CN111573769A - Method for separating and recovering acid and metal ions in steel pickling waste liquid - Google Patents
Method for separating and recovering acid and metal ions in steel pickling waste liquid Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 88
- 239000002253 acid Substances 0.000 title claims abstract description 87
- 239000002699 waste material Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 53
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 51
- 239000010959 steel Substances 0.000 title claims abstract description 51
- 238000005554 pickling Methods 0.000 title claims abstract description 47
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 13
- 238000011084 recovery Methods 0.000 claims abstract description 96
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 51
- 239000003480 eluent Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000007790 solid phase Substances 0.000 claims abstract description 41
- 238000011068 loading method Methods 0.000 claims abstract description 31
- 238000005191 phase separation Methods 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 238000010828 elution Methods 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 238000013375 chromatographic separation Methods 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- -1 hydrogen ions Chemical class 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 238000004064 recycling Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 11
- 238000012856 packing Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 238000005070 sampling Methods 0.000 description 10
- 235000003891 ferrous sulphate Nutrition 0.000 description 9
- 239000011790 ferrous sulphate Substances 0.000 description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 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 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 150000002505 iron Chemical class 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
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- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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- 238000004364 calculation method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- 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
- C02F2303/16—Regeneration of sorbents, filters
Abstract
The invention discloses a method for separating and recovering acid and metal ions in steel pickling waste liquid, which comprises the following steps: (1) loading: loading the iron and steel pickling waste liquid containing ferrous ions into a chromatographic separation column containing a solid-phase adsorption material, and collecting effluent liquid in three sections, namely low-concentration recovery area effluent liquid, ferrous ion recovery area effluent liquid and original-concentration recovery area effluent liquid; (2) and (3) elution: eluting with eluent, collecting the eluent in three sections, namely the original concentrated recovery area eluent, the acid recovery area eluent and the low concentrated recovery area eluent; (3) and (3) repeating the step (1) and the step (2) until the solid phase separation material has no separation effect on the acid and the ferrous ions, and stopping circulation. Compared with the prior art, the inventionThe technical process is reasonable and controllable, the equipment requirement is low, the separation efficiency is high, the acid recovery rate is higher than 95%, and the metal ion recovery rate is higher than 98%. Acid recovery concentration ct/c0Not less than 80 percent, and the recovery concentration c of metal saltt/c0≥90％。
Description
Technical Field
The invention belongs to the technical field of waste liquid recycling treatment, and particularly relates to a method for separating and recycling acid and metal ions in steel pickling waste liquid.
Background
A large amount of sulfuric acid and hydrochloric acid are used in the production process of steel enterprises in China, however, most of sulfuric acid cannot be converted into products, mainly exists in the form of waste acid, generally has no recovery value for low-concentration acid, and is normally discharged or recycled after acidic and other harmful substances are removed by a neutralization method. However, for high acid concentrations (acid concentrations above 5%), recycling is a major concern.
In recent years, a large amount of research and exploration are carried out on the treatment of the steel pickling waste liquid by scholars at home and abroad. Various treatment technologies and schemes are provided for the steel pickling waste liquid, and certain application results are obtained. At present, the methods for treating the steel pickling waste liquid mainly comprise a neutralization method, an iron salt crystallization method, an evaporation method, a roasting method, a flocculant preparation method, an ion exchange resin method and an acid retardation method.
Chemical neutralization: the pH value of the waste liquid is adjusted to 5.5-7.5 by adding alkaline substances into the acidic waste liquid. Thereby achieving the national standard and then discharging. Current chemical neutralization methods are generally classified into a dosing neutralization method, a filtration neutralization method, and a lye wastewater neutralization method. The neutralization method can only be used for low-concentration acid, and for high-concentration acid, the energy consumption is higher and the wastewater amount is high.
