CN115537042B - 利用铁尾矿制备环境友好型绿色复合颜料的方法 - Google Patents
利用铁尾矿制备环境友好型绿色复合颜料的方法 Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000000049 pigment Substances 0.000 title claims abstract description 40
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 38
- 239000011174 green composite Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 17
- 239000010452 phosphate Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 8
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 6
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 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 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 229940005740 hexametaphosphate Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 235000007686 potassium Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000000976 ink Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000005060 rubber Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 239000001023 inorganic pigment Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OEFNHCPKKJVIDJ-UHFFFAOYSA-L P(=O)(OO)([O-])[O-].[Fe+2] Chemical compound P(=O)(OO)([O-])[O-].[Fe+2] OEFNHCPKKJVIDJ-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- CDFHZYKFWDNWGX-UHFFFAOYSA-N arsoric acid;copper Chemical compound [Cu].O[As](O)(O)=O CDFHZYKFWDNWGX-UHFFFAOYSA-N 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- -1 hydroxyl ferric phosphate Chemical compound 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3045—Treatment with inorganic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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Abstract
本发明为一种利用铁尾矿制备环境友好型绿色复合颜料的方法。该方法包括以下步骤：将球磨得到的铁尾矿细粉分散于铁盐溶液中，机械搅拌形成悬浮液；再在剧烈搅拌条件下加入磷酸盐，继续剧烈搅拌直至磷酸盐全部溶解，然后在140‑200℃油浴条件下机械搅拌反应；最后固液分离，得到环境友好型绿色复合颜料。本发明制得的绿色复合颜料颜色艳丽，色度值a*＝‑38.03，着色力100％，遮盖力强，不含重金属及其他有害元素，环境友好，成本低廉，耐候性强，可应用于建材、橡胶、塑料、涂料、玻璃、墨水等多个领域，具有很强的工业化应用前景。
Description
技术领域
本发明涉及一种环境友好型绿色复合颜料的制备方法，尤其涉及一种利用铁尾矿制备环境友好型绿色复合颜料的方法，属于大宗固体废弃物高附加值利用和环保型复合颜料制备技术领域。
背景技术
