CN108557765B - Post-treatment method of pickling waste liquid containing zinc and iron ions - Google Patents
Post-treatment method of pickling waste liquid containing zinc and iron ions Download PDFInfo
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- CN108557765B CN108557765B CN201810427993.9A CN201810427993A CN108557765B CN 108557765 B CN108557765 B CN 108557765B CN 201810427993 A CN201810427993 A CN 201810427993A CN 108557765 B CN108557765 B CN 108557765B
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- 238000000034 method Methods 0.000 title claims abstract description 66
- 239000007788 liquid Substances 0.000 title claims abstract description 60
- 239000002699 waste material Substances 0.000 title claims abstract description 53
- 238000005554 pickling Methods 0.000 title claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000011701 zinc Substances 0.000 title claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- -1 iron ions Chemical class 0.000 title claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 129
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 109
- 230000003647 oxidation Effects 0.000 claims abstract description 101
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 32
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 28
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011592 zinc chloride Substances 0.000 claims abstract description 17
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 14
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 12
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 12
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 claims abstract description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007738 vacuum evaporation Methods 0.000 claims abstract description 12
- 238000011084 recovery Methods 0.000 claims abstract description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 57
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 56
- 229960002089 ferrous chloride Drugs 0.000 claims description 52
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 52
- 230000008569 process Effects 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 239000001301 oxygen Substances 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000011001 backwashing Methods 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005246 galvanizing Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 235000021110 pickles Nutrition 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 29
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 29
- 239000000047 product Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 7
- 239000011019 hematite Substances 0.000 description 6
- 229910052595 hematite Inorganic materials 0.000 description 6
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101100226347 Escherichia phage lambda exo gene Proteins 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a post-treatment method of pickling waste liquid containing zinc and iron ions. The existing spray roasting method of the pickling waste liquid can regenerate hydrochloric acid and produce ferric oxide at more than seven hundred degrees, and the Bory method can regenerate hydrochloric acid and produce ferric oxide at 150 ℃ and 7 atmospheric pressures. The technical scheme adopted by the invention comprises the following steps: recovering zinc chloride by ion exchange resin, recovering red iron oxide by vacuum evaporation concentration and heating oxidation reaction, recovering black iron oxide and regenerated hydrochloric acid by hydrothermal synthesis, and controlling the interior of the oxidation kettle and hydrothermal synthesis kettle to be in micro-negative pressure. The invention realizes the recovery of high-purity zinc chloride, ferric oxide and regenerated hydrochloric acid from the pickling waste liquid containing zinc and iron ions at medium temperature, and has the advantages of low energy consumption, low investment, low operation cost, no secondary pollution and the like.
Description
Technical Field
The invention belongs to the field of pickling waste liquid treatment, and particularly relates to a method for post-treating pickling waste liquid containing zinc and iron ions, and a method for recycling zinc chloride, iron oxide and regenerated hydrochloric acid for post-treating the pickling waste liquid in the process.
Background
The pickle liquor (generally called as pickle liquor, called WPL for short) produced in the hot galvanizing industry is mainly solution containing ferrous chloride. Such solutions are usually disposed of by a process known as pyrolysis, in which the spent pickling solution is sprayed into hot combustion gases at 900 ℃ and at 700 ℃ the ferrous iron is oxidised to ferric iron and decomposed to give hydrochloric acid and iron oxide products, the hydrochloric acid concentration obtained in this way not exceeding 18%; the high energy consumption and high investment make this method difficult to be universally used by other industries except large steel mills.
Yet another PORI process (PORI process) also recovers hydrochloric acid and iron oxide from WPL. The process is a non-conventional hydrometallurgical process, which achieves the regeneration of hydrochloric acid by obtaining a precipitate of hematite from a ferric chloride/ferrous chloride solution. This process is divided into two main steps:
1) an oxidation step: evaporation of excess water and oxidation of ferrous iron to ferric iron;
2) a hydrolysis step: in the presence of water, ferric chloride is converted to hematite and hydrochloric acid.
In the first step of the process (oxidation step), an aqueous solution of ferrous chloride, such as spent hydrochloric acid wash, is oxidized. The reaction equation (1) is:
12FeCl2(aq)+3O2(g)＝8FeCl3(aq)+2Fe2O3(s) (1)
this oxidation step reaction takes place in an autoclave: at 150 ℃ and 7 atm, air was sprayed into the ferrous chloride solution in the form of mist to produce ferric chloride and hematite, which produced one third of the total hematite.
