CN108557765A - A kind of pickle liquor post-processing approach including zinc and iron ion - Google Patents
A kind of pickle liquor post-processing approach including zinc and iron ion Download PDFInfo
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- CN108557765A CN108557765A CN201810427993.9A CN201810427993A CN108557765A CN 108557765 A CN108557765 A CN 108557765A CN 201810427993 A CN201810427993 A CN 201810427993A CN 108557765 A CN108557765 A CN 108557765A
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- Prior art keywords
- hydrochloric acid
- chloride
- iron
- stills
- air blowing
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 235000021110 pickles Nutrition 0.000 title claims abstract description 47
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 35
- 239000011701 zinc Substances 0.000 title claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 21
- 238000012805 post-processing Methods 0.000 title claims abstract description 7
- 238000013459 approach Methods 0.000 title claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 149
- 238000000034 method Methods 0.000 claims abstract description 69
- 238000007664 blowing Methods 0.000 claims abstract description 68
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 43
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 23
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 iron ion Chemical class 0.000 claims abstract description 16
- 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 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011592 zinc chloride Substances 0.000 claims abstract description 13
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 11
- 238000007738 vacuum evaporation Methods 0.000 claims abstract description 10
- 230000008929 regeneration Effects 0.000 claims abstract description 8
- 238000011069 regeneration method Methods 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract 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 claims abstract description 6
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 44
- 239000001301 oxygen Substances 0.000 claims description 44
- 229910052760 oxygen Inorganic materials 0.000 claims description 44
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 41
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 38
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000007254 oxidation reaction Methods 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 28
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 229960002089 ferrous chloride Drugs 0.000 claims description 23
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 22
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 18
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 16
- 239000002699 waste material Substances 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 238000006701 autoxidation reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 101100226347 Escherichia phage lambda exo gene Proteins 0.000 claims description 3
- 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
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 description 24
- 230000003647 oxidation Effects 0.000 description 23
- 239000000047 product Substances 0.000 description 15
- 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
- 239000000126 substance Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000005246 galvanizing Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 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
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention discloses a kind of pickle liquor post-processing approach including zinc and iron ion.Current pickle liquor spray roasting will could regenerate hydrochloric acid in more than 700 degree and produce iron oxide, and Pori's method could regenerate hydrochloric acid under 150 DEG C and 7 atmospheric pressure and produce iron oxide.The technical solution adopted by the present invention includes：Ion exchange resin recycles zinc chloride, vacuum evaporation and heated oxide and reacts recycling red iron oxide, hydrothermal synthesis recycling black iron oxide and regeneration hydrochloric acid, and it is in tiny structure that it is interior with hydrothermal synthesis kettle, which to control stills for air blowing,.The present invention realizes the zinc chloride for recycling high-purity under medium temperature to the pickle liquor comprising zinc, iron ion, iron oxide and regeneration hydrochloric acid, and saving energy, small investment, operating cost are low, and not will produce the advantageous effects such as secondary pollution.
Description
Technical field
The invention belongs to pickle liquor process fields, specifically a kind of to be directed to the pickle liquor comprising zinc and iron ion
The method of post-processing, and recycle zinc chloride, iron oxide and regenerated hydrochloric acid in the process and recycle for after pickle liquor
The method of processing.
Background technology
The pickle liquor (commonly known as pickle liquor, abbreviation WPL) that galvanizing industry generates mainly contains protochloride
The solution of iron.This kind of solution is typically to be disposed by a kind of method being referred to as high temperature pyrolysis, at 700-900 DEG C, acid
It washes in the gas for the burning that waste liquid is injected into heat, it is ferrous oxidising at ferric iron, then obtain hydrochloric acid and iron oxide production through decomposing
Product, the concentration of hydrochloric acid obtained with this method do not exceed 18%；It is high energy consumption, with high investment so that this side in addition to large-scale steel mill
Method is difficult to be commonly used in other industries.
And another PORI flow (Pori's method), hydrochloric acid and iron oxide can be also recycled from WPL.The flow be it is a kind of very
The Wet-process metallurgy method of rule, by obtaining the precipitation of bloodstone from iron chloride/solution of ferrous chloride, to realize hydrochloric acid again
It is raw.This flow is divided into two main steps：
1) oxidation step：The evaporation of excessive water and ferrous oxidising at ferric iron；
2) hydrolysing step：In the presence of water, iron chloride converts to form bloodstone and hydrochloric acid.
In first step of this flow (oxidation step), the aqueous solution of frerrous chloride, such as abraum salt pickle, by oxygen
Change.Reaction equation (1) is：
12FeCl2(aq)+3O2(g)=8FeCl3(aq)+2Fe2O3(s) (1)
The reaction of this oxidation step is happened in autoclave：Under 150 DEG C, 7 atmospheric pressure, air sprays into chlorination in misty
Generate iron chloride and bloodstone while ferrous iron solution, the step for generate the one third of bloodstone total amount.
