CN1544347A - Processing method of cupric ion of phthalocyanine green waste water using 335 type alkalescence anion resin - Google Patents
Processing method of cupric ion of phthalocyanine green waste water using 335 type alkalescence anion resin Download PDFInfo
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- CN1544347A CN1544347A CNA2003101063442A CN200310106344A CN1544347A CN 1544347 A CN1544347 A CN 1544347A CN A2003101063442 A CNA2003101063442 A CN A2003101063442A CN 200310106344 A CN200310106344 A CN 200310106344A CN 1544347 A CN1544347 A CN 1544347A
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- exchange resin
- weak base
- base anion
- water
- flow velocity
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- 239000002351 wastewater Substances 0.000 title claims abstract description 89
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 54
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011347 resin Substances 0.000 title claims abstract description 39
- 229920005989 resin Polymers 0.000 title claims abstract description 39
- 150000001450 anions Chemical class 0.000 title 1
- 238000003672 processing method Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 194
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 120
- 229910001868 water Inorganic materials 0.000 claims abstract description 119
- 239000008367 deionised water Substances 0.000 claims abstract description 83
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 75
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 70
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 51
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 108
- 238000001179 sorption measurement Methods 0.000 claims description 81
- 238000004519 manufacturing process Methods 0.000 claims description 48
- 238000004140 cleaning Methods 0.000 claims description 37
- 230000007704 transition Effects 0.000 claims description 33
- 238000003795 desorption Methods 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 27
- 238000002203 pretreatment Methods 0.000 claims description 25
- 229920006395 saturated elastomer Polymers 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 238000004065 wastewater treatment Methods 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract description 47
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 83
- 239000000243 solution Substances 0.000 description 22
- 238000007599 discharging Methods 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum ion Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
A process for treat copper in phthalocyanine green waste water by using type 335 weak alkaline anion exchange resin comprising, pre-processing the type 335 weak alkaline anion exchange resin, placing the type 335 weak alkaline anion exchange resin into adsorbing column, flowing dilute hydrochloric acid through adsorbing column containing the type 335 alkaline anion exchange resin at a low flow rate, rinsing the resin column with water or deionized water, processing the resin column by weak alkaline liquor with low flow rate, finally rinsing the resin column with water or deionized water until water exhibits weak alkalinity, adjusting the pH of phthalocyanine green waste water, making it pass through the pretreated ion exchange resin at a low flow rate, controlling the processing temperature and passing through another ion exchange resin adsorbing column. The process can substantially remove the copper ions in the phthalocyanine green waste water.
Description
Technical field
The present invention relates to a kind of wastewater treatment method of producing phthalocyanine green pigment, specifically a kind of usefulness 335 type weak base anion-exchange resins are handled the method for cupric ion in the wastewater from phthalocyanine green production.
Background technology
Phthalocyanine green is an industrial application pigment very widely, produce the strongly acid wastewater that contains high density copper, aluminium, chlorine in a large number in its production process, industrial treatment scheme is that waste water is neutralized with alkaline matters such as lime at present, remove wherein copper and aluminum ion, dilute with water is eliminated the influence of chlorion to follow-up biochemical treatment afterwards.Certainly will produce the waste residue of a large amount of metal hydroxide-containing in this technology, metallics wherein can form potential to its ecotope of stacking ground and threaten.
The inorganic flocculating agent polymerize aluminum chloride is a kind of inorganic polymer flocculant of developing in recent years, and contain a large amount of compositions of producing this flocculation agent in the wastewater from phthalocyanine green production, just can carry out but cupric ion wherein must be removed when preparing the inorganic flocculating agent polymerize aluminum chloride with phthalocyanine green.Both can not remove cupric ion in the wastewater from phthalocyanine green production and directly discharging and still have at present, the wastewater from phthalocyanine green production cupric ion that can utilize wastewater from phthalocyanine green production to prepare flocculation agent is again removed effective ways.
Summary of the invention
The purpose of this invention is to provide a kind of employing 335 type weak base anion-exchange resins and handle wastewater from phthalocyanine green production, and the cupric ion of inciting somebody to action wherein reclaims, waste water after the processing can prepare the method for inorganic macromolecule flocculant poly aluminum chloride or the direct discharging in dilution back, thereby reaches the purpose of administering waste water and realizing resource utilization.
