CN108569722A - The method that hydrochloric acid pickling waste liquor prepares iron oxide and ammonium sulfate - Google Patents
The method that hydrochloric acid pickling waste liquor prepares iron oxide and ammonium sulfate Download PDFInfo
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- CN108569722A CN108569722A CN201710136923.3A CN201710136923A CN108569722A CN 108569722 A CN108569722 A CN 108569722A CN 201710136923 A CN201710136923 A CN 201710136923A CN 108569722 A CN108569722 A CN 108569722A
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- solid
- liquid separation
- phase material
- hydrochloric acid
- ammonium sulfate
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 141
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 66
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052921 ammonium sulfate Inorganic materials 0.000 title claims abstract description 45
- 238000005554 pickling Methods 0.000 title claims abstract description 45
- 235000011130 ammonium sulphate Nutrition 0.000 title claims abstract description 44
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 193
- 239000007788 liquid Substances 0.000 claims abstract description 83
- 238000000926 separation method Methods 0.000 claims abstract description 75
- 235000011167 hydrochloric acid Nutrition 0.000 claims abstract description 67
- 239000007791 liquid phase Substances 0.000 claims abstract description 53
- 239000007790 solid phase Substances 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002425 crystallisation Methods 0.000 claims abstract description 32
- 230000008025 crystallization Effects 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000004090 dissolution Methods 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000006073 displacement reaction Methods 0.000 claims abstract description 16
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 10
- 239000010959 steel Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 235000021110 pickles Nutrition 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 238000009834 vaporization Methods 0.000 claims abstract description 6
- 230000008016 vaporization Effects 0.000 claims abstract description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 54
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 50
- 239000011790 ferrous sulphate Substances 0.000 claims description 49
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 41
- 238000001704 evaporation Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 230000008020 evaporation Effects 0.000 claims description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 27
- 239000012535 impurity Substances 0.000 claims description 24
- 239000007792 gaseous phase Substances 0.000 claims description 22
- 238000007906 compression Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 17
- 239000012043 crude product Substances 0.000 claims description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052603 melanterite Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 239000002910 solid waste Substances 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- NGWKGSCSHDHHAJ-YPFQVHCOSA-N Liquoric acid Chemical compound C1C[C@H](O)C(C)(C)C2CC[C@@]3(C)[C@]4(C)C[C@H]5O[C@@H]([C@](C6)(C)C(O)=O)C[C@@]5(C)[C@@H]6C4=CC(=O)C3[C@]21C NGWKGSCSHDHHAJ-YPFQVHCOSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000470 constituent Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 19
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 235000014413 iron hydroxide Nutrition 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- -1 papermaking Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229940095054 ammoniac Drugs 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
- C01B7/0712—Purification ; Separation of hydrogen chloride by distillation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
-
- 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
- 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)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of methods that hydrochloric acid pickling waste liquor prepares iron oxide and ammonium sulfate, be using hydrochloric acid solution be pickle carries out pickling processes to remove the chlorhydric acid pickling waste containing iron obtained during oxide on surface as raw material by steel members, and steps are as follows for the method：(1) it is separated by solid-liquid separation；(2) pre-heating temperature elevation；(3) miscible displacement；(4) flash vaporization；(5) evaporative crystallization；(6) it is separated by solid-liquid separation；(7) mixed dissolution；(8) pH value is adjusted；(9) adsorption-edulcoration；(10) it is separated by solid-liquid separation；(11) oxidation is neutralized；(12) it is separated by solid-liquid separation：Liquid phase material further prepares ammonium sulfate product, and solid-phase material further prepares iron oxide product；And ammonium sulfate byproduct can be prepared when further preparing ammonium sulfate product.Present invention process is reasonable, and method is simple, and environmental protection and energy saving, manufacturing cost is low, good product quality, and valuable constituent utilization rate is high.
Description
Technical field
The present invention relates to a kind of method that hydrochloric acid pickling waste liquor prepares iron oxide and ammonium sulfate, being will by pickle of hydrochloric acid solution
Steel members carry out pickling processes to remove the chlorhydric acid pickling waste containing iron obtained during oxide on surface as raw material, are provided
The method that source comprehensive utilization prepares iron oxide and ammonium sulfate, belongs to environment chemical engineering field.
Background technology
Iron oxide is hexagonal crystal system, and molecular formula is α-Fe2O3, have the characteristics that nontoxic, alkaline-resisting, heat-resisting, 1560 DEG C of decomposition temperature,
In light red brown, become grey black in strong row calcination, but shape of being clayed into power becomes red again.Iron oxide is widely used in
The industries such as building materials, paint, coating, papermaking, rubber, ceramics, glass and ink.The method for preparing iron oxide has dry and wet two
Kind.Dry method is also known as green vitriol method, is to be dehydrated green vitriol in the equipment such as rotary kiln, tunnel oven, and oxidizing roasting removes SO4 2-, generate oxygen
Change iron.It will produce a large amount of dust in the calcination process of dry process iron oxide, environmental pollution is larger；In addition, dry process
Iron oxide product is second-rate.Wet method is also known as the precipitation method, makees raw material with green vitriol or ferric trichloride, alkali is added to be neutralized, utilize crystalline substance
Kind crystallization, oxidation, precipitation obtain Fe (OH)3, roast and obtain iron oxide.Wet method prepares iron oxide in the process without SO2Exhaust emission,
Product quality is high.
