CN107200359A - A kind of iron oxide pigment and its production method - Google Patents
A kind of iron oxide pigment and its production method Download PDFInfo
- Publication number
- CN107200359A CN107200359A CN201610154540.4A CN201610154540A CN107200359A CN 107200359 A CN107200359 A CN 107200359A CN 201610154540 A CN201610154540 A CN 201610154540A CN 107200359 A CN107200359 A CN 107200359A
- Authority
- CN
- China
- Prior art keywords
- iron
- iron oxide
- ferrous
- liquor
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000001034 iron oxide pigment Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 190
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 160
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- 229910052742 iron Inorganic materials 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 56
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000012452 mother liquor Substances 0.000 claims abstract description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- -1 ferrous compound Chemical class 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 22
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008139 complexing agent Substances 0.000 claims abstract description 16
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 235000004279 alanine Nutrition 0.000 claims abstract description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims abstract description 6
- 235000014304 histidine Nutrition 0.000 claims abstract description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims abstract description 6
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims abstract description 5
- 235000018977 lysine Nutrition 0.000 claims abstract description 5
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims abstract description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004475 Arginine Substances 0.000 claims abstract description 4
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 claims abstract description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims abstract description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004471 Glycine Substances 0.000 claims abstract description 4
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims abstract description 4
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims abstract description 4
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims abstract description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 4
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims abstract description 4
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims abstract description 4
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims abstract description 4
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims abstract description 4
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims abstract description 4
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims abstract description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004472 Lysine Substances 0.000 claims abstract description 4
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims abstract description 4
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims abstract description 4
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004473 Threonine Substances 0.000 claims abstract description 4
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000009697 arginine Nutrition 0.000 claims abstract description 4
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000009582 asparagine Nutrition 0.000 claims abstract description 4
- 229960001230 asparagine Drugs 0.000 claims abstract description 4
- 235000003704 aspartic acid Nutrition 0.000 claims abstract description 4
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960001484 edetic acid Drugs 0.000 claims abstract description 4
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000013922 glutamic acid Nutrition 0.000 claims abstract description 4
- 239000004220 glutamic acid Substances 0.000 claims abstract description 4
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000004554 glutamine Nutrition 0.000 claims abstract description 4
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 4
- 235000008729 phenylalanine Nutrition 0.000 claims abstract description 4
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000013930 proline Nutrition 0.000 claims abstract description 4
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000004400 serine Nutrition 0.000 claims abstract description 4
- 235000008521 threonine Nutrition 0.000 claims abstract description 4
- 235000014393 valine Nutrition 0.000 claims abstract description 4
- 239000004474 valine Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 41
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 29
- 230000001590 oxidative effect Effects 0.000 claims description 23
- 239000011790 ferrous sulphate Substances 0.000 claims description 21
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 19
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000292 calcium oxide Substances 0.000 claims description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 7
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 239000011133 lead Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 150000001553 barium compounds Chemical class 0.000 claims description 5
- 239000011011 black crystal Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000009790 rate-determining step (RDS) Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 241001272567 Hominoidea Species 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 229920004890 Triton X-100 Polymers 0.000 claims description 4
- 239000013504 Triton X-100 Substances 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- 229940070765 laurate Drugs 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 150000003057 platinum Chemical class 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 238000009423 ventilation Methods 0.000 claims 1
- 235000013980 iron oxide Nutrition 0.000 description 84
- 239000000243 solution Substances 0.000 description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 238000007254 oxidation reaction Methods 0.000 description 30
- 230000003647 oxidation Effects 0.000 description 29
- 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 25
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 230000008569 process Effects 0.000 description 20
- 239000002994 raw material Substances 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 229910001448 ferrous ion Inorganic materials 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 239000003513 alkali Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 239000000084 colloidal system Substances 0.000 description 12
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 229960004887 ferric hydroxide Drugs 0.000 description 9
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000001117 sulphuric acid Substances 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001447 ferric ion Inorganic materials 0.000 description 3
- 229960002989 glutamic acid Drugs 0.000 description 3
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000008547 L-phenylalanines Chemical class 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- FRTNIYVUDIHXPG-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical class CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN FRTNIYVUDIHXPG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000002169 ethanolamines Chemical class 0.000 description 2
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 description 2
- 229940051164 ferric oxide yellow Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002411 histidines Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012928 buffer substance Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229960002377 dixanthogen Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 150000002669 lysines Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical class [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- 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
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a kind of iron oxide pigment and its production method, method includes：1) reaction solution of the configuration containing complexing agent, indifferent salt, pH value between 7.0 13.0, adds scrap iron or ferrous compound or ferric iron compound, wherein impurity is separated after dissolving, iron-containing liquor is obtained thereto；2) oxygen-containing gas is passed through into iron-containing liquor, the ferrous iron in iron-containing liquor is oxidized to iron oxide yellow or iron oxide red or iron oxide black precipitation, isolated iron oxide pigment and reaction mother liquor；Its complexing agent is one or both of methylamine, ethamine, ethylenediamine, propane diamine, monoethanolamine, imidazoles, Diethylenetriamine, three second tetramines, ethylenediamine tetra-acetic acid, EDDA, nitrilotriacetic acid, glutamic acid, valine, histidine, aspartic acid, alanine, proline, serine, phenylalanine, arginine, threonine, glycine, lysine, asparagine and glutamine.
Description
Technical field
The invention belongs to chemical field, a kind of iron oxide pigment and its production method are particularly belonged to.
Background technology
Iron oxide pigment includes the pigment such as iron oxide red, iron oxide black, iron oxide yellow, cologne earth, transparent ferric oxide.Iron oxide pigment so that its color is more, chromatogram is wide, it is nontoxic, inexpensive the characteristics of, be widely used in the industries such as coating, building materials, plastics, electronics, tobacco, optical glass polishing agent, medicine, senior ground material, feed for pet additive.Wherein iron oxide yellow is the important composition in iron oxide pigment.