The next hydrolysis step is carried out under atmospheric pressure conditions, the conversion of the ferric chloride produced in equation (1) above into hydrochloric acid and hematite is calculated in equation (2):
2FeCl3(aq)+3H2O(l)＝6HCl(g)+Fe2O3(s) (2)
in the hydrolysis step, the ferric chloride solution was pumped into another vessel and heated to-200 ℃ at atmospheric pressure. FeCl according to the above reaction equation (1)3Completely converted into gaseous HCl and hematite products with average particle size of 20-40 μm. The hydrochloric acid concentration obtained with this method can reach 30%, but this method is not suitable for solutions containing other chloride salts than ferric chloride. In addition, the cost of the corrosion-resistant material of the autoclave is also huge because the autoclave needs to work under 7 atmospheres and at the temperature of 150 ℃; similarly, it is difficult to accept the steel products from other industries besides large steel mills.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a method for recovering zinc chloride, ferric oxide and regenerated hydrochloric acid from the pickling waste liquid containing zinc and iron ions, which has mild reaction conditions and low equipment cost.
Therefore, the technical scheme adopted by the invention is as follows: a post-treatment method of pickling waste liquid containing zinc and iron ions comprises the following steps:
1) zinc chloride recovery
a) Containing zinc and iron ionsThe acid pickling waste liquor of the seed is treated with Zn2+Obtaining Zn by using no-load ion exchange resin with high selective adsorption2+Loading ion exchange resin and dezincification acid washing waste liquid;
b)Zn2+carrying out backwashing on the loaded ion exchange resin with water to obtain zinc chloride, recovering the resin after backwashing into no-load ion exchange resin, and returning to the step a);
2) recovery of red iron oxide
c) Carrying out vacuum evaporation and concentration on the dezincification pickling waste liquid to obtain a first dilute hydrochloric acid and a ferrous chloride solution;
d) introducing a ferrous chloride solution into an oxidation kettle under normal pressure, introducing oxygen into the oxidation kettle from the bottom of the oxidation kettle, allowing the oxygen to enter the oxidation kettle, allowing the reaction temperature in the oxidation kettle to be 120-;
3) recovery of black iron oxide and regeneration of hydrochloric acid
e) And d) the ferric chloride solution in the step d) enters a hydrothermal synthesis kettle for hydrothermal synthesis, the temperature of the hydrothermal synthesis kettle is 150-.
Preferably, in the step a), Zn is contained in the dezincification pickling waste liquid2+Less than 0.1 g/l.
Preferably, in the step c), the dezincification pickling waste liquid is subjected to negative pressure vacuum evaporation concentration at-50 to-90 Kpa and 60 to 100 ℃.
Most preferably, in step c), the dezincification pickling waste liquid is evaporated and concentrated under negative pressure and vacuum at-70 Kpa and 80 ℃.
As mentioned abovePreferably, in the step c), after vacuum evaporation concentration is finished, the mass concentration of HCl in the obtained first dilute hydrochloric acid is 5-15%, and FeCl in the obtained ferrous chloride solution2The mass concentration of (A) is 35-45%.
Preferably, in the step d), the concentration of ferric chloride is controlled to be 3-10mol/L, and the mass ratio of ferrous chloride to ferric chloride is 1: 10-30.
Preferably, in the step d), the oxidation kettle is a conical oxidation kettle, the oxygen source is selected from pure oxygen or air, the oxygen is from the bottom of the oxidation kettle and enters the oxidation kettle in a spraying manner, and fine microbubbles are formed in the oxidation kettle to perform a back mixing reaction with the ferrous chloride solution.
Preferably, in the step d), the concentration of ferric chloride is controlled by controlling the flow rate of oxygen or air injected into the oxidation reaction kettle, and the mass ratio of ferrous chloride/ferric chloride is controlled by controlling the feeding rate of ferrous chloride in the oxidation reaction kettle.
Preferably, in the step d), the upper opening of the conical oxidation kettle is provided with a reflux condenser.
Preferably, in the step d), a diversion barrel sleeved on the stirrer is arranged in the conical oxidation kettle, and the upper end and the lower end of the diversion barrel are both opened; the middle part of the stirrer is provided with a layer of stirring head positioned in the guide barrel, and the bottom of the stirrer is provided with a layer of stirring head positioned below the guide barrel; the ferrous chloride solution directly enters the diversion barrel when being guided into the oxidation kettle. Through the diversion barrel and the layer of stirring head positioned in the diversion barrel, the ferrous chloride is prevented from flowing out quickly, the retention time of the ferrous chloride in the kettle is prolonged, and the ferrous chloride is oxidized more completely.
