CN114075002A - Method for resource utilization of copper-zinc catalyst production wastewater - Google Patents
Method for resource utilization of copper-zinc catalyst production wastewater Download PDFInfo
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- CN114075002A CN114075002A CN202010828956.6A CN202010828956A CN114075002A CN 114075002 A CN114075002 A CN 114075002A CN 202010828956 A CN202010828956 A CN 202010828956A CN 114075002 A CN114075002 A CN 114075002A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000001728 nano-filtration Methods 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000010949 copper Substances 0.000 claims abstract description 48
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000909 electrodialysis Methods 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000004064 recycling Methods 0.000 claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 24
- 230000008929 regeneration Effects 0.000 claims abstract description 23
- 238000011069 regeneration method Methods 0.000 claims abstract description 23
- 239000012492 regenerant Substances 0.000 claims abstract description 18
- 238000005516 engineering process Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000000084 colloidal system Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 51
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 229920002492 poly(sulfone) Polymers 0.000 claims description 9
- 230000001172 regenerating effect Effects 0.000 claims description 9
- 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 7
- 239000004952 Polyamide Substances 0.000 claims description 7
- 239000003456 ion exchange resin Substances 0.000 claims description 7
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012510 hollow fiber Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920006221 acetate fiber Polymers 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 23
- 239000000243 solution Substances 0.000 abstract description 10
- 238000003795 desorption Methods 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 17
- 229910052725 zinc Inorganic materials 0.000 description 17
- 239000011701 zinc Substances 0.000 description 17
- 239000012530 fluid Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- 239000013505 freshwater Substances 0.000 description 7
- 238000005374 membrane filtration Methods 0.000 description 7
- 230000000149 penetrating effect Effects 0.000 description 7
- 239000003513 alkali Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000013522 chelant Substances 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
Abstract
The invention relates to a resource utilization method of copper-zinc catalyst production wastewater, which mainly comprises an ultrafiltration unit, an adsorption unit, an electrodialysis unit and a nanofiltration unit. a. Removing SS and colloid in the catalyst production wastewater by using an ultrafiltration system unit, and enabling the produced water to enter an adsorption unit; b. the adsorption unit selectively and efficiently enriches copper and zinc ions in the ultrafiltration produced water, the produced water enters an electrodialysis unit for salt concentration, an acid regenerant is used for carrying out desorption regeneration on resin, and the regenerated liquid enters a nanofiltration system; c. concentrating the water salt solution produced by the resin by using an electrodialysis technology, and enabling the concentrated solution to enter a salt recovery system; d. and (3) performing acid salt separation on the regenerated liquid by using a nanofiltration technology, recycling the separated copper and zinc ions for the catalyst production process, and recycling the acid for the resin regeneration process. The method provided by the invention can be used for efficiently recycling the wastewater generated in the production of the copper-zinc catalyst, realizes near zero emission of the catalyst wastewater, and has remarkable economic and social benefits.
Description
Technical Field
The invention belongs to the field of water treatment, and relates to a method for recycling wastewater produced by a copper-zinc catalyst.
Background
In the production process of the copper-zinc catalyst, a large amount of high-salinity wastewater and copper-zinc ions with certain concentration are generated, and if the copper-zinc ions are directly discharged, the water body is polluted and serious harm is caused to organisms. Copper and zinc are essential trace elements for life, but more than a certain amount can produce toxic effect on organisms. Recent studies have shown that: in some typical watershed water bodies in China, copper and zinc have higher ecological risks relative to other toxic heavy metals, mainly because the copper and zinc are higher in concentration in partial surface water environment due to higher production and consumption of the copper and zinc in China; meanwhile, the sensitivity of aquatic organisms to copper and zinc is far higher than that of human bodies, so that the aquatic organisms have higher ecological risk. Therefore, the treatment and control of the catalyst production wastewater are needed to ensure the safety of the water ecosystem and recover the wastewater resources.
CN201010212313 discloses a method for removing and recovering copper and zinc in copper-zinc catalyst wastewater, which adopts an alkali regulation-ultrafiltration-precipitation process flow, can effectively remove copper and zinc ions in the wastewater to perform concentration and winning of copper and zinc colloid substances to perform effective separation, and the separated or concentrated copper and zinc compounds can be reused in the production process of a copper-zinc catalyst. The method adds alkali to adjust the pH value, and recovers the copper hydroxide and the zinc hydroxide in a precipitation form, thereby not only increasing the input of the alkali, but also being difficult to recycle the precipitation form. The method only recovers copper and zinc, and does not further treat high-salinity wastewater.