Next hydrolysing step in atmospheric conditions, above reaction equation (1) generated iron chloride conversion computer
The reaction equation (2) of hydrochloric acid and bloodstone：
2FeCl3(aq)+3H2O (l)=6HCl (g)+Fe2O3(s) (2)
Ferric chloride solution is pumped into another container in hydrolysing step, and under normal pressure, temperature is heated to~200
℃.According to above-mentioned reaction equation (1), FeCl3It is fully converted into gaseous HCl and hematite product, average grain diameter exists
20-40μm.The concentration of hydrochloric acid obtained with this method can reach 30%, but this method is not suitable for containing in addition to iron chloride
There is the solution of other chloride salts.In addition, due to working at a temperature of autoclave will be under 7 atmospheric pressure, 150 DEG C, pressurization
The price of the corrosion-resistant material of kettle is also expensive surprising；Likewise, in addition to large-scale steel mill, it is also difficult to be received by other industries.
Invention content
The technical problem to be solved by the present invention is to overcome the problems of the above-mentioned prior art, a kind of reaction condition is provided
Milder, low equipment cost recycles zinc chloride, iron oxide and the side for regenerating hydrochloric acid from the pickle liquor comprising zinc, iron ion
Method.
For this purpose, the technical solution adopted by the present invention is：A kind of pickle liquor post-processing approach including zinc and iron ion,
Including step：
1) chlorination zinc recovering
A) pickle liquor containing zinc and iron ion passes through to Zn2+The unloaded ion exchange resin for having high-selectivity adsorption, obtains
Zn2+Supported ionic exchanger resin and dezincification pickle liquor；
b)Zn2+Supported ionic exchanger resin carries out backwash zinc with water, forms zinc chloride, and the resin after backwash reverts to zero load
Ion exchange resin returns to step a)；
2) red iron oxide is recycled
C) dezincification pickle liquor obtains the first dilute hydrochloric acid and solution of ferrous chloride through vacuum evaporation；
D) under normal pressure, solution of ferrous chloride imports in stills for air blowing, and the bottom of source of oxygen autoxidation kettle enters in kettle, stills for air blowing
120-170 DEG C of interior reaction temperature, oxidation reaction 100-600min, and it is in tiny structure to control in stills for air blowing, tiny structure control-
0.04MPa~-5kPa, through sedimentation concentration device detach red iron oxide thickened pulp and ferric chloride solution, recycle red oxygen
Change iron, remaining HCl is formed by evaporation to HCl gases simultaneously in solution of ferrous chloride, and HCl gases absorb to be formed through the first dilute hydrochloric acid
Second dilute hydrochloric acid；
3) recycling black iron oxide and regeneration hydrochloric acid
E) ferric chloride solution of step d), which enters, carries out hydrothermal synthesis, hydrothermal synthesis kettle temperature degree 150- in hydrothermal synthesis kettle
200 DEG C, and it is in tiny structure to control in hydrothermal synthesis kettle, tiny structure control is kept in -0.04MPa~-5kPa in hydrothermal synthesis kettle
The concentration of iron chloride injects the first dilute hydrochloric acid of part or pure water, reaction time 200-500min is obtained high-purity in 5~12mol/L
Black iron oxide and hydrogen chloride gas, hydrogen chloride gas absorb to form concentrated hydrochloric acid through the second dilute hydrochloric acid.
As the preferred of the above method, in step a), Zn in dezincification pickle liquor2+Less than 0.1 grams per liter.
As the preferred of the above method, in step c), dezincification pickle liquor at -50~-90Kpa and 60~100 DEG C into
Row negative-pressure vacuum is concentrated by evaporation.
Most preferably as the above method, in step c), it is true that dezincification pickle liquor carries out negative pressure at -70Kpa and 80 DEG C
Sky is concentrated by evaporation.
As the preferred of the above method, in step c), after the completion of vacuum evaporation, HCl in the first obtained dilute hydrochloric acid
Mass concentration 5~15%, FeCl in obtained solution of ferrous chloride2Mass concentration 35~45%.
As the preferred of the above method, in step d), in stills for air blowing, control ferric chloride concn is in 3~10mol/L, chlorine
The mass ratio for changing ferrous iron/iron chloride is 1:10~30.
As the preferred of the above method, in step d), stills for air blowing select taper stills for air blowing, source of oxygen to be selected from purity oxygen or sky
The bottom of gas, source of oxygen autoxidation kettle is entered by way of injection in stills for air blowing, formed in stills for air blowing tiny microvesicle with
Solution of ferrous chloride carries out reverse hybrid reaction.