Ammonium sulfate is commonly called as ammonium sulphate, and the salt generated is reacted with ammonia for sulfuric acid, is colourless rhomboidal crystal, soluble easily in water.Ammonium sulfate master
To be used as fertilizer, be suitable for various soil and crop, it may also be used for weaving, leather, medicine etc..
Steel members will pass through chlorohydric acid pickling process to remove the oxide of metal surface before the galvanizing of surface, and chlorohydric acid pickling is useless
Liquid is the chlorhydric acid pickling waste containing iron generated to remove metal steel members oxide on surface.Contain in hydrochloric acid pickling waste liquor
120Kg/m3~180Kg/m3Frerrous chloride, 30Kg/m3~50Kg/m3Hydrochloric acid, 1Kg/m3~2Kg/m3Pickling additive, steel
Contain the organic addition of the rust remover used, corrosion inhibiter, fog inhibitor in foreign ion and acid cleaning process in the waste water of chlorohydric acid pickling
Agent.Hydrochloride pickle liquor is in strength hydrochloric acid, if direct emission necessarily leads to the waste of resource and the pollution of environment, on the one hand
So that the valuable constituent in hydrochloric acid pickling waste liquor is unable to get sufficient utilization, cause a large amount of wasting of resources, increases production expense
With on the other hand causing Heavy environmental pollution；And if processing cost can be greatly increased by individually carrying out harmless treatment, it is high
Processing cost and extremely low cost performance make individually to carry out harmless treatment to be difficult to be applied in practice.Therefore to hydrochloric acid acid
The processing for washing waste liquid is always an insoluble problem, and the comprehensive utilization and treatment method for developing hydrochloric acid pickling waste liquor is solution
The certainly new way of this problem.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide rational technology, the simple and environmentally-friendly energy saving, preparations of preparation method
It is at low cost, prepare the high a kind of comprehensive utilization of resources of good product quality, valuable constituent utilization rate and processing steel hydrochloric acid pickling
The method that waste liquid prepares iron oxide and ammonium sulfate.
Realizing above-mentioned purpose technical solution is：A kind of method that hydrochloric acid pickling waste liquor prepares iron oxide and ammonium sulfate, is with hydrochloric acid
Solution is that pickle gives up steel members progress pickling processes to remove the ferrous contained hydrochloric acid pickling obtained during oxide on surface
Liquid is raw material, carries out the method that comprehensive utilization of resources prepares iron oxide and ammonium sulfate, steps are as follows for the method：
(1) solid- liquid separation：In solid- liquid separation equipment, hydrochloric acid pickler is subjected to solid- liquid separation, is obtained through solid- liquid separation
Liquid phase material enter in next step, solid-phase material be waste residue go to be further processed；
(2) pre-heating temperature elevation：Liquid phase material obtained in the previous step is entered and carries out heat exchange operation in indirect heat exchanger, to liquid phase material
Heat temperature raising；
(3) miscible displacement：Material obtained in the previous step and sulfuric acid are mixed in miscible displacement equipment, in hydrochloric acid pickling waste liquor
Frerrous chloride, which mixes to occur to replace to react with sulfuric acid, generates ferrous sulfate and hydrochloric acid, and the material after reaction enters in next step；
(4) flash vaporization：In vacuum flashing equipment, material obtained in the previous step is subjected to vacuum flashing, gaseous phase materials are chlorine
Change hydrogen and water vapour, hydrochloric acid is recycled after further condensing, the liquid phase material after vacuum flashing enters in next step；
(5) evaporative crystallization：In thermo-compression evaporation crystallizer, material obtained in the previous step is evaporated crystallization, gaseous phase materials
For water vapour, recycles and use after further condensing, liquid phase material cools down, ferrous sulfate FeSO4·7H2O is crystallized
It is precipitated, material enters in next step；
(6) solid- liquid separation：In solid- liquid separation equipment, previous step material is subjected to solid- liquid separation, solid phase is ferrous sulfate
FeSO4·7H2O crude products, liquid phase material are used as the feedstock circulation of hydrochloric acid pickler mixed ingredients；
(7) mixed dissolution：Ferrous sulfate crude product obtained in the previous step and water are mixed in mixed dissolution equipment, while adding iron
Powder, the Fe that will contain in ferrous sulfate crude product3+It is reduced to Fe2+, the material after mixed dissolution enters in next step；
(8) pH value is adjusted：In material obtained in the previous step, pH adjusting agent is added, pH will be adjusted and be adjusted to 6~8, make material
In foreign ion generate precipitation, material enter in next step；
(9) adsorption-edulcoration：In material obtained in the previous step, it is directly added into adsorbent and carries out adsorbing and removing impurity, adsorption-edulcoration
Material enters in next step afterwards；
(10) solid- liquid separation：In solid- liquid separation equipment, material obtained in the previous step is subjected to solid- liquid separation, liquid phase material
Into in next step, solid-phase material is that solid waste goes to be further processed；