Technical scheme of the present invention is:
A kind of usefulness 335 type weak base anion-exchange resins are handled the method for copper in the wastewater from phthalocyanine green production, are divided into for three steps to carry out, and it is characterized in that:
(1) 335 type weak base anion-exchange resins is carried out pre-treatment: select for use 335 type weak base anion-exchange resins to put into adsorption column, flow through with low flow velocity with dilute hydrochloric acid then the adsorption column of 335 type basic anion exchange resins is housed, handle the back water and clean this resin column, handle this resin column with sig water with low flow velocity then, last water cleans this resin column and is weakly alkaline until water outlet, promptly gets the OH type weak base anion-exchange resin behind the 335 type ion exchange resin conversions; At least answer the OH type weak base anion-exchange resin post behind the 335 type ion exchange resin conversions of pre-treatment more than two, use in order to series connection.
(2) wastewater treatment: make 335 type weak base anion-exchange resin posts after wastewater from phthalocyanine green production makes the transition by above-mentioned pre-treatment with low flow velocity, and treatment temp is controlled between the normal temperature to 50 ℃, waste water after this resin column is handled is 335 type weak base anion-exchange resin posts after another one is equipped with pre-treatment transition equally again, can make copper ion concentration in the wastewater from phthalocyanine green production satisfy secondary standard in " integrated wastewater discharge standard GB8978-1996 "; In order to save cost, the recycling resin also can carry out the desorption and the regeneration of following ion exchange resin to above-mentioned resin saturated after the wastewater treatment.
(3) desorption of saturated ion exchange resin column and regeneration: water cleans 335 saturated type weak base anion-exchange resin posts, to remove residual waste water in the ion exchange resin column, afterwards with in the hydrochloric acid of concentration be under the condition of normal temperature to 50 ℃ cupric ion to be carried out desorption in temperature, being about to the cupric ion of absorption exchange on ion exchange resin column removes substantially, water cleans this ion exchange resin column again, handle this ion exchange resin column with sig water then, last water cleans this ion exchange resin column and is weakly alkaline until water outlet, adsorb the cupric ion desorption that exchanges on the previous 335 saturated type weak base anion-exchange resin posts this moment and finish, and this 335 type weak base anion-exchange resin has made the transition to OH type weak base anion-exchange resin so that reuse next time.
The preferred plan that 335 type weak base anion-exchange resins of the present invention carry out pretreatment process is: select for use 335 type weak base anion-exchange resins to put into adsorption column, use then and be mixed with 2～6% dilute hydrochloric acid solution by analytical pure hydrochloric acid and water (preferably using deionized water), flow through with the flow velocity of 4～6BV/h the adsorption column of 335 type basic anion exchange resins is housed, the processing volume is 3～6BV, back water (preferably using deionized water) cleans this resin column, the cleaning flow velocity is 6～8BV/h, the cleaning volume is 4～6BV, use the volume of handling this resin column 3～4BV by 2～6%NaOH dilute alkaline soln of analytical pure NaOH and water (or deionized water) preparation with 4～6BV/h flow velocity then, last water (or deionized water) cleans this resin column with the flow velocity of 6～8BV/h and is weakly alkaline until water outlet, promptly gets the OH type weak base anion-exchange resin of 335 type ion exchange resin conversions.
The preferred plan of wastewater treatment of the present invention is: with pH less than 4 the wastewater from phthalocyanine green production of (the pH value of the wastewater from phthalocyanine green production of general industry discharging is about 1.5) with the flow velocity of 1BV/h～6BV/h, under 45～50 ℃ of temperature by 335 type weak base anion-exchange resin posts after pre-treatment transition, 335 type weak base anion-exchange resin posts after another one is equipped with pre-treatment transition equally again, cupric ion in the wastewater from phthalocyanine green production can be removed substantially, be made the secondary standard in the copper ion concentration satisfied " integrated wastewater discharge standard GB8978-1996 " in the wastewater from phthalocyanine green production.