Iron salt crystallization method: by changing the physical and chemical properties of the waste acid liquid. The acid was separated by precipitation of iron salt. The purpose of resource recycling is achieved. However, the method has high energy consumption, high requirements on the corrosion resistance of equipment and is easy to generate secondary pollution.
An evaporation method: the method for treating the acid pickling waste liquid of volatile acid (nitric acid, hydrochloric acid and hydrofluoric acid) utilizes the volatility of the acid, and evaporates the acid into gas by reduced pressure distillation for resource recycling, but distillation mother liquid crystallization is easy to block equipment, and the treatment raw materials have limitations.
A direct roasting method: the volatile acid waste liquid is directly sprayed into a roasting furnace to contact with high-temperature gas, water is evaporated under the high-temperature condition, and ferrous salt is oxidized and hydrolyzed to obtain ferric oxide and regenerated acid. The method has the advantages of thorough treatment of the volatile acid waste liquid, large treatment capacity and high recovery rate. But the requirement on equipment is extremely high and the running cost is high; and also has certain limitations for processing raw materials.
The method for preparing the flocculant comprises the following steps: the hydroxyl partially replaces sulfate ions and chloride ions to carry out polymerization reaction, so as to prepare novel inorganic polymeric flocculants such as ferric chloride (PFC), Polymeric Ferric Sulfate (PFS) and the like.
The ion exchange resin method separates ferrous ions and acid in the steel pickling waste liquid through ion exchange resin, but the ion exchange resin is easily affected by high-concentration ferrous ions and acid, and resin poisoning is easily caused.
Acid retardation method: separating the acid and the corresponding iron salt solution by adopting a physical separation mode; after the separation is finished, the acid and the corresponding iron salt solution can still keep the original concentration, the salt solution is recovered as an industrial byproduct, the acid is recovered to a production line as a reaction raw material, and the reduction, recycling and harmless treatment is finished.
In patent CN 109467239A, an ultrafiltration membrane device, a nanofiltration membrane device, an electrodialysis device, a reverse osmosis device and a distillation device are used for treating the steel pickling waste liquid, the concentration of the recovered hydrochloric acid is 5-20 wt%, and the method has high equipment requirement and high treatment cost.
Patent CN 102828192A discloses a recycling method of pickling waste liquid in steel industry, which adopts strong base anion exchange resin to separate acid, wherein the initial acid concentration of the treated waste liquid is 5%, and the acid recovery rate is 82%.
In view of the above limitations, the invention develops a new steel pickling waste liquid recycling method, which takes a separation material as a stationary phase, samples the steel pickling waste liquid, elutes the steel pickling waste liquid, and the whole separation process is divided into four regions for recycling, so that the steel pickling waste liquid can be effectively recycled.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a method for recycling steel pickling waste liquid, namely a method for separating and recycling acid and metal ions in the steel pickling waste liquid, aiming at the defects of the prior art.
The invention idea is as follows: the technical idea of the invention is mainly based on the principle of acid retardation, namely that hydrogen ions in the mixed solution are retarded on the surface of a pore formed between a stationary phase and then the hydrogen ions are eluted by pure water. While the present invention selects a particular particle size distribution ratio, i.e., homogeneity, as shown in the mass transfer diagram of fig. 1, conventional resins are unlikely to develop the mass transfer efficiency and recovery rate required for acid blocking. The current related projects research the highest acid recovery rate of 80% and the metal ion recovery rate of 85% by using 100 micron ion exchange resin by foreign ECO company. The domestic research level is hardly reported for acid with the concentration of 20 wt%, and the recovery rate of the acid with the concentration of 5-10 wt% is not higher than 70%. The recovery rate of the acid of the prior art can reach more than 98 percent for the acid with the high concentration of more than 20 percent. The recovery rate of ferrous iron is 99%.