Preferably, in the step e), the temperature of the injected first dilute hydrochloric acid and water is controlled to be 50-95 ℃.
As a preference for the above process, in step e), the HCl mass concentration in the concentrated hydrochloric acid is not less than 25%.
Preferably, the pickling waste liquid containing zinc and iron ions is selected from the group consisting of: one or more of acid washing waste liquid of hot galvanizing, mineral leaching liquid using hydrochloric acid as a leaching agent, etching waste liquid and back extraction iron waste liquid generated in the solvent extraction process.
In the above method, the red iron oxide is preferably red α -type iron oxide, and the black iron oxide is preferably black α -type iron oxide.
Preferably, the vacuum evaporation concentration is a multi-stage vacuum evaporation concentration.
Preferably, the oxidation kettle is a multi-stage tapered oxidation kettle formed by connecting a plurality of single-stage tapered oxidation kettles in series.
Preferably, the micro-negative pressure in step d) or step e) is between-20 and-10 kPa.
And c), evaporating a large amount of water in the dezincification acid washing waste liquid into water vapor through the evaporation process in the vacuum evaporation and concentration process, evaporating most of HCl gas in the waste liquid out of the solution along with the water vapor, condensing the water vapor into water through heat exchange and condensation, and absorbing the HCl gas into the water to form dilute hydrochloric acid, namely the first dilute hydrochloric acid. Most of water and HCl are evaporated from the dezincification pickling waste liquor through evaporation to form a concentrated ferrous chloride solution, so that a first dilute hydrochloric acid and the concentrated ferrous chloride solution are respectively obtained.
The micro negative pressure of the step d) or the step e) can ensure the smooth outflow of the gas in the oxidation kettle and the hydrothermal synthesis kettle in a micro negative pressure state, thereby ensuring the normal operation of the mass transfer oxidation process and the hydrothermal synthesis process; secondly, the reaction speed in the processes of mass transfer oxidation and hydrothermal synthesis can be improved by controlling the micro negative pressure and considering the reaction kinetics, thereby being beneficial to the reaction; and moreover, the reaction temperature in the mass transfer oxidation process and the hydrothermal synthesis process is reduced.
The oxidation kettle adopts a conical oxidation kettle, a reflux condenser is arranged at the top (namely the upper opening) of the reaction kettle, and the liquid level of the oxidation reaction kettle is controlled by controlling the heat exchange of the condenser, so that the full oxidation time of the ferrous chloride is ensured. In the oxidation kettle, oxygen enters in a spraying mode, the lower space of the conical oxidation kettle is favorable for heating air or oxygen in the kettle, and is favorable for the gas to be broken into micro bubbles under stirring, so that the rising space of the micro bubbles is prolonged, and the utilization rate of the oxygen is further improved. When a plurality of single-stage conical oxidation kettles are connected in series to form the multi-stage conical oxidation kettle for use, the contact time of ferrous chloride and oxygen is fully ensured, and the oxidation of the ferrous chloride is more complete.
When the hydro-thermal synthesis is carried out in the step e), when the mass concentration of HCl in the first dilute hydrochloric acid is less than 15%, the first dilute hydrochloric acid is completely adopted as the hydro-thermal synthesis requirement; when the mass concentration of HCl in the first dilute hydrochloric acid is higher than 15%, adopting pure water or the first dilute hydrochloric acid diluted by the pure water as a feed liquid for hydrothermal synthesis; when the amount of the first dilute hydrochloric acid is less and cannot meet the hydrothermal synthesis liquid inlet amount, pure water is adopted.