The saturated ion exchange resin column desorption and the regenerated best approach of the present invention is: water or deionized water clean 335 saturated type weak base anion-exchange resin posts with the flow velocity of 4～8BV/h, the cleaning volume is 2～10BV, to remove residual waste water in the resin column, use then by the preparation of analytical pure hydrochloric acid and water (preferably using deionized water) 8%～14% in the concentration hydrochloric acid soln, in temperature is normal temperature to 50 ℃, flow velocity is under the condition of 1BV/h～4BV/h cupric ion to be carried out desorption, water or deionized water clean this ion exchange resin column with the flow velocity of 6～8BV/h again, the cleaning volume is 4～6BV, use again by 2～6%NaOH dilute alkaline soln of analytical pure NaOH and water (preferably using deionized water) preparation and handle this ion exchange resin column, flow velocity is 4～6BV/h, the processing volume is 3～4BV, last water or deionized water clean this ion exchange resin column with the flow velocity of 6～8BV/h and are weakly alkaline until water outlet, the cupric ion of absorption exchange is that desorption is finished on the 335 before saturated type weak base anion-exchange resin posts, and this 335 type weak base anion-exchange resin has made the transition to OH type weak base anion-exchange resin so that reuse next time.
Beneficial effect of the present invention:
1, the present invention utilizes 335 type weak base anion-exchange resins to remove the dual purpose that cupric ion in the wastewater from phthalocyanine green production has realized that wastewater treatment and resource reclaim, and it is simple to have technology, and equipment all can adopt conventional equipment, less investment, the characteristics of instant effect.
2, utilize that 335 type weak base anion-exchange resins single-column under more excellent condition can be handled about 20BV, the twin columns series connection can handle the wastewater from phthalocyanine green production about 60BV; and concentration one step that makes the water outlet cupric ion reaches or is lower than secondary standard in " integrated wastewater discharge standard GB8978-1996 "; reduced pollution, helped protecting environment environment.
3, the waste water after 335 type weak base anion-exchange resins are handled is for next step has created favourable condition by certain prepared flocculant of polymeric aluminium chloride.
4, the cupric ion after concentrating can reclaim, and its cycles of concentration can reach more than 15 times, has increased the economic benefit of original undertaking.
5,335 type weak base anion-exchange resin life cycles are long and reusable among the present invention, and it is low to have processing cost, can realize the characteristics of resource utilization
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Illustrate:
BV: be meant that in plastic resin treatment waste water generally adopt dynamichandling, promptly resin device is in adsorption column, waste water is handled from top to bottom, and the volume of resin is the i.e. BV of a bed volume in the adsorption column and be contained in.
BV/h: be meant per hour BV flow velocity.
Embodiment 1.
Get 335 weak base anion-exchange resins that 10ml dispatches from the factory and pack in the outer adsorption column that heating jacket arranged that (the adsorption column diameter is 1.5cm into, height is 25cm), use 2% dilute hydrochloric acid solution that is mixed with by analytical pure hydrochloric acid and water or deionized water then, flow through with the flow velocity of 2BV/h the adsorption column of 335 type basic anion exchange resins is housed, the processing volume is 3BV, this adsorption column of back water or washed with de-ionized water, the cleaning flow velocity is 6BV/h, the cleaning volume is 4BV, use then by the 2%NaOH sig water solution of analytical pure NaOH and water or deionized water preparation and handle this resin column with the 4BV/h flow velocity, the processing volume is 3BV, use deionized water (or clear water) to clean this adsorption column at last and be weakly alkaline, promptly get the OH type weak base anion-exchange resin of 335 type ion exchange resin conversions until water outlet with the flow velocity of 6BV/h.
The pH value is 1.5 wastewater from phthalocyanine green production of (the pH value of the wastewater from phthalocyanine green production of general industry discharging is about 1.5) is with the flow velocity of 1BV/h, 335 type weak base anion-exchange resin single-columns after making the transition by pre-treatment under 45 ℃ of temperature, the adsorption column of 335 type weak base anion-exchange resins after pre-treatment makes the transition is housed equally through another one again, cupric ion in the wastewater from phthalocyanine green production can be removed substantially, be made the secondary standard in the copper ion concentration satisfied " integrated wastewater discharge standard GB8978-1996 " in the waste water.Water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 4BV/h then, the cleaning volume is 3BV, to remove residual waste water in the resin column, use then by the preparation of analytical pure hydrochloric acid and deionized water 8% in the concentration hydrochloric acid soln, 25 ℃ of temperature, flow velocity is under the condition of 1BV/h cupric ion to be carried out desorption, water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 6BV/h again, the cleaning volume is 4BV, use 2%NaOH sig water solution again by analytical pure NaOH and water or deionized water preparation, be to handle this ion exchange resin adsorption column under the condition of 4BV/h at flow velocity, the processing volume is 3BV, last water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 6BV/h and are weakly alkaline until water outlet, the cupric ion of absorption exchange is that desorption is finished on the 335 before saturated type weak base anion-exchange resin posts, and this 335 type weak base anion-exchange resin has made the transition to OH type weak base anion-exchange resin so that reuse next time.