绿色无机颜料具有有机颜料无法比拟的耐高温性、耐候性、化学稳定性，在彩色玻璃、工程塑料、建筑涂料、道路标志涂料、绘画涂料等领域应用非常广泛。然而，天然绿色无机颜料非常稀少，常见的有孔雀石绿[CuCO3·Cu(OH)2]和碱式氯化铜[Cu2(OH)3Cl]。为了适应工业发展的需要，西欧等国于18世纪开始工业化生产砷酸铜绿，19世纪后颜料工业逐步发展成为以科研为基础的产业。
已报道的绿色无机颜料有氧化铬绿(Journal of Alloys and compounds,2019,785:747-753.)、锌酸钴绿(Ceramics International,2019,45(3):3306-3312.)、稀土基绿(Dyes and Pigments,2015,113:336-340.)等。然而重金属铬具有剧毒，钴元素和稀土元素价格昂贵，限制了绿色无机颜料的应用。目前，颜色鲜艳、环保无毒、价格低廉的绿色无机颜料的合成仍具有很大挑战。
虽然已有产业化的氧化铁绿，但氧化铁绿是氧化铁黄与有机颜料复合而成的，其耐候性较差。发明人在研究铁尾矿制备铁红颜料时发现(ZL201910269525.8)，磷酸盐的加入可使红色的产物变为绿色，但绿色不够鲜艳，可能由于铁尾矿是多种硅酸盐矿物的复合物，各矿物结构复杂，致使铁尾矿与磷酸盐的反应情况非常复杂。因此，通过铁尾矿制备效果稳定、优异的、鲜艳的绿色颜料是一个亟待解决的课题。目前针对铁尾矿的研究多集中于建筑、陶瓷、微晶玻璃等方面，尚未见以铁尾矿为原料合成绿色无机颜料的报道，也没有工业化应用先例。
发明内容
本发明是针对绿色无机颜料合成技术中的不足，提供一种以铁尾矿为原料，采用油浴法制备环境友好型绿色复合颜料的方法，具有极强的工业化应用前景。本颜料只含有硅、铁、铝、镁、磷等元素，不含任何重金属或稀土元素，绿色环保，成本低廉。本发明提供的绿色复合颜料充分挖掘了铁尾矿的资源禀赋特性和硅酸盐复合矿结构特点，发现了其在制备铁系绿色复合颜料中的不可或缺性，为我国堆存量巨大的铁尾矿的高附加值功能化利用开辟新途径，为环境友好型绿色复合颜料的制备提出新策略。
本发明的技术方案是：
一种利用铁尾矿制备环境友好型绿色复合颜料的方法，该方法包括以下步骤：
将球磨得到的铁尾矿粉末分散于铁盐溶液中，机械搅拌30～50min形成悬浮液；再在剧烈搅拌条件下加入磷酸盐，继续剧烈搅拌1～2h直至磷酸盐全部溶解，然后在140-200℃油浴条件下机械搅拌反应10～24h；最后固液分离，得到环境友好型绿色复合颜料。
其中，铁盐溶液的浓度为0.10～0.30mol/L，每升铁盐溶液中加入25～75g铁尾矿，0.3～0.6mol磷酸盐固体；
铁尾矿粉末的粒径为50-75μm。
所述的铁尾矿中SiO2的质量百分含量为20％～75％，Al2O3的质量百分含量为6％～36％，Fe2O3的质量百分含量为2％～16％；
所述的铁盐为硫酸铁、硝酸铁、氯化铁、硫酸亚铁、硝酸亚铁、氯化亚铁中的一种或两种；
所述的的磷酸盐为磷酸一氢钠、磷酸二氢钠、磷酸三钠、磷酸一氢钾、磷酸二氢钾、磷酸三钾、焦磷酸钠、焦磷酸钾、六偏磷酸钠、六偏磷酸钾的一种或两种；
所述的机械搅拌速度为300～1000r/min；
所述的剧烈搅拌速度为2000～4000r/min；
本发明的有益效果是：
本发明是一种以铁尾矿为原料，采用油浴法制备环境友好型绿色复合颜料的方法，得到的颜料的色度值a*＝-38.03，颜色艳丽，着色力100％、遮盖力强，不含重金属及其他有害元素，环境友好，成本低廉，耐候性强，可应用于建材、橡胶、塑料、涂料、玻璃、墨水等多个领域，具有很强的工业化应用前景。本发明弥补了绿色无机颜料合成的空白，为环境友好型绿色复合颜料的制备提出新策略，可为我国堆存量巨大的铁尾矿的高附加值功能化利用开辟新途径。
附图说明
图1为实施例1得到的环境友好型绿色复合颜料的数码照片；
图2为实施例1得到的环境友好型绿色复合颜料的XRD谱图；
图3为实施例1得到的环境友好型绿色复合颜料的SEM照片。
具体实施方式
下面结合实施例对本发明的技术解决方案做进一步说明，这些实施例不能理解为是对技术方案的限制。实施例所用铁尾矿为河北省承德市堆存的铁尾矿，其SiO2的质量百分含量为56％，Al2O3的质量百分含量为12％，Fe2O3的质量百分含量为5％，MgO的质量百分含量为15％。
实施例1：
称取32.0kg FeCl3·6H2O(即118mol)加入到600L去离子水中配成浓度为0.20mol/L的Fe3+溶液；称取30.0kg粒径为75μm(过筛得到)的铁尾矿粉末分散于铁盐溶液中，机械搅拌(500r/min)40min形成均一悬浮液；剧烈搅拌(3000r/min)条件下加入240.0mol磷酸三钠(39.4kg)，继续剧烈搅拌1h直至磷酸盐全部溶解；将悬浮液转至电加热导热油炉，在180℃油浴条件下机械搅拌(500r/min)反应12h；最后通过压滤机固液分离，洗涤、干燥、研磨得到环境友好型绿色复合颜料。