The invention adopts another specific technical scheme that: a post-treatment method of pickling waste liquid containing zinc and iron ions comprises the following steps:
1) selective pair of Zn2+The no-load ion exchange resin with high selective adsorption is used for removing Zn from the waste pickling liquid containing Zn and Fe ions2+Adsorbing to resin to become loaded resin;
2) performing multi-stage vacuum evaporation concentration on the dezincification pickling waste liquid treated in the step 1), and concentrating to generate two products: one is dilute hydrochloric acid, the HCl concentration is 5-15%; the other is a concentrated ferrous chloride solution, and the concentration of the ferrous chloride solution is 35-45%; in the process of vacuum evaporation and concentration of the dezincification acid washing waste liquid, a large amount of water in the waste liquid is evaporated into water vapor through the evaporation process, most of HCl gas in the waste liquid is volatilized from the solution along with the water vapor, and the water vapor is condensed into water through heat exchange and condensation, and the HCl gas is absorbed in the water, so that dilute hydrochloric acid, namely first dilute hydrochloric acid, is formed; evaporating the dezincification pickling waste liquor to evaporate most of water and HCl from the waste liquor to form a concentrated ferrous chloride solution;
3) the concentrated ferrous chloride solution treated in the step 2) enters a multistage conical oxidation kettle, oxygen is sprayed into the kettle from the bottom of the conical oxidation kettle, the concentration of ferric chloride is controlled to be 3-10mol/L, the mass ratio of the ferrous chloride to the ferric chloride is controlled to be 1: 10-30, the reaction temperature in the kettle is 120-; the ferrous chloride is oxidized into red alpha-type ferric oxide with pigment performance and ferric chloride solution; adjusting the concentration of ferric chloride solution to be kept at 3-10mol/L at the outlet of the conical oxidation kettle, evaporating HCl remained in the ferrous chloride solution to form HCl gas at the same time, and absorbing the HCl gas by first dilute hydrochloric acid to form second dilute hydrochloric acid; carrying out the next operation on the obtained ferric chloride solution;
the dilute hydrochloric acid treated in the step 2) is respectively used as a reactant in the hydrothermal synthesis process and an absorption liquid for generating HCl gas, and the next operation is carried out;
4) enabling the ferric chloride solution treated in the step 3) to flow into a kettle for hydrothermal synthesis, further increasing the temperature of the ferric chloride solution to 150-:
a. the reaction temperature in the hydrothermal synthesis process is controlled, and the temperature condition in the kettle directly influences the reaction rate;
b. the concentration of ferric chloride is continuously reacted with ferric chloride by adding dilute hydrochloric acid, and the addition amount of the dilute hydrochloric acid influences the concentration of the ferric chloride in the kettle. Therefore, the addition amount of the dilute hydrochloric acid must be adjusted according to factors such as the temperature in the kettle, the concentration of ferric chloride and the like, so as to ensure the smooth operation of the hydrothermal synthesis process;
controlling the temperature of the dilute hydrochloric acid at 50-95 ℃, controlling the reaction time at 200-; under the condition that the first dilute hydrochloric acid is insufficient or the acid content of the first dilute hydrochloric acid is too high and the mass concentration is higher than 15 percent and can not completely meet the requirement of hydrothermal synthesis feed liquor, supplementing or simply using pure water; if the addition amount of the dilute hydrochloric acid is too large: a. when the temperature in the kettle can not be maintained at 150-; b. and the ferric chloride in the kettle is diluted without reaction, which reduces the concentration of the ferric chloride and leads to the reduction of the yield of the black ferric oxide;
the products are black high-purity alpha-type ferric oxide and regenerated hydrogen chloride gas, and the obtained HCl gas is subjected to the next operation;
5) carrying out backwashing on the loaded resin treated in the step 1) by using pure water to obtain ZnCl2The product, the resin after the back washing becomes the no-load ion exchange resin again, and the step 1) is returned;
6) absorbing the HCl gas treated in the step 4) by the dilute hydrochloric acid treated in the step 2) to obtain a concentrated hydrochloric acid product with the concentration not lower than 25%.
The acid pickling waste liquid after dezincification can be further separated by vacuum distillation, and the concentrated ferrous chloride solution with the concentration of 35-45% can ensure Fe2+The ions are fully contacted with FeOCl and oxygen.
Oxygen (or oxygen-containing gas) enters the conical oxidation kettle and is mixed with the concentrated ferrous chloride solution, so that Fe is generated2+The ions are oxidized to form an oxygen mass transfer substance FeOCl, the FeOCl is an intermediate product of ferrous chloride and oxygen (or air), the solubility of the oxygen in the ferric chloride solution can be increased, and the FeOCl is a continuous catalyst and can accelerate the oxidation of the ferrous chloride in the ferric chloride solution. Continuously and fully mixing the concentrated ferrous chloride solution with FeOCl in an aerobic atmosphere in a multistage conical oxidation kettle as long as FeCl exists in the mixed solution2All of which need to have a Fe2+Is oxidized into Fe3+Is necessary to change iron to red Fe2O3And in the process of adsorbing and removing other impurity ions in the solution, after the impurities are removed, the purity of the black iron oxide product generated in the subsequent hydrothermal synthesis process is improved. The chemical reaction equation for this process is as follows:
temperature control interval (T120-
4FeCl2+O2→2FeCl3+2FeOCl (3)
4FeCl2+4FeOCl+O2→2Fe2O3+4FeCl3 (4)
12FeCl2+3O2→8FeCl3+2Fe2O3 (5)
The reaction formula (5) is the total reaction formula of the reaction formula (3) + the reaction formula (4).