Embodiment 2.
Get 335 weak base anion-exchange resins that 10ml dispatches from the factory and pack in the outer adsorption column that heating jacket arranged that (the adsorption column diameter is 1.5cm into, height is 25cm), use 3% dilute hydrochloric acid solution that is mixed with by analytical pure hydrochloric acid and water or deionized water then, flow through with the flow velocity of 3BV/h the adsorption column of 335 type basic anion exchange resins is housed, the processing volume is 4BV, this adsorption column of back water or washed with de-ionized water, the cleaning flow velocity is 6BV/h, the cleaning volume is 5BV, use then by the 3%NaOH sig water solution of analytical pure NaOH and water or deionized water preparation and handle this resin column with the 4BV/h flow velocity, the processing volume is 4BV, use deionized water (or clear water) to clean this adsorption column at last and be weakly alkaline, promptly get the OH type weak base anion-exchange resin of 335 type ion exchange resin conversions until water outlet with the flow velocity of 7BV/h.
It is 2 (the pH value of the wastewater from phthalocyanine green production of general industry discharging is about 1.5) that wastewater from phthalocyanine green production is regulated the pH value, make it with 2BV/h flow velocity, under 50 ℃ of temperature by 335 type weak base anion-exchange resin single-columns after pre-treatment transition, the adsorption column of 335 type weak base anion-exchange resins after pre-treatment makes the transition is housed equally through another one again, cupric ion in the wastewater from phthalocyanine green production can be removed substantially, be made the secondary standard in the copper ion concentration satisfied " integrated wastewater discharge standard GB8978-1996 " in the waste water.Water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 5BV/h then, the cleaning volume is 4BV, to remove residual waste water in the resin column, use then by the preparation of analytical pure hydrochloric acid and deionized water 9% in the concentration hydrochloric acid soln, 30 ℃ of temperature, flow velocity is under the condition of 2BV/h cupric ion to be carried out desorption, water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 7BV/h again, the cleaning volume is 5BV, use 3%NaOH sig water solution again by analytical pure NaOH and water or deionized water preparation, be to handle this ion exchange resin adsorption column under the condition of 5BV/h at flow velocity, the processing volume is 3BV, last water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 7BV/h and are weakly alkaline until water outlet, the cupric ion of absorption exchange is that desorption is finished on the 335 before saturated type weak base anion-exchange resin posts, and this 335 type weak base anion-exchange resin has made the transition to OH type weak base anion-exchange resin so that reuse next time.
Embodiment 3.
Get 335 weak base anion-exchange resins that 10ml dispatches from the factory and pack in the outer adsorption column that heating jacket arranged that (the adsorption column diameter is 1.5cm into, height is 25cm), use 3.5% dilute hydrochloric acid solution that is mixed with by analytical pure hydrochloric acid and water or deionized water then, flow through with the flow velocity of 4BV/h the adsorption column of 335 type basic anion exchange resins is housed, the processing volume is 5BV, this adsorption column of back water or washed with de-ionized water, the cleaning flow velocity is 8BV/h, the cleaning volume is 5BV, use then by the 4%NaOH sig water solution of analytical pure NaOH and water or deionized water preparation and handle this resin column with the 6BV/h flow velocity, the processing volume is 4BV, use deionized water (or clear water) to clean this adsorption column at last and be weakly alkaline, promptly get the OH type weak base anion-exchange resin of 335 type ion exchange resin conversions until water outlet with the flow velocity of 8BV/h.
It is 3 (the pH value of the wastewater from phthalocyanine green production of general industry discharging is about 1.5) that wastewater from phthalocyanine green production is regulated the pH value, make it with 3BV/h flow velocity, under 50 ℃ of temperature by 335 type weak base anion-exchange resin single-columns after pre-treatment transition, the adsorption column of 335 type weak base anion-exchange resins after pre-treatment makes the transition is housed equally through another one again, cupric ion in the wastewater from phthalocyanine green production can be removed substantially, be made the secondary standard in the copper ion concentration satisfied " integrated wastewater discharge standard GB8978-1996 " in the waste water.Water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 6BV/h then, the cleaning volume is 6BV, to remove residual waste water in the resin column, use then by the preparation of analytical pure hydrochloric acid and deionized water 10% in the concentration hydrochloric acid soln, 35 ℃ of temperature, flow velocity is under the condition of 3BV/h cupric ion to be carried out desorption, water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 8BV/h again, the cleaning volume is 6BV, use 4%NaOH sig water solution again by analytical pure NaOH and water or deionized water preparation, be to handle this ion exchange resin adsorption column under the condition of 6BV/h at flow velocity, the processing volume is 3BV, last water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 8BV/h and are weakly alkaline until water outlet, the cupric ion of absorption exchange is that desorption is finished on the 335 before saturated type weak base anion-exchange resin posts, and this 335 type weak base anion-exchange resin has made the transition to OH type weak base anion-exchange resin so that reuse next time.