As the preferred of the above method, in step d), in stills for air blowing, control oxygen or air is injected into oxidation reaction
The concentration of flow control iron chloride in kettle controls the mass ratio of charging rate control frerrous chloride/iron chloride of frerrous chloride.
As the preferred of the above method, in step d), the suitable for reading of taper stills for air blowing carries reflux condenser.
As the preferred of the above method, a water conservancy diversion being sleeved on blender is equipped in step d), in the kettle of taper stills for air blowing
Bucket, the diversing bucket upper and lower end are open；The middle part of the blender is equipped with one layer of stirring-head being located in diversing bucket, blender
Bottom be equipped be located at diversing bucket below two layers of stirring-head；Solution of ferrous chloride is directly entered diversing bucket when importing in stills for air blowing
It is interior.By diversing bucket and one in diversing bucket layer of stirring-head, avoids frerrous chloride from quickly flowing out, exist to extend frerrous chloride
Residence time in kettle makes frerrous chloride obtain more completely aoxidizing.
As the preferred of the above method, in step e), the first dilute hydrochloric acid of injection and the temperature of water are controlled at 50~95 DEG C.
As the preferred of the above method, in step e), HCl mass concentrations are not less than 25% in concentrated hydrochloric acid.
As the preferred of the above method, the pickle liquor comprising zinc, iron ion is selected from：The pickle liquor of galvanizing,
One kind in the back extraction iron waste liquid generated in leaching of ores liquid, etching waste liquor, solvent extraction process using hydrochloric acid as leaching agent
Or it is several.
As the preferred of the above method, the red iron oxide is red α types iron oxide, black iron oxide is black α
Type iron oxide.
As the preferred of the above method, the vacuum evaporation is concentrated by evaporation for multi-stage vacuum.
As the preferred of the above method, the stills for air blowing are the multi-stage taper being connected by multiple single-stage taper stills for air blowing
Stills for air blowing.
As the preferred of the above method, the tiny structure of step d) or step e) are in -20~-10kPa.
Step c) is big in waste liquid by the progress of evaporation process during dezincification pickle liquor is through vacuum evaporation
The water of amount is evaporated into water vapour, and most of HCl gases in waste liquid can also be evaporated with water vapour from solution, passes through
Heat exchange condensation, water vapour are condensed into water, and HCl gases are absorbed in water, to form dilute hydrochloric acid, that is, the first dilute hydrochloric acid.
Dezincification pickle liquor is by evaporation, and by most water, HCl after being evaporated in waste liquid, the frerrous chloride for forming concentration is molten
Liquid, to respectively obtain the solution of ferrous chloride of the first dilute hydrochloric acid and concentration.
The tiny structure of step d) or step e), under micro-vacuum state, it is ensured that stills for air blowing, hydrothermal synthesis gas reactor
Unimpeded outflow, to ensure that mass transfer oxidation process, hydrothermal synthesis process are normally carried out；Secondly, by the control of tiny structure,
From kinetics consider, can improve mass transfer oxidation, hydrothermal synthesis process reaction speed, be conducive to reaction progress；And
And reduce mass transfer oxidation process, the reaction temperature of hydrothermal synthesis process.
Stills for air blowing select taper stills for air blowing, and (i.e. suitable for reading) with reflux condenser at the top of reaction kettle, pass through control
The heat exchange of condenser, to control the liquid level of oxidizing reactor, to ensure that frerrous chloride has sufficient oxidization time.In stills for air blowing
Interior, oxygen is entered by way of injection, and the lower space of taper stills for air blowing not only contributes to the heating of air or oxygen in kettle, and
And be conducive to gas square i.e. broken formation microvesicle under stiring, the space of microvesicle rising is extended, to further improve
The utilization rate of oxygen.Multi-stage taper stills for air blowing are connected into use, having fully ensured that protochloride by multiple single-stage taper stills for air blowing
The time of contact of iron and oxygen keeps the oxidation of frerrous chloride more complete.
When step e) carries out hydrothermal synthesis, when HCl mass concentrations then use first completely less than 15% in the first dilute hydrochloric acid
Dilute hydrochloric acid is as hydrothermal synthesis requirement；After HCl mass concentrations are higher than 15% in the first dilute hydrochloric acid, then pure water is used or using pure
Feed liquor of water-reducible first dilute hydrochloric acid as hydrothermal synthesis；When the amount of the first dilute hydrochloric acid is less, cannot meet hydrothermal synthesis into
When liquid measure, then pure water is used.
