CN1253386C - Polymeric aluminum chloride flocculant preparation method using phthalocyanine green waste water - Google Patents
Polymeric aluminum chloride flocculant preparation method using phthalocyanine green waste water Download PDFInfo
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- CN1253386C CN1253386C CN200310106345.7A CN200310106345A CN1253386C CN 1253386 C CN1253386 C CN 1253386C CN 200310106345 A CN200310106345 A CN 200310106345A CN 1253386 C CN1253386 C CN 1253386C
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- exchange resin
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- base anion
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- 239000002351 wastewater Substances 0.000 title claims abstract description 137
- 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 74
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 179
- 229910001868 water Inorganic materials 0.000 claims abstract description 112
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 107
- 239000008367 deionised water Substances 0.000 claims abstract description 88
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000011347 resin Substances 0.000 claims abstract description 70
- 229920005989 resin Polymers 0.000 claims abstract description 70
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 67
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000010438 heat treatment Methods 0.000 claims abstract description 43
- 239000000047 product Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 12
- 239000012263 liquid product Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 135
- 238000004519 manufacturing process Methods 0.000 claims description 68
- 238000001179 sorption measurement Methods 0.000 claims description 57
- 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 description 55
- 239000003456 ion exchange resin Substances 0.000 claims description 55
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 43
- 238000004140 cleaning Methods 0.000 claims description 34
- 238000003795 desorption Methods 0.000 claims description 33
- 230000007704 transition Effects 0.000 claims description 33
- 238000002203 pretreatment Methods 0.000 claims description 32
- 229920006395 saturated elastomer Polymers 0.000 claims description 32
- 238000011282 treatment Methods 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 239000012141 concentrate Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- 238000004065 wastewater treatment Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000000088 plastic resin Substances 0.000 claims description 3
- 238000009418 renovation Methods 0.000 claims 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract description 44
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract 1
- 230000003113 alkalizing effect Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 76
- 238000007599 discharging Methods 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- -1 aluminum ion Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The present invention relates to a preparation method of a polymeric aluminum chloride flocculant by phthalocyanine green waste water, which is characterized in that 335 type alkalescence anion exchange resin is selected and put in an adsorbing column; then, dilute hydrochloric acid flows through the adsorbing column; the resin column is washed with water or deionized water; then, the resin column is treated with diluted alkali solution; finally, the adsorbing column is washed with the water or the deionized water until outlet water has alkalescence; the pH value of phthalocyanine green waste water is adjusted so that the phthalocyanine green waste water passes through a pretreated and converted 335 type alkalescence anion exchange resin column at the temperature of ordinary temperature to 50 DEG C and passes through the other adsorbing column of the anion exchange resin for obtaining the phthalocyanine green waste water of which copper ion concentration satisfies a secondary standard in sewage comprehensive discharge standards; the phthalocyanine green waste water processed by the resin is concentrated; under the condition of stir and heating, an alkalizing agent is simultaneously added for a reaction; the waste water is adjusted to subacidity and continuously stirred for a heating reaction for obtaining a liquid product or a solid finished product of the present invention. The 335 type alkalescence anion exchange resin can also be desorbed and regenerated for recovering resources and repeatedly using the resin for saving treating cost. The preparation method realizes the purpose of waste utilization, and is favorable for environmental protection.
Description
Technical field
The present invention relates to a kind of preparation method of flocculant of polymeric aluminium chloride, specifically a kind of method for preparing flocculant of polymeric aluminium chloride with 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, at present also not by recycling.Flocculant of polymeric aluminium chloride is a kind of well behaved inorganic polymer flocculant.Its industrial preparation method mainly contains: metallic aluminium direct synthesis technique, aluminium hydroxide synthesis method, aluminum chloride preparation method, kamig process kamig, aluminium ore, clay are the preparation method of raw material.These several preparation methods compare the pH narrow range shortcomings such as (can only handle the waste water of pH in 4-10) that exists cost height, complex process, processing waste water with the present invention.