Step 4) and 5) concentrating FeCl in ferrous chloride solution2The concentration is preferably 38-43%.
The temperature of the mass transfer oxidation reaction in step 6) is preferably 135-155 ℃, during which Fe is in the ferric chloride solution2+Mass transfer material FeOCl is preferentially generated with the oxygen-containing gas and is continuously generated, which can accelerate the oxidation process of ferrous chloride in ferric chloride solution.
In the step 6), the concentration of ferric chloride is preferably controlled to be 4-8 mol/L, the mass ratio of ferrous chloride to ferric chloride is controlled to be 1: 15-25, and the oxidation time is controlled to be 200-300 min.
In the multistage conical oxidation kettle under the conditions, oxygen (or oxygen-containing gas) enters the kettle from the bottom of the conical oxidation kettle in a spraying mode, and fine microbubbles are formed in the kettle to perform a reverse mixing reaction with the concentrated ferrous chloride solution; the top of the reaction kettle is provided with a condenser, and the liquid level of the oxidation reaction kettle is controlled by controlling the heat exchange of the condenser, so that the sufficient oxidation time of the ferrous chloride is ensured.
In the multi-stage conical oxidation kettle with the above conditions, ferrous chloride is oxidized into red alpha-type ferric oxide with pigment performance and ferric chloride.
The outlet of the multistage tapered oxidation kettle under the conditions is controlled by an adjusting valve, and the concentration of ferric chloride is kept between 3 and 10 mol/L.
In the hot synthesis kettle for ferric chloride, the solution temperature of ferric chloride is kept at 185 ℃ of 165-.
Preferably, dilute hydrochloric acid or pure water treated in the step 5) is added into the ferric chloride hydrothermal synthesis kettle under the above conditions to perform hydrothermal synthesis reaction, and the temperature of the fed dilute hydrochloric acid or pure water is controlled to be 50-95 ℃.
Preferably, in the ferric chloride hydrothermal synthesis kettle under the above conditions, the hydrothermal reaction product of ferric chloride is black high-purity alpha-type ferric oxide and regenerated hydrogen chloride gas.
Preferably, the dilute hydrochloric acid generated in the step 2) is used as a reactant to react with ferric chloride in a hot synthesis kettle of ferric chloride to generate HCl gas, and the HCl concentration in the concentrated hydrochloric acid obtained by absorption is not lower than 25%.
Preferably, in the two-stage processes of oxidation and hydrothermal synthesis, the red iron oxide and the black iron oxide are both alpha-type iron oxide.
Preferably, the pickling waste liquid containing zinc and iron ions is one or more of pickling waste liquid from the hot galvanizing industry, mineral leaching liquid using hydrochloric acid as a leaching agent, etching waste liquid and back extraction iron waste liquid generated in a solvent extraction process.
After ferrous chloride is fully oxidized, the obtained red ferric oxide is separated from ferric chloride liquid, and the separated ferric chloride enters a hydrothermal reaction kettle to react to prepare black ferric oxide. In addition, the micro negative pressure in the oxidation kettle and the oxidation kettle of the hydrothermal synthesis kettle is controlled, and in the hydrothermal synthesis stage, the solution only contains ferric chloride in the initial state, and the control of the reaction condition of the ferric chloride in the hydrothermal reaction kettle is beneficial to forming a black ferric oxide product with a specific shape and appearance.
Compared with the current spray roasting method of pickling waste liquid, the method can regenerate hydrochloric acid and produce ferric oxide at more than seven hundred degrees, and the method can regenerate hydrochloric acid and produce ferric oxide at 150 ℃ and 7 atmospheric pressures. The invention has the following beneficial effects: the invention realizes the recovery of high-purity zinc chloride, ferric oxide and regenerated hydrochloric acid from the pickling waste liquid containing zinc and iron ions at medium temperature, and has the advantages of low energy consumption, low investment and low operation cost.
Drawings
FIG. 1 is a process flow diagram of recovery of zinc chloride, ferric chloride and regenerated hydrochloric acid from pickling waste liquid in an embodiment of the present invention;
FIG. 2 is a flow chart of the recovery of zinc chloride from the acid pickling waste liquid by adsorption dezincification of resin in the embodiment of the present invention;
FIG. 3 is a flow chart of the recovery of iron oxide and regeneration of hydrochloric acid from the spent pickling solution after dezincification in the embodiment of the present invention;
FIG. 4 is a graph of the solubility of ferric chloride at various temperatures according to an example of the present invention;
FIG. 5 is a schematic structural view of a single-stage conical oxidation vessel in an embodiment of the present invention.