The present invention use another specific technical solution for：A kind of pickle liquor post-processing side including zinc and iron ion
Method comprising following steps：
1) selection is to Zn2+The unloaded ion exchange resin for having high-selectivity adsorption, the pickling comprising zinc and iron ion is given up
Zn in liquid2+It is adsorbed onto on resin, becomes loaded resin；
2) multi-stage vacuum evaporation and concentration is carried out through step 1) treated dezincification pickle liquor, concentration generates two kinds of products：
One is dilute hydrochloric acid, and HCl concentration is 5%~15%；Another kind is concentration solution of ferrous chloride, and solution of ferrous chloride concentration is 35
~45%；During dezincification pickle liquor is through vacuum evaporation, by the progress of evaporation process, a large amount of water quilt in waste liquid
Water vapour is flashed to, and most of HCl gases in waste liquid can also be evaporated with water vapour from solution, by heat exchange
Condensation, water vapour is condensed into water, HCl gases are absorbed in water, to form dilute hydrochloric acid, that is, the first dilute hydrochloric acid；Dezincification
Pickle liquor is by evaporation, by most water, HCl after being evaporated in waste liquid, forms concentration solution of ferrous chloride；
3) through step 2) treated concentration solution of ferrous chloride enter in multi-stage taper stills for air blowing, oxygen from taper aoxidize
The base injcction of kettle enters in kettle, and control ferric chloride concn is in 3~10mol/L, control frerrous chloride/iron chloride mass ratio 1:
10~30,120-170 DEG C of kettle interior reaction temperature, and it is in tiny structure to control in stills for air blowing, tiny structure control -0.04MPa~-
5kPa, control oxidization time is in 100-600min, and in the case of oxygen abundance, in ferric chloride solution, frerrous chloride is rapid
FeOCl is formed, FeOCl is a kind of lasting oxygen transfer substance, can accelerate the oxidation of frerrous chloride；Frerrous chloride is oxidized to red
Color has the α types iron oxide and ferric chloride solution of pigment performance；In the outlet of taper stills for air blowing, the dense of ferric chloride solution is adjusted
Degree is maintained at 3-10mol/L, and remaining HCl is formed by evaporation to HCl gases simultaneously in solution of ferrous chloride, and HCl gases are through first
Dilute hydrochloric acid absorbs to form the second dilute hydrochloric acid；Obtained ferric chloride solution carries out next step operation；
Step 2) treated dilute hydrochloric acid, respectively as during hydrothermal synthesis reactant and generate the suctions of HCl gases
Liquid is received, next step operation is carried out；
4) it is flowed into through step 3) treated ferric chloride solution and carries out hydrothermal synthesis in kettle, further increase the molten of iron chloride
Liquid temperature is to 150-200 DEG C, and it is in tiny structure to control in hydrothermal synthesis kettle, and tiny structure control is kept in -0.04MPa~-5kPa
The concentration of iron chloride is in 5~12mol/L in kettle, and part is added, and through step 2), treated that dilute hydrochloric acid is reacted, this part
Dilute hydrochloric acid usage amount and adding speed are controlled according to the response situation in kettle：
A. the control of the reaction temperature of hydrothermal synthesis process, the temperature conditions in kettle will directly affect the rate of reaction；
B. the concentration of iron chloride is constantly reacted with iron chloride by the addition of dilute hydrochloric acid, and dilute hydrochloric acid additive amount will
It can influence the concentration of the iron chloride in kettle.Thus the additive amount of dilute hydrochloric acid must be according to the concentration etc. of temperature, iron chloride in kettle
Factor is adjusted, to ensure being smoothed out for hydrothermal synthesis process；
At 50~95 DEG C, the reaction time controls in 200-500min, in hydrothermal synthesis kettle, chlorine for the temperature control of dilute hydrochloric acid
In addition the hydro-thermal reaction for changing iron, water needed for reaction inject or come from dilute hydrochloric acid, is preferred from dilute salt of system
Acid；Hydro-thermal conjunction cannot be fully met higher than 15% by crossing high concentration in the first dilute hydrochloric acid deficiency or the first dilute hydrochloric acid acid content
Under conditions of feed liquor, pure water will be added or used merely；If the additive amount of dilute hydrochloric acid is excessive：A. will so that temperature in the kettle from
When maintaining 150-200 DEG C, the reaction rate of hydrothermal synthesis will be directly reduced；B. iron chloride also unreacted, that is, quilt and in kettle
Dilution, will reduce ferric chloride concn, the yield of black iron oxide is caused to reduce；
Product is that high-purity α types iron oxide of black and regeneration hydrogen chloride gas, obtained HCl gases carry out next step behaviour
Make；
5) backwash zinc is carried out with pure water through step 1) treated loaded resin, forms ZnCl2Product, the resin after backwash
Become unloaded ion exchange resin again, returns to step 1)；
6) through step 2) treated dilute hydrochloric acid, absorb that treated that HCl gases obtain concentration is not less than through step 4)
25% concentrated hydrochloric acid product.
Vacuum distillation can further detach the pickle liquor after dezincification, and 35~45% concentration solution of ferrous chloride can
To ensure Fe2+Ion and FeOCl, oxygen come into full contact with.