And contain the composition of a large amount of flocculant of polymeric aluminium chloride produced in the wastewater from phthalocyanine green production, take certain method that cupric ion is wherein removed, can utilize wherein aluminum ion, chlorion to prepare flocculant of polymeric aluminium chloride, but, the cupric ion in the wastewater from phthalocyanine green production still do not have method preferably because removing, so cause in handling in the present wastewater from phthalocyanine green production only is to adopt the way of routine to handle directly discharging of back, it is the serious wasting of resources, though directly discharge the requirement of regulation that to be up to state standards, but still can have a negative impact to environment.
Summary of the invention
The purpose of this invention is to provide a kind of preparation polymerize aluminum chloride required most of composition of agent of wadding a quilt with cotton with fixed attention that makes it to keep after by certain pretreatment process the cupric ion in the waste water being removed, the method for preparing flocculant of polymeric aluminium chloride then, the final purpose of realization utilization of waste material, optimizing network resource utilization.
Technical scheme of the present invention is:
A kind ofly prepare the method for flocculant of polymeric aluminium chloride, it is characterized in that with wastewater from phthalocyanine green production:
(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, handle back water or this resin column of washed with de-ionized water, handle this resin column with sig water with low flow velocity then, last water or this resin column of washed with de-ionized water are weakly alkaline until water outlet, promptly get 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 adsorption columns after another one is equipped with pre-treatment transition equally again, can obtain the wastewater from phthalocyanine green production that copper ion concentration satisfies the secondary standard in " integrated wastewater discharge standard GB8978-1996 ";
(3) will be concentrated into concentration ratio through the wastewater from phthalocyanine green production of above-mentioned plastic resin treatment between 10%～80%, wastewater from phthalocyanine green production after concentrating is added basifier carry out reacting by heating under agitation condition, regulate waste water and be slightly acidic, continue to stir and carry out reacting by heating, promptly obtain liquid product of the present invention; Also the aforesaid liquid finished product can be made after drying its solid finished product.
Preferred plan of the present invention is:
(1) 335 type weak base anion-exchange resins is carried out pre-treatment, its best approach 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 or deionized water, flow through with the flow velocity of 4～6BV/h the adsorption column of 335 type weak base anion-exchange resins is housed, the processing volume is 3～6BV, this resin column of water or 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 water or deionized water preparation with 4～6BV/h flow velocity then, last water or deionized water clean this resin column with the flow velocity of 6-8BV/h and are weakly alkaline until water outlet, promptly get the OH type weak base anion-exchange resin of 335 type ion exchange resin conversions.
(2) carry out wastewater treatment, its preferred plan is: with pH less than 4 wastewater from phthalocyanine green production 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, 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.
(3) will concentrate by following preferred plan through the wastewater from phthalocyanine green production of ion exchange resin treatment: adopt heating to concentrate or the spissated method of steam will to be concentrated into concentration ratio through the wastewater from phthalocyanine green production of ion exchange resin treatment be 25%-50%, to add concentration under agitation condition be 10%～100% sodium hydroxide or lime solution as the pH value of basifier adjusting waste water between 3～5 with the wastewater from phthalocyanine green production after concentrating, carry out reacting by heating simultaneously, after making it to be slightly acidic, continue to stir and carry out reacting by heating 1h-10h, the reacting by heating temperature is 30 ℃～100 ℃, promptly obtain liquid product of the present invention, also the aforesaid liquid finished product can be made after drying its solid finished product.
For saving cost, when the ion exchange resin column of handling waste water is saturated, can carry out desorption and regeneration, its method is: with 335 saturated type weak base anion-exchange resin posts of washed with de-ionized water, to remove residual waste water in the ion exchange resin column, be that the hydrochloric acid of the middle concentration of 8%-14% is under the condition of normal temperature to 50 ℃ cupric ion to be carried out desorption in temperature with concentration afterwards, being about to the cupric ion of absorption exchange on ion exchange resin column removes substantially, this ion exchange resin column of water or washed with de-ionized water again, handle this ion exchange resin column with sig water then, last water or this ion exchange resin column of washed with de-ionized water are 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 post has made the transition to OH type weak base anion-exchange resin so that reuse next time.