The domestic iron oxide yellow of production at present mainly has wet method air oxidation process, catalysis method, three kinds of methods of aniline process.
1) wet method air oxidation process
China's iron oxide yellow is largely that wet method is produced using wet method air oxidation process.Wherein wet processing includes two kinds of acid system and alkaline process.Acid system is also known as crystal seed method, is subdivided into two kinds of techniques of iron sheet method and dripping method, and acid system prepares iron oxide yellow and mainly divides two steps to carry out：
(1) FeSO is used4·7H2O, NaOH or NH3·H2O, air oxidation prepare crystal seed；
(2) with crystal seed, FeS04, iron sheet, air carry out second oxidation output iron oxide yellow.
Herein, NaOH or NH3·H2O is used as precipitating reagent, with FeSO4Reaction generation ferrous hydroxide precipitation；Air is used as oxidant；Iron sheet is and FeSO4Sulfuric acid reaction produced by oxidizing process maintains the pH value of solution there is provided the ferrous ion needed for reaction system.
Course of reaction is：
4FeSO4+O2+6H2O → 4FeOOH (iron oxide yellow)+4H2SO4
4H2SO4+4Fe→4FeSO4+4H2
If replacing iron sheet, and the acid for being added dropwise in ammoniacal liquor or sodium hydroxide and being produced in oxidizing process by the way that copperas solution is added dropwise in second oxidation, then this method is referred to as dripping method.
Course of reaction is：
4FeSO4+O2+ 8NaOH → 4FeOOH (iron oxide yellow)+2H2O+4Na2SO4
2) oxidizing process production iron oxide yellow
Make oxidant using sodium chlorate etc., concentration, reaction temperature, time and the pH value of certain ferrous sulfate are controlled, by Fe2+It is oxidized to Fe3+It is eventually converted into iron oxide yellow.
3) aniline process
In aniline process production process iron oxide yellow is generated with iron reduction nitrobenzene.
Current ferric oxide yellow pigment is produced using crystal seed method mostly：
1) reacted first by ferrous sulfate and alkali, in certain alkali than R values (R=2OH-/Fe2+) under generate ferrous hydroxide colloid, be subsequently passed air oxidation, by ferrous hydroxide colloidal silica be iron oxide yellow crystal seed.
2) on the basis of iron oxide yellow crystal seed, it is continuously replenished ferrous sulfate (dripping method) or iron sheet (iron sheet method) and is passed through air, control ph within the specific limits, makes iron oxide yellow crystal seed constantly grow up, and finally gives qualified iron oxide yellow.
During ferrous sulfate is used for the dripping method production iron oxide yellow of raw material, ferrous sulfate needs refined in advance, removing impurity therein first, in order to avoid the quality of these impurity effect iron oxide yellows.Crystal seed second oxidation process needs to consume the acid produced in the higher ammoniacal liquor of value or sodium hydroxide and in oxidizing process afterwards, the relatively low sodium sulphate of value or ammonium sulfate waste water are produced, wherein the mol ratio of the alkali (ammoniacal liquor or sodium hydroxide) consumed and ferrous sulfate is 2：1.Ferrous sulfate can produce sulfuric acid during iron oxide yellow is oxidized to, lack buffer substance in solution, to maintain the stabilization of solution ph (between pH value about 2.5-4.0), therefore need to be continuously replenished alkali maintenance solution ph during second oxidation, wherein product iron oxide yellow is solid, it must be soluble sulphate that alkali and sulfuric acid, which neutralize and obtains sulfate, therefore integrated cost considers, sodium hydroxide or ammoniacal liquor can only be used to be used as the alkali of neutralisation of sulphuric acid.
During iron sheet is used for the iron sheet method production iron oxide yellow of raw material, iron sheet is converted into iron oxide yellow as raw material, period such as does not filter at the dedoping step, the impurity of iron sheet can be transferred completely into iron oxide yellow product, therefore the higher iron sheet of quality is needed, it is general to use low-carbon iron sheet, to ensure the quality of iron oxide yellow product.
During the second oxidation that crystal seed method produces iron oxide yellow, solution presents acid, ferrous ion is weaker compared to alkaline environment reproducibility in sour environment, therefore the time needed for ferrous ion oxidation by air is longer, and the synthesis of iron oxide yellow can just be completed by generally requiring 30-60 hours.
Oxidizing process production iron oxide yellow needs to consume substantial amounts of oxidant, such as sodium chlorate, significantly higher compared to the crystal seed method production cost for using air as oxidant.
Therefore, in the production process of existing iron oxide yellow, to ensure the quality of iron oxide yellow, raw material sulphuric acid ferrous iron, which needs to refine in advance, removes impurity or from the less low-carbon iron sheet of impurity as raw material, limits the raw material sources of iron oxide yellow.And using ferrous sulfate in the dripping method of raw material, it is necessary to use ammoniacal liquor or sodium hydroxide as the acid produced in alkali with second oxidation process.Finally because ferrous ions are slower, the production cycle of iron oxide yellow is very long, it is necessary to which 30-60 hours can just complete.
The content of the invention
In view of the shortcomings of the prior art, present invention mainly solves the problem of iron oxide yellow raw material sulphuric acid is ferrous, iron sheet quality requirement is higher by the present invention.