Oxygen (or oxygen containing gas) enters in taper stills for air blowing, is mixed with concentration solution of ferrous chloride so that Fe2+Ion
Oxidation forms the intermediate product that oxygen transfer object FeOCl, FeOCl are frerrous chloride and oxygen (or air), can not only increase oxygen
Solubility in ferric chloride solution, it is even more a kind of to continue catalyst, it can speed up oxygen of the frerrous chloride in ferric chloride solution
Change.Concentration solution of ferrous chloride has in multi-stage taper stills for air blowing is continuously sufficiently mixed with FeOCl under oxygen atmosphere, only
Want in mixed solution that there is FeCl2, it is required for there are one by Fe2+It is oxidized to Fe3+Process, this process is indispensable
, it is that iron is become into red Fe2O3Product and by the process of other foreign ion Adsorptions in solution, after removing impurity, postorder
The black iron oxide product purity generated during hydrothermal synthesis improves.The chemical equation of this process is as follows：
Between temperature-controlled area (T=120-170 DEG C)
4FeCl2+O2→2FeCl3+2FeOCl (3)
4FeCl2+4FeOCl+O2→2Fe2O3+4FeCl3 (4)
12FeCl2+3O2→8FeCl3+2Fe2O3 (5)
Reaction equation (5) is the net reaction of reaction equation (3)+reaction equation (4).
Step 4), 5) in concentration solution of ferrous chloride in FeCl2Concentration is preferably 38~43%.
The temperature of mass transfer oxidation reaction in step 6) is preferably at 135-155 DEG C, during this, in ferric chloride solution,
Fe2+It can be preferentially produced mass transfer object FeOCl with oxygen-containing gas, and FeOCl is constantly generated, and frerrous chloride can be accelerated in chlorination
Oxidation process in ferrous solution.
In step 6) preferably in multi-stage taper stills for air blowing, 4~8mol/L of control ferric chloride concn, control frerrous chloride/
Iron chloride mass ratio is 1:15~25, control oxidization time is in 200-300min.
In the multi-stage taper stills for air blowing of above-mentioned condition, oxygen (or oxygen-containing gas) is passed through from the bottom of taper stills for air blowing
The mode of injection enters in kettle, and forms tiny microvesicle in kettle and carry out reverse hybrid reaction with concentration solution of ferrous chloride；
Condenser is carried at the top of reaction kettle, by controlling the heat exchange of condenser, to control the liquid level of oxidizing reactor, to ensure
Frerrous chloride has sufficient oxidization time.
In the multi-stage taper stills for air blowing of aforementioned condition, frerrous chloride is oxidized to the red α types oxygen with pigment performance
Change iron and iron chloride.
The multi-stage taper stills for air blowing of aforementioned condition export, and are controlled by regulating valve, keep the concentration of iron chloride in 3-
10mol/L。
In aforementioned iron chloride hydrothermal synthesis kettle, keeps the solution temperature of iron chloride to 165-185 DEG C, keep the dense of iron chloride
Degree controls in 6~10mol/L, reaction time in 300-400min, and tiny structure is preferably in -20~-10kPa ranges.
Preferably, in the iron chloride hydrothermal synthesis kettle of above-mentioned condition, be added through step 5) treated dilute hydrochloric acid or
Pure water carries out hydrothermal synthesis reaction, and the dilute hydrochloric acid of entrance or the temperature of pure water are controlled at 50~95 degree.
Preferably, in the iron chloride hydrothermal synthesis kettle of above-mentioned condition, the hydro-thermal reaction product of iron chloride is black
High-purity α types iron oxide and regeneration hydrogen chloride gas.
Preferably, the dilute hydrochloric acid that step 2) generates reacts in iron chloride hydrothermal synthesis kettle with iron chloride as reactant
HCl gases are generated, then HCl concentration is not less than 25% in the concentrated hydrochloric acid obtained through its absorption.
Preferably, oxidation, in hydrothermal synthesis two-stage process, two kinds of obtained red, black iron oxide are the oxidation of α types
Iron.
Preferably, it is described comprising zinc, iron ion pickle liquor from the pickle liquor of galvanizing industry, use hydrochloric acid
As one or more of the back extraction iron waste liquid generated in the leaching of ores liquid, etching waste liquor, solvent extraction process of leaching agent.
The present invention is first divided obtained red iron oxide and chlorination iron liquid after the completion of frerrous chloride is fully oxidized
From the iron chloride after detaching, which enters back into hydrothermal reaction kettle, to carry out reaction and prepare black iron oxide.In addition, and control stills for air blowing with
It is in tiny structure in hydrothermal synthesis kettle stills for air blowing, and in the hydrothermal synthesis stage, solution only contains iron chloride in initial state, and
The control of reaction condition of the iron chloride in hydrothermal reaction kettle advantageously forms the black oxidation iron product of specific morphology, appearance.