The desorption and the regenerated best approach are: 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 ion exchange resin column, use then by analytical pure hydrochloric acid and water or deionized water preparation 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 2～6%NaOH dilute alkaline soln again by analytical pure NaOH and water or deionized water preparation, be to handle this ion exchange resin column under the condition of 4～6BV/h at flow velocity, 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 post has made the transition to OH type weak base anion-exchange resin so that reuse next time.
Beneficial effect of the present invention:
1, utilizes the discarded composition in the wastewater from phthalocyanine green production to prepare flocculation agent, realized the purpose of utilization of waste material, have low, the advantage of simple technology of cost, improved resource utilization, reduced pollution, help environment protection environment.
2, both solved the difficult problem of phthalocyanine green pigment manufacturing enterprise wastewater treatment, and increased the new channel of extra earning again for it, and the equipment of handling usefulness is conventional equipment, need not big input can realize.
But 3, organic waste waters such as the flocculation agent extensive treatments oily(waste)water for preparing with the inventive method, dyeing waste water, slaughterhouse wastewater.
4, handle the pH value wide ranges of waste water with the flocculation agent of the inventive method preparation, tangible treatment effect is all arranged between 4～10.
5, handle waste water with the flocculation agent of the inventive method preparation and have that coagulation performance is good, flco is big, consumption is few, efficient is high, settling velocity is fast, applied widely, advantage such as chromaticity removing effect is good.
6, the liquid polymerization aluminum chloride flocculant ratio of extracting from wastewater from phthalocyanine green production with method provided by the invention has bigger prospects for commercial application up to more than 10%.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Relevant parameter declaration:
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.
Concentration ratio: certain amount of fluid is under heating or other condition, and volume reduces, and final remaining volume is concentration ratio with the ratio of original volume.
Embodiment 1.
With preparation double centner flocculant of polymeric aluminium chloride is example.
Resin pre-treatment: select for use 335 type weak base anion-exchange resins to put into adsorption column, use then and be mixed with 2% dilute hydrochloric acid solution by analytical pure hydrochloric acid and water or deionized water, 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 resin 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 dilute alkaline soln 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 resin 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.
Get the pH value of discharging in the phthalocyanine green production process of chemical plant, Jiangsu and be 1000 kilograms of (wastewater from phthalocyanine green production of preferably selecting for use absorption workshop section to discharge of waste water of 1.5, because the content of its cupric ion is the highest), flow velocity with 1BV/h, 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.
Adopt heating to concentrate or the spissated method of steam will to be concentrated into concentration ratio through the wastewater from phthalocyanine green production of ion exchange resin treatment be 10%, is 10% sodium hydroxide or lime solution with the wastewater from phthalocyanine green production after concentrating stirring, add under the condition of heating concentration, the pH value of regulating waste water is 3, continue to stir and carry out reacting by heating 1h afterwards, the reacting by heating temperature is 30 ℃, promptly obtain liquid product of the present invention, also the aforesaid liquid finished product can be made after drying its solid finished product.
For saving cost, when the ion exchange resin column of handling waste water is saturated, can carry out desorption and regeneration, its method is: water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 4BV/h, 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 washed with de-ionized water are cleaned this ion exchange resin 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 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 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.
With preparation double centner flocculant of polymeric aluminium chloride is example.
Resin pre-treatment: select for use 335 type weak base anion-exchange resins to put into adsorption column, use then and be mixed with 3% dilute hydrochloric acid solution by analytical pure hydrochloric acid and water or deionized water, 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 resin 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 dilute alkaline soln 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 resin 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.
Get 1000 kilograms of (wastewater from phthalocyanine green production of preferably selecting for use absorption workshop section to discharge of waste water of discharging in the phthalocyanine green production process of chemical plant, Jiangsu, because the content of its cupric ion is the highest), regulate its pH value to 2, flow velocity with 2BV/h, 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.
Adopt heating to concentrate or the spissated method of steam will to be concentrated into concentration ratio through the wastewater from phthalocyanine green production of ion exchange resin treatment be 25%, is 20% sodium hydroxide or lime solution with the wastewater from phthalocyanine green production after concentrating stirring, add under the condition of heating concentration, the pH value of regulating waste water is 3.5, continue to stir and carry out reacting by heating 3h afterwards, the reacting by heating temperature is 80 ℃, promptly obtain liquid product of the present invention, also the aforesaid liquid finished product can be made after drying its solid finished product.