The technical scheme that present invention solution above-mentioned technical problem is taken is as follows：
A kind of production method of iron oxide pigment, including：
1) reaction solution of the configuration containing complexing agent, indifferent salt, pH value between 7.0-13.0, adds scrap iron or ferrous compound or ferric iron compound, wherein impurity is separated after dissolving, iron-containing liquor is obtained thereto；
2) oxygen-containing gas is passed through into iron-containing liquor, the ferrous iron in iron-containing liquor is oxidized to iron oxide yellow or iron oxide red or iron oxide black precipitation, isolated iron oxide pigment and reaction mother liquor；
Its complexing agent is one or both of methylamine, ethamine, ethylenediamine, propane diamine, monoethanolamine, imidazoles, Diethylenetriamine, three second tetramines, ethylenediamine tetra-acetic acid, EDDA, nitrilotriacetic acid, glutamic acid, valine, histidine, aspartic acid, alanine, proline, serine, phenylalanine, arginine, threonine, glycine, lysine, asparagine and glutamine.
Preferably, step 2) in, further comprise：
Configuration and reaction mother liquor composition identical solution use reaction mother liquor as bottom liquid, and oxygen-containing gas is passed through thereto, iron-containing liquor is by way of being added dropwise or being added portionwise, added in 0.1-40 hours in mother liquor, and continue reaction 0.1-40 hours, obtain iron oxide yellow or iron oxide red or iron oxide black precipitation, isolated iron oxide pigment and reaction mother liquor.
Preferably, step 1) in, scrap iron is metallic iron of the iron content more than 80%, ferrous compound is the one or more in ferrous sulfate, frerrous chloride, ferrous oxide, ferrous nitrate, ferric iron compound is the one or more in ferric sulfate, iron chloride, ferric nitrate, oxygen-containing gas is one kind in oxygen, oxygen-enriched air, air and other gases for containing oxygen, and indifferent salt is the one or more in sodium, potassium, the sulfate of ammonium ion, carbonate, nitrate, chloride, acetate, phosphate.
Preferably, step 1), step 2) in reaction temperature between 0-110 DEG C, and using organic base, inorganic base, organic acid, inorganic acid rate-determining steps 1), step 2) in solution ph between 7.0-13.0, complexing agent concentration is 0.1-5.0mol/L, inertia salinity is no more than 4.5mol/L, iron concentration is 0.01-5.0mol/L in iron-containing liquor, oxygen-containing gas temperature is between 0-110 DEG C, humidity is between 5-90%, and the ratio of oxygen-containing gas throughput/liquor capacity per minute is no more than 10.
It is further preferred that using ammoniacal liquor, sodium hydroxide, potassium hydroxide, sulfuric acid, hydrochloric acid, nitric acid rate-determining steps 1), step 2) in solution ph between 7.0-13.0.
Preferably, step 1) in, in addition to：Oxidant or catalyst are added, to promote metallic iron to dissolve faster.
Preferably, the oxidant is the one or more in chlorate, hydrogen peroxide, nitrate, perchlorate, chlorate, the catalyst is the one or more in mantoquita, nickel salt, platinum salt, gold salt, silver salt, cobalt salt, and the concentration of oxidant and catalyst is no more than 3.5mol/L.
Preferably, step 2) in, in addition to：The crystal seed no more than 100g/L or other are added into solution can produce the material of nucleus, the crystal seed is the iron oxide yellow or iron oxide red or iron oxide black crystal seed synthesized using disclosed method, and other described materials that can produce nucleus are the one or more in copper, zinc, lead, cadmium, nickel, cobalt, aluminium, barium compound.
Preferably, in step 1) or step 2) in, in addition to：Surfactant, including anionic surfactant, cationic surface active agent, zwitterionic surfactant, nonionic surface active agent are added, wherein surfactant addition is no more than 10g/L.
Preferably, the surfactant is that stearic acid, oleic acid, laurate, quaternary ammonium salt, cocounut oil phthalein amine CAB, dodecyl alanine, isomery alcohol polyoxyethylene poly-oxygen propylene aether, polyethylene adjoin one or more in pyrrolidone, OPEO, Triton X-100, polyoxyethylene sorbitan fatty acid ester, dodecyl sodium sulfate, lauryl sodium sulfate, APES.
Preferably, step 2) in, in addition to：Calcium oxide or barium monoxide are added into reaction mother liquor, sulfate radical excessive in reaction mother liquor is changed into calcium sulfate or barium sulfate precipitate, obtains desulphurization reaction mother liquor, desulphurization reaction mother liquor can be with return to step 1) recycle
Preferably, the temperature of reaction mother liquor desulfurization is 0-110 DEG C, and calcium oxide or barium monoxide addition are not less than 0.01mol/L.
A kind of iron oxide pigment prepared according to above method.
After the above method, it uses complexing agent as solvent, ferrous ion is dissolved in weakly alkaline solution, reoxidize as iron oxide pigment, and cheap calcium oxide is used as alkali, neutralisation of sulphuric acid ferrous iron is converted into the acid produced during iron oxide yellow, using ferrous ion it is more oxidizable in alkaline environment the characteristics of, significantly shorten iron oxide yellow the oxidation production cycle.
Other features and advantages of the present invention will be illustrated in the following description, also, is partly become apparent from specification, or is understood by implementing the present invention.The purpose of the present invention and other advantages can be realized and obtained by specifically noted method in the specification, claims write, step.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the production method of iron oxide pigment of the present invention.
Embodiment
Describing embodiments of the present invention in detail below with reference to embodiment, how application technology means solve technical problem to the present invention whereby, and reaching the implementation process of technique effect can fully understand and implement according to this.As long as it should be noted that not constituting conflict, each embodiment in the present invention and each feature in each embodiment can be combined with each other, and the technical scheme formed is within protection scope of the present invention.
As shown in figure 1, a kind of production method of iron oxide pigment, including：
1) reaction solution of the configuration containing complexing agent, indifferent salt, pH value between 7.0-13.0, adds scrap iron or ferrous compound or ferric iron compound, wherein impurity is separated after dissolving, iron-containing liquor is obtained thereto；
2) oxygen-containing gas is passed through into iron-containing liquor, the ferrous iron in iron-containing liquor is oxidized to iron oxide yellow or iron oxide red or iron oxide black precipitation, isolated iron oxide pigment and reaction mother liquor；
Its complexing agent is one or both of methylamine, ethamine, ethylenediamine, propane diamine, monoethanolamine, imidazoles, Diethylenetriamine, three second tetramines, ethylenediamine tetra-acetic acid, EDDA, nitrilotriacetic acid, glutamic acid, valine, histidine, aspartic acid, alanine, proline, serine, phenylalanine, arginine, threonine, glycine, lysine, asparagine and glutamine.