(11) oxidation is neutralized：In and in oxidation reaction apparatus, while neutralizer and oxidant progress neutralization reaction and oxygen is added
Change reaction, obtains iron oxide crystallization；
(12) solid- liquid separation：In solid- liquid separation equipment, material obtained in the previous step is subjected to solid- liquid separation, liquid phase material
Ammonium sulfate product is further prepared into the 17th step, solid-phase material further prepares iron oxide product into the 13rd step；
(13) it washs：Solid-phase material obtained in the previous step is washed, washings enter water of the 7th step as mixed dissolution
It uses, solid-phase material enters in next step；
(14) it dehydrates：Solid-phase material carried out at 105 DEG C~120 DEG C dehydration and drying treated solid-phase material enter it is next
Step；
(15) it calcines：By previous step, through dehydration and drying, treated that material is calcined at 600 DEG C~800 DEG C, obtains solid-phase material oxygen
Change iron；
(16) crushing packing：Solid-phase material obtained in the previous step is crushed and is packaged to be iron oxide product；
(17) removing impurities by oxidation：In removing impurities by oxidation consersion unit, in the liquid phase material that the 12nd step solid- liquid separation is obtained simultaneously
Neutralizer is added and neutralization reaction and oxidation reaction occur for oxidant, obtains the oxide precipitation of metal impurities；
(18) solid- liquid separation：In solid- liquid separation equipment, previous step is obtained into the carry out solid- liquid separation of material, solid-phase material
It goes to be further processed for waste residue, liquid phase material enters in next step；
(19) evaporating, concentrating and crystallizing：In thermo-compression evaporation condensing crystallizing equipment, liquid phase material obtained in the previous step is evaporated
Concentration, gaseous phase materials condense to obtain water into the 24th step, recycle and use as the tenth three steps of washing water, liquid phase material passes through
Ammonium sulfate crystallization is precipitated after cooling, and material enters in next step；
(20) solid- liquid separation：In solid- liquid separation equipment, previous step is obtained into the carry out solid- liquid separation of material, solid-phase material
Enter in next step for ammonium sulfate crystallization, liquid phase material enters the 25th step and carries out evaporation drying, and it is sulfuric acid to obtain solid-phase material
Ammonium byproduct；
(21) dry：The ammonium sulfate that 20th step solid- liquid separation obtains is dried to obtain sulphur in 110 DEG C~120 DEG C temperature
Sour ammonium product.
Further, in second step pre-heating temperature elevation, liquid phase material is heated to 80 DEG C~120 DEG C.
Further, in third walks miscible displacement, the miscible displacement equipment is in static mixer or tube mixer
Any one, the remaining weight percentage that the frerrous chloride in hydrochloric acid pickling waste liquor mixes sulfuric acid after generation displacement is reacted with sulfuric acid is dense
Degree is the 5.0%~15.0% of material.
Further, the absolute pressure operated in the 4th step vacuum flashing equipment is 0.02MPa~0.08MPa.
Further, in the 5th step evaporative crystallization, using heat pump techniques, the gaseous phase materials of thermo-compression evaporation concentration is pressurizeed and are compressed
Enter heat exchanger afterwards, the heat that gaseous phase materials are removed is as the heat source of reboiler, the ferrous sulfate weight percent after evaporation and concentration
The 40%~60% of a concentration of material, during liquid phase material cools down crystallization, material cools to 0 DEG C~40
℃。
Further, the iron powder in the 7th step mixed dissolution add dosage be material in ferrous sulfate quality 1.0%~
5.0%.
Further, the adsorption-edulcoration agent in the 9th step adsorption-edulcoration is any one in molecular sieve or activated carbon or diatomite
Kind or arbitrary two kinds or arbitrary three kinds of components mixture, adsorption-edulcoration agent adds dosage to be ferrous sulfate quality in material
1.0%~5.0%.
Further, the 11st step neutralizes in oxidation, and neutralizer is any one in ammonia or ammonium hydrogen carbonate, and oxidant is
Air.
Further, in the 17th step removing impurities by oxidation, neutralizer is any one in ammonia or ammonium hydrogen carbonate, and oxidant is
Hydrogen peroxide.
Further, in the 19th step evaporating, concentrating and crystallizing, using heat pump techniques, the gaseous phase materials that thermo-compression evaporation concentrates are added
Enter heat exchanger after pressure compression, the heat that gaseous phase materials are removed is as the heat source of reboiler, the ammonium sulfate weight after evaporation and concentration
Percentage concentration is the 50%~80% of material, and during liquid phase material cools down crystallization, material cools to 0 DEG C
~40 DEG C.
The present invention key reaction principle be：
(1)FeCl2+H2SO4→FeSO4+ 2HCl replaces reaction principle, and utilizes FeSO4And FeCl2It is molten in acidic aqueous solution
Solution degree difference and changes in solubility rule with temperature.The concentrated sulfuric acid is added in hydrochloric acid pickling waste liquor, makes in hydrochloric acid pickling waste liquor
Frerrous chloride be changed into ferrous sulfate and hydrochloric acid, using crystallization technique be precipitated as the original to make paints with water treatment agent etc.
Material, while obtaining regeneration hydrochloric acid, the key technology and technique of the hydrochloric acid lotion recycling that makes that treated.