For saving cost, when the ion exchange resin column of handling waste water is saturated, can carry out desorption and regeneration, its method is: water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 5BV/h, 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 washed with de-ionized water are cleaned this ion exchange resin 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 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 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.
With preparation double centner flocculant of polymeric aluminium chloride is example.
Resin pre-treatment: select for use 335 type weak base anion-exchange resins to put into adsorption column, use then and be mixed with 3.5% dilute hydrochloric acid solution by analytical pure hydrochloric acid and water or deionized water, 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 resin 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 dilute alkaline soln 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 resin 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.
Get 1000 kilograms of (wastewater from phthalocyanine green production of preferably selecting for use absorption workshop section to discharge of waste water of discharging in the phthalocyanine green production process of chemical plant, Jiangsu, because the content of its cupric ion is the highest), regulate its pH value to 3, flow velocity with 3BV/h, 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.
Adopt heating to concentrate or the spissated method of steam will to be concentrated into concentration ratio through the wastewater from phthalocyanine green production of ion exchange resin treatment be 40%, is 40% sodium hydroxide or lime solution with the wastewater from phthalocyanine green production after concentrating stirring, add under the condition of heating concentration, the pH value of regulating waste water is 4, continue to stir and carry out reacting by heating 5h afterwards, the reacting by heating temperature is 90 ℃, promptly obtain liquid product of the present invention, also the aforesaid liquid finished product can be made after drying its solid finished product.
For saving cost, when the ion exchange resin column of handling waste water is saturated, can carry out desorption and regeneration, its method is: water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 6BV/h, 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 washed with de-ionized water are cleaned this ion exchange resin 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 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 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.
With preparation double centner flocculant of polymeric aluminium chloride is example.
Resin pre-treatment: select for use 335 type weak base anion-exchange resins to put into adsorption column, use then and be mixed with 4% dilute hydrochloric acid solution by analytical pure hydrochloric acid and water or deionized water, 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 resin 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 dilute alkaline soln 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 resin 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.
Get 1000 kilograms of (wastewater from phthalocyanine green production of preferably selecting for use absorption workshop section to discharge of waste water of discharging in the phthalocyanine green production process of chemical plant, Jiangsu, because the content of its cupric ion is the highest), regulate its pH value to 2.5, flow velocity with 4BV/h, 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.
Adopt heating to concentrate or the spissated method of steam will to be concentrated into concentration ratio through the wastewater from phthalocyanine green production of ion exchange resin treatment be 50%, is 50% sodium hydroxide or lime solution with the wastewater from phthalocyanine green production after concentrating stirring, add under the condition of heating concentration, the pH value of regulating waste water is 4, continue to stir and carry out reacting by heating 7h afterwards, the reacting by heating temperature is 60 ℃, promptly obtain liquid product of the present invention, also the aforesaid liquid finished product can be made after drying its solid finished product.
For saving cost, when the ion exchange resin column of handling waste water is saturated, can carry out desorption and regeneration, its method is: water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 7BV/h, 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 washed with de-ionized water are cleaned this ion exchange resin 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 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 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.
With preparation double centner flocculant of polymeric aluminium chloride is example.
Resin pre-treatment: select for use 335 type weak base anion-exchange resins to put into adsorption column, use then and be mixed with 4.5% dilute hydrochloric acid solution by analytical pure hydrochloric acid and water or deionized water, 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 resin 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 dilute alkaline soln 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 resin 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.
Get 1000 kilograms of (wastewater from phthalocyanine green production of preferably selecting for use absorption workshop section to discharge of waste water of discharging in the phthalocyanine green production process of chemical plant, Jiangsu, because the content of its cupric ion is the highest), regulate its pH value to 3.5, flow velocity with 4BV/h, 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.