Embodiment 4.
Get 335 weak base anion-exchange resins that 10ml dispatches from the factory and pack in the outer adsorption column that heating jacket arranged that (the adsorption column diameter is 1.5cm into, height is 25cm), use 4% dilute hydrochloric acid solution that is mixed with by analytical pure hydrochloric acid and water or deionized water then, flow through with the flow velocity of 4BV/h the adsorption column of 335 type basic anion exchange resins is housed, the processing volume is 3BV, this adsorption column of back water or washed with de-ionized water, the cleaning flow velocity is 7BV/h, the cleaning volume is 4BV, use then by the 4.5%NaOH sig water solution of analytical pure NaOH and water or deionized water preparation and handle this resin column with the 5BV/h flow velocity, the processing volume is 3BV, use deionized water (or clear water) to clean this adsorption column at last and be weakly alkaline, promptly get the OH type weak base anion-exchange resin of 335 type ion exchange resin conversions until water outlet with the flow velocity of 6BV/h.
It is 2.5 (the pH value of the wastewater from phthalocyanine green production of general industry discharging is about 1.5) that wastewater from phthalocyanine green production is regulated the pH value, make it with 4BV/h flow velocity, under 45 ℃ of temperature by 335 type weak base anion-exchange resin single-columns after pre-treatment transition, the adsorption column of 335 type weak base anion-exchange resins after pre-treatment makes the transition is housed equally through another one again, cupric ion in the wastewater from phthalocyanine green production can be removed substantially, be made the secondary standard in the copper ion concentration satisfied " integrated wastewater discharge standard GB8978-1996 " in the waste water.Water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 7BV/h then, the cleaning volume is 8BV, to remove residual waste water in the resin column, use then by the preparation of analytical pure hydrochloric acid and deionized water 11% in the concentration hydrochloric acid soln, 40 ℃ of temperature, flow velocity is under the condition of 3BV/h cupric ion to be carried out desorption, water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 6BV/h again, the cleaning volume is 5BV, use 3%NaOH sig water solution again by analytical pure NaOH and water or deionized water preparation, be to handle this ion exchange resin adsorption column under the condition of 4BV/h at flow velocity, the processing volume is 4BV, last water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 6BV/h and are weakly alkaline until water outlet, the cupric ion of absorption exchange is that desorption is finished on the 335 before saturated type weak base anion-exchange resin posts, and this 335 type weak base anion-exchange resin has made the transition to OH type weak base anion-exchange resin so that reuse next time.
Embodiment 5.
Get 335 weak base anion-exchange resins that 10ml dispatches from the factory and pack in the outer adsorption column that heating jacket arranged that (the adsorption column diameter is 1.5cm into, height is 25cm), use 4.5% dilute hydrochloric acid solution that is mixed with by analytical pure hydrochloric acid and water or deionized water then, flow through with the flow velocity of 5BV/h the adsorption column of 335 type basic anion exchange resins is housed, the processing volume is 4BV, this adsorption column of back water or washed with de-ionized water, the cleaning flow velocity is 7BV/h, the cleaning volume is 5BV, use then by the 5%NaOH sig water solution of analytical pure NaOH and water or deionized water preparation and handle this resin column with the 5BV/h flow velocity, the processing volume is 4BV, use deionized water (or tap water) to clean this adsorption column at last and be weakly alkaline, promptly get the OH type weak base anion-exchange resin of 335 type ion exchange resin conversions until water outlet with the flow velocity of 7BV/h.
