CN110316992B - 一种钢渣基水泥六价铬固体还原剂 - Google Patents
一种钢渣基水泥六价铬固体还原剂 Download PDFInfo
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- 239000004568 cement Substances 0.000 title claims abstract description 34
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 29
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002893 slag Substances 0.000 title claims abstract description 29
- 239000010959 steel Substances 0.000 title claims abstract description 29
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 27
- 239000007787 solid Substances 0.000 title claims abstract description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims abstract description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- -1 and simultaneously Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/60—Methods for eliminating alkali metals or compounds thereof, e.g. from the raw materials or during the burning process; methods for eliminating other harmful components
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Public Health (AREA)
- Toxicology (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明公开了一种钢渣基水泥六价铬固体还原剂,各组分及其质量百分比为钢渣88‑99.8份,激发剂0.1‑1份,络合剂0.1‑1份,吸附剂0‑10份;所述激发剂为氢氧化钠或氢氧化钾中的一种或两种以任意比例混合得到的混合物;所述络合剂为三乙醇胺或二乙醇单异丙醇胺中的一种或两种以任意比例混合得到的混合物;所述吸附剂为草酸或者丙二酸中的一种或两种以任意比例混合得到的混合物。本钢渣基水泥六价铬固体还原剂不仅能大幅度降低水泥中六价铬的含量,同时,利用协同处置的设计理念,实现工业固废钢渣的资源综合利用;而且该固体还原剂还具备制备方便,价格便宜,保质期长和易于运输等优点。
Description
技术领域
本发明涉及六价铬还原剂和工业废弃物资源化综合利用领域,特别涉及一种钢渣基水泥六价铬固体还原剂。
背景技术
水泥是当前经济建设的基础性材料,由于原料、生产工艺等原因,水泥及其制品中往往含有少量的镉、铬、铅等有毒、有害物质,其中以六价铬(Cr6+)的危害最为严重。以前我国对水泥中六价铬的危害不够重视,直到2015年9月11日,我国才发布了限制水泥中六价铬含量的强制性标准GB 31893-2015《水泥中水溶性铬(VI)的限量及测定方法》,规定水泥中水溶性六价铬含量不大于10mg/kg。六价铬易溶于水,很容易被人体吸收,可在体内蓄积。而三价铬不溶于水,可吸附在固体物质上而存在于沉积物中,因此水泥可溶性六价铬的降铬措施就是利用六价铬的强氧化作用,加入还原剂将六价铬还原为三价铬。因此,如何有效地控制水泥中的六价铬含量,减少六价铬的危害至关重要,添加还原剂无疑是一种简单可行有效的方式。
目前关于水泥六价铬固体还原剂主要是硫酸亚铁和硫酸锰等还原剂,但它们易氧化,化学稳定性差、添加量大且具有一定的刺激性和毒性,导致使用受到限制。
钢渣是炼钢过程中的一种工业副产品,钢渣中含有大量的硅酸二钙和部分玻璃相,可作为混合材用于生产水泥。由于钢渣中含有的RO相是以铁、锰元素的固溶物存在,不易被激发出零价铁、亚铁离子和二价锰离子,故目前还未见将钢渣用于还原水泥中六价铬的相关研究。
发明内容
有鉴于此,本发明提供了一种钢渣基水泥六价铬固体还原剂,该固体还原剂由钢渣、激发剂、络合剂、吸附剂组成。本发明制备的钢渣基水泥六价铬固体还原剂不仅能大幅度降低水泥中六价铬的含量,同时,利用协同处置的设计理念,钢渣作为一种固体废弃物,还能实现其资源再利用。
为实现上述目的,本发明采用如下技术方案:
本发明提出的一种钢渣基水泥六价铬固体还原剂,其特征在于,该还原剂由以下原料制备得到,各原料及其质量百分比为:
所述激发剂为氢氧化钠或氢氧化钾中的一种或两种以任意比例混合得到的混合物;
所述络合剂为三乙醇胺或二乙醇单异丙醇胺中的一种或两种以任意比例混合得到的混合物;
所述吸附剂为草酸或者丙二酸中的一种或两种以任意比例混合得到的混合物。
进一步地,所述钢渣的粒径分布为D50<5mm,且含铁量在10%~20%。
本发明的特点及有益效果:
本发明首次以钢渣作为水泥六价铬还原剂的基体,钢渣无毒、无刺激性,在常规环境下,稳定存在,而且含有大量的RO相,主要由铁、锰元素组成,钢渣在激发剂的作用下,在水泥水化的过程中快速、大量地形成零价铁、亚铁离子以及二价锰离子,与水泥中的Cr(VI)发生氧化还原反应,将Cr(VI)还原成Cr(III)。本发明还原剂中的三乙醇胺或者二乙醇单异丙醇胺不仅能帮助钢渣在水泥中分散均匀,而且能络合亚铁离子和二价锰离子,帮助其在浆液中稳定存在。而草酸或者丙二酸能够吸附还原后的三价铬,使其更容易被固化在水泥硬化产物中。本发明所涉及的化学反应如下:
本发明充分利用钢渣中的铁相与水泥中六价铬的氧化还原特性,协同处置固废与有害元素;此外,本固体还原剂还具备制备方便,价格便宜,保质期长和易于运输等优点。
具体实施方式
本发明提出的一种钢渣基水泥六价铬固体还原剂,各原料及其质量百分比为:
所述激发剂为氢氧化钠或氢氧化钾中的一种或两种以任意比例混合得到的混合物;
所述络合剂为三乙醇胺或二乙醇单异丙醇胺中的一种或两种以任意比例混合得到的混合物;
所述吸附剂为草酸或者丙二酸中的一种或两种以任意比例混合得到的混合物。
进一步地,所述钢渣的粒径分布为D50<5mm,且含铁量(以Fe2O3计)在10%~20%。通过限制钢渣的粒径,来降低粉磨难度。将钢渣的含铁量限制在10%~20%时,即能保证还原效果,同时可避免因含铁量过多而导致的水泥性能下降。
本发明中所涉及的各原材料均为常规材料。
使用本发明还原剂时,首先将各原料按照上述比例混合均匀(可采用在钢渣中加入激发剂、络合剂和吸附剂的方式,对于激发剂、络合剂和吸附剂的加入顺序无特殊要求,然后搅拌匀,均匀搅拌后为粉体),制得还原剂,将该还原剂按照水泥物料质量的1%~5%掺入水泥物料中,粉磨后得到水泥制品。
下面通过实例,对本发明做进一步详细的说明。
从表中可以看出,将本发明实施例的还原剂掺入水泥中,可将水泥中六价铬的含量均控制在10mg/kg内,满足强制性标准GB 31893-2015《水泥中水溶性铬(VI)的限量及测定方法》。本发明将钢渣作为还原剂基体,变废为宝,能实现其资源再利用,且制得的还原剂稳定性好。
以上实施案例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
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CN103833249A (zh) * | 2014-03-17 | 2014-06-04 | 山东宏艺科技股份有限公司 | 一种除铬增强剂及其制备方法 |
CN106830725A (zh) * | 2017-02-21 | 2017-06-13 | 辽宁天宝华瑞建材有限公司 | 水泥六价铬消减剂 |
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