Adopt heating to concentrate or the spissated method of steam will to be concentrated into concentration ratio through the wastewater from phthalocyanine green production of ion exchange resin treatment be 60%, is 70% sodium hydroxide or lime solution with the wastewater from phthalocyanine green production after concentrating stirring, add under the condition of heating concentration, the pH value of regulating waste water is 4.5, continue to stir and carry out reacting by heating 8h afterwards, the reacting by heating temperature is 70 ℃, promptly obtain liquid product of the present invention, also the aforesaid liquid finished product can be made after drying its solid finished product.
For saving cost, when the ion exchange resin column of handling waste water is saturated, can carry out desorption and regeneration, its method is: water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 5BV/h, 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 washed with de-ionized water are cleaned this ion exchange resin 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 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 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.
With preparation double centner flocculant of polymeric aluminium chloride is example.
Resin pre-treatment: select for use 335 type weak base anion-exchange resins to put into adsorption column, use then and be mixed with 5% dilute hydrochloric acid solution by analytical pure hydrochloric acid and water or deionized water, 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 resin 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 dilute alkaline soln 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 resin 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.
Get 1000 kilograms of (wastewater from phthalocyanine green production of preferably selecting for use absorption workshop section to discharge of waste water of discharging in the phthalocyanine green production process of chemical plant, Jiangsu, because the content of its cupric ion is the highest), regulate its pH value to 4, flow velocity with 5BV/h, 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.
Adopt heating to concentrate or the spissated method of steam will to be concentrated into concentration ratio through the wastewater from phthalocyanine green production of ion exchange resin treatment be 70%, is 80% sodium hydroxide or lime solution with the wastewater from phthalocyanine green production after concentrating stirring, add under the condition of heating concentration, the pH value of regulating waste water is 5, continue to stir and carry out reacting by heating 9h afterwards, the reacting by heating temperature is 90 ℃, promptly obtain liquid product of the present invention, also the aforesaid liquid finished product can be made after drying its solid finished product.
For saving cost, when the ion exchange resin column of handling waste water is saturated, can carry out desorption and regeneration, its method is: water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 4BV/h, 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 washed with de-ionized water are cleaned this ion exchange resin 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 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 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.
With preparation double centner flocculant of polymeric aluminium chloride is example.
Resin pre-treatment: select for use 335 type weak base anion-exchange resins to put into adsorption column, use then and be mixed with 6% dilute hydrochloric acid solution by analytical pure hydrochloric acid and water or deionized water, 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 resin 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 dilute alkaline soln 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 resin 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.
Get 1000 kilograms of (wastewater from phthalocyanine green production of preferably selecting for use absorption workshop section to discharge of waste water of discharging in the phthalocyanine green production process of chemical plant, Jiangsu, because the content of its cupric ion is the highest), regulate its pH value to 4, flow velocity with 6BV/h, 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.
Adopt heating to concentrate or the spissated method of steam will to be concentrated into concentration ratio through the wastewater from phthalocyanine green production of ion exchange resin treatment be 80%, is 100% sodium hydroxide or lime solution with the wastewater from phthalocyanine green production after concentrating stirring, add under the condition of heating concentration, the pH value of regulating waste water is 5, continue to stir and carry out reacting by heating 10h afterwards, the reacting by heating temperature is 100 ℃, promptly obtain liquid product of the present invention, also the aforesaid liquid finished product can be made after drying its solid finished product.
For saving cost, when the ion exchange resin column of handling waste water is saturated, can carry out desorption and regeneration, its method is: water or deionized water clean 335 saturated type weak base anion-exchange resin adsorption columns with the flow velocity of 8BV/h, 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 washed with de-ionized water are cleaned this ion exchange resin 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 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 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 (6)
1, a kind ofly prepare the method for flocculant of polymeric aluminium chloride, it is characterized in that with wastewater from phthalocyanine green production:
(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, 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;
(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 adsorption columns after another one is equipped with pre-treatment transition equally again, promptly obtain the wastewater from phthalocyanine green production that copper ion concentration satisfies the secondary standard in " integrated wastewater discharge standard GB8978-1996 ";
(3) will concentrate through the wastewater from phthalocyanine green production of above-mentioned plastic resin treatment, control its concentration ratio between 10%～80%, wastewater from phthalocyanine green production after concentrating is added basifier carry out reacting by heating under agitation condition, regulate waste water and be slightly acidic, continue to stir and carry out reacting by heating, promptly obtain liquid product of the present invention; The aforesaid liquid finished product is made its solid finished product after drying.