As shown in FIG. 2, the purpose of the method is to solve the problem of recycling the steel pickling waste liquid. The invention is suitable for the separation problem of metal ions and acid in the steel pickling waste liquid and other pickling waste liquids. Simple technical process, low equipment requirement, high separation efficiency and high resource recovery rate. The recovery rate of acid is higher than 95 percent, and goldThe recovery rate of the metal ions is higher than 98 percent. Acid recovery concentration ct/c0Not less than 80 percent, and the recovery concentration c of metal saltt/c0≥90％。
In order to solve the technical problem, the invention discloses a method for separating and recovering acid and metal ions in steel pickling waste liquid, which comprises the following steps:
(1) loading: controlling the sample loading volume and flow rate, loading the iron and steel pickling waste liquid containing ferrous ions into a chromatographic separation column containing a solid phase adsorption material, and collecting the effluent liquid of the lower layer in three sections, namely the effluent liquid of a low-concentration recovery area, the effluent liquid of a ferrous ion recovery area and the effluent liquid of an original-concentration recovery area;
(2) and (3) elution: eluting with eluent, collecting the eluent in three sections, namely the original concentrated recovery area eluent, the acid recovery area eluent and the low concentrated recovery area eluent;
(3) and (3) repeating the step (1) and the step (2) until the solid phase separation material has no separation effect on the hydrogen ions and the ferrous ions, and stopping circulation.
Wherein, the effluent of the ferrous ion recovery zone in the step (1) and the effluent of the acid recovery zone in the step (2) are collected; wherein, the effluent liquid of the ferrous ion recovery area is used for further separation and purification to obtain ferrous salt; the eluent in the acid recovery area can be directly reused in the production process of steel enterprises.
In the step (1), the concentration of acid in the steel acid waste liquid is 5-30 wt%, and the concentration of ferrous ions is 2-10 wt%; wherein the acid is sulfuric acid; the ferrous ion is derived from ferrous sulfate.
Preferably, the steel acid waste liquid is a mixed aqueous solution of sulfuric acid and ferrous sulfate; wherein, the concentration of the sulfuric acid is below 5-30 wt%, and the concentration of the ferrous sulfate is 2-10 wt%; more preferably, the concentration of sulfuric acid is 20 wt% to 30 wt%.
In the step (1), the solid-phase adsorption material is solid particles with a styrene-divinylbenzene copolymer as a skeleton structure and quaternary ammonium modification at the tail end; wherein, the content of the quaternary ammonium structure is 10 to 15 percent of the total mass of the solid-phase adsorbing material; preferably, the solid-phase adsorption material is quaternary amine modified polystyrene microspheres.
In the step (1), the particle size of the solid-phase adsorbing material is 30-100 μm, and the distribution difference of the particle size is +/-10 μm; preferably, the solid-phase adsorbent has a particle size of 85 μm and a particle size distribution difference of ± 10 μm.
In the step (1), the column packing conditions of the chromatographic separation column containing the solid-phase adsorbing material are as follows:
the type of the filler is as follows: quaternary amine modified polystyrene microsphere.
Column specification: DAC dynamic column DAC50
Column loading pressure: 2.5MPa (25bar)
The amount of the filler: 300mL microsphere +500mL ultrapure water
Ultrasonic: the microscopic examination is carried out for 15-20 min to be qualified, and no agglomeration and mutual adhesion exist.
And (4) finishing column filling: and washing the ultrapure water mobile phase until no turbidity exists. (pressure maintaining 2.5 MPa: Polymer beads having an expansion ratio of 10%)
In the step (1), the sample loading flow rate of the steel pickling waste liquid is 0.2-5BV/min, preferably 0.2 BV/min.
In the step (1), the sample loading amount of the steel pickling waste liquid is 1-5 BV.