(2) ferrous sulfate crude product separation and purification.First, ferrous sulfate crude product is dissolved in the water, iron powder, then, root is added
It is different according to the solubility product of each ion hydroxide, using the method for being passed through ammonia, make ion precipitation.Adsorbent is added, is removed molten
Solid waste in liquid and organic matter obtain refined ferrous sulfate solution by solid- liquid separation.In the sulfuric acid water of ferrous sulfate
Iron powder is added in solution, reduction reaction, which is occurred, for the ferric sulfate contained in ferrous sulfate crude product and iron powder generates ferrous sulfate, and
And addition iron powder can be replaced with other torpescence metal ions, the preliminary purpose for removing metal heteroion.
Then, it according to the solubility product difference of foreign ion in solution and ferrous hydroxide, adopts and is passed through ammonia in alignment solution
Method, make the Fe in solution3+Ion forms hydroxide precipitation.It is added in the ferrous sulfate solution of removing metal heteroion
Adsorption-edulcoration agent carries out adsorption-edulcoration operation, further removes rust remover, corrosion inhibiter, the fog inhibitor etc. added in hydrochloric acid pickler
The organic matter carried secretly in material is especially carried out adsorption-edulcoration by impurity.
(3) ferrous sulfate solution prepares the principle of iron oxide：Make full use of Fe2+It is oxidizable at Fe3+, Fe3+Hydroxide it is molten
Xie Du ratios Fe2+Hydroxide it is small, mainly use air for oxidant, a small amount of Fe2+Using hydrogen peroxide as oxidant, make
Ferrous ion occurs oxidation reaction and generates precipitation.First convert ferrous sulfate to iron hydroxide or ferric carbonate.Using ammonium hydrogen carbonate
Either ammonia as neutralizer makes ferrous ion be converted into iron hydroxide or after ferric carbonate obtains iron hydroxide or ferric carbonate,
Contain NH in remaining liquid phase4+、SO4 2And a small amount of Cl-、Fe2+。Fe2+It meets ammonium hydroxide and generates precipitation, the method may be used by Fe2+It removes
It goes.Ammonium chloride starts to volatilize at 100 DEG C, and ammonium sulfate is not volatile, therefore, not according to the volatility of ammonium chloride and ammonium sulfate
Together, two kinds of ammonium salts can be detached, heating makes ammonium chloride volatilize, and obtains ammonium sulfate sterling.Using ammonium hydrogen carbonate or ammonia in
The reaction equation that iron oxide is prepared with agent is as follows：
Ammonium hydrogen carbonate is neutralizer：
FeSO4·7H2O+2NH4HCO3=PeCO3↓+(NH4)2SO4+CO2↑+8H2O
2FeCO3+nH2O+1/2O2=Fe2O3·nH2O+2CO2↑
Fe2O3+nH2O=Fe2O3·nH2O
Ammonia is neutralizer：
2FeSO4+1/2O2+4NH3·H2O=α-Fe2O3·H2O+2(NH4)2SO2+H2O
Fe2O3+nH2O=Fe2O3·nH2O
Realize that the major process unit that the present invention needs is：Solid- liquid separation equipment, indirect heat exchanger, miscible displacement equipment, decompression
Flashing apparatus, mixed dissolution equipment, neutralizes oxidation reaction apparatus, removing impurities by oxidation consersion unit and heat at thermo-compression evaporation crystallizer
Pump evaporating, concentrating and crystallizing equipment etc..Decanter type or filtering type or centrifugal or vane type solid-liquid may be used in solid- liquid separation equipment
Any one in separator.
It is using the benefit of above-mentioned technical proposal：Present invention process is reasonable, and preparation method is simple, and environmental protection and energy saving, manufacturing cost is low,
Good product quality is prepared, valuable constituent utilization rate is high.It is in particular in：
(1) before displacement reaction occurs for sulfuric acid and frerrous chloride, hydrochloric acid pickling waste liquor is utilized to the waste heat of galvanizing production process
Into heat exchange operation is carried out in indirect heat exchanger, advantage is provided for flash vaporization step, while taking full advantage of energy, saved
Energy effect is good.
(2) be sufficiently mixed with the hydrochloric acid pickling waste liquor of preheating in miscible displacement equipment, be conducive in this way material be uniformly mixed and
Displacement reaction easily carries out thorough under high temperature, and valuable constituent is made to be sufficiently displaced from, while making full use of the heat of dilution of sulfuric acid as flash distillation
The heat source of evaporation step further reduced energy consumption, energy-saving.
(3) hydrochloric acid in hydrochloric acid pickling waste liquor is entered into gaseous phase materials using the method for vacuum flashing, after further condensing
Hydrochloric acid is recycled after being absorbed with water, recycles and uses after further condensing, be the part water in next step removing process, to obtain
The equilibrium water for meeting production technology provides condition.
(4) the characteristics of taking full advantage of heat pump techniques, in evaporation and crystal process, the gaseous phase materials evaporated release latent heat conduct
Reboiler heat source, capacity usage ratio is high, increases substantially capacity usage ratio, reduces the heat exchange area of heat exchanger, reduces operating cost
With.
