CN114586645A - 一种以煤矸石固废制备营养土的方法 - Google Patents
一种以煤矸石固废制备营养土的方法 Download PDFInfo
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- CN114586645A CN114586645A CN202210319964.7A CN202210319964A CN114586645A CN 114586645 A CN114586645 A CN 114586645A CN 202210319964 A CN202210319964 A CN 202210319964A CN 114586645 A CN114586645 A CN 114586645A
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- coal gangue
- nutrient soil
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- solid waste
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Images
Classifications
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- A—HUMAN NECESSITIES
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- A—HUMAN NECESSITIES
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- A—HUMAN NECESSITIES
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- A—HUMAN NECESSITIES
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- Fertilizers (AREA)
Abstract
本发明公开了一种以煤矸石固废制备营养土的方法,该方法是将煤矸石破碎磨细后混成煤矸石浆料后使用直接正浮选的方法进行浮选,在浮选药剂的作用下,含有价元素的颗粒物与气泡充分接触,并聚集在气泡表面上升到液面泡沫层,收集泡沫层后即可得到含有价元素的混合物,煤矸石中较重的矿物颗粒则会停留在矿浆中收集,水溶性的重金属脱离煤矸石颗粒以离子态进入液相,将浮选后排放的浆料进行脱水干燥并活化,活化后的煤矸石与其它配料搅拌混匀后陈化制得营养土;本发明在分选出有价元素的同时脱除水溶性的重金属,再以低热值褐煤作为活化材料协同固定溶出的重金属,既实现了煤矸石固废高效资源化的目的,也大大提高了营养土的质量。
Description
技术领域
本发明属于煤矸石固体废弃物资源化利用领域,具体涉及一种以煤矸石固废制备营养土的方法。
背景技术
煤矸石是采煤过程和洗煤过程中排放的固体废物,是经成煤作用后以黑灰色岩石形态与煤层伴生的碳含量较低、比煤坚硬的矿石。主要包括掘进过程中的矸石、采掘过程中采出的矸石以及洗煤过程中挑出的矸石。我国堆积煤矸石现存量已超过 50 亿吨,并且每年增速保持在3~7亿吨左右,现存煤矸石山中约有2000座存在自燃风险或已经发生自燃,占比达30%以上。含硫煤矸石堆积过程解离加重了有害重金属离浸出,并容易对周围土地和水体造成酸污染;煤矸石堆积产生的高温环境易排放出大量SO2、H2S等有毒有害气体,比产生的固体粉尘颗粒更具破坏性。煤矸石的主要成分是Al2O3和SiO2,以及数量不等的Fe2O3、CaO、MgO、K2O、P2O5和稀散元素(镓、钒、钛、钴),稀有元素常从酸浸剩余母液提取。
煤矸石含碳量可达20%~30%,并含少量腐殖酸,添加煤矸石的土壤调理剂腐植酸、有机质等有效成分明显提高,可以帮助土壤释放有利于植物吸收的各种营养元素,是治理土壤板结、沙化、盐碱化现象和提高土壤渗透性的优选材料之一。营养土是为了满足苗木花卉等生长发育而专门配制的含有多种矿质营养,疏松通气,保水保肥能力强,无病虫害的土。营养土材料的质地必须致密均匀但也不能太粘,既能抓牢种子与苗木也不容易板结,不同栽培环境中含水率变化时对体积影响不大,而且体积相对较大营养土产品不利于降低生产和运输成本。因此,营养土应朝以下几个方向发展并进一步改进以权衡经济与环境效益:①盐含量低,良好的保水保肥性能;②有足够的孔隙度,有良好通气、透水性能;③材料源重量适中,来源广泛,价格低廉;④不带病虫和杂草种子。