It is 3.5 (the pH value of the wastewater from phthalocyanine green production of general industry discharging is about 1.5) that wastewater from phthalocyanine green production is regulated the pH value, make it with 3BV/h flow velocity, under 45 ℃ of temperature by 335 type weak base anion-exchange resin single-columns after pre-treatment transition, the adsorption column of 335 type weak base anion-exchange resins after pre-treatment makes the transition is housed equally through another one again, cupric ion in the wastewater from phthalocyanine green production can be removed substantially, be made the secondary standard in the copper ion concentration satisfied " integrated wastewater discharge standard GB8978-1996 " in the waste water.Water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 5BV/h then, the cleaning volume is 5BV, to remove residual waste water in the resin column, use then by the preparation of analytical pure hydrochloric acid and deionized water 12% in the concentration hydrochloric acid soln, 45 ℃ of temperature, flow velocity is under the condition of 1BV/h cupric ion to be carried out desorption, water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 7BV/h again, the cleaning volume is 5BV, use 5%NaOH sig water solution again by analytical pure NaOH and water or deionized water preparation, be to handle this ion exchange resin adsorption column under the condition of 5BV/h at flow velocity, the processing volume is 4BV, last water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 8BV/h and are weakly alkaline until water outlet, the cupric ion of absorption exchange is that desorption is finished on the 335 before saturated type weak base anion-exchange resin posts, and this 335 type weak base anion-exchange resin has made the transition to OH type weak base anion-exchange resin so that reuse next time.
Embodiment 6.
Get 335 weak base anion-exchange resins that 10ml dispatches from the factory and pack in the outer adsorption column that heating jacket arranged that (the adsorption column diameter is 1.5cm into, height is 25cm), use 5% dilute hydrochloric acid solution that is mixed with by analytical pure hydrochloric acid and water or deionized water then, flow through with the flow velocity of 5BV/h the adsorption column of 335 type basic anion exchange resins is housed, the processing volume is 5BV, this adsorption column of back water or washed with de-ionized water, the cleaning flow velocity is 7BV/h, the cleaning volume is 6BV, use then by the 5.5%NaOH sig water solution of analytical pure NaOH and water or deionized water preparation and handle this resin column with the 5BV/h flow velocity, the processing volume is 4BV, use deionized water (or clear water) to clean this adsorption column at last and be weakly alkaline, promptly get the OH type weak base anion-exchange resin of 335 type ion exchange resin conversions until water outlet with the flow velocity of 7BV/h.
It is 4 (the pH value of the wastewater from phthalocyanine green production of general industry discharging is about 1.5) that wastewater from phthalocyanine green production is regulated the pH value, make it with 5BV/h flow velocity, under 50 ℃ of temperature by 335 type weak base anion-exchange resin single-columns after pre-treatment transition, the adsorption column of 335 type weak base anion-exchange resins after pre-treatment makes the transition is housed equally through another one again, cupric ion in the wastewater from phthalocyanine green production can be removed substantially, be made the secondary standard in the copper ion concentration satisfied " integrated wastewater discharge standard GB8978-1996 " in the waste water.Water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 4BV/h then, the cleaning volume is 7BV, to remove residual waste water in the resin column, use then by the preparation of analytical pure hydrochloric acid and deionized water 13% in the concentration hydrochloric acid soln, 50 ℃ of temperature, flow velocity is under the condition of 3BV/h cupric ion to be carried out desorption, water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 7BV/h again, the cleaning volume is 5BV, use 5%NaOH sig water solution again by analytical pure NaOH and water or deionized water preparation, be to handle this ion exchange resin adsorption column under the condition of 5BV/h at flow velocity, the processing volume is 4BV, last water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 8BV/h and are weakly alkaline until water outlet, the cupric ion of absorption exchange is that desorption is finished on the 335 before saturated type weak base anion-exchange resin posts, and this 335 type weak base anion-exchange resin has made the transition to OH type weak base anion-exchange resin so that reuse next time.
Embodiment 7.
Get 335 weak base anion-exchange resins that 10ml dispatches from the factory and pack in the outer adsorption column that heating jacket arranged that (the adsorption column diameter is 1.5cm into, height is 25cm), use 6% dilute hydrochloric acid solution that is mixed with by analytical pure hydrochloric acid and water or deionized water then, flow through with the flow velocity of 6BV/h the adsorption column of 335 type basic anion exchange resins is housed, the processing volume is 6BV, this adsorption column of back water or washed with de-ionized water, the cleaning flow velocity is 8BV/h, the cleaning volume is 6BV, use then by the 6%NaOH sig water solution of analytical pure NaOH and water or deionized water preparation and handle this resin column with the 6BV/h flow velocity, the processing volume is 4BV, use deionized water (or clear water) to clean this adsorption column at last and be weakly alkaline, promptly get the OH type weak base anion-exchange resin of 335 type ion exchange resin conversions until water outlet with the flow velocity of 8BV/h.