(5) hydrochloric acid pickling waste liquor is further removed using the liquid phase material evaporative crystallisation process after the removing hydrochloric acid of vacuum flashing
Part water in technique improves the ferrous sulfate concentration of liquid phase material, the crystallization precipitation FeSO after further cooling down4·7H2O,
Gaseous phase materials are that water vapour recycles use after further condensing, and the method for the present invention is conducive to the selection of equipment.
(6) the characteristics of taking full advantage of the hydrochloric acid pickler of galvanizing production process, by the mother liquor of ferrous sulfate after solid- liquid separation
It is used directly as the feedstock circulation of hydrochloric acid pickler mixed ingredients, material utilizes abundant, valuable cost availability height.In hydrochloric acid
The concentrated sulfuric acid is added in pickle liquor, so that the frerrous chloride in hydrochloric acid pickling waste liquor is changed into ferrous sulfate and hydrochloric acid, utilizes crystallization
FeSO is precipitated in technology4·7H2O obtains regeneration hydrochloric acid as the raw material to make paints with water treatment agent etc..
(7) iron powder is added in the aqueous sulfuric acid of ferrous sulfate, the ferric sulfate contained in ferrous sulfate crude product and iron powder is sent out
Raw reduction reaction generates ferrous sulfate, and addition iron powder can be replaced with other torpescence metal ions, not precipitate weight
Metal ion is reduced to metal and generates deposition sedimentation simultaneously, to reduce the dosage of removing impurity by means of precipitation agent.
(8) FeSO is made full use of4The weakly acidic feature of aqueous solution (pH=3), and Cu2+、pb 2+Equal impurity metal ions are weak
The characteristics of being precipitated in alkali, using NH3HCO3、NH3It is about 7 to adjust pH value, makes impurity metal ion that precipitation occur and remove.Through de-
It after impurity metal ion, is directly added into adsorbent and carries out removing organic impurities, then directly solid- liquid separation technology is used to remove
Solid matter, after removing inorganic, organic impurities, to FeSO4NH is directly added into refined liquid3Oxidation and neutralization reaction are carried out, it is raw
At Fe (OH)3Precipitation.
(9) adsorption-edulcoration agent is added in the ferrous sulfate solution of removing metal heteroion and carries out adsorption-edulcoration operation, further
The impurity such as rust remover, corrosion inhibiter, the fog inhibitor added in removing hydrochloric acid pickler, it is especially that the organic matter carried secretly in material is miscellaneous
Matter carries out adsorption-edulcoration.
(10) the characteristics of taking full advantage of sulfuric acid and the volatilization of ferrous sulfate difficulty, the refined FeSO of process4Solution is evaporated concentration,
The ferrous sulfate concentration for improving liquid phase material, the crystallization precipitation FeSO after further cooling down4·7H2O, obtained cooling water are made
For the slurry of the 9th step.
(11) the characteristics of taking full advantage of heat pump techniques, in evaporating concentration process, the gaseous phase materials steamed release latent heat conduct
Reboiler heat source, capacity usage ratio is low, increases substantially capacity usage ratio, reduces the heat exchange area of heat exchanger, reduces operating cost
With.
(12) particularity of the separation and purification process of ferrous sulfate is taken full advantage of, the side of crystallisation by cooling is used after evaporation and concentration
Method makes material cool, and further reduced the content of impurity in ferrous sulfate product, improves the purity of product.By the tenth
Washings after the solid-phase material that two steps obtain is washed are directly entered the 7th step and are used as the water of mixed dissolution, and cycle makes
With material is using fully.
(13) after obtaining ferrous sulfate solution, it is passed through ammonia into solution or ammonium hydrogen carbonate is added, while being passed through air, makes sulfuric acid
Ferrous oxidation neutralizes, and obtains ferric hydroxide precipitate.Iron hydroxide and solution are detached using solid- liquid separation.Hydroxide will be precipitated
Iron washs, and washings, which are recycling in, dissolves ferrous sulfate crude product, after iron hydroxide drying, is placed in 600 DEG C~800
It is calcined at DEG C, iron oxide product is obtained after crushing, obtain raw material of the iron oxide product as iron oxide pigment.
The present invention produces iron oxide using wet method comprehensive utilization steel hydrochloric acid pickling waste water, as preparing iron oxide and ammonium sulfate
Method.The method of the present invention is easily achieved continuous operation, comprehensively utilizes and handles especially suitable for extensive hydrochloric acid pickling waste liquor, this
Invented technology is reasonable, and preparation method is simple, and environmental protection and energy saving, manufacturing cost is low, and operating cost is low, prepares good product quality,
Valuable constituent utilization rate is high, and the utilization of resources is abundant, treated, and waste liquid all returns recycles, process makes full use object
The particularity of matter feature and process makes operation become simple, conveniently.The present invention solves hydrochloric acid pickling waste liquor processing and recycling profit
Technical barrier.Inventive method had not only solved the problems, such as that spent acid was difficult to dispose, but also turned waste into wealth, and can both prepare sulfate of ammoniac
Product can also prepare one kind as good iron oxide product, can also prepare byproduct of ammonium sulfate, the present invention is finally secondary
The solid, liquid, gas emission of generation reaches the discharge standard of national regulation.Zero-emission is realized, is real clean preparation method.