Preferably, step 2) in, further comprise：
Configuration and reaction mother liquor composition identical solution use reaction mother liquor as bottom liquid, and oxygen-containing gas is passed through thereto, iron-containing liquor is by way of being added dropwise or being added portionwise, added in 0.1-40 hours in mother liquor, and continue reaction 0.1-40 hours, obtain iron oxide yellow or iron oxide red or iron oxide black precipitation, isolated iron oxide pigment and reaction mother liquor.
Preferably, step 1) in, scrap iron is metallic iron of the iron content more than 80%, ferrous compound is the one or more in ferrous sulfate, frerrous chloride, ferrous oxide, ferrous nitrate, ferric iron compound is the one or more in ferric sulfate, iron chloride, ferric nitrate, oxygen-containing gas is one kind in oxygen, oxygen-enriched air, air and other gases for containing oxygen, and indifferent salt is the one or more in sodium, potassium, the sulfate of ammonium ion, carbonate, nitrate, chloride, acetate, phosphate.
Preferably, step 1), step 2) in reaction temperature between 0-110 DEG C, and using organic base, inorganic base, organic acid, inorganic acid rate-determining steps 1), step 2) in solution ph between 7.0-13.0, complexing agent concentration is 0.1-5.0mol/L, inertia salinity is no more than 4.5mol/L, iron concentration is 0.01-5.0mol/L in iron-containing liquor, oxygen-containing gas temperature is between 0-110 DEG C, humidity is between 5-90%, and the ratio of oxygen-containing gas throughput/liquor capacity per minute is no more than 10.
It is further preferred that using ammoniacal liquor, sodium hydroxide, potassium hydroxide, sulfuric acid, hydrochloric acid, nitric acid rate-determining steps 1), step 2) in solution ph between 7.0-13.0.
Preferably, step 1) in, in addition to：Oxidant or catalyst are added, to promote metallic iron to dissolve faster.
Preferably, the oxidant is the one or more in chlorate, hydrogen peroxide, nitrate, perchlorate, chlorate, the catalyst is the one or more in mantoquita, nickel salt, platinum salt, gold salt, silver salt, cobalt salt, and the concentration of oxidant and catalyst is no more than 3.5mol/L.
Preferably, step 2) in, in addition to：The crystal seed no more than 100g/L or other are added into solution can produce the material of nucleus, the crystal seed is the iron oxide yellow or iron oxide red or iron oxide black crystal seed synthesized using disclosed method, and other described materials that can produce nucleus are can be with the one or more in the copper of ferric ion formation precipitation, zinc, lead, cadmium, nickel, cobalt, aluminium, barium compound.
Preferably, in step 1) or step 2) in, in addition to：Surfactant, including anionic surfactant, cationic surface active agent, zwitterionic surfactant, nonionic surface active agent are added, wherein surfactant addition is no more than 10g/L.
Preferably, the surfactant is that stearic acid, oleic acid, laurate, quaternary ammonium salt, cocounut oil phthalein amine CAB, dodecyl alanine, isomery alcohol polyoxyethylene poly-oxygen propylene aether, polyethylene adjoin one or more in pyrrolidone, OPEO, Triton X-100, polyoxyethylene sorbitan fatty acid ester, dodecyl sodium sulfate, lauryl sodium sulfate, APES.
Preferably, step 2) in, in addition to：Calcium oxide or barium monoxide are added into reaction mother liquor, sulfate radical excessive in reaction mother liquor is changed into calcium sulfate or barium sulfate precipitate, obtains desulphurization reaction mother liquor, desulphurization reaction mother liquor can be with return to step 1) recycle
Preferably, the temperature of reaction mother liquor desulfurization is 0-110 DEG C, and calcium oxide or barium monoxide addition are not less than 0.01mol/L.
A kind of iron oxide pigment prepared according to above method.
After the above method, it uses complexing agent as solvent, ferrous ion is dissolved in weakly alkaline solution, reoxidize as iron oxide pigment, and cheap calcium oxide is used as alkali, neutralisation of sulphuric acid ferrous iron is converted into the acid produced during iron oxide yellow, using ferrous ion it is more oxidizable in alkaline environment the characteristics of, significantly shorten iron oxide yellow the oxidation production cycle.
Wherein, the present invention will be described in conjunction with the embodiments.
Wherein, in embodiment, complexing agent is ammonia carboxylation compound or organic amine compound (being illustrated below by taking complexones as an example), there is stronger complexing power to ferrous ion, the ferrous compound of solubility is formed with ferrous ion, ferrous ion is not produced precipitation between pH value 7.0-13.0, exist in the form of soluble ferrous complex.Ferrous sulfate and complexones formation ferrous complex and sulfate radical, hydrogen ion or oxidizing or by catalyst (such as relatively low metallic compound of mantoquita, nickel salt, platinum salt, gold salt, silver salt, cobalt salt hydrogen overvoltage by other in metallic iron displacement complexones, by replacing in iron surface formation metal level, accelerate the dissolving of metallic iron using galvanic effect) catalysis, obtain ferrous complex.Now, in alkaline solution, the major impurity in ferrous sulfate, metallic iron, including carbon, silicon, magnesium, titanium etc., exist in solid chemical compound form, clean iron-containing liquor can obtain by the separation of a simple step.Current iron oxide yellow production technology, lacks the dedoping step of raw material, need to be refined in advance when the use of ferrous sulfate being raw material, to separate wherein impurity, the higher low-carbon iron sheet of quality need to be used as raw material when the use of metallic iron being raw material, to ensure the quality of iron oxide yellow.