Compared to current pickle liquor spray roasting will more than 700 degree could regenerate hydrochloric acid with produce iron oxide,
And Pori's method wants that hydrochloric acid could be regenerated under 150 DEG C and 7 atmospheric pressure and produces iron oxide.The device have the advantages that
It is as follows：The present invention realize the zinc chloride for recycling high-purity under medium temperature to the pickle liquor comprising zinc, iron ion, iron oxide and
Hydrochloric acid is regenerated, saving energy, small investment, operating cost are low.
Description of the drawings
Fig. 1 is to recycle zinc chloride, iron chloride and regeneration hydrochloric acid process flow chart in the embodiment of the present invention from pickle liquor；
Fig. 2 is that resin adsorbs the flow chart that zinc chloride is recycled in dezincification from pickle liquor in the embodiment of the present invention；
Fig. 3 is to recycle iron oxide from pickle liquor after dezincification in the embodiment of the present invention and regenerate the flow chart of hydrochloric acid；
Fig. 4 is the solubility curve figure of iron chloride at different temperatures in the embodiment of the present invention；
Fig. 5 is the schematic configuration diagram of single-stage taper stills for air blowing in the embodiment of the present invention.
Fig. 6 is the signal connection figure of multi-stage oxidizing kettle in the embodiment of the present invention；
Fig. 7 a are red iron oxide grain size distribution in the embodiment of the present invention；
Fig. 7 b are black iron oxide grain size distribution in the embodiment of the present invention.
Specific implementation mode
The invention will be further described with specific implementation mode with reference to the accompanying drawings of the specification.
The FeOCl being used in the present invention is an important mass transfer oxidation carrier, is that ferric chloride solution temperature at least exists
120 DEG C or more can make Fe2+Ion is formed by chlorine oxygen compound by mode of oxidizing, and this chlorine oxygen compound can be in chlorine
Change the solubility for increasing oxygen in ferrous solution, play the role of mass transfer oxygen, to accelerate and promote the oxidation of ferrous ion.
Following description is the specific embodiment of the principle illustrated the present invention, is to explain and not limit the present invention
Principle for the purpose of.
In the slave pickle liquor of the present invention recycling zinc chloride, iron chloride and regeneration hydrochloric acid process flow chart as shown in Figure 1, Figure 2, figure
Shown in 3：Pickle liquor from galvanizing industry, typical pickle liquor include that chemical analysis is as follows：Fe2+：~180 grams/
It rises, Zn2+：10~100 grams per liters, HCl：3~5% (mass concentration) chloride systems.
Pickle liquor pass through with to Zn2+After ion has highly selective contacts ionic exchange resin, Zn2+After ion is adsorbed, become
To load ZnCl2Resin, loaded resin elute ZnCl through pure water2Afterwards, become unloaded resin, be recycled back into system and pickling
Waste liquid contacts；The ZnCl of elution2Become anhydrous zinc chloride powder product after dehydration.Key reaction equation is as follows：
2RCl+Zn2++2Cl-→R2(ZnCl4) (Ⅰ)
R2(ZnCl4)→2RCl+Zn2++2Cl- (Ⅱ)
RCl in equation is chloride type resin, and R is resin group；R2(ZnCl4) it is presence after resin adsorption zinc chloride
Form.
Acid solution waste liquid after dezincification is concentrated through vacuum distillation, the dilute hydrochloric acid that output HCl mass concentrations are 5%~15%
And FeCl2Mass concentration is 35~45% frerrous chloride concentrates；Dilute hydrochloric acid as in hydrolysis reaction reactant and production
The absorbent of raw HCl gases, concentration protochloride iron rule are passed through oxygen-containing gas and are aoxidized.
Temperature when frerrous chloride oxidation is concentrated at 120~170 DEG C, and it is in tiny structure, tiny structure control to control in stills for air blowing
System preferably remains in -20~-10kPa in -0.04MPa~-5kPa；Fe in solution at this time2+Ion is quickly oxidized into
FeOCl, under the atmosphere for being constantly passed through oxygen-containing gas, FeOCl will accelerate the frerrous chloride in solution to be transformed into iron chloride,
The solubility of Chlorine in Solution iron is as shown in Figure 4 under different temperatures.Red iron oxide slurry is will produce during this, by heavy
Inspissator separation is dropped, obtained red solid oxidation iron product；Ferric chloride solution enters iron oxide hydrothermal synthesis process.
Within the temperature range of 120~170 DEG C, oxygen containing gas enters in concentration solution of ferrous chloride, accelerates Fe2+Ion
Oxidation forms the process of FeOCl, and FeOCl is constantly formed, and frerrous chloride is sufficiently mixed with oxygen, FeOCl to react, and generates red oxygen
Change iron and iron chloride.