Specific implementation mode
Embodiment one
Major process unit is static mixer, indirect heat exchanger, vacuum flashing equipment, mixed dissolution equipment, neutralizes oxidation instead
Answer equipment, removing impurities by oxidation consersion unit, thermo-compression evaporation crystallizer, filtering type solid- liquid separation device, vane type solid- liquid separation
Device, dehydrogenation drying equipment etc..
A kind of method that hydrochloric acid pickling waste liquor prepares iron oxide and ammonium sulfate, be using hydrochloric acid solution as pickle by steel members into
Row pickling processes carry out comprehensive resource profit to remove the chlorhydric acid pickling waste containing iron obtained during oxide on surface as raw material
With the method for preparing iron oxide and ammonium sulfate, steps are as follows for the method：
(1) solid- liquid separation：By 1m3Contain 160Kg frerrous chlorides, 40Kg/ m3Hydrochloric acid, 1.5Kg pickling additive hydrochloric acid
Pickle liquor removes the waste residue in hydrochloric acid pickler in vane type solid- liquid separation device, and the chlorohydric acid pickling by slagging-off is useless
Liquid enters in next step；
(2) pre-heating temperature elevation：Liquid phase material obtained in the previous step is subjected to heat exchange operation in indirect heat exchanger, to liquid phase material plus
Heat is raised to 100 DEG C；
(3) miscible displacement：Liquid phase material obtained in the previous step and 98% sulfuric acid are inputted into static mixer using corrosion-resistant pump respectively
Middle mixing, the frerrous chloride in hydrochloric acid pickling waste liquor is mixed with sulfuric acid to be occurred displacement and react to generate ferrous sulfate and hydrochloric acid, is reacted
The remaining weight percentage concentration of sulfuric acid is the 10% of material afterwards, and the material after reaction enters in next step；
(4) flash vaporization：In vacuum flashing equipment, material obtained in the previous step is carried out in the case where absolute pressure is 0.06MPa
Vacuum flashing, gaseous phase materials are hydrogen chloride and water vapour, and hydrochloric acid is recycled after the further condensed absorbent of water stream injection pump, and decompression is dodged
Liquid phase material after steaming enters in next step；
(5) evaporative crystallization：In thermo-compression evaporation crystallizer, material obtained in the previous step is evaporated crystallization, is tied in evaporation
During crystalline substance, the gaseous phase materials evaporated release latent heat as reboiler heat source, and gaseous phase materials are water vapour, by further cold
It recycles and uses after solidifying, liquid phase material cools to 20 DEG C, and ferrous sulfate crystallization is precipitated, and material enters in next step, is concentrated by evaporation
Ferrous sulfate concentration expressed in percentage by weight afterwards is the 50% of material；
(6) solid- liquid separation：In filtering type solid- liquid separation device filter, previous step material is subjected to solid- liquid separation, solid phase
For ferrous sulfate crude product, liquid phase material adds hydrochloric acid, rust remover, corrosion inhibiter, fog inhibitor and is recycled as hydrochloric acid pickler；
(7) mixed dissolution：Ferrous sulfate crude product obtained in the previous step and water are mixed in mixed dissolution equipment, while adding iron
Powder, iron powder add dosage to be 3.0% of ferrous sulfate quality in material, the Fe that will contain in ferrous sulfate crude product3+It is reduced to Fe2+,
The ferric sulfate contained in ferrous sulfate crude product occurs reduction reaction with iron powder and generates ferrous sulfate, and the material after mixed dissolution enters
In next step；
(8) pH value is adjusted：In material obtained in the previous step, pH adjusting agent is added, pH will be adjusted and be adjusted to 8, be warming up to 80
DEG C, so that the foreign ion in material is generated precipitation, material enters in next step；
(9) adsorption-edulcoration：In material obtained in the previous step, it is directly added into adsorbent and carries out adsorbing and removing impurity, adsorption-edulcoration
Agent is the mixture of 50% activated carbon and 50% diatomite molecular sieve, and adsorption-edulcoration agent adds dosage to be ferrous sulfate quality in material
3.0%, material enters in next step after adsorption-edulcoration；
(10) solid- liquid separation：In filtering type solid- liquid separation device, material obtained in the previous step is subjected to solid- liquid separation, liquid
Phase materials enter in next step, and solid-phase material is that solid waste goes to be further processed；
(11) oxidation is neutralized：In and in oxidation reaction apparatus, while neutralizer and oxidant progress neutralization reaction and oxygen is added
Change reaction, obtains iron oxide crystallization, neutralizer is ammonia, and oxidant is air；
(12) solid- liquid separation：In filtering type solid- liquid separation device, material obtained in the previous step is subjected to solid- liquid separation, liquid
Phase materials further prepare ammonium sulfate product into the 17th step, and solid-phase material further prepares iron oxide production into the 13rd step
Product；
(13) it washs：Solid-phase material obtained in the previous step is washed, washings enter water of the 7th step as mixed dissolution
It uses, solid-phase material enters in next step；
(14) it dehydrates：In dehydrogenation drying equipment, solid-phase material carries out dehydration and drying treated solid-phase material at 110 DEG C
Into in next step；
(15) it calcines：By previous step, through dehydration and drying, treated that material is calcined at 700 DEG C, obtains solid-phase material iron oxide；
