94%, and the hydrochloric acid recovery utilization rate is compared neutralizing treatment mode in the past greater than 95%, and processing cost can be saved about 550 yuan of/ton abraum salt acid.
Embodiment 10
Select three identical adsorption towers of specification (Φ 0.55 * 3.5 m) for use, volume Shang number is respectively I, II and III, every tower filling D201 polymeric adsorbent 0.5 m
3(about 340 kg), wherein the D201 resin is provided by Yongtai, Jiangsu Environmental Protection Technology Co., Ltd, is skeleton with vinylbenzene-divinyl interpolymer, and specific surface area is 28 m
2/ g, the quaternary amines of being with is a triethylamine, exchange capacity is 4.2mmol/g.12 m of production plant discharging
3Zinc casting abraum salt pickle solution, HCl concentration is about 6.5 mol/L, and zinc ion content is about 1050mg/L, through filtering; Squeeze into the resin absorption tower, the method that adsorption tower adopts I, II double-column in series to dezincify, flow is 1.5 BV/h; Temperature is 25 ℃, the effluent after the processing, and HCl concentration is about 6.5 mol/L; The about concentration of zine ion is 50mg/L, returns production process after can adding industrial concentrated hydrochloric acid enrichment HCl concentration, recycles as the zinc casting hydrochloric acid lotion.
12 m will have been handled
3The I resin absorption tower of zinc casting abraum salt pickle solution is regenerated with zero(ppm) water.Earlier raffinate in the I tower is drained, use 1 m
3Zero(ppm) water gets into adsorption tower as the downward following current of D201 resin regeneration agent, and the regenerative process service temperature is 25 ℃, and the regenerator flow is 0.5BV/h, and the eluting rate of zine ion is about 100%, has just begun effusive 0.6 m
3The wash-out regenerated liquid includes zine ion 19000mg/L, can be used as the soldering flux sub product and uses, effusive 0.4 m in back
3Lower concentration wash-out regenerated liquid can overlap the resin regeneration agent that is used for the back, to form the high density regenerated liquid.The second road adsorption tower when the I dezincification tower behind the regeneration ending will dezincify operation as the 3rd batch of abraum salt pickle solution (when handling second batch of abraum salt pickle solution, road adsorption tower headed by the II tower, the III tower is the second road adsorption tower).Can guarantee that through the present invention whole controlling device moves continuously.Adopt the inventive method, the zine ion recovery utilization rate is about 95%, and the hydrochloric acid recovery utilization rate is compared neutralizing treatment mode in the past greater than 95%, and processing cost can be saved about 620 yuan of/ton abraum salt acid.
Strongly basic anion exchange resin among the embodiment 1～9 is adopted 201 * 4, or 201 * 7, or 202 * II; Or D296, or NDA96, or NDA1106; Or the NDA1107 resin, or Amberlite IRA-900, or Amberlite IRA-400; Or Duolite A-101D resin, other operational conditions remain unchanged, except that every batch processing amount and resin change work-ing life to some extent; Other result is basic identical, and above-mentioned resin is a skeleton with vinylbenzene-divinyl interpolymer, and its correlation parameter is as shown in table 1.
Table 1 resin information table
Claims (3)
1. a method of comprehensive utilization that contains the acid of zinc abraum salt the steps include:
(A), be 4-8 mol/L with HCl concentration, zinc ion content is that the zinc casting abraum salt pickle solution of 500-2000mg/L is removed suspended substance through sand filtration;
(B), the zinc casting abraum salt pickle solution after step (A) is handled; Service temperature be 0-40 ℃ with working flow be under the condition of 1.0-3.0BV/h through being filled with strongly basic anion exchange resin and having the ADSORPTION IN A FIXED BED tower of insulation jacket, HCl concentration is 4-8mol/L, zinc ion concentration≤100mg/L in the effluent after the processing;
(C), the effluent after step (B) handled adds technical hydrochloric acid, enrichment HCl concentration is returned production process to 8mol/L, recycle as the zinc casting hydrochloric acid lotion;
(D), with zero(ppm) water or deionized water as regenerator; Regenerator passes through resin bed; The zinc complex anion of exchange on strongly basic anion exchange resin in the step (B) eluted, form the aqueous solution that contains zinc chloride, can directly use as the soldering flux sub product; The service temperature of regenerative process is 5-40 ℃, and working flow is 0.5-2.0BV/h.