After iron-containing liquor purification, air is passed through thereto, oxygen therein can aoxidize ferrous complex, control oxidizing temperature, oxidization time, oxidation rate can respectively obtain the products such as iron oxide yellow, iron oxide red, iron oxide black.Ferrous iron can produce hydrogen ion during iron oxide pigment is oxidized to and be neutralized, it is necessary to add alkali, maintain the stabilization of solution ph.The complexing agent complexones that the present invention is used is weak acid, organic amine is weak base, complexones is cushioning liquid with its conjugate base composition solution, organic amine compound and its conjugate acid composition solution, and there is stronger buffer capacity between pH value 7.0-13.0, hydrogen ion can be absorbed and the pH value of solution is changed little.Ferrous iron can produce hydrogen ion in oxidizing process, and hydrogen ion can be absorbed by the Conjugate Acid-Base Pairs in cushioning liquid, maintain solution ph stable.Therefore, extra alkali or iron sheet control ph need not be added during ferrous oxidation, the stabilization of solution ph can be maintained using the buffer capacity of reaction solution.
During iron-containing liquor is aoxidized, in order to obtain, form and aspect are pure, the suitable iron oxide pigment of particle size is, it is necessary to control the oxidation rate of ferrous iron.In the present invention, ferrous oxidation speed is together decided on by throughput, oxygen concentration, ferrous iron concentration, therefore the oxidation rate of ferrous iron can be directly controlled by way of changing throughput, gas oxygen content；On the other hand, the mode that ferrous iron concentration in solution can be changed controls oxidation rate, in order to reduce operating process, the iron-containing liquor containing higher concentration ferrous ion can be pre-configured with, using step 2) in oxidation terminate after reaction mother liquor be used as bottom liquid, oxygen-containing gas is passed through thereto, iron-containing liquor is added using the mode for being added dropwise or being added portionwise, by way of controlling iron-containing liquor and adding speed, control the ferrous iron concentration in oxidizing process solution, and then ferrous oxidation rate is controlled, obtain that form and aspect are pure, the suitable iron oxide pigment of particle size.
Further, can also be to step 2) in into solution add no more than 100g/L crystal seed or other can produce the material of nucleus, the crystal seed is the iron oxide yellow or iron oxide red or iron oxide black crystal seed synthesized using disclosed method, and other described materials that can produce nucleus are can be with the one or more in the copper of ferric ion formation precipitation, zinc, lead, cadmium, nickel, cobalt, aluminium, barium compound.
Iron oxide yellow, iron oxide red, the nucleating condition of iron oxide black are closer to, and also have certain difference, such as when ferrous iron concentration is higher, can preferentially obtain iron oxide black product, when temperature is higher, throughput is larger, preferentially obtain iron oxide red product.Weakly alkaline solution used in the present invention is different from the acid solution and strong alkali solution of current commercial Application, by strict temperature control, time, oxidation rate, ferrous iron concentration, even if without iron oxide yellow, iron oxide red or iron oxide black product can also be directly obtained under conditions of crystal seed.In the present invention, ferrous oxidation by air first is ferric hydroxide colloid, and ferric hydroxide colloid obtains iron oxide pigment by polymerization, recrystallization again.In general, the polymerization of colloid, recrystallization can by thermal polymerization, saltout and add extra crystal seed and realize, in the present invention, by way of being combined heating, saltouing or both, iron oxide pigment, specifically, step 2 are obtained under conditions of without crystal seed) in a scheme being more highly preferred to be 50-110 DEG C of reaction temperature, inertia salinity 1.0-3.5mol/L, by ferrous ions and can be eventually converted into iron oxide yellow or oxidationization iron oxide red or iron oxide black.Ferric hydroxide colloid can also be converted into corresponding iron oxide pigment by the present invention by mode associated with individually adding crystal seed or addition crystal seed and thermal polymerization, saltouing.In general, crystal seed is divided into two kinds, it is a kind of be particle it is smaller, can be with the crystal of continued growth, such as iron oxide yellow, iron oxide red, iron oxide black crystal seed, these crystal seeds can use existing industry application method thereof or other disclosed technical data synthesis；It is another to be and iron oxide yellow, iron oxide red, iron oxide black has other materials of similar crystal structure, because crystal structure is similar, ferric hydroxide colloid can adsorb on these materials and be converted into iron oxide yellow or iron oxide red or iron oxide black, finally give iron oxide pigment product, these materials include zinc ferrite, barium ferrite, cobalt ferrite, nickel ferrite based magnetic loaded, ferrous acid cadmium, ferrous acid lead, coppe ferrite, aluminum oxyhydroxide, aluminium hydroxide, aluminum oxide etc., therefore copper can be added, zinc, lead, cadmium, nickel, cobalt, aluminium, barium compound, corresponding ferrite or other compounds are obtained in the solution as crystal seed, ferric hydroxide colloid is set to be eventually converted into iron oxide pigment, specifically, step 2) in a scheme being more highly preferred to be 40-90 DEG C of reaction temperature, inertia salinity 0.5-1.5mol/L, add the iron oxide yellow crystal seed of existing iron oxide yellow commercial synthesis, by ferrous ions and qualified ferric oxide yellow pigment can be eventually converted into.