(16) crushing packing：Solid-phase material obtained in the previous step is crushed and is packaged to be iron oxide product；
(17) removing impurities by oxidation：In removing impurities by oxidation consersion unit, in the liquid phase material that the 12nd step solid- liquid separation is obtained simultaneously
Neutralizer is added and neutralization reaction and oxidation reaction occur for oxidant, obtains the oxide precipitation of metal impurities, neutralizer is
Ammonia, oxidant H2O2；
(18) solid- liquid separation：In filtering type solid- liquid separation device, previous step is obtained into the carry out solid- liquid separation of material, Gu
Phase materials are that waste residue goes to be further processed, and liquid phase material enters in next step；
(19) evaporating, concentrating and crystallizing：In thermo-compression evaporation condensing crystallizing equipment, liquid phase material obtained in the previous step is evaporated
Concentration will enter heat exchanger, by gas using heat pump techniques after the gaseous phase materials pressurization compression in thermo-compression evaporation condensing crystallizing equipment
Heat source of the heat as reboiler that phase materials remove, the ammonium sulfate concentration expressed in percentage by weight after evaporation and concentration is the 70% of material, gas
Phase materials condense to obtain water into the 24th step, recycle and use as the tenth three steps of washing water, liquid phase material is dropped through supercooling
Ammonium sulfate FeSO after temperature4·7H2O crystallization be precipitated, during liquid phase material cools down crystallization, material cool to
25 DEG C, material enters in next step；
(20) solid- liquid separation：In solid- liquid separation equipment, previous step is obtained into the carry out solid- liquid separation of material, solid-phase material
Enter in next step for ammonium sulfate crystallization, liquid phase material enters the 25th step and carries out evaporation drying, and evaporation drying uses outer circulation
Formula evaporation drying equipment, operation temperature are 110 DEG C, and it is ammonium sulfate byproduct to obtain solid-phase material；
(21) dry：In dehydrogenation drying equipment, the ammonium sulfate that the 20th step solid- liquid separation is obtained is dried in 115 DEG C of temperature
Processing obtains ammonium sulfate product.
In addition to the implementation, every technical parameter of the invention can also arbitrarily select within the scope of preferred value.Such as preheat liter
Liquid phase material is heated to other numerical value in 80 DEG C~120 DEG C in warm step, the operation in flash vaporization step it is exhausted
Other numerical value in 0.02MPa~0.08MPa can be also chosen to pressure, the liquid phase material in evaporative crystallization steps carries out cooling drop
Other numerical value etc. in temperature to 0 DEG C~40 DEG C.The ammonium sulfate byproduct that 20th step of the invention obtains, process further refines can
To obtain ammonium sulfate product.
Except above-described embodiment, embodiment of the present invention is also very much, all using equivalent or equivalence replacement technical solution, exists
Within protection scope of the present invention.
Claims (3)
1. be using hydrochloric acid solution it is pickle by steel members a kind of method that hydrochloric acid pickling waste liquor prepares iron oxide and ammonium sulfate
Pickling processes are carried out to remove the chlorhydric acid pickling waste containing iron obtained during oxide on surface as raw material, carry out comprehensive resource
Utilize the method for preparing iron oxide and ammonium sulfate, it is characterised in that steps are as follows for the method:
(1) solid- liquid separation：In solid- liquid separation equipment, hydrochloric acid pickler is subjected to solid- liquid separation, is obtained through solid- liquid separation
Liquid phase material enter in next step, solid-phase material be waste residue go to be further processed；
(2) pre-heating temperature elevation：Liquid phase material obtained in the previous step is entered and carries out heat exchange operation in indirect heat exchanger, to liquid phase material
Heat temperature raising；
(3) miscible displacement：Material obtained in the previous step and sulfuric acid are mixed in miscible displacement equipment, in hydrochloric acid pickling waste liquor
Frerrous chloride, which mixes to occur to replace to react with sulfuric acid, generates ferrous sulfate and hydrochloric acid, and the material after reaction enters in next step；
(4) flash vaporization：In vacuum flashing equipment, material obtained in the previous step is subjected to vacuum flashing, gaseous phase materials are chlorine
Change hydrogen and water vapour, hydrochloric acid is recycled after further condensing, the liquid phase material after vacuum flashing enters in next step；
(5) evaporative crystallization：In thermo-compression evaporation crystallizer, material obtained in the previous step is evaporated crystallization, gaseous phase materials
For water vapour, recycles and use after further condensing, liquid phase material cools down, ferrous sulfate FeSO4·7H2O is crystallized
It is precipitated, material enters in next step；
(6) solid- liquid separation：In solid- liquid separation equipment, previous step material is subjected to solid- liquid separation, solid phase is ferrous sulfate
FeSO4·7H2O crude products, liquid phase material are used as the feedstock circulation of hydrochloric acid pickler mixed ingredients；
(7) mixed dissolution：Ferrous sulfate crude product obtained in the previous step and water are mixed in mixed dissolution equipment, while adding iron