2. a kind of method of comprehensive utilization that contains zinc abraum salt acid according to claim 1 is characterized in that: in the step (B), strongly basic anion exchange resin is to be skeleton with vinylbenzene-divinyl interpolymer, and specific surface area is 27-500 m
2/ g, the exchange capacity that contains Trimethylamine 99, triethylamine, Tributylamine, pyrimidyl, pyridyl, pyranyl, dimethyl propanol amine, methyldiethanolamine or dioctyl thanomin group is the resin of 0.5-4.5 mmol/g.
3. a kind of method of comprehensive utilization that contains the acid of zinc abraum salt according to claim 2, it is characterized in that: the strongly basic anion exchange resin in the step (B) is D201, or 201 * 4, or 201 * 7; Or 202 * II, or D296, or NDA900, or NDA96; Or NDA1106, or the NDA1107 resin, or Amberlite IRA-900; Or Amberlite IRA-96, or Amberlite IRA-400, or Duolite A-101D resin.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105696010A (en) * | 2016-01-12 | 2016-06-22 | 惠州市斯瑞尔环境化工有限公司 | Method for recycling iron and zinc containing waste hydrochloric acid solution |
| CN109897967A (en) * | 2019-04-01 | 2019-06-18 | 中南大学 | A method of separating and recovering zinc from complicated chloride system |
| CN110117043A (en) * | 2019-05-09 | 2019-08-13 | 江苏南大环保科技有限公司 | A kind of regeneration method for the method and resin removing heavy metal ions in wastewater using ion exchange resin |
| CN110841331A (en) * | 2019-10-23 | 2020-02-28 | 江苏永葆环保科技有限公司 | Method for separating iron and zinc in iron-containing waste acid |
| CN111495024A (en) * | 2020-04-30 | 2020-08-07 | 南京金环生物技术有限公司 | Resource recycling method of waste pickling tank liquor in aluminum alloy hub pickling |
| CN113651365A (en) * | 2021-09-16 | 2021-11-16 | 徐州美利圆环保科技有限公司 | Hot galvanizing pickling waste hydrochloric acid-containing liquid resource utilization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105696010A (en) * | 2016-01-12 | 2016-06-22 | 惠州市斯瑞尔环境化工有限公司 | Method for recycling iron and zinc containing waste hydrochloric acid solution |
| CN105696010B (en) * | 2016-01-12 | 2018-07-06 | 惠州市斯瑞尔环境化工有限公司 | A kind of recoverying and utilizing method of iron content abraum salt containing zinc acid solution |
| CN109897967A (en) * | 2019-04-01 | 2019-06-18 | 中南大学 | A method of separating and recovering zinc from complicated chloride system |
| CN109897967B (en) * | 2019-04-01 | 2020-04-21 | 中南大学 | Method for separating and recovering zinc from complex chloride system |
| CN110117043A (en) * | 2019-05-09 | 2019-08-13 | 江苏南大环保科技有限公司 | A kind of regeneration method for the method and resin removing heavy metal ions in wastewater using ion exchange resin |
| CN110841331A (en) * | 2019-10-23 | 2020-02-28 | 江苏永葆环保科技有限公司 | Method for separating iron and zinc in iron-containing waste acid |
| CN110841331B (en) * | 2019-10-23 | 2021-02-09 | 江苏永葆环保科技有限公司 | Method for separating iron and zinc in iron-containing waste acid |
| CN111495024A (en) * | 2020-04-30 | 2020-08-07 | 南京金环生物技术有限公司 | Resource recycling method of waste pickling tank liquor in aluminum alloy hub pickling |
| CN113651365A (en) * | 2021-09-16 | 2021-11-16 | 徐州美利圆环保科技有限公司 | Hot galvanizing pickling waste hydrochloric acid-containing liquid resource utilization method |
| CN115321641A (en) * | 2022-08-01 | 2022-11-11 | 福建坚石电力线路器材有限公司 | Process for separating zinc ions in waste pickle liquor by multistage countercurrent ion exchange |
| CN115318346A (en) * | 2022-08-01 | 2022-11-11 | 福建坚石电力线路器材有限公司 | Multi-stage countercurrent exchange absorption and desorption combined process |
| CN115321641B (en) * | 2022-08-01 | 2024-03-12 | 福建坚石电力线路器材有限公司 | Process for separating zinc ions in waste acid washing liquid by multistage countercurrent ion exchange |
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