复合颜料的数码照片如图1所示，颜料呈粉末状，粉质细腻，颜色苍翠欲滴，其色度值a*＝-38.03(X-Rite,Ci 7800,USA)，着色力为100％(GB/T 13451.2-1992)；复合颜料表现出优异的耐候性，将其放置于室外暴晒30天，色度值a*变化率仅2.5％(X-Rite,Ci 7800,USA)。
由图2可知，复合颜料的物相组成为石英、Fe5(PO4)4(OH)3·2H2O，以及微量的黑云母、钠长石和斜绿泥石(Bruker D8,German)；由图3可知，复合颜料的微观形貌为规则的三角双锥(FE-SEM,Quanta 450FEG,USA)，粒径约为2.5μm，复合颜料较均匀的形貌、较小的粒径有利于其在分散介质中的分散。
实施例2：
称取32.0kg FeCl3·6H2O(即118mol)加入到600L去离子水中配成浓度为0.20mol/L的Fe3+溶液；剧烈搅拌(2500r/min)条件下加入240.0mol磷酸三钠(39.4kg)，继续剧烈搅拌直至磷酸盐全部溶解；将悬浮液转至电加热导热油炉，在180℃油浴条件下机械搅拌(500r/min)反应12h；最后通过压滤机固液分离，洗涤、干燥、研磨得到产品。但由于没有铁尾矿的加入，产品呈淡黄色，不是绿色。
实施例3：
称取30.0kg Fe2(SO4)3(即75mol)加入到500L去离子水中配成浓度为0.30mol/L的Fe3+溶液；称取25.0kg粒径小于75μm的铁尾矿粉末分散于铁盐溶液中，机械搅拌(600r/min)40min形成均一悬浮液；剧烈搅拌(3500r/min)条件下加入150.0mol磷酸三钠(24.6kg)、60mol六偏磷酸钠(36.7kg)，继续剧烈搅拌直至磷酸盐全部溶解；将悬浮液转至电加热导热油炉，在200℃油浴条件下机械搅拌(600r/min)反应10h；最后通过压滤机固液分离，洗涤、干燥、研磨得到环境友好型绿色复合颜料。复合颜料的色度值a*＝-34.03(X-Rite,Ci7800,USA)，着色力为99％(GB/T 13451.2-1992)。复合颜料表现出优异的耐候性，将其放置于室外暴晒60天，色度值a*变化率仅4.2％(X-Rite,Ci 7800,USA)
实施例4：
称取30.0kg Fe2(SO4)3(即75mol)加入到500L去离子水中配成浓度为0.30mol/L的Fe3+溶液；称取25.0kg粒径小于75μm的铁尾矿粉末分散于铁盐溶液中，机械搅拌(800r/min)40min形成均一悬浮液；将悬浮液转至电加热导热油炉，在200℃油浴条件下机械搅拌(800r/min)反应10h；最后通过压滤机固液分离，洗涤、干燥、研磨得到产品，但由于没有磷酸盐的加入，羟基磷酸铁没有生成，产品呈砖红色，不是绿色。
实施例5：
称取30.0kg FeSO4(即108mol)加入到500L去离子水中配成浓度为0.21mol/L的Fe2 +溶液；称取30.0kg粒径小于75μm的铁尾矿粉末分散于铁盐溶液中，机械搅拌(900r/min)40min形成均一悬浮液；剧烈搅拌(4000r/min)条件下加入150.0mol磷酸三钠(24.6kg)、60mol六偏磷酸钠(36.7kg)，继续剧烈搅拌直至磷酸盐全部溶解；然后通过压滤机固液分离，洗涤、干燥、研磨得到产品，但由于没有热驱动，没有生成羟基磷酸铁，产品呈土黄色，不是绿色。
本发明未尽事宜为公知技术。
Claims (4)
1.一种利用铁尾矿制备环境友好型绿色复合颜料的方法，其特征为该方法包括以下步骤：
将球磨得到的铁尾矿粉末分散于铁盐溶液中，机械搅拌30～50min形成悬浮液；再在剧烈搅拌条件下加入磷酸盐，继续剧烈搅拌1～2h直至磷酸盐全部溶解，然后在140-200℃油浴条件下机械搅拌反应10～24h；最后固液分离，得到环境友好型绿色复合颜料；
其中，铁盐溶液的浓度为0.10～0.30mol/L，每升铁盐溶液中加入25～75g铁尾矿，0.3～0.6mol磷酸盐固体；
所述的铁盐为硫酸铁、硝酸铁、氯化铁、硫酸亚铁、硝酸亚铁、氯化亚铁中的一种或两种；
所述的磷酸盐为磷酸一氢钠、磷酸二氢钠、磷酸三钠、磷酸一氢钾、磷酸二氢钾、磷酸三钾、焦磷酸钠、焦磷酸钾、六偏磷酸钠、六偏磷酸钾的一种或两种。
2.如权利要求1所述的利用铁尾矿制备环境友好型绿色复合颜料的方法，其特征为铁尾矿粉末的粒径为50-75μm。
3.如权利要求1所述的利用铁尾矿制备环境友好型绿色复合颜料的方法，其特征为所述的铁尾矿中SiO2的质量百分含量为20％～75％，Al2O3的质量百分含量为6％～36％，Fe2O3的质量百分含量为2％～16％。
4.如权利要求1所述的利用铁尾矿制备环境友好型绿色复合颜料的方法，其特征为所述的机械搅拌速度为300～1000r/min；所述的剧烈搅拌速度为2000～4000r/min。
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