Disclosure of Invention
In view of the problems mentioned in the method of the background technology, the invention discloses a method for recycling wastewater produced by a copper-zinc catalyst, aiming at the recycling of the wastewater produced by the copper-zinc catalyst, combining a membrane separation technology, an efficient adsorption technology and an electrodialysis technology, effectively separating copper and zinc components in the wastewater, efficiently recycling the copper and zinc components, and treating a high-salt part to realize near zero emission of the wastewater.
The main technical scheme of the invention is as follows: the method for resource utilization of the production wastewater of the copper-zinc catalyst is characterized by comprising the following steps of: (1) an ultrafiltration unit: pretreating the catalyst production wastewater by using an ultrafiltration technology, removing SS and colloid in the wastewater, and feeding the produced water into an adsorption unit; (2) an adsorption unit: purifying the ultrafiltration produced water salt solution, selectively and efficiently enriching copper and zinc ions, feeding the produced water into an electrodialysis unit to improve the salt concentration, regenerating by using an acid regenerant, and feeding the regenerated liquid into a nanofiltration unit; (3) concentrating the resin produced water salt solution by using an electrodialysis technology, and recycling water in produced water; (4) and (3) performing acid salt separation on the regenerated liquid by using a nanofiltration technology, recycling the separated copper and zinc ions for the catalyst production process, and recycling the acid for the resin regeneration process.
Generally, the main water quality characteristics of the wastewater are as follows: the SS concentration is 5-100mg/L, the copper ion concentration is 0.5-20 mg/L, the zinc ion concentration is 0.5-20 mg/L, and the sodium nitrate content is 1000-30000 mg/L.
The membrane component used by the ultrafiltration unit in the step (1) is one of a tubular type, a roll type or a hollow fiber type.
The aperture of the membrane material used by the ultrafiltration unit in the step (1) is 5-30 nm.
The adsorbing material used by the adsorbing unit in the step (2) is one of strong acid type ion exchange resin, weak acid type ion exchange resin or chelating type ion exchange resin.
In the step (2), the filtering temperature of the adsorption unit is 5-40 ℃, and the filtering speed is 0.5-3 m/h.
And (3) the acid regenerant used by the adsorption unit in the step (2) is one of hydrochloric acid, nitric acid or sulfuric acid.
The concentration of the regenerant is 0.5-2 mol/L.
The dosage of the regenerant is 0.5-5 BV, the operation temperature is 5-40 ℃, and the regeneration rate is 0.5-3 m/h.
The type of the electrodialysis membrane material used by the electrodialysis unit in the step (3) is one of polysulfone, polyphenylene oxide or polyethyleneimine.
In the step (3), the material flow rate of the electrodialysis unit is 100-400L/h, the operating voltage is 10-30V, and the operating temperature is 5-40 ℃.
The nanofiltration membrane component of the nanofiltration unit in the step (4) is in one of plate type, tubular type or roll type; the nanofiltration membrane material of the nanofiltration unit is one of polysulfone, polyamide or acetate fiber.
The invention discloses a typical method for recycling wastewater produced by a copper-zinc catalyst, which mainly comprises the following steps:
(1) an ultrafiltration unit: pretreating the catalyst production wastewater by using a tubular, spiral-wound or hollow fiber ultrafiltration membrane, wherein the pore diameter of the membrane is 5-30nm, removing SS and colloid in the wastewater, and feeding the produced water into an adsorption unit;
(2) an adsorption unit: selectively adsorbing the water produced by the ultrafiltration unit in the step (1) by using strong acid type, weak acid or chelating type ion exchange resin, wherein the filtration temperature is 5-40 ℃, the filtration speed is 0.5-3 m/h, the copper and zinc ions are selectively and efficiently enriched, the produced water enters an electrodialysis unit to improve the salt concentration, the regeneration is carried out by using 0.5-2 mol/L hydrochloric acid, nitric acid or sulfuric acid regenerant, the using amount of the regenerant is 0.5-5 BV, the operation temperature is 5-40 ℃, the regeneration speed is 0.5-3 m/h, and the obtained regenerated liquid enters a nanofiltration unit;
(3) an electrodialysis unit: performing salt concentration on the water produced by the adsorption unit in the step (2) by using a polysulfone, polyphenyl ether or polyethyleneimine type electrodialysis membrane, wherein the material flow rate is 100-400L/h, the operating voltage is 10-30V, the operating temperature is 5-40 ℃, and the water in the produced water is recycled and concentrated to enter a salt recovery system;
(4) and (3) nanofiltration unit: and (3) carrying out acid-salt separation on the regenerated liquid by using a plate-type, tubular or rolled nanofiltration membrane, recycling the separated copper and zinc ions for the catalyst production process, and recycling the acid for the resin regeneration process.
