CN106187146A - 一种干法解毒铬渣的工艺 - Google Patents
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- 239000011651 chromium Substances 0.000 title claims abstract description 33
- 239000002893 slag Substances 0.000 title claims abstract description 33
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 231100001261 hazardous Toxicity 0.000 abstract description 2
- 229910052596 spinel Inorganic materials 0.000 abstract description 2
- 239000011029 spinel Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002910 solid waste Substances 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000012241 calcium silicate Nutrition 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- ULNANYUIHXBXRN-UHFFFAOYSA-L calcium dihydroxy(dioxo)chromium Chemical compound [Ca+2].O[Cr](O)(=O)=O ULNANYUIHXBXRN-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明涉及一种干法解毒铬渣的工艺，属于铬渣干法解毒技术以及有害固体废物处置领域。采用Al2O3含量为96%以上的氧化铝粉占30~50wt%、QM‑95以上级别轻烧镁粉占30~50wt%、无烟煤粉占0~40wt%制备添加剂，然后与铬渣混合焙烧，使铬渣中的六价铬还原为三价铬并将其在常温下固定。该方法组成材料均为市售商品，制作成本较低，用于铬渣干法解毒工艺，掺加量较少，可有效降低干法解毒工艺过程所需温度，促进终含镁渣尖晶石结构形成，采用一段式工艺处理即可达标，终渣不返黄。
Description
技术领域
本发明涉及一种干法解毒铬渣的工艺，属于铬渣干法解毒技术以及有害固体废物处置领域。
背景技术
铬渣由于含有高毒、致癌性的Cr（Ⅵ）而具有毒性。铬渣中Cr（Ⅵ）随雨水浸出，进入周围的河流、土壤，对环境和人的健康造成巨大的危害。铬渣中有害六价铬有多种存在状态，在硅酸钙-铬酸钙固溶体、铁铝酸钙-铬酸钙固溶体中，铬酸钙（CaCrO4）存在于硅酸钙或铁铝酸钙晶格内，属于酸溶Cr6+。要消除这两种Cr6+，必须破坏硅酸钙和铁铝酸钙晶格，或在极高温度特别是有酸性氧化物存在下使六价铬游离而分解，或者利用还原性气体（如CO，H2）于高温下扩散将硅酸钙和铁铝酸钙晶格内CrO4 2-还原为Cr3+。
铬渣干法解毒是采用回转窑或立窑作为煅烧设备，在高温下利用还原性物质将铬渣中的六价铬还原为三价铬并将其在常温下固定的工艺过程。目前国内一般采用高温炉窑处置含铬废弃物，但该工艺所需温度较高，一般在1300℃以上，且出渣容易返黄，需用硫酸亚铁等还原剂进一步还原，以保证终渣的稳定性。
发明内容
有鉴于现有干法解毒工艺的不足，本发明的目的在于提供一种干法解毒铬渣的工艺，有效降低干法解毒铬渣工艺所需温度，并使还原成三价后的铬有效固定在尖晶石晶格中，无需后续还原处理。
本发明通过以下技术方案实现：
（1）添加剂制备：Al2O3含量为96%以上的氧化铝粉（粒径≤75μm）占30~50wt%、QM-95以上级别轻烧镁粉占30~50wt%、无烟煤粉占0~40wt%，三种原料自由水含水率≤5%；先将氧化铝粉和无烟煤粉进行混合，再加入轻烧镁粉混合后共磨成粉（粒径≤3mm），即得添加剂；
（2）还原焙烧：将步骤（1）制得的添加剂与铬渣（粒径≤3mm，含水率＜5%）按照质量比为0.05~0.15:1混合均匀，混合后的碱度，即（MgO wt%+CaO wt%）/（SiO2 wt%+Al2O3 wt%）的比值，控制在1.0~1.3之间；然后在还原性气氛下600~1000℃焙烧20~40min。