In general, colloid can be stabilized under lower temperature and relatively low salinity, therefore in the scheme that the application is proposed, ferric iron compound can also be used as raw material, specifically, under conditions of control temperature and inertia salinity, ferric iron compound reacts with reaction solution first, obtain ferric hydroxide colloid, ferric hydroxide colloid particle diameter is smaller, can obtain clean ferric hydroxide colloid solution (iron-containing liquor) by filtering, then by means such as heating, addition crystal seeds, ferric hydroxide colloid is set to be converted into iron oxide pigment.The source of ferrous sulfate is than wide; a certain amount of ferric iron would generally be contained and ferrous sulfate is easily oxidized, therefore in ferrous sulfate, in the method as proposed in the present invention; ferric iron in ferrous sulfate does not constitute influence to whole technique, has widened the ferrous applicability of raw material sulphuric acid.Simultaneously, comprise only ferric compound, such as ferric sulfate, raw material is can act also as in the present invention to use, difference is that ferric sulfate has been ferric form, oxygen need not be passed through again to be aoxidized, by thermal polymerization, saltout and add extra crystal seed and ferric sulfate can be converted into iron oxide pigment.
In addition, during air oxidation, ferrous iron concentration, oxidation rate can be controlled, and then the granular size of iron oxide pigment is controlled, various sizes of iron oxide pigment is obtained, in order to prevent the reunion of iron oxide pigment, surfactant can be added, including anionic surfactant, cationic surface active agent, zwitterionic surfactant, nonionic surface active agent, the reunion between iron oxides pigment particles is prevented, the iron oxide pigment of polymolecularity is obtained.These surfactants include stearic acid, oleic acid, laurate, quaternary ammonium salt, cocounut oil phthalein amine CAB, dodecyl alanine, isomery alcohol polyoxyethylene poly-oxygen propylene aether, polyethylene adjoins pyrrolidone, OPEO, Triton X-100, polyoxyethylene sorbitan fatty acid ester, dodecyl sodium sulfate, lauryl sodium sulfate, in APES and other organic or inorganics that can produce absorption on iron oxide pigment surface have the material of surface-active action.
In addition, during ferrous oxidation, hydrogen ion can be produced, in the present invention, these hydrogen ions are received by the reaction solution with buffer capacity containing complexing agent Conjugate Acid-Base Pairs, keep reacting liquid pH value to stablize relatively, in order to recycle reaction solution, the regeneration of reaction solution need to just can be achieved with alkaline matter and/or being replaced into hydrogen in the hydrogen ion of absorption, and recycles.When specifically, using metallic iron as raw material, iron can replace the hydrogen ion in reaction solution, produce hydrogen, i.e., the hydrogen ion produced ferrous ions process is converted into the acidity in hydrogen discharge, elimination reaction solution.During for using ferrous sulfate as raw material, on the one hand, the hydrogen ion that ferrous ions process is produced is enriched with the solution, another aspect sulfate radical can be also enriched with the solution, therefore need to remove hydrogen ion unnecessary in solution and sulfate ion, in the technical scheme that the application is proposed, sulfate radical exists in the form of Soluble Anions, calcium can be used, the oxide or hydroxide of barium, on the one hand unnecessary sulfate radical is converted into insoluble calcium sulfate or barium sulfate precipitate, another aspect calcium oxide or barium monoxide are used as basic anhydride, can be with the hydrogen ion in neutralization reaction liquid, realize the recycling of reaction solution.And calcium oxide is worth the ammoniacal liquor and sodium hydroxide well below current iron oxide yellow industrial application, can greatly reduce the production cost of iron oxide yellow as cheap alkali.
Embodiment 1：
1) configuration 50L contains 1.0mol/L ethylenediamines, 1.5mol/L monoethanolamines, 1.5mol/L sodium sulphate, the reaction solution of 1g/L lauryl sodium sulfate, feed grade green vitriol 14kg is added at 60 DEG C, solution ph is maintained between 9.0-9.5 using sulfuric acid, reaction 0.5 hour, filtering, obtains iron-containing liquor.
2) to step 1) in obtain being passed through air in iron-containing liquor, control air themperature is not less than 50 DEG C, humidity is not less than 50%, throughput 50L/min, reaction temperature is controlled between 95-100 DEG C, during which maintains solution ph between 9.0-9.5 using sulfuric acid, 8 hours reaction time, filtering, washing, obtain product iron oxide red and reaction mother liquor.
3) addition 3kg calcium oxide in 20L reaction mother liquors is taken, reaction temperature is controlled between 60-65 DEG C, in 2 hours reaction time, filtering, washing obtain desulphurization reaction mother liquor and gypsum.
4) by step 2), step 3) gained reaction mother liquor, desulphurization reaction mother liquor merge, be back to step 1) in, recycled as reaction solution.
Embodiment 2：
1) configuration 5L contains 0.5mol/L alanine, 1.0mol/L histidines, 0.01mol/L sulfuric acid Co catalysts, 0.01mol/L potassium chlorate oxidant, the reaction solution of 0.5mol/L potassium sulfates, scrap iron 70g is added at 90 DEG C, solution ph is maintained between 8.0-8.5 using potassium hydroxide, reaction 10 hours, filtering, obtains iron-containing liquor.
2) to step 1) in obtain in iron-containing liquor add aluminum sulfate 10g as crystal seed additive, and air is passed through thereto, control air themperature is not less than 80 DEG C, humidity is not less than 90%, and throughput 0.5L/min, reaction temperature is controlled between 90-95 DEG C, period maintains solution ph between 8.0-8.5 using potassium hydroxide, in 6 hours reaction time, filtering, washing obtain product iron oxide yellow and reaction mother liquor.
3) by step 2) gained reaction mother liquor be back to step 1) in, recycled as reaction solution.
Embodiment 3：
1) configuration 500L contains 2.0mol/L phenylalanines, 0.5mol/L monoethanolamines, 1.0mol/L sodium sulphate, the reaction solution of 0.1g/L enuatrols, technical grade green vitriol 100kg is added at 80-85 DEG C, solution ph is maintained between 10.0-10.5 using sodium hydroxide, reaction 1.0 hours, filtering, obtains iron-containing liquor.