In the step (1), the three-section collection comprises the following steps:
(i) a low concentration recovery zone: when the molar concentration of ferrous ions in the initial effluent is more than 0.2 times of the molar concentration of ferrous ions in the steel pickling waste liquid (namely when the molar concentration is more than 0.2 times, the step (ii) is carried out), and the effluent obtained in the interval is low-concentration acid liquid;
(ii) a ferrous ion recovery area: (iv) when the molar concentration of the hydrogen ions in the effluent liquid after the step (i) is finished is more than 0.8 times of the molar concentration of the hydrogen ions in the steel pickling waste liquid (namely when the molar concentration is more than 0.8 time, the step (iii) is carried out), and the effluent liquid obtained in the interval is the effluent liquid containing ferrous ions;
(iii) an original concentration recovery area: (iii) when the effluent after the step (ii) is finished till the loading is finished, the effluent obtained in the interval is the stock solution.
In the step (2), the eluent is water; the flow rate of the eluent is 0.2-5BV/min (preferably 0.2BV/min), and the sample loading amount of the eluent is the same as that of the steel pickling waste liquid.
In the step (2), the three-section collection comprises the following steps:
(I) an original concentration recovery area: initiating the eluent until the molar concentration of ferrous ions in the eluent is less than 0.8 times of the molar concentration of ferrous ions in the steel pickling waste liquid, wherein the eluent obtained in the interval is the stock solution;
(II) an acid recovery zone: when the molar concentration of hydrogen ions in the eluent is less than 0.2 times of the molar concentration of hydrogen ions in the steel pickling waste liquid, the eluent obtained in the interval is the eluent containing acid;
(III) a low-concentration recovery zone: and (3) when the eluent obtained after the step (II) is finished and the sample loading of the eluent is finished, obtaining the eluent with low concentration in the interval.
Wherein, the determination of the molar concentrations of the hydrogen ions and the ferrous ions involved in the processes of the step (1) and the step (2) has certain errors in the actual operation process, and preferably 0.2 and 0.8.
In the step (3), in the process of repeatedly circulating the step (1) and the step (2), any one or two of the effluent liquid of the low concentration recovery area in the step (1) and the eluent of the low concentration recovery area in the step (2) is used as the eluent in the step (2); when the dosage is not enough, the water is used for supplementing.
In the step (3), in the process of repeatedly circulating the step (1) and the step (2), the stock solution in the original concentration recovery area is collected and used as the iron and steel acid waste liquid containing ferrous ions in the step (1), and the iron and steel acid waste liquid is loaded to the chromatographic separation column containing the solid-phase adsorption material again.
In the step (3), the solid phase separation material has no separation effect on hydrogen ions and ferrous ions, namely, when the concentration of the hydrogen ions and the concentration of the ferrous ions in the effluent liquid from the start of loading the sample are not lower than 0.8 of the concentration of the hydrogen ions and the concentration of the ferrous ions in the original steel pickling waste liquid, the separation effect is not generated; the cycle times of the step (1) and the step (2) are more than or equal to 10000.
In the process, the separation stage is divided into four stages: (1) a low concentration recovery area, (2) a ferrous ion recovery area, (3) an original concentration circulation area, and (4) an acid recovery area. Specific definitions for each region are shown in table 1 and fig. 2:
TABLE 1
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the invention has reasonable and controllable technology, low equipment requirement, high separation efficiency, acid recovery rate higher than 95 percent and metal ion recovery rate higher than 98 percent. Acid recovery concentration ct/c0Not less than 80 percent, and the recovery concentration c of metal saltt/c0≥90％。
(2) The method can recover high-concentration pickling stock solution, has good separation and recovery effects on waste liquid with acid concentration higher than 20 wt%, and has the acid recovery rate of over 98% and the ferrous recovery rate of 99%.
(3) The invention has low waste liquid amount, and the recovery liquid in four areas can be recycled, thus completely realizing zero emission.
(4) The solid phase separation material has high mass transfer rate and high separation efficiency, and does not produce iron ion poisoning. Can be recycled for more than 10000 times.
(5) The treatment process of the invention has high efficiency, and 300mL of the column bed can treat at least 600mL of waste liquid per hour. Only a single-column short bed is needed for operation even in industrialization, the usage amount of resin and the amount of waste resin can be reduced, and the occupied area is reduced.