Fig. 5 is the schematic configuration diagram of the single-stage taper stills for air blowing of the present invention, the stirring systems of single-stage taper stills for air blowing 30 by
Stirring motor 1, speed reducer 2, rack 3, mass transfer stills for air blowing stirring port mounting plate 26, one layer of stirring-head 8 of blender, two layers of blender
The components such as stirring-head 9, blender agitating shaft 15 form, the mass transfer stills for air blowing stirring port which passes through single-stage taper stills for air blowing 30
25 are mounted on 14 top of mass transfer stills for air blowing autoclave body.Single-stage taper stills for air blowing 30 aoxidize autoclave leg 7 by mass transfer and are mounted on workshop
On spandrel girder.
Solution of ferrous chloride after concentration is entered by the mass transfer stills for air blowing material inlet 18 of single-stage taper stills for air blowing 30 and is led
It flows in bucket 16, enters in mass transfer stills for air blowing autoclave body 14 after being mixed with solution in kettle by one layer of stirring-head 8 of blender and carry out
Oxidation reaction.Oxygen (oxygen-containing gas) is entered by oxygen inlet 12 in kettle, which is carried out by two layers of stirring-head 9 of blender
Dispersion forms micro air bubble and enters participation oxidation reaction in kettle.Autoclave body heating uses conduction oil or steam, according to conduction oil plus
Heat, then conduction oil is by the entrance autoclave body heat conduction of heat conductive oil inlet 11 chuck 10, from the outflow of conduction oil outlet 17 to reaction kettle progress
Heating.According to steam, then steam enters autoclave body heat conduction chuck 10 from conduction oil outlet 17 and is heated to autoclave body, steam condensation
Water is flowed out from steam condensate (SC) outlet 11.
Oxygen (oxygen-containing gas) after the completion of reaction, passes through mass transfer stills for air blowing gas vent 19 in mass transfer stills for air blowing autoclave body 14
Discharge is aoxidized at this time since the higher water vapour of some of temperature in the kettle is discharged from gas vent together therewith by mass transfer
Kettle kettle mouth condenser-air entrance 20 enters mass transfer stills for air blowing kettle mouth condenser 22 and is condensed, and in condensation process, water vapour is cold
It is flowed back into stills for air blowing after solidifying, on-condensible gas is discharged from mass transfer stills for air blowing kettle mouth condenser-air outlet 24.The condenser changes
Thermal recovery carries out cooling down with recirculated cooling water, and recirculated cooling water passes through mass transfer stills for air blowing kettle mouth condenser cooling cycle water inlet
23 enter the shell side of condenser, are discharged by mass transfer stills for air blowing kettle mouth condenser cooling cycle water out 21 after heat exchange.
Fig. 6 is the signal connection figure of the multi-stage oxidizing kettle of the present invention, is used in series when selecting multiple single-stage taper stills for air blowing
When, after the completion of oxidation, the red iron oxide slurry in kettle is discharged by the stills for air blowing material outlet 6 of single-stage taper stills for air blowing 30,
Entering another single-stage taper stills for air blowing 30 by mass transfer stills for air blowing connection short tube 40, the reaction was continued, and slurry is by way of gravity flow
Into in next taper stills for air blowing, shorten slurry residence time on the outside of kettle, evades slurry due to causing temperature into pipeline
Degree loss and crystallization and the problem of block pipeline.
The grain size that mass transfer oxidation panel obtains red oxidization iron product is shown in shown in Fig. 7 a, the product its by other impurity in solution
The process of ionic adsorption removal, after removing impurity, the high-purity black iron oxide of generation during postorder iron oxide hydrothermal synthesis
Product.The chemical equation of this process is as follows：
4FeCl2+O2→2FeCl3+2FeOCl (3)
4FeCl2+4FeOCl+O2→2Fe2O3(red)+4FeCl3 (4)
Concentration frerrous chloride is oxidized to FeCl3After solution, within the temperature range of 150 DEG C -200 DEG C, and oxidation is controlled
It is in tiny structure in kettle, tiny structure is controlled in -0.04MPa~-5kPa, preferably remains in -20~-10kPa；Hydro-thermal occurs with water to close
At reaction, reaction generates black iron oxide and HCl gases, and key reaction formula is as follows：
2FeCl3+3H2O→Fe2O3(black)+6HCl (6)
The red iron oxide that oxidation process generates and the black iron oxide chemical purity that hydrolytic process generates are different, see
The following table 1.
Red iron oxide can take away a large amount of Al2O3、SiO2、SO4 2-、Cr2O3、Cl-Equal impurity, play the work of purified solution
With generally may be used as pigment；And the iron oxide purity of black is higher, can be used in soft magnetic materials.The grain of black iron oxide
Diameter is shown in shown in Fig. 7 b.