2) to step 1) in obtain being passed through air in iron-containing liquor, control air themperature is not less than 60 DEG C, humidity is not less than 70%, throughput 800L/min, reaction temperature is controlled between 80-85 DEG C, during which maintains solution ph between 10.0-10.5 using sodium hydroxide, 6 hours reaction time, filtering, washing, obtain product iron oxide black and reaction mother liquor.
3) 100L reaction mother liquors are taken, the calcium oxide of 12kg effective contents 70% is added thereto, reaction temperature is controlled between 80-85 DEG C, in 4 hours reaction time, filtering, washing obtain desulphurization reaction mother liquor and gypsum.
4) by step 2), step 3) gained reaction mother liquor, desulphurization reaction mother liquor merge, be back to step 1) in, recycled as reaction solution.
Embodiment 4：
1) configuration 3000L contains 1.0mol/L glutamic acid, 0.5mol/L lysines, 1.0mol/L phenylalanines, the reaction solution of 1.5mol/L potassium chloride, titanium white by product green vitriol 350kg is added at 60-65 DEG C, solution ph is maintained between 9.5-10.5 using potassium hydroxide, reaction 1.0 hours, filtering, obtains iron-containing liquor.
2) to step 1) in add iron oxide yellow crystal seed 10kg (with the efficient oxidation iron oxide seed crystal solid content meter, wherein iron oxide yellow crystal seed uses ferrous sulfate, sodium hydroxide is raw material, alkali compares 0.45, 20 DEG C of temperature, synthesized using existing iron oxide yellow acid system crystal seed preparation technology), backward iron-containing liquor in be passed through air, control air themperature is not less than 30 DEG C, humidity is not less than 75%, throughput 1500L/min, reaction temperature is controlled between 80-85 DEG C, period maintains solution ph between 9.5-10.5 using potassium hydroxide, 9 hours reaction time, filtering, washing, obtain product iron oxide yellow and reaction mother liquor.
3) 1000L reaction mother liquors are taken, the calcium oxide of 70kg effective contents 80% is added thereto, reaction temperature is controlled between 80-85 DEG C, in 3 hours reaction time, filtering, washing obtain desulphurization reaction mother liquor and gypsum.
4) by step 2), step 3) gained reaction mother liquor, desulphurization reaction mother liquor merge, be back to step 1) in, recycled as reaction solution.
Embodiment 5：
1) configuration 1000L contains 1.0mol/L histidines, 0.1mol/L ethylenediamine tetra-acetic acids, 0.2mol/L nitrilotriacetic acids, the reaction solution of 2.5mol/L ammonium nitrate, industrial by-product green vitriol 300kg is added at 70-75 DEG C, solution ph is maintained between 7.0-7.5 using ammoniacal liquor, reaction 0.2 hour, filtering, obtains iron-containing liquor.
2) configuration 1000L and reaction mother liquor composition identical solution, it is used as starting bottom liquid, wherein containing 1.0mol/L ethylenediamine tetra-acetic acids acid, 1.0mol/L nitrilotriacetic acid, 2.5mol/L ammonium chloride, iron oxide yellow crystal seed 2kg is added (with the efficient oxidation iron oxide seed crystal solid content meter, wherein iron oxide yellow crystal seed uses ferrous sulfate, sodium hydroxide is raw material, alkali compares 0.45, 20 DEG C of temperature, synthesized using existing iron oxide yellow acid system crystal seed preparation technology), backward bottom liquid in be passed through the oxygen-enriched air of 80% oxygen, control air themperature is not less than 50 DEG C, humidity is not less than 55%, throughput 2000L/min；Using the mode of dropwise addition by step 1) gained iron-containing liquor is gradually added into starting bottom liquid, adds speed 2L/min, after iron-containing liquor all adds bottom liquid, continue to react 2 hours, filtering, washing obtain iron oxide yellow product and reaction mother liquor.Solution temperature is maintained in course of reaction at 70-75 DEG C, and solution ph is maintained between 7.0-7.5 using ammoniacal liquor.
3) calcium oxide that 20kg effective contents 80% are added in 500L reaction mother liquors is taken, reaction temperature is controlled between 70-75 DEG C, in 3 hours reaction time, filtering, washing obtain desulphurization reaction mother liquor and gypsum.
4) by step 2), step 3) gained reaction mother liquor, desulphurization reaction mother liquor merge, take wherein 1000L to be back to step 1) in, recycled as reaction solution, remaining 1000L is used as step 2) in starting bottom liquid be continuing with.
It should be noted that, for above method embodiment, in order to be briefly described, therefore it is all expressed as to a series of combination of actions, but those skilled in the art should know, the application is not limited by described sequence of movement, because according to the application, some steps can be carried out sequentially or simultaneously using other.Secondly, those skilled in the art should also know, embodiment described in this description belongs to preferred embodiment, necessary to involved action and module not necessarily the application.
Finally it should be noted that：It the foregoing is only the preferred embodiments of the present invention, it is not intended to limit the invention, although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it can still modify to the technical scheme described in foregoing embodiments, or carry out equivalent substitution to which part technical characteristic.Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection.
Claims (12)
1. a kind of production method of iron oxide pigment, it is characterised in that including：
1) reaction solution of the configuration containing complexing agent, indifferent salt, pH value between 7.0-13.0, adds scrap iron or ferrous compound or ferric iron compound, wherein impurity is separated after dissolving, iron-containing liquor is obtained thereto；
2) oxygen-containing gas is passed through into iron-containing liquor, the ferrous iron in iron-containing liquor is oxidized to iron oxide yellow or iron oxide red or iron oxide black precipitation, isolated iron oxide pigment and reaction mother liquor；
Its complexing agent is one or both of methylamine, ethamine, ethylenediamine, propane diamine, monoethanolamine, imidazoles, Diethylenetriamine, three second tetramines, ethylenediamine tetra-acetic acid, EDDA, nitrilotriacetic acid, glutamic acid, valine, histidine, aspartic acid, alanine, proline, serine, phenylalanine, arginine, threonine, glycine, lysine, asparagine and glutamine.