Drawings
FIG. 1 is a diagram showing the manner of stacking a solid phase separation material bed and the mass transfer process of the present invention in comparison with the manner of stacking a solid phase separation material bed and the mass transfer process of a conventional ion exchange resin bed.
Fig. 2 is a diagram of the division of the regions of the present invention.
FIG. 3 is a microscope photograph of a solid phase separation material according to the present invention.
FIG. 4 is a mass balance diagram of example 1.
FIG. 5 is a graph showing the effect of multiple separations according to the present invention.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
The detection method of ferrous ions and hydrogen ions in the following examples is as follows:
H+ion concentration detection (sodium hexametaphosphate method): 1mL of a sample to be measured and 4g of a 10% sodium hexametaphosphate solution are put into a measuring cup, 20mL of water is added, and the mixture is stirred uniformly. Titration was carried out with 0.1mol/L NaOH solution. The sodium hexametaphosphate is complexed with ferrous sulfate, the initial pH of the sodium hexametaphosphate is 6, and the sodium hydroxide consumed when the pH is lower than 6.0 is the hydrogen ion consumption. The titration endpoint was selected to be 6.0.
CH+＝CNaOH*VNaOH/VTo be measured
Fe2+Ion detection: 2mL of the sample, 1mL of 20% sulfuric acid, was added to the measuring cup, and 20mL of water was added. And (4) stirring uniformly. Potentiometric titration of 0.01mol/L potassium dichromate.
The reaction equation is as follows: 6Fe2++Cr2O7 2-+14H+＝6Fe3++2Cr3++7H2O
CFe2+(6C) Potassium dichromate V Potassium dichromate/V to be tested
Calculating the acid recovery rate: (1-m)1/m2)*100％
m1Amount of acid lost in iron recovery, m2Total iron in each cycle
Calculating the iron recovery rate: (1-m)3/m4)*100％
m3Amount of acid lost in iron recovery, m4Total iron in each cycle
Calculation of the recovery concentration of acid: the concentration of acid in the acid recovery zone compared to the concentration of acid in the feedstock;
calculating the recovery concentration of ferrous ions: the concentration of ferrous ions in the ferrous ion recovery zone is compared to the concentration of ferrous ions in the feed material.
Example 1
(1) Preparing a chromatographic separation column: 300mL of solid phase separation material was dispersed in 500mL of water and subjected to ultrasonic oscillation for 15min, and the microscopic image thereof is shown in FIG. 3. And (4) carrying out wet column packing on the dispersed solid phase separation material. 300mL of solid phase separation material was placed in a cartridge (DAC dynamic column DAC50) and the remainder was filled with water to ensure no air bubbles. The column loading pressure is 2.5 MPa. After the completion of column packing, the column was washed with 3BV of pure water until no turbidity occurred (pressure maintained 2.5 MPa: 10% expansion ratio of polymer beads).
Wherein the solid phase separation material is quaternary amine (-N)+(CH3)3) Modified styrene-divinylbenzene copolymer particles (quaternary ammonium structure content 15.12%). The particle size is 85 micrometers, and the particle size difference is +/-10 micrometers; specific surface area 800m2Per g, pore diameter of 50A and pore volume of 1.2cm3/g。
(2) Loading: sampling the steel pickling waste liquid (300 mL of 5 wt% ferrous sulfate and 20 wt% sulfuric acid mixed aqueous solution) according to 0.2BV/min, wherein the sampling amount is 1BV, and detecting by sectional collection (1 bottle per 15 mL). The regions were partitioned according to fig. 2 based on the measured concentrations of hydrogen and ferrous ions in the respective bottles.
(3) And (3) elution: after the sample loading is finished, eluting with pure water at the elution rate of 0.2BV/min and the elution amount of 1BV, and detecting by sectional collection (collecting 1 bottle per 15 mL). The regions were partitioned according to fig. 2 based on the measured concentrations of hydrogen and ferrous ions in the respective bottles.