The invention aims at the resource utilization of the copper-zinc catalyst wastewater, effectively recycles copper-zinc ions through the combination of a membrane separation technology, an adsorption technology and an electrodialysis technology, and simultaneously treats and recycles high-salt water. The method realizes near zero discharge of the catalyst production wastewater, and has remarkable economic and social benefits.
Drawings
FIG. 1 is a flow chart of a method for resource utilization of wastewater from copper-zinc catalyst production in an embodiment of the invention.
Detailed Description
The following specific examples and the accompanying drawings are used to further illustrate the technical solutions of the present invention in detail.
Example 1
The quality of wastewater: c (SS) =5 mg/L, C (Cu)2+)=0.5 mg/L，C(Zn2+)=0.5 mg/L，C(NaNO3) And (5) =1000 mg/L. The hollow fiber ultrafiltration membrane with the aperture of 5 nm is used for pretreating the wastewater, and the membrane flux is 500L/(m)2H) Water production by ultrafiltration membranes C (SS)<0.01 mg/L. The water produced by the ultrafiltration unit enters an adsorption unit which takes strong acid type resin as a main body, the filtration temperature is 5 ℃, the filtration speed is 3 m/h, and the concentration of copper and zinc ions of the water produced after resin filtration is less than 0.05 mg/L. The resin produced water enters an electrodialysis unit, and salt concentration is carried out on the resin produced water by utilizing a polysulfone electrodialysis membrane, the material flow rate is 100L/h, the operating voltage is 10V, the operating temperature is 5 ℃, and the fresh water is dilutedThe water in the water is recycled, and the concentration of the concentrated water sodium nitrate is 125 g/L, and the concentrated water sodium nitrate enters a salt recovery system. Regenerating resin with 0.5 mol/L nitric acid, wherein the amount of a regenerant is 5 BV, the operation temperature is 5 ℃, the regeneration rate is 3 m/h, the regenerated liquid enters a nanofiltration unit, acid salt separation is carried out on the regenerated liquid by using a polysulfone plate-type nanofiltration membrane, and nanofiltration concentrated liquid C (Cu)2+)=25 g/L，C(Zn2+) And (5) allowing the nanofiltration concentrated solution to enter a copper-zinc recovery system, wherein the recovery rate of copper and zinc is 99.1%, and the nanofiltration penetrating fluid is recovered and reused for resin regeneration.
Example 2
The quality of wastewater: c (SS) =50 mg/L, C (Cu)2+)=10 mg/L，C(Zn2+)=10 mg/L，C(NaNO3) =10000 mg/L. The wastewater is pretreated by a roll-type ultrafiltration membrane with the aperture of 10 nm, and the membrane flux is 400L/(m)2H) Water production by ultrafiltration membranes C (SS)<0.01 mg/L. The water produced by the ultrafiltration unit enters an adsorption unit which takes weak acid type resin as a main body, the filtration temperature is 25 ℃, the filtration speed is 1.5 m/h, and the concentration of copper and zinc ions of the water produced after resin filtration is less than 0.05 mg/L. And (3) enabling resin produced water to enter an electrodialysis unit, performing salt concentration on the resin produced water by utilizing a polyphenylene ether electrodialysis membrane, enabling the material flow rate to be 250L/h, the operating voltage to be 20V, the operating temperature to be 25 ℃, recycling fresh water and enabling concentrated water to have the concentration of 140 g/L, and enabling the resin produced water to enter a salt recovery system. Regenerating resin with 1mol/L hydrochloric acid, the amount of the regenerant is 2 BV, the operation temperature is 25 ℃, the regeneration rate is 1.5 m/h, the regenerated liquid enters a nanofiltration unit, acid salt separation is carried out on the regenerated liquid by using a polyamide tubular nanofiltration membrane, and nanofiltration concentrated liquid C (Cu)2+)=30 g/L，C(Zn2+) And (4) the nanofiltration concentrated solution enters a copper-zinc recovery system, the recovery rate of copper and zinc is 99.3%, and the nanofiltration penetrating fluid is recovered and reused for resin regeneration.