The HCl gas temperatures generated during iron oxide hydrothermal synthesis are at~120 DEG C, with the hydrogen chloride of oxidation process generation
Absorbing liquid carries out cyclic absorption, can generate the finished product hydrochloric acid that HCl concentration is not less than 25%.
1 iron oxide chemical analysis table of table
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form.It is all
It is that this is each fallen within to any simple modification, equivalent change and modification made by above example according to the technical essence of the invention
In the protection domain of invention.
Claims (10)
1. a kind of pickle liquor post-processing approach including zinc and iron ion, which is characterized in that including step：
1) chlorination zinc recovering
A) pickle liquor comprising zinc and iron ion passes through to Zn2+The unloaded ion exchange resin for having high-selectivity adsorption, obtains Zn2+
Supported ionic exchanger resin and dezincification pickle liquor；
b)Zn2+Supported ionic exchanger resin carries out backwash zinc with water, forms zinc chloride, and the resin after backwash reverts to unloaded ion
Exchanger resin returns to step a)；
2) red iron oxide is recycled
C) dezincification pickle liquor obtains the first dilute hydrochloric acid and solution of ferrous chloride through vacuum evaporation；
D) under normal pressure, solution of ferrous chloride imports in stills for air blowing, and the bottom of source of oxygen autoxidation kettle enters in kettle, anti-in stills for air blowing
Answer 120-170 DEG C of temperature, oxidation reaction 100-600min, and it is in tiny structure to control in stills for air blowing, tiny structure control-
0.04MPa~-5kPa, through sedimentation concentration device detach red iron oxide thickened pulp and ferric chloride solution, recycle red oxygen
Change iron, remaining HCl is formed by evaporation to HCl gases simultaneously in solution of ferrous chloride, and HCl gases absorb to be formed through the first dilute hydrochloric acid
Second dilute hydrochloric acid；
3) recycling black iron oxide and regeneration hydrochloric acid
E) ferric chloride solution of step d), which enters, carries out hydrothermal synthesis in hydrothermal synthesis kettle, 150-200 DEG C of hydrothermal synthesis kettle temperature degree,
And it is in tiny structure to control in hydrothermal synthesis kettle, tiny structure control keeps iron chloride in hydrothermal synthesis kettle in -0.04MPa~-5kPa
Concentration in 5~12mol/L, inject the first dilute hydrochloric acid of part or pure water, reaction time 200-500min, obtain high-purity black oxygen
Change iron and hydrogen chloride gas, hydrogen chloride gas absorb to form concentrated hydrochloric acid through the second dilute hydrochloric acid.
2. according to the method described in claim 1, it is characterized in that, in step a), Zn in dezincification pickle liquor2+Less than 0.1 gram/
It rises.
3. according to the method described in claim 1, it is characterized in that, in step c), dezincification pickle liquor in -50~-90Kpa and
Negative-pressure vacuum evaporation and concentration is carried out at 60~100 DEG C.
4. according to the method described in claim 1, it is characterized in that, in step c), after the completion of vacuum evaporation, obtain
The mass concentration of HCl is 5~15% in one dilute hydrochloric acid, FeCl in obtained solution of ferrous chloride2Mass concentration 35~
45%.
5. according to the method described in claim 1, it is characterized in that, in step d), in stills for air blowing, control ferric chloride concn exists
The mass ratio of 3~10mol/L, frerrous chloride/iron chloride are 1:10~30.
6. according to the method described in claim 1, it is characterized in that, in step d), stills for air blowing select taper stills for air blowing, source of oxygen
Selected from purity oxygen or air, the bottom of source of oxygen autoxidation kettle is entered by way of injection in stills for air blowing, the shape in stills for air blowing
Reverse hybrid reaction is carried out at tiny microvesicle and solution of ferrous chloride.
7. according to the method described in claim 1, it is characterized in that, in step e), the first dilute hydrochloric acid of injection or the temperature of water
Control is at 50~95 DEG C.
8. according to the method described in claim 1, it is characterized in that, in step e), HCl mass concentrations are not less than in concentrated hydrochloric acid
25%.
9. according to the method described in claim 1, it is characterized in that, the pickle liquor comprising zinc and iron ion is selected from：Heat
The back extraction generated in zinc-plated pickle liquor, the leaching of ores liquid using hydrochloric acid as leaching agent, etching waste liquor, solvent extraction process
One or more of iron waste liquid.
10. according to the method described in any one of claim 1-9, which is characterized in that the red iron oxide is red α types
Iron oxide, black iron oxide are black α type iron oxide.
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| CN110841331A (en) * | 2019-10-23 | 2020-02-28 | 江苏永葆环保科技有限公司 | Method for separating iron and zinc in iron-containing waste acid |
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| DE112022005924T5 (en) * | 2021-12-10 | 2024-10-02 | Basf Se | Process for refining iron oxides, resulting iron oxides and their use |
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