2, the method for preparing flocculant of polymeric aluminium chloride with wastewater from phthalocyanine green production according to claim 1, it is characterized in that and to adopt heating to concentrate or the spissated method of steam concentrates through the wastewater from phthalocyanine green production of ion exchange resin treatment, and to be concentrated into concentration ratio be 25%-50%, wastewater from phthalocyanine green production after concentrating is added concentration under agitation condition be that 10%～100% sodium hydroxide or lime solution are as basifier, in heating, regulate the pH value of waste water between 3～5, after making it to be slightly acidic, continue to stir and carry out reacting by heating 1h-10h, the reacting by heating temperature is 30 ℃～100 ℃, promptly obtain liquid product of the present invention, the aforesaid liquid finished product is made its solid finished product after drying.
3, the method for preparing flocculant of polymeric aluminium chloride with wastewater from phthalocyanine green production according to claim 1, it is characterized in that 335 type weak base anion-exchange resins are carried out pretreated method 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 deionized water, flow through with the flow velocity of 4～6BV/h the adsorption column of 335 type weak base anion-exchange resins is housed, the processing volume is 3～6BV, the back is cleaned this resin column with deionized water with the flow velocity of 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.
4, the method for preparing flocculant of polymeric aluminium chloride with wastewater from phthalocyanine green production according to claim 1, 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 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 is removed, made the secondary standard in the copper ion concentration satisfied " integrated wastewater discharge standard GB8978-1996 " in the waste water.
5, the method for preparing flocculant of polymeric aluminium chloride with wastewater from phthalocyanine green production according to claim 1, it is characterized in that desorption and renovation process when the ion exchange resin column that uses in handling the waste water process is saturated are: water cleans 335 saturated type weak base anion-exchange resin posts, to remove residual waste water in the ion exchange resin column, be that the hydrochloric acid of the middle concentration of 8%-14% is under the condition of normal temperature to 50 ℃ cupric ion to be carried out desorption in temperature with concentration afterwards, being about to the cupric ion of absorption exchange on ion exchange resin column removes, 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, the copper desorption that adsorbed on the 335 before saturated at this moment type weak base anion-exchange resin posts is finished, and this 335 type weak base anion-exchange resin post has made the transition to OH type weak base anion-exchange resin so that reuse next time.
6, the method for preparing flocculant of polymeric aluminium chloride with wastewater from phthalocyanine green production according to claim 5, it is characterized in that desorption and renovation process when the ion exchange resin adsorption column that uses in the wastewater treatment process is saturated are: with flow velocity is 335 saturated type weak base anion-exchange resin posts of 4～8BV/h washed with de-ionized water, 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 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, clean this ion exchange resin column with deionized water with the flow velocity of 6～8BV/h again, clean 4～6BV, use 2～6%NaOH dilute alkaline soln again by analytical pure NaOH and deionized water preparation, be to handle this ion exchange resin column under the condition of 4～6BV/h at flow velocity, 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 post has made the transition to OH type weak base anion-exchange resin so that reuse next time.
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| CN200310106345.7A CN1253386C (en) | 2003-11-19 | 2003-11-19 | Polymeric aluminum chloride flocculant preparation method using phthalocyanine green waste water |
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| CN102912128B (en) * | 2012-11-05 | 2014-06-04 | 中国海洋石油总公司 | Method for separating and purifying rhodium through anion exchange resin |
| CN103386204A (en) * | 2013-08-13 | 2013-11-13 | 长沙自洁换热器科技有限公司 | Heat pump evaporating and heat pump drying energy saving technology for production of polyaluminium chloride |
| CN106673040B (en) * | 2016-12-19 | 2018-09-04 | 天津利安隆新材料股份有限公司 | Aluminium polychloride method is recycled using the aluminium trichloride waste water of synthesis of triazine ultra-violet absorber |
| CN115259431A (en) * | 2022-06-11 | 2022-11-01 | 宁夏中科生物新材料有限公司 | Purification and reuse method for long-chain binary acid washing wastewater |
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