Example 3
The quality of wastewater: c (SS) =100 mg/L, C (Cu)2+)=20 mg/L，C(Zn2+)=20 mg/L，C(NaNO3) =30000 mg/L. The tubular ultrafiltration membrane with the aperture of 30nm is used for pretreating the wastewater, and the membrane flux is 300L/(m)2H) Water production by ultrafiltration membranes C (SS)<0.01 mg/L. The water produced by the ultrafiltration unit enters an adsorption unit taking chelate resin as a main body to be filteredThe temperature is 40 ℃, the filtering speed is 0.5 m/h, and the concentration of copper and zinc ions in the produced water after resin filtration is less than 0.05 mg/L. And (3) enabling resin produced water to enter an electrodialysis unit, performing salt concentration on the resin produced water by utilizing a polyethyleneimine electrodialysis membrane, enabling the material flow rate to be 400L/h, the operating voltage to be 30V, the operating temperature to be 40 ℃, recycling fresh water and enabling concentrated water sodium nitrate to have a concentration of 180 g/L, and enabling the concentrated water to enter a salt recovery system. Regenerating resin with 2mol/L sulfuric acid, with the use amount of 0.5 BV as regenerant, the operation temperature of 40 deg.C and the regeneration rate of 0.5 m/h, introducing the regenerated liquid into a nanofiltration unit, separating acid salt from the regenerated liquid with a polyamide rolled nanofiltration membrane, and nanofiltration concentrating the solution C (Cu)2+)=32 g/L，C(Zn2+) And (5) the nanofiltration concentrated solution enters a copper-zinc recovery system, the recovery rate of copper and zinc is 99.6%, and the nanofiltration penetrating fluid is recovered and reused for resin regeneration.
Example 4
The quality of wastewater: c (SS) =55 mg/L, C (Cu)2+)=5 mg/L，C(Zn2+)=5 mg/L，C(NaNO3) =5100 mg/L. The hollow fiber ultrafiltration membrane with the aperture of 10 nm is used for pretreating the wastewater, and the membrane flux is 480L/(m)2H) Water production by ultrafiltration membranes C (SS)<0.01 mg/L. The water produced by the ultrafiltration unit enters an adsorption unit which takes strong acid type resin as a main body, the filtration temperature is 10 ℃, the filtration speed is 2.5 m/h, and the concentration of copper and zinc ions of the water produced after resin filtration is less than 0.05 mg/L. And (3) enabling resin produced water to enter an electrodialysis unit, performing salt concentration on the resin produced water by utilizing a polysulfone electrodialysis membrane, enabling the material flow rate to be 200L/h, the operating voltage to be 20V, the operating temperature to be 25 ℃, recycling fresh water and enabling concentrated water to have the concentration of 175 g/L of sodium nitrate, and enabling the concentrated water to enter a salt recovery system. Regenerating resin with 1.0 mol/L nitric acid, the amount of the regenerant is 2.5 BV, the operation temperature is 15 ℃, the regeneration rate is 1.3 m/h, the regenerated liquid enters a nanofiltration unit, acid salt separation is carried out on the regenerated liquid by using a polyamide roll-type nanofiltration membrane, and nanofiltration concentrated liquid C (Cu)2 +)=35 g/L，C(Zn2+) And (5) the nanofiltration concentrated solution enters a copper-zinc recovery system, the recovery rate of copper and zinc is 99.5%, and the nanofiltration penetrating fluid is recovered and reused for resin regeneration.
Example 5
The quality of wastewater: c (SS) =80 mg/L, C (Cu)2+)=10 mg/L，C(Zn2+)=13 mg/L，C(NaNO3) =18000 mg/L. The wastewater is pretreated by a roll-type ultrafiltration membrane with the aperture of 15 nm, and the membrane flux is 420L/(m)2H) Water production by ultrafiltration membranes C (SS)<0.01 mg/L. The water produced by the ultrafiltration unit enters an adsorption unit which takes weak acid type resin as a main body, the filtration temperature is 35 ℃, the filtration speed is 1.0 m/h, and the concentration of copper and zinc ions of the water produced after resin filtration is less than 0.05 mg/L. And (3) enabling resin produced water to enter an electrodialysis unit, performing salt concentration on the resin produced water by utilizing a polyphenylene ether electrodialysis membrane, enabling the material flow rate to be 210L/h, the operating voltage to be 25V, the operating temperature to be 35 ℃, recycling fresh water and enabling concentrated water to have sodium nitrate concentration of 160 g/L, and enabling the resin produced water to enter a salt recovery system. Regenerating the resin with 1.5mol/L hydrochloric acid, wherein the consumption of the regenerant is 2.4 BV, the operation temperature is 20 ℃, the regeneration rate is 2.0 m/h, the regenerated liquid enters a nanofiltration unit, acid salt separation is carried out on the regenerated liquid by using a polyamide tubular nanofiltration membrane, and nanofiltration concentrated liquid C (Cu)2+)=28 g/L，C(Zn2+) And (4) the nanofiltration concentrated solution enters a copper-zinc recovery system, the recovery rate of copper and zinc is 99.2%, and the nanofiltration penetrating fluid is recovered and reused for resin regeneration.