FIG. 6 is a schematic connection diagram of a multi-stage oxidation reactor in an embodiment of the present invention;
FIG. 7a is a graph showing a distribution of red iron oxide particle sizes in accordance with an embodiment of the present invention;
FIG. 7b is a graph showing the distribution of the black iron oxide particle size in the example of the present invention.
Detailed Description
The invention is further described with reference to the drawings and the detailed description.
FeOCl used in the invention is an important mass transfer oxidation carrier, and the temperature of ferric chloride solution is at least above 120 ℃ to enable Fe2+The ions form chlorine-oxygen compound through oxidation, and the chlorine-oxygen compound can increase the solubility of oxygen in the ferric chloride solution, and play a role in transferring oxygen, thereby accelerating and promoting the oxidation of ferrous ions.
The following description is of specific embodiments which illustrate the principles of the invention, and is intended to be illustrative and not limiting of the principles of the invention.
The process flow chart of the invention for recovering zinc chloride, ferric chloride and regenerated hydrochloric acid from the pickling waste liquid is shown in figure 1, figure 2 and figure 3: the pickle liquor from the hot galvanizing industry typically comprises the following chemical components: fe2+: 180 g/l, Zn2+: 10-100 g/l, HCl: 3-5% (mass concentration) of a chloride salt system.
Acid pickling waste liquid and para-Zn2+After the ion exchange resin with high ion selectivity contacts, Zn2+After the ion is absorbed, the ion is changed into loaded ZnCl2ZnCl eluted by pure water from resin and loaded resin2Then the resin is changed into no-load resin, and the resin is recycled and returned to the system to be contacted with the pickling waste liquid; eluted ZnCl2Dehydrated to form the anhydrous zinc chloride powder product. The main reaction equation is as follows:
2RCl+Zn2++2Cl-→R2(ZnCl4) (Ⅰ)
R2(ZnCl4)→2RCl+Zn2++2Cl- (Ⅱ)
RCl in the equation is a chlorine type resin, R is a resin group; r2(ZnCl4) Is the existing form of the resin after absorbing the zinc chloride.
Concentrating the dezincification acid liquor waste liquid by vacuum distillation to produce dilute hydrochloric acid with HCl mass concentration of 5-15% and FeCl2A ferrous chloride concentrated solution with the mass concentration of 35-45%; dilute hydrochloric acid is used as a reactant and an absorbent of HCl gas generated in the hydrolysis reaction process, and oxygen-containing gas is introduced for oxidation when the ferric chloride is concentrated.
The temperature of the concentrated ferrous chloride during oxidation is 120-170 ℃, and the micro negative pressure in the oxidation kettle is controlled to be-0.04 MPa to-5 kPa, preferably-20 kPa to-10 kPa; fe in solution at this time2+The ions are rapidly oxidized into FeOOCl, under the atmosphere of continuously introducing oxygen-containing gas, FeOOCl accelerates the conversion of ferrous chloride in the solution into ferric chloride, and the solubility of ferric chloride in the solution at different temperatures is shown in figure 4. Red iron oxide slurry is generated in the process, and is separated by a settling concentrator to obtain a red solid iron oxide product; the ferric chloride solution enters the hot synthesis process of the ferric oxide water.
At the temperature of 120-170 ℃, oxygen-containing gas enters a concentrated ferrous chloride solution to accelerate Fe2+The iron chloride is fully mixed with oxygen and FeOCl to react to generate red ferric oxide and ferric chloride.
Fig. 5 is a schematic structural diagram of the single-stage tapered oxidation kettle of the present invention, and a stirring system of the single-stage tapered oxidation kettle 30 is composed of a stirring motor 1, a speed reducer 2, a frame 3, a mass transfer oxidation kettle stirring port mounting plate 26, a stirrer first-layer stirring head 8, a stirrer second-layer stirring head 9, a stirrer stirring shaft 15, and the like, and the stirring is mounted above a mass transfer oxidation kettle body 14 through a mass transfer oxidation kettle stirring port 25 of the single-stage tapered oxidation kettle 30. The single-stage conical oxidation kettle 30 is arranged on a bearing beam of a factory building through a mass transfer oxidation kettle support 7.