本发明与现有技术相比有如下显著效果：
（1）本发明通过添加一定配比的氧化镁粉、氧化铝粉、无烟煤粉混合物，可以使还原反应在相对较低的温度即可高效完成还原过程，且还原后终渣无需进行后续还原处理即可保证稳定达标；
（2）本发明根据冶金反应工程学原理，以控制混合料的化学组分为核心，使终渣形成稳定的含铬尖晶石，克服了现有技术中解毒铬渣返黄问题，且终渣可得到资源化综合利用，无二次污染。
（3）本方法所用原料均为市售商品，且掺加量较少，采用一段式工艺处理即可达标，工艺成本较低。
附图说明
图1 为本发明工艺流程图。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1-3所采用的配料及配比如表1-表3所示：
表1 各实施例配料及配比
。
表2 铬渣铬形态及含量（%）
。
表3 铬渣化学成分分析（%）
。
将氧化铝粉、轻烧镁粉、无烟煤粉烘干至自由水含水率≤5%；将铬渣烘干至含水率低于5%，磨细至粒径≤3mm。
实施例1
按表1配比，取氧化铝粉和轻烧镁粉混合后共磨至粒径≤3mm制得添加剂，将添加剂与铬渣混合均匀，碱度为1.23，放入真空管式炉，控制还原性气体CO含量为80~90%，在600℃下还原焙烧30min，测定反应后六价铬浸出毒性为0.130mg/kg，置于自然条件下放置3个月后测定六价铬浸出毒性为0.137mg/kg。
实施例2
按表1配比，先将氧化铝粉和无烟煤粉进行混合，再加入轻烧镁粉混合后共磨至粒径≤3mm制得添加剂，将添加剂与铬渣混合均匀，碱度为1.28，放入真空管式炉，控制还原性气体CO含量为80~90%，在800℃下还原焙烧30min，测定反应后六价铬浸出毒性为0.064mg/kg，置于自然条件下放置3个月后测定六价铬浸出毒性为0.067mg/kg。
实施例3
按表1配比，先将氧化铝粉和无烟煤粉进行混合，再加入轻烧镁粉混合后共磨至粒径≤3mm制得添加剂，将添加剂与铬渣混合均匀，碱度为1.17，放入真空管式炉，控制还原性气体CO含量为80~90%，在1000℃下还原焙烧20min，测定反应后六价铬浸出毒性为0.011mg/kg，置于自然条件下放置3个月后测定六价铬浸出毒性为0.015mg/kg。
Claims (7)
1.一种干法解毒铬渣的工艺，包括以下步骤：
（1）添加剂制备：氧化铝粉占30~50wt%、轻烧镁粉占30~50wt%、无烟煤粉占0~40wt%，先将氧化铝粉和无烟煤粉进行混合，再加入轻烧镁粉混合后共磨成粉，即得添加剂；
（2）还原焙烧：将步骤（1）制得的添加剂与铬渣按照质量比为0.05~0.15:1混合均匀后，在还原性气氛下600~1000℃焙烧20~40min。
2.根据权利要求1所述的工艺，其特征在于，氧化铝粉粒径≤75μm，且其中Al2O3含量为96%以上。
3.根据权利要求1所述的工艺，其特征在于，轻烧镁粉为QM-95以上级别。
4.根据权利要求1所述的工艺，其特征在于，步骤（1）中三种原料自由水含水率≤5%。
5.根据权利要求1所述的工艺，其特征在于，步骤（1）中三种原料混合后共磨成粉，粒径≤3mm。
6.根据权利要求1所述的工艺，其特征在于，步骤（2）中的铬渣粒径≤3mm，含水率＜5%。
7.根据权利要求1所述的工艺，其特征在于，步骤（2）中添加剂与铬渣混合后的碱度，即（MgO wt%+CaO wt%）/（SiO2 wt%+Al2O3 wt%）的比值为1.0~1.3。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107234125A (zh) * | 2017-07-11 | 2017-10-10 | 中州大学 | 一种处理有毒性铬渣的工艺方法 |
| CN114558271A (zh) * | 2022-01-12 | 2022-05-31 | 湖南国发控股有限公司 | 一种两步法铬渣解毒配方及协同工艺 |
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| CN114558271B (zh) * | 2022-01-12 | 2023-11-28 | 湖南国发控股有限公司 | 一种两步法铬渣解毒配方及协同工艺 |
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