Example 6
The quality of wastewater: c (SS) =90 mg/L, C (Cu)2+)=15 mg/L，C(Zn2+)=17 mg/L，C(NaNO3) =25000 mg/L. The tubular ultrafiltration membrane with the aperture of 20 nm is used for pretreating the wastewater, and the membrane flux is 350L/(m)2H) Water production by ultrafiltration membranes C (SS)<0.01 mg/L. The water produced by the ultrafiltration unit enters an adsorption unit taking chelate resin as a main body, the filtration temperature is 30 ℃, the filtration speed is 1.5 m/h, and the concentration of copper and zinc ions produced by the resin after filtration is less than 0.05 mg/L. And (3) enabling resin produced water to enter an electrodialysis unit, performing salt concentration on the resin produced water by utilizing a polyethyleneimine electrodialysis membrane, enabling the material flow rate to be 300L/h, the operating voltage to be 25V, the operating temperature to be 30 ℃, recycling fresh water, and enabling concentrated water sodium nitrate to enter a salt recovery system, wherein the concentration of the concentrated water sodium nitrate is 150 g/L. Regenerating resin with 2mol/L sulfuric acid, with a regenerant dosage of 1.5 BV, an operating temperature of 40 deg.C, a regeneration rate of 2.5 m/h, introducing the regenerated liquid into a nanofiltration unit, performing acid salt separation on the regenerated liquid with polysulfone-type plate nanofiltration membrane, and nanofiltration of concentrated liquid C (Cu)2+)=33 g/L，C(Zn2+) And (5) the nanofiltration concentrated solution enters a copper-zinc recovery system, the recovery rate of copper and zinc is 99.6%, and the nanofiltration penetrating fluid is recovered and reused for resin regeneration.
Example 7
The quality of wastewater: c (SS) =55 mg/L, C (Cu)2+)=5 mg/L，C(Zn2+)=5 mg/L，C(NaNO3) =5100 mg/L. The hollow fiber ultrafiltration membrane with the aperture of 10 nm is used for pretreating the wastewater, and the membrane flux is 400L/(m)2H) Water production by ultrafiltration membranes C (SS)<0.01 mg/L. The water produced by the ultrafiltration unit enters an adsorption unit which takes strong acid type resin as a main body, the filtration temperature is 35 ℃, the filtration speed is 2.5 m/h, and the concentration of copper and zinc ions of the water produced after resin filtration is less than 0.05 mg/L. And (3) enabling resin produced water to enter an electrodialysis unit, performing salt concentration on the resin produced water by utilizing a polysulfone electrodialysis membrane, enabling the material flow rate to be 200L/h, the operating voltage to be 20V, the operating temperature to be 35 ℃, recycling fresh water and enabling concentrated water to have the concentration of 175 g/L of sodium nitrate, and enabling the concentrated water to enter a salt recovery system. Regenerating resin with 1.0 mol/L nitric acid, the amount of the regenerant is 2.5 BV, the operation temperature is 15 ℃, the regeneration rate is 1.3 m/h, the regenerated liquid enters a nanofiltration unit, acid salt separation is carried out on the regenerated liquid by using a polyamide roll-type nanofiltration membrane, and nanofiltration concentrated liquid C (Cu)2 +)=35 g/L，C(Zn2+) And (5) the nanofiltration concentrated solution enters a copper-zinc recovery system, the recovery rate of copper and zinc is 99.5%, and the nanofiltration penetrating fluid is recovered and reused for resin regeneration.