The concentrated ferrous chloride solution enters the diversion barrel 16 through the material inlet 18 of the mass transfer oxidation kettle of the single-stage conical oxidation kettle 30, is mixed with the solution in the kettle through the stirring head 8 at the first layer of the stirrer, and then enters the kettle body 14 of the mass transfer oxidation kettle for oxidation reaction. Oxygen (oxygen-containing gas) enters the kettle through an oxygen inlet 12, and the gas is dispersed through a second-layer stirring head 9 of the stirrer to form micro-fine bubbles which enter the kettle to participate in oxidation reaction. The kettle body is heated by adopting heat conduction oil or steam, if the kettle body is heated by adopting the heat conduction oil, the heat conduction oil enters the kettle body heat conduction jacket 10 through the heat conduction oil inlet 11 and flows out from the heat conduction oil outlet 17 to heat the reaction kettle. If steam is adopted, the steam enters the kettle body heat conduction jacket 10 from the heat conduction oil outlet 17 to heat the kettle body, and steam condensate water flows out from the steam condensate water outlet 11.
After the reaction of oxygen (oxygen-containing gas) in the mass transfer oxidation kettle body 14 is finished, the oxygen (oxygen-containing gas) is discharged through a gas outlet 19 of the mass transfer oxidation kettle, at the moment, a part of water vapor is discharged from a gas outlet along with the water vapor due to the higher temperature in the kettle, the water vapor enters a condenser 22 at the kettle mouth of the mass transfer oxidation kettle through a gas inlet 20 of the condenser at the kettle mouth of the mass transfer oxidation kettle to be condensed, the water vapor flows back into the oxidation kettle after being condensed in the condensation process, and the non-condensable gas is discharged from a gas outlet 24 of the condenser at the kettle mouth of. The heat exchange of the condenser adopts circulating cooling water for cooling, the circulating cooling water enters the shell pass of the condenser through a cooling circulating water inlet 23 of a kettle mouth condenser of the mass transfer oxidation kettle, and is discharged through a cooling circulating water outlet 21 of the kettle mouth condenser of the mass transfer oxidation kettle after heat exchange.
Fig. 6 is a schematic connection diagram of a multi-stage oxidation kettle of the present invention, when a plurality of single-stage tapered oxidation kettles are selected for serial use, after oxidation is completed, red iron oxide slurry in the kettle is discharged through an oxidation kettle material outlet 6 of the single-stage tapered oxidation kettle 30, enters another single-stage tapered oxidation kettle 30 through a mass transfer oxidation kettle connection short pipe 40 for continuous reaction, and enters the next tapered oxidation kettle in a self-flowing manner, so that the retention time of the slurry outside the kettle is shortened, and the problem that the slurry is crystallized and blocks the pipeline due to temperature loss caused by entering the pipeline is avoided.
The grain size of the red iron oxide product obtained in the mass transfer oxidation stage is shown in figure 7a, the product is used for adsorbing and removing other impurity ions in the solution, and after the impurities are removed, the high-purity black iron oxide product is generated in the subsequent iron oxide hot synthesis process. The chemical reaction equation for this process is as follows:
4FeCl2+O2→2FeCl3+2FeOCl (3)
4FeCl2+4FeOCl+O2→2Fe2O3(Red) +4FeCl3 (4)
The concentrated ferrous chloride is oxidized to FeCl3After the solution is dissolved, the temperature is in the range of 150 ℃ to 200 ℃, the micro negative pressure is controlled in the oxidation kettle, the micro negative pressure is controlled to be-0.04 MPa to-5 kPa, and the micro negative pressure is preferably kept to be-20 kPa to-10 kPa; the black iron oxide and HCl gas are generated by hydrothermal synthesis reaction with water, and the main reaction formula is as follows:
2FeCl3+3H2O→Fe2O3(Black) +6HCl (6)
The red iron oxide produced by the oxidation process is chemically different from the black iron oxide produced by the hydrolysis process, as shown in table 1 below.
The red iron oxide can carry away a large amount of Al2O3、SiO2、SO4 2-、Cr2O3、Cl-And the like, which act as a pure solution and can be generally used as a pigment; and the black iron oxide has higher purity and can be used in soft magnetic materials. The particle size of the black iron oxide is shown in FIG. 7 b.
The temperature of HCl gas generated in the hot synthesis process of the molten iron oxide is between 120 ℃, and hydrogen chloride absorption liquid generated in the oxidation process is used for cyclic absorption, so that finished hydrochloric acid with HCl concentration not lower than 25% can be generated.