It is 4 (the pH value of the wastewater from phthalocyanine green production of general industry discharging is about 1.5) that wastewater from phthalocyanine green production is regulated the pH value, make it with 6BV/h flow velocity, under 50 ℃ of temperature by 335 type weak base anion-exchange resin single-columns after pre-treatment transition, the adsorption column of 335 type weak base anion-exchange resins after pre-treatment makes the transition is housed equally through another one again, cupric ion in the wastewater from phthalocyanine green production can be removed substantially, be made the secondary standard in the copper ion concentration satisfied " integrated wastewater discharge standard GB8978-1996 " in the waste water.Water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 8BV/h then, the cleaning volume is 10BV, to remove residual waste water in the resin column, use then by the preparation of analytical pure hydrochloric acid and deionized water 14% in the concentration hydrochloric acid soln, 50 ℃ of temperature, flow velocity is under the condition of 4BV/h cupric ion to be carried out desorption, water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 8BV/h again, the cleaning volume is 6BV, use 6%NaOH sig water solution again by analytical pure NaOH and water or deionized water preparation, be to handle this ion exchange resin adsorption column under the condition of 6BV/h at flow velocity, the processing volume is 4BV, last water or deionized water clean this ion exchange resin adsorption column with the flow velocity of 8BV/h and are weakly alkaline until water outlet, the cupric ion of absorption exchange is that desorption is finished on the 335 before saturated type weak base anion-exchange resin posts, and this 335 type weak base anion-exchange resin has made the transition to OH type weak base anion-exchange resin so that reuse next time.
Claims (4)
1, a kind of usefulness 335 type weak base anion-exchange resins are handled the method for copper in the wastewater from phthalocyanine green production, it is characterized in that:
(1) 335 type weak base anion-exchange resins is carried out pre-treatment: select for use 335 type weak base anion-exchange resins to put into adsorption column, flow through with low flow velocity with dilute hydrochloric acid then the adsorption column of 335 type weak base anion-exchange resins is housed, water cleans this resin column afterwards, handle this resin column with sig water with low flow velocity then, last water cleans this resin column and is weakly alkaline until water outlet, promptly gets the OH type weak base anion-exchange resin behind the 335 type ion exchange resin conversions;
(2) wastewater treatment: make 335 type weak base anion-exchange resin posts after wastewater from phthalocyanine green production makes the transition by above-mentioned pre-treatment with low flow velocity, and treatment temp is controlled between the normal temperature to 50 ℃, waste water after this resin column is handled is 335 type weak base anion-exchange resin posts after another one is equipped with pre-treatment transition equally again, can make the concentration of cupric ion in the wastewater from phthalocyanine green production after the processing satisfy secondary standard in " integrated wastewater discharge standard GB8978-1996 ";
(3) desorption of saturated ion exchange resin column and regeneration: water cleans 335 saturated type weak base anion-exchange resin posts, to remove residual waste water in the ion exchange resin column, afterwards with in the hydrochloric acid of concentration be under the condition of normal temperature to 50 ℃ cupric ion to be carried out desorption in temperature, being about to the cupric ion of absorption exchange on ion exchange resin column removes substantially, water cleans this ion exchange resin column again, handle this ion exchange resin column with sig water then, last water cleans this ion exchange resin column and is weakly alkaline until water outlet, adsorb the cupric ion desorption that exchanges on the previous 335 saturated type weak base anion-exchange resin posts this moment and finish, and this 335 type weak base anion-exchange resin has made the transition to OH type weak base anion-exchange resin so that reuse next time.
2, usefulness 335 type weak base anion-exchange resins according to claim 1 are handled the method for copper in the wastewater from phthalocyanine green production, it is characterized in that 335 type weak base anion-exchange resins carry out pretreated method and are: select for use 335 type weak base anion-exchange resins to put into adsorption column, use then and be mixed with 2～6% dilute hydrochloric acid solution by analytical pure hydrochloric acid and deionized water, flow through with the flow velocity of 2～6BV/h the adsorption column of 335 type basic anion exchange resins is housed, the processing volume is 3～6BV, back with this resin column of washed with de-ionized water, the cleaning flow velocity is 6～8BV/h, the cleaning volume is 4～6BV, use the volume of handling this resin column 3～4BV by 2～6%NaOH dilute alkaline soln of analytical pure NaOH and deionized water preparation with 4～6BV/h flow velocity then, clean this resin column with deionized water with the flow velocity of 6～8BV/h at last and be weakly alkaline, promptly get the OH type weak base anion-exchange resin of 335 type ion exchange resin conversions until water outlet.