Claims (10)
1. A method for resource utilization of wastewater produced by a copper-zinc catalyst is characterized by comprising the following steps: (1) an ultrafiltration unit: pretreating the catalyst production wastewater by using an ultrafiltration technology, removing SS and colloid in the wastewater, and feeding the produced water into an adsorption unit; (2) an adsorption unit: purifying the ultrafiltration produced water salt solution, selectively and efficiently enriching copper and zinc ions, feeding the produced water into an electrodialysis unit to improve the salt concentration, regenerating by using an acid regenerant, and feeding the regenerated liquid into a nanofiltration unit; (3) concentrating the resin produced water salt solution by using an electrodialysis technology, and recycling water in produced water; (4) and (3) performing acid salt separation on the regenerated liquid by using a nanofiltration technology, recycling the separated copper and zinc ions for the catalyst production process, and recycling the acid for the resin regeneration process.
2. The resource utilization method of the wastewater generated in the copper-zinc catalyst production according to claim 1, characterized in that the main water quality characteristics of the wastewater are as follows: the SS concentration is 5-100mg/L, the copper ion concentration is 0.5-20 mg/L, the zinc ion concentration is 0.5-20 mg/L, and the sodium nitrate content is 1000-30000 mg/L.
3. The resource utilization method of the copper-zinc catalyst production wastewater according to claim 1, characterized in that the membrane module used by the ultrafiltration unit in the step (1) is one of a tubular type, a roll type or a hollow fiber type.
4. The resource utilization method of the copper-zinc catalyst production wastewater according to claim 1, characterized in that the pore diameter of the membrane material used by the ultrafiltration unit in step (1) is 5-30 nm.
5. The method for recycling wastewater from copper-zinc catalyst production according to claim 1, wherein the adsorbent used in the adsorption unit in step (2) is one of strong acid type ion exchange resin, weak acid type ion exchange resin or chelating type ion exchange resin.
6. The resource utilization method of the copper-zinc catalyst production wastewater according to claim 1, characterized in that the filtration temperature of the adsorption unit in the step (2) is 5-40 ℃, and the filtration speed is 0.5-3 m/h.
7. The method for recycling wastewater from copper-zinc catalyst production according to claim 1, wherein the acid regenerant used in the adsorption unit in step (2) is one of hydrochloric acid, nitric acid or sulfuric acid; the concentration of the regenerant is 0.5-2 mol/L; the dosage of the regenerant is 0.5-5 BV, the operation temperature is 5-40 ℃, and the regeneration rate is 0.5-3 m/h.
8. The method for recycling wastewater from copper-zinc catalyst production according to claim 1, wherein the type of the electrodialysis membrane material used in the electrodialysis unit in step (3) is one of polysulfone, polyphenylene oxide and polyethyleneimine.
9. The method for recycling wastewater from copper-zinc catalyst production as claimed in claim 1, wherein the flow rate of the materials of the electrodialysis unit in the step (3) is 100-400L/h, the operating voltage is 10-30V, and the operating temperature is 5-40 ℃.
10. The resource utilization method of wastewater generated in copper-zinc catalyst production according to claim 1, characterized in that the nanofiltration membrane component of the nanofiltration unit in step (4) is in one of plate type, tubular type or roll type; the nanofiltration membrane material of the nanofiltration unit is one of polysulfone, polyamide or acetate fiber.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311180A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Method for removing and recovering copper and zinc in wastewater of copper-zinc catalysts |
| CN107235590A (en) * | 2017-05-17 | 2017-10-10 | 中国石油化工股份有限公司 | The handling process that a kind of zero-emission of containing wastewater from catalyst and recycling are recycled |
| CN107311361A (en) * | 2017-07-31 | 2017-11-03 | 江苏久吾高科技股份有限公司 | A kind of technique and device for handling catalytic cracking and desulfurizing waste water |
| CN110104865A (en) * | 2019-06-13 | 2019-08-09 | 合众思(北京)环境工程有限公司 | Spent acid, salkali waste, the wastewater zero discharge system of crystal salt recycling and method can be achieved |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311180A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Method for removing and recovering copper and zinc in wastewater of copper-zinc catalysts |
| CN107235590A (en) * | 2017-05-17 | 2017-10-10 | 中国石油化工股份有限公司 | The handling process that a kind of zero-emission of containing wastewater from catalyst and recycling are recycled |
| CN107311361A (en) * | 2017-07-31 | 2017-11-03 | 江苏久吾高科技股份有限公司 | A kind of technique and device for handling catalytic cracking and desulfurizing waste water |
| CN110104865A (en) * | 2019-06-13 | 2019-08-09 | 合众思(北京)环境工程有限公司 | Spent acid, salkali waste, the wastewater zero discharge system of crystal salt recycling and method can be achieved |
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