Powder, the Fe that will contain in ferrous sulfate crude product3+It is reduced to Fe2+, the material after mixed dissolution enters in next step；
(8) pH value is adjusted：In material obtained in the previous step, pH adjusting agent is added, pH is adjusted to 6~8, is made in material
Foreign ion generates precipitation, and material enters in next step；
(9) adsorption-edulcoration：In material obtained in the previous step, be directly added into activated carbon, molecular sieve one or two kinds of is
Adsorbent carries out adsorbing and removing impurity, and material enters in next step after adsorption-edulcoration；
(10) solid- liquid separation：In solid- liquid separation equipment, material obtained in the previous step is subjected to solid- liquid separation, liquid phase material
Into in next step, solid-phase material is that solid waste goes to be further processed；
(11) oxidation is neutralized：In and in oxidation reaction apparatus, while during any one being added in ammonia or ammonium hydrogen carbonate is
And agent, air are that oxidant carries out neutralization reaction and oxidation reaction, obtain iron oxide crystallization；
(12) solid- liquid separation：In solid- liquid separation equipment, material obtained in the previous step is subjected to solid- liquid separation, liquid phase material
Ammonium sulfate product is further prepared into (17) step, solid-phase material further prepares iron oxide product into (13) step；
(13) it washs：Solid-phase material obtained in the previous step is washed, washings enter water of (7) step as mixed dissolution
It uses, solid-phase material enters in next step；
(14) it dehydrates：Solid-phase material carried out at 105 DEG C~120 DEG C dehydration and drying treated solid-phase material enter it is next
Step；
(15) it calcines：By previous step, through dehydration and drying, treated that material is calcined at 600 DEG C~800 DEG C, obtains solid-phase material oxygen
Change iron；
(16) crushing packing：Solid-phase material obtained in the previous step is crushed and is packaged to be iron oxide product；
(17) removing impurities by oxidation：In removing impurities by oxidation consersion unit, in the liquid phase material that (12) step solid- liquid separation is obtained simultaneously
Any one in addition ammonia or ammonium hydrogen carbonate is neutralizer, and hydrogen peroxide is that oxidant occurs neutralization reaction and aoxidizes anti-
It answers, obtains the oxide precipitation of metal impurities；
(18) solid- liquid separation：In solid- liquid separation equipment, previous step is obtained into the carry out solid- liquid separation of material, solid-phase material
It goes to be further processed for waste residue, liquid phase material enters in next step；
(19) evaporating, concentrating and crystallizing：In thermo-compression evaporation condensing crystallizing equipment, liquid phase material obtained in the previous step is evaporated
Concentration, gaseous phase materials condense to obtain water, recycle and use as (13) step washings, liquid phase material sulfuric acid after cooling
Crystalline ammonium is precipitated, and material enters in next step；
(20) solid- liquid separation：In solid- liquid separation equipment, previous step is obtained into the carry out solid- liquid separation of material, solid-phase material
Enter in next step for ammonium sulfate crystallization, liquid phase material is evaporated drying, and it is ammonium sulfate byproduct to obtain solid-phase material；
(21) dry：The ammonium sulfate that (20) step solid- liquid separation obtains is dried to obtain sulphur in 110 DEG C~120 DEG C temperature
Sour ammonium product.
2. the method that hydrochloric acid pickling waste liquor prepares iron oxide and ammonium sulfate according to claim 1, it is characterised in that：
(2) in step pre-heating temperature elevation, liquid phase material is heated to 80 DEG C~120 DEG C；In (3) step miscible displacement, described is mixed
It is any one in static mixer or tube mixer, the frerrous chloride in hydrochloric acid pickling waste liquor and sulfuric acid to close replacing apparatus
The remaining weight percentage concentration that sulfuric acid after displacement is reacted occurs for mixing is the 5.0%~15.0% of material；Described (4) step depressurizes
The absolute pressure operated in flashing apparatus is 0.02MPa~0.08MPa；In described (5) step evaporative crystallization, heat pump skill is utilized
Art will enter heat exchanger after the gaseous phase materials pressurization compression of thermo-compression evaporation concentration, and the heat that gaseous phase materials are removed is as reboiler
Heat source, the ferrous sulfate concentration expressed in percentage by weight after evaporation and concentration is the 40%~60% of material, and liquid phase material carries out cooling drop
During temperature crystallization, material cools to 0 DEG C~40 DEG C.
3. the method that hydrochloric acid pickling waste liquor prepares iron oxide and ammonium sulfate according to claim 1, it is characterised in that:(7)
Iron powder in step mixed dissolution adds dosage to be 1.0%~5.0% of ferrous sulfate quality in material；The absorption of described (9) step removes
Adsorption-edulcoration agent in miscellaneous adds dosage to be 1.0%~5.0% of ferrous sulfate quality in material；Described (19) step is concentrated by evaporation
In crystallization, using heat pump techniques, heat exchanger will be entered after the gaseous phase materials pressurization compression of thermo-compression evaporation concentration, gaseous phase materials are moved
Heat source of the heat gone out as reboiler, the ammonium sulfate concentration expressed in percentage by weight after evaporation and concentration are the 50%~80% of material, liquid phase
During material cools down crystallization, material cools to 0 DEG C~40 DEG C.
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