(4) The acid recovery rate is 98.2 percent, and the ferrous ion recovery rate is 98.7 percent. Acid recovery concentration ct/c00.982, metal salt recovery concentration ct/c0＝0.987。
(5) The steps (1) and (2) are repeated for a cycle, and it can be seen from FIG. 5 that the performance is almost completely not degraded in the cycle test, and therefore, it can be estimated that the solid phase separation material can be cycled at least 10000 times or more. The material balance diagram of this example is shown in FIG. 4.
Example 2
(1) Preparing a chromatographic separation column: dispersing 300mL of solid phase separation material in 500mL of waterAnd ultrasonically shaking for 15 min. And (4) carrying out wet column packing on the dispersed solid phase separation material. 300mL of solid phase separation material was placed in a cartridge (DAC dynamic column DAC50) and the remainder was filled with water to ensure no air bubbles. The column loading pressure is 2.5 MPa. After the completion of column packing, the column was washed with 3BV of pure water until no turbidity occurred (pressure maintained 2.5 MPa: 10% expansion ratio of polymer beads). Wherein, the solid phase separation material is quaternary amine modified styrene-divinylbenzene copolymer particles (the content of quaternary ammonium structure is 12.76%). Particle size 35 microns, particle size difference +10 microns; specific surface area 800m2Per g, pore diameter of 50A and pore volume of 1.2cm3/g。
(2) And (3) sampling, namely sampling the steel pickling waste liquid (5 wt% ferrous sulfate and 20 wt% sulfuric acid mixed solution) according to 0.2BV/min, wherein the elution amount is 1BV, and detecting by sectional collection (collecting 1 bottle per 15 mL). The regions were partitioned according to fig. 2 based on the measured concentrations of hydrogen and ferrous ions in the respective bottles.
(3) After the sample loading is finished, eluting with pure water at the elution rate of 0.2BV/min and the elution amount of 1BV, and detecting by sectional collection (collecting 1 bottle per 15 mL). The regions were partitioned according to fig. 2 based on the measured concentrations of hydrogen and ferrous ions in the respective bottles.
(4) The acid recovery rate is 97.2 percent, and the ferrous ion recovery rate is 98.6 percent. Acid recovery concentration ct/c00.962, metal salt recovery concentration ct/c0＝0.946。
(5) And (3) repeating the step (1) and the step (2) for circulation.
Example 3
(1) Preparing a chromatographic separation column: 300mL of solid phase separation material is dispersed in 500mL of water and ultrasonically vibrated for 15 min. And (4) carrying out wet column packing on the dispersed solid phase separation material. 300mL of solid phase separation material was placed in a cartridge (DAC dynamic column DAC50) and the remainder was filled with water to ensure no air bubbles. The column loading pressure is 2.5 MPa. After the completion of column packing, the column was washed with 3BV of pure water until no turbidity occurred (pressure maintained 2.5 MPa: 10% expansion ratio of polymer beads). The solid phase separation material is quaternary amine modified styrene-divinylbenzene copolymer particles (the content of quaternary ammonium structure is 13.45%). The particle size is 50 microns, and the particle size difference is +/-10 microns; specific surface area 800m2Per g, pore diameter 50A, pore volume 1.2cm3/g。
(2) And (3) sampling, namely sampling the steel pickling waste liquid (5 wt% ferrous sulfate and 20 wt% sulfuric acid mixed solution) according to 0.6 BV/min. Detection was performed by fractionated collection (1 vial per 15 mL). Loading for 1 BV. The regions are divided according to fig. 2.
(3) After the sample loading is finished, eluting with pure water, wherein the elution rate is 0.6BV/min, the elution amount is 1BV, and detecting by sectional collection (collecting 1 bottle per 15 mL). The regions were partitioned according to fig. 2 based on the measured concentrations of hydrogen and ferrous ions in the respective bottles.