3, usefulness 335 type weak base anion-exchange resins according to claim 1 are handled the method for copper in the wastewater from phthalocyanine green production, the method that it is characterized in that wastewater treatment is: with pH less than 4 wastewater from phthalocyanine green production flow velocity with 1BV/h～6BV/h, under 45～50 ℃ of temperature by 335 type weak base anion-exchange resin posts after pre-treatment transition, the adsorption column of 335 type weak base anion-exchange resins after pre-treatment makes the transition is housed equally through another one again, cupric ion in the wastewater from phthalocyanine green production can be removed substantially, be made the secondary standard in the copper ion concentration satisfied " integrated wastewater discharge standard GB8978-1996 " in the wastewater from phthalocyanine green production.
4, usefulness 335 type weak base anion-exchange resins according to claim 1 are handled the method for copper in the wastewater from phthalocyanine green production, it is characterized in that saturated ion exchange resin column desorption and regenerated method are: with the flow velocity cleaning saturated 335 type weak base anion-exchange resin posts of deionized water with 4～8BV/h, the cleaning volume is 3～10BV, to remove residual wastewater from phthalocyanine green production in the resin column, use then by the preparation of analytical pure hydrochloric acid and deionized water 8%～14% in the hydrochloric acid soln of concentration, in temperature is normal temperature to 50 ℃, flow velocity is under the condition of 1BV/h～4BV/h cupric ion to be carried out desorption, clean this ion exchange resin column with deionized water with the flow velocity of 6～8BV/h again, the cleaning volume is 4～6BV, use 2～6%NaOH dilute alkaline soln again by analytical pure NaOH and deionized water preparation, handle this exchange resin column with the flow velocity of 4～6BV/h, the processing volume is 3～4BV, clean this ion exchange resin column with deionized water with the flow velocity of 6～8BV/h at last and be weakly alkaline until water outlet, the cupric ion of absorption exchange is that desorption is finished on the 335 before saturated type weak base anion-exchange resin posts, and this 335 type weak base anion-exchange resin has made the transition to OH type weak base anion-exchange resin so that reuse next time.
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| CN200310106344.2A CN1253385C (en) | 2003-11-19 | 2003-11-19 | Processing method of cupric ion of phthalocyanine green waste water using 335 type alkalescence anion resin |
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| CN200310106344.2A CN1253385C (en) | 2003-11-19 | 2003-11-19 | Processing method of cupric ion of phthalocyanine green waste water using 335 type alkalescence anion resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348512C (en) * | 2005-12-06 | 2007-11-14 | 河北工业大学 | Technique for reclaiming ethylene alkali-washing waste liquid |
| CN101993386A (en) * | 2010-11-03 | 2011-03-30 | 天津大学 | Method for preparing electronic-grade N, N-dimethylformamide by ion exchange resin method |
| CN102285704A (en) * | 2010-07-30 | 2011-12-21 | 深圳东江华瑞科技有限公司 | Ion exchange resin arsenic removal method for acidic etching liquid, resin regeneration method and treatment system thereof |
-
2003
- 2003-11-19 CN CN200310106344.2A patent/CN1253385C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348512C (en) * | 2005-12-06 | 2007-11-14 | 河北工业大学 | Technique for reclaiming ethylene alkali-washing waste liquid |
| CN102285704A (en) * | 2010-07-30 | 2011-12-21 | 深圳东江华瑞科技有限公司 | Ion exchange resin arsenic removal method for acidic etching liquid, resin regeneration method and treatment system thereof |
| CN102285704B (en) * | 2010-07-30 | 2013-07-03 | 深圳东江华瑞科技有限公司 | Ion exchange resin arsenic removal method for acidic etching liquid, resin regeneration method and treatment system thereof |
| CN101993386A (en) * | 2010-11-03 | 2011-03-30 | 天津大学 | Method for preparing electronic-grade N, N-dimethylformamide by ion exchange resin method |
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