TABLE 1 iron oxide chemical composition Table
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Any simple modification, equivalent change and modification of the above embodiments according to the technical spirit of the present invention fall within the scope of the present invention.
Claims (9)
1. A post-treatment method of pickling waste liquid containing zinc and iron ions is characterized by comprising the following steps:
1) zinc chloride recovery
a) The pickling waste liquid containing zinc and iron ions is treated by the treatment of Zn2+Obtaining Zn by using no-load ion exchange resin with high selective adsorption2+Loading ion exchange resin and dezincification acid washing waste liquid;
b)Zn2+carrying out backwashing on the loaded ion exchange resin with water to obtain zinc chloride, recovering the resin after backwashing into no-load ion exchange resin, and returning to the step a);
2) recovery of red iron oxide
c) Carrying out vacuum evaporation and concentration on the dezincification pickling waste liquid to obtain a first dilute hydrochloric acid and a ferrous chloride solution;
d) under normal pressure, ferrous chloride solution is led into an oxidation kettle, the oxidation kettle is a conical oxidation kettle, the top of the oxidation kettle is provided with a reflux condenser, the liquid level of the oxidation kettle is controlled by controlling the heat exchange of the condenser, a diversion barrel sleeved on a stirrer is arranged in the kettle of the oxidation kettle, the upper end and the lower end of the diversion barrel are both opened, the middle part of the stirrer is provided with a layer of stirring head positioned in the diversion barrel, the bottom of the stirrer is provided with a two-layer stirring head positioned below the diversion barrel, the ferrous chloride solution enters the diversion barrel from a material inlet of the oxidation kettle, oxygen enters the kettle from an oxygen inlet at the bottom of the oxidation kettle in a spraying mode, the reaction temperature in the oxidation kettle is 120-, recovering red ferric oxide, evaporating residual HCl in the ferrous chloride solution to form HCl gas, and absorbing the HCl gas by first dilute hydrochloric acid to form second dilute hydrochloric acid;
3) recovery of black iron oxide and regeneration of hydrochloric acid
e) And d) the ferric chloride solution in the step d) enters a hydrothermal synthesis kettle for hydrothermal synthesis, the temperature of the hydrothermal synthesis kettle is 150-.
2. The method as claimed in claim 1, wherein in step a), Zn is contained in dezincification pickling waste liquid2+Less than 0.1 g/l.
3. The method according to claim 1, wherein in the step c), the dezincification pickling waste liquid is subjected to negative pressure vacuum evaporation concentration at-50 to-90 Kpa and 60 to 100 ℃.
4. The method according to claim 1, wherein in step c), after vacuum evaporation concentration is completed, the mass concentration of HCl in the obtained first dilute hydrochloric acid is 5-15%, and FeCl in the obtained ferrous chloride solution is obtained2The mass concentration of (A) is 35-45%.
5. The method as claimed in claim 1, wherein in the step d), the concentration of ferric chloride is controlled to be 3-10mol/L, and the mass ratio of ferrous chloride to ferric chloride is 1: 10-30.
6. The method as claimed in claim 1, wherein in step d), the oxidation kettle is a conical oxidation kettle, the oxygen source is selected from pure oxygen or air, the oxygen is from the bottom of the oxidation kettle and enters the oxidation kettle by means of spraying, and fine microbubbles are formed in the oxidation kettle to perform back mixing reaction with the ferrous chloride solution.
7. The method according to claim 1, wherein the temperature of the injected first dilute hydrochloric acid or water in step e) is controlled to 50-95 ℃.
8. The process of claim 1, wherein in step e), the HCl mass concentration in the concentrated hydrochloric acid is not less than 25%.
9. The method according to claim 1, characterized in that the spent pickle liquor comprising zinc and iron ions is selected from the group consisting of: one or more of acid washing waste liquid of hot galvanizing, mineral leaching liquid using hydrochloric acid as a leaching agent, etching waste liquid and back extraction iron waste liquid generated in the solvent extraction process.
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| CN115246663A (en) * | 2021-12-17 | 2022-10-28 | 徐州瑞马智能技术有限公司 | Hot-dip galvanizing zinc-containing waste acid treatment process |
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| JP4688399B2 (en) * | 2002-10-18 | 2011-05-25 | 富士工機株式会社 | Method of recovering hydrochloric acid from iron hydrochloric acid treatment waste liquid |
| US7445721B2 (en) * | 2003-12-03 | 2008-11-04 | Idaho Research Foundation, Inc. | Reactive filtration |
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