(4) The acid recovery rate is 96.2 percent, and the ferrous ion recovery rate is 98.1 percent. Acid recovery concentration ct/c0Metal salt recovery concentration c of 0.932t/c0＝0.951。
(5) And (3) repeating the step (1) and the step (2) for circulation.
Example 4
(1) Preparing a chromatographic separation column: 300mL of solid phase separation material is dispersed in 500mL of water and ultrasonically vibrated for 15 min. And (4) carrying out wet column packing on the dispersed solid phase separation material. 300mL of solid phase separation material was placed in a cartridge (DAC dynamic column DAC50) and the remainder was filled with water to ensure no air bubbles. The column loading pressure is 2.5 MPa. After the completion of column packing, the column was washed with 3BV of pure water until no turbidity occurred (pressure maintained 2.5 MPa: 10% expansion ratio of polymer beads). The solid phase separation material is quaternary amine modified styrene-divinylbenzene copolymer particles (the content of quaternary ammonium structure is 15.12%). The particle size is 85 micrometers, and the particle size difference is +/-10 micrometers; specific surface area 800m2Per g, pore diameter of 50A and pore volume of 1.2cm3/g。
(2) And (3) sampling, namely sampling the steel pickling waste liquid (5 wt% ferrous sulfate and 20 wt% sulfuric acid mixed solution) according to 0.6 BV/min. Detection was performed by fractionated collection (1 vial per 15 mL). Loading 2 BV. The regions are divided according to fig. 2.
(3) After the sample loading is finished, eluting with pure water, wherein the elution rate is 0.6BV/min, the elution amount is 2BV, and detecting by sectional collection (collecting 1 bottle per 15 mL). The regions were partitioned according to fig. 2 based on the measured concentrations of hydrogen and ferrous ions in the respective bottles.
(4) The recovery rate of acid is 95.1 percent, and the recovery rate of ferrous ions is 98.0 percent.Acid recovery concentration ct/c0Metal salt recovery concentration c 0.941t/c0＝0.94。
(5) And (3) repeating the step (1) and the step (2) for circulation.
Comparative example 1:
(1) preparing a chromatographic separation column: 300mL of solid phase separation material is dispersed in 500mL of water and ultrasonically vibrated for 15 min. And (4) carrying out wet column packing on the dispersed solid phase separation material. 300mL of solid phase separation material was placed in a cartridge (DAC dynamic column DAC50) and the remainder was filled with water to ensure no air bubbles. The column loading pressure is 2.5 MPa. After the completion of column packing, the column was washed with 3BV of pure water until no turbidity occurred (pressure maintained 2.5 MPa: 10% expansion ratio of polymer beads). The solid phase separation material is quaternary amine modified styrene-divinylbenzene copolymer particles (the content of quaternary ammonium structure is 15.12%). The particle size is 300 microns, and the particle size difference is +/-50 microns; specific surface area 800m2Per g, pore diameter of 50A and pore volume of 1.2cm3/g。
(2) And (3) sampling, namely sampling the steel pickling waste liquid (5 wt% ferrous sulfate and 20 wt% sulfuric acid mixed solution) according to 0.2 BV/min. Detection was performed by fractionated collection (1 vial per 15 mL). Loading for 1 BV. The regions are divided according to fig. 2.
(3) After the sample loading is finished, eluting with pure water, wherein the elution rate is 0.6BV/min, the elution amount is 1BV, and detecting by sectional collection (collecting 1 bottle per 15 mL). The regions were partitioned according to fig. 2 based on the measured concentrations of hydrogen and ferrous ions in the respective bottles.
(4) The acid recovery rate is 68.6 percent, and the ferrous ion recovery rate is 54.2 percent. Acid recovery concentration ct/c00.69, metal salt recovery concentration ct/c0＝0.54。
(5) And (3) repeating the step (1) and the step (2) for circulation.