2. the production method of iron oxide pigment according to claim 1, it is characterised in that step 2) in, further comprise：
Configuration and reaction mother liquor composition identical solution use reaction mother liquor as bottom liquid, and oxygen-containing gas is passed through thereto, iron-containing liquor is by way of being added dropwise or being added portionwise, added in 0.1-40 hours in mother liquor, and continue reaction 0.1-40 hours, obtain iron oxide yellow or iron oxide red or iron oxide black precipitation, isolated iron oxide pigment and reaction mother liquor.
3. the production method of iron oxide pigment according to claim 1, it is characterized in that, step 1) in, scrap iron is metallic iron of the iron content more than 80%, ferrous compound is ferrous sulfate, frerrous chloride, ferrous oxide, one or more in ferrous nitrate, ferric iron compound is ferric sulfate, iron chloride, one or more in ferric nitrate, oxygen-containing gas is oxygen, oxygen-enriched air, air and other contain one kind in the gas of oxygen, indifferent salt is sodium, potassium, the sulfate of ammonium ion, carbonate, nitrate, chloride, acetate, one or more in phosphate.
4. according to claim 1, the production method of iron oxide pigment described in 2, it is characterized in that, step 1), step 2) in reaction temperature between 0-110 DEG C, and use organic base, inorganic base, organic acid, inorganic acid rate-determining steps 1), step 2) in solution ph between 7.0-13.0, complexing agent concentration is 0.1-5.0mol/L, inertia salinity is no more than 4.5mol/L, iron concentration is 0.01-5.0mol/L in iron-containing liquor, oxygen-containing gas temperature is between 0-110 DEG C, humidity is between 5-90%, the ratio of oxygen-containing gas gas ventilation amount/liquor capacity per minute is no more than 10.
5. the production method of iron oxide pigment according to claim 1, it is characterised in that step 1) in, in addition to：Oxidant or catalyst are added, to promote metallic iron to dissolve faster.
6. the production method of iron oxide pigment according to claim 5, it is characterized in that, the oxidant is the one or more in chlorate, hydrogen peroxide, nitrate, perchlorate, chlorate, the catalyst is the one or more in mantoquita, nickel salt, platinum salt, gold salt, silver salt, cobalt salt, and the concentration of oxidant and catalyst is no more than 3.5mol/L.
7. the production method of iron oxide pigment according to claim 1, it is characterised in that step 2) in, in addition to：The crystal seed no more than 100g/L or other are added into solution can produce the material of nucleus, the crystal seed is the iron oxide yellow or iron oxide red or iron oxide black crystal seed synthesized using disclosed method, and other described materials that can produce nucleus are the one or more in copper, zinc, lead, cadmium, nickel, cobalt, aluminium, barium compound.
8. the production method of iron oxide pigment according to claim 1, it is characterised in that in step 1) or step 2) in, in addition to：Surfactant, including anionic surfactant, cationic surface active agent, zwitterionic surfactant, nonionic surface active agent are added, wherein surfactant addition is no more than 10g/L.
9. the production method of iron oxide pigment according to claim 8, adjoin one or more in pyrrolidone, OPEO, Triton X-100, polyoxyethylene sorbitan fatty acid ester, dodecyl sodium sulfate, lauryl sodium sulfate, APES characterized in that, the surfactant is stearic acid, oleic acid, laurate, quaternary ammonium salt, cocounut oil phthalein amine CAB, dodecyl alanine, isomery alcohol polyoxyethylene poly-oxygen propylene aether, polyethylene.
10. the production method of iron oxide pigment according to claim 1, it is characterised in that step 2) in, in addition to：Calcium oxide or barium monoxide are added into reaction mother liquor, sulfate radical excessive in reaction mother liquor is changed into calcium sulfate or barium sulfate precipitate, obtains desulphurization reaction mother liquor, desulphurization reaction mother liquor can be with return to step 1) recycle.
11. the production method of iron oxide pigment according to claim 10, it is characterised in that the temperature of reaction mother liquor desulfurization is 0-110 DEG C, and calcium oxide or barium monoxide addition are not less than 0.01mol/L.
12. a kind of iron oxide pigment prepared according to claim 1~11 either method.
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| CN108455681A (en) * | 2018-02-05 | 2018-08-28 | 吉林建筑大学 | A method of preparing iron oxide yellow using iron content, aluminum i ndustry waste water |
| CN109456619A (en) * | 2018-11-19 | 2019-03-12 | 岳西县邦玉铁系颜料有限公司 | A kind of iron oxide pigment that high chroma is oxidation-stabilized |
| CN109665566A (en) * | 2019-01-23 | 2019-04-23 | 深圳市长隆科技有限公司 | A kind of preparation method and sewage water treatment method of magnetic nano ferroferric oxide |
| CN113213522A (en) * | 2021-06-09 | 2021-08-06 | 龙蟒佰利联集团股份有限公司 | Method for co-producing barium sulfate and sodium sulfide from titanium white waste acid and iron-based pigment wastewater |
| CN113652558A (en) * | 2021-07-30 | 2021-11-16 | 葫芦岛锌业股份有限公司 | Method for recovering germanium from germanium-containing waste liquid |
| CN113772741A (en) * | 2021-09-06 | 2021-12-10 | 江苏宇星科技有限公司 | Method for producing iron oxide black by liquid phase synthesis |
| CN114105213A (en) * | 2021-11-17 | 2022-03-01 | 湖南特种金属材料有限责任公司 | Preparation method of spherical porous iron oxide, product and application thereof |
| CN114105213B (en) * | 2021-11-17 | 2023-11-21 | 湖南特种金属材料有限责任公司 | Preparation method of spherical porous ferric oxide and product and application thereof |
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