The invention provides a method and a thought for separating and recovering acid and metal ions in steel pickling waste liquid, and a method and a way for realizing the technical scheme are many, the above description is only a preferred embodiment of the invention, and it should be noted that for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations are also regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A method for separating and recovering acid and metal ions in steel pickling waste liquid is characterized by comprising the following steps:
(1) loading: loading the iron and steel pickling waste liquid containing ferrous ions into a chromatographic separation column containing a solid-phase adsorption material, and collecting effluent liquid in three sections, namely low-concentration recovery area effluent liquid, ferrous ion recovery area effluent liquid and original-concentration recovery area effluent liquid;
(2) and (3) elution: eluting with eluent, collecting the eluent in three sections, namely the original concentrated recovery area eluent, the acid recovery area eluent and the low concentrated recovery area eluent;
(3) and (3) repeating the step (1) and the step (2) until the solid phase separation material has no separation effect on the hydrogen ions and the ferrous ions, and stopping circulation.
2. The method according to claim 1, wherein in the step (1), the acid concentration of the steel acid waste liquid is 5-30 wt%, and the ferrous ion concentration is 2-10 wt%.
3. The method according to claim 1, wherein in the step (1), the solid-phase adsorbent material has a styrene-divinylbenzene copolymer as a skeleton structure, and the styrene-divinylbenzene copolymer has a terminal quaternary ammonium structure.
4. The method according to claim 1, wherein in the step (1), the solid-phase adsorbent material has a particle size of 30 to 100 μm, and the particle size distribution has a difference of ± 10 μm.
5. The method according to claim 1, wherein in the step (1), the sample flow rate of the steel pickling waste liquid is 0.2-5 BV/min.
6. The method according to claim 1, wherein the sample amount of the steel pickling waste liquid in the step (1) is 1 to 5 BV.
7. The method of claim 1, wherein in step (1), said collecting in three segments comprises the steps of:
(i) a low concentration recovery zone: when the molar concentration of ferrous ions in the initial effluent liquid is more than 0.2 times of the molar concentration of ferrous ions in the steel pickling waste liquid, the effluent liquid obtained in the interval is low-concentration acid liquid;
(ii) a ferrous ion recovery area: (ii) when the molar concentration of hydrogen ions in the effluent liquid after the step (i) is finished is more than 0.8 times of the molar concentration of hydrogen ions in the steel pickling waste liquid, the effluent liquid obtained in the interval is the effluent liquid containing ferrous ions;
(iii) an original concentration recovery area: (iii) when the effluent after the step (ii) is finished till the loading is finished, the effluent obtained in the interval is the stock solution.
8. The method according to claim 1, wherein in step (2), the eluent is water; the flow rate of the eluent is 0.2-5BV/min, and the sample loading amount of the eluent is the same as that of the steel pickling waste liquid.
9. The method of claim 1, wherein in step (2), said collecting in three segments comprises the steps of:
(I) an original concentration recovery area: initiating the eluent until the molar concentration of ferrous ions in the eluent is less than 0.8 times of the molar concentration of ferrous ions in the steel pickling waste liquid, wherein the eluent obtained in the interval is the stock solution;
(II) an acid recovery zone: when the molar concentration of hydrogen ions in the eluent is less than 0.2 times of the molar concentration of hydrogen ions in the steel pickling waste liquid, the eluent obtained in the interval is the eluent containing acid;
(III) a low-concentration recovery zone: and (3) when the eluent obtained after the step (II) is finished and the sample loading of the eluent is finished, obtaining the eluent with low concentration in the interval.
10. The method according to claim 1, wherein in the step (3), either one or both of the effluent from the low concentration recovery zone in the step (1) and the effluent from the low concentration recovery zone in the step (2) are used as the eluent in the step (2) in the course of repeatedly circulating the step (1) and the step (2); when the dosage is not enough, the water is used for supplementing.
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