《一种利用煤矸石和草木灰改性制备土壤改良剂的方法》(CN 107880897A)公开了一种利用煤矸石和草木灰改性制备土壤改良剂的方法,该发明首先将煤矸石超微活化,然后利用煤矸石和草木灰在600~900℃条件焙烧0.5~2h制备成硅钾肥,其中煤矸石和草木灰的质量比为1:(0.5~16)。利用草木灰中的K2CO3催化活化煤矸石中的晶体SiO2转变为可被植物吸收利用的有效硅,同时草木灰中的K元素由速溶态K2CO3转变为K、Ca、Mg、Si共存的可溶态化合物。利用硅钾肥与风化煤/有机肥复配制备土壤改良剂,增加土壤有机养分并改善土壤团聚结构和透气保水性能。《煤矸石压缩营养土的生产方法》(CN 104119190A)将煤矸石压缩营养土的配料搅拌均匀后输入压片机中压缩为片状物,其中配料为酸化后的煤矸石、酸化后的污泥、高粘凹凸棒石粘土、沼液浸泡后的碎石形凹凸棒花卉陶粒、粉碎后的泥炭、沼渣、粉碎后的植物纤维、膨胀蛭石、膨胀珍珠岩和高吸水树脂。再将片状物输送到微波带式干燥灭菌机中进行30~120分钟的低温灭菌和干燥,冷却后包装为煤矸石压缩营养土的成品。《一种利用煤基固废改善农业土壤的改良剂及方法》(CN 111363555A)中的改良剂由粉煤灰、煤矸石、污泥、膨润土、硅藻土、生物表面活性剂、凝胶剂、稳定剂组成;其制备方法为:以粉煤灰、经微生物活化处理后的煤矸石为原料,与污泥混合后,再依次加入凝胶剂溶液、膨润土、硅藻土、生物表面活性剂后加入稳定剂,经低温干燥处理后得到改良剂。
现有煤矸石制备营养土/土壤改良剂的技术与方法需进行活化以激发煤矸石中可利用营养元素,常见的处理方式有高温焙烧活化、微生物活化以及加酸活化,活化后的煤矸石有更高的重金属浸出风险并造成了稀散元素流失,经过酸化处理的煤矸石尤为严重,而且高温煅烧活化大大浪费了煤矸石中的碳氢化合物。
煤矸石的高效资源化利用是本领域亟待解决的问题,是否可以对煤矸石进行预选提取其中的稀散金属的同时除重金属,减少后续制备营养土/改良剂过程中稳定剂的使用量,以提高产品的环境安全性。
发明内容
针对现有煤矸石在制备土壤改良剂或营养土过程中利用率低,重金属潜在污染风险大以及有价元素资源浪费大的问题,本发明提供了一种以煤矸石固废制备营养土的方法,该工艺方法基于理想土壤粒径分布进行破碎磨细后浮选,分选出有价元素的同时也脱除水溶性的重金属,再以低热值褐煤作为活化材料协同固定溶出的重金属,既实现了煤矸石固废高效资源化的目的,同时也大大提高了营养土的质量。
本发明方法是煤矸石原料在破碎磨细装置中进行破碎和筛分,将筛分获得的不同粒径的煤矸石等比例混合,加水制成浆料,浆料通入到浮选设备中,搅拌后分别通过进药充气装置中加入浮选药剂和充气,浮选后刮取泡沫层获得含有价元素的矸石矿物;上层浆料通过循环泵泵入浮选设备内继续分选,下层浆料通过管道排入脱水干燥装置中进行脱水干燥,脱水后浆料与褐煤在搅拌装置中搅拌混合均匀后,进入活化罐中活化,活化后产物与其它配料混匀后在陈化罐中陈化,风干粉碎后得到的营养土。
本发明方法将煤矸石破碎细磨后使用直接正浮选的方法进行浮选,煤矸石浆料在浮选设备中实现矿物分离,在浮选药剂的作用下,含镓、钒、钛、钴等元素的颗粒物与气泡充分接触,并聚集在气泡表面上升到液面泡沫层,收集泡沫层后即可得到含有价元素的混合物;煤矸石中较重的高岭石、石英、铝土矿、硫铁矿等矿物颗粒则会停留在矿浆中收集,水溶性的重金属脱离煤矸石颗粒以离子态进入液相。将浮选后排放的浆料进行脱水干燥并活化,活化后的煤矸石与其它配料搅拌混匀后陈化制得营养土。
所述破碎细磨为将煤矸石原料粒径小于0.075mm,筛分后获得粒径0.05~0.75mm的中砂粒、粒径0.002~0.05mm的粉粒、粒径<0.002mm的黏粒,绝干混合煤矸石的密度大于1400kg/m3。
所使用的水为低钙镁含量的软水或去离子水,加水制成质量浓度7%~40%的浆料。
所述浮选设备为充气式浮选机、混合式浮选机或充气搅拌式浮选机,兼有搅拌与充气的作用。
所述浮选药剂包括捕获剂、分散剂,其中能促使含钛、钴、镓等元素的矸石颗粒与气泡充分接触聚集而上浮至泡沫层的捕获剂为油酸钠、十二烷基硫酸钠、辛基异羟肟酸、丁基黄原酸钾、邻氨基苯酸、氨基酸、十二胺等,使用量为0.5~3.5 kg/t。防止低粒径粉粒和黏粒聚集的分散剂为六偏磷酸钠、多聚磷酸钠及焦磷酸钠、水玻璃、碳酸钠等,使用量为0.1~0.5 kg/t。
所述脱水干燥装置处理后产物的含水率在40%以下。
所述脱水后浆料与褐煤质量比为1 : 0.05~0.5,其中褐煤粒径≥60目,褐煤中腐植酸含量≥23%,混合均匀后在活化罐中活化3~21天。
所述活化后产物和其它配料按如下重量百分比混合:活化后产物55%~85%、发酵污泥3%~20%、草木灰0.1%~15%、保水材料0.1%~4%、磷肥0.5%~4%。
其中保水材料为半纤维素、高吸水性树脂、锯末、蛭石、聚丙烯酰胺、粉煤灰中的一种或几种,磷肥为过磷酸钙、磷矿粉、磷石膏、钙镁磷肥、磷尾矿粉、磷酸铵中的一种或几种。
煤矸石活化后增加了有效硅铝含量,具有良好的疏孔和保水保肥性能,大量的腐殖酸提升养分的同时能络合煤矸石活化过程中释放的铜、铅、锌等重金属元素,进一步降低煤矸石利用过程的污染风险。发酵污泥中易降解有机质已初步降解,难降解有机物将进一步提供给微生物营养源,其中含有的大量微生物可进一步对煤矸石颗粒进行活化释放有效硅、铁、铝元素。草木灰提供了植物所需的其它矿质元素,其碱性能维持营养土的pH值为6~7并起预防酸化的作用,偏酸体系中微生物在常温条件下仍可在养分和活性提高、臭味减少方面起作用。保水材料具有吸水、释水以及疏孔保肥的性能,能维持营养土中微生物代谢所需要的水分和空气。磷肥提供了营养土主要的磷源,陈化过程中钙-磷成分解离能增加有效磷含量并提供游离的Ca2+与腐殖酸等有机质反应形成微团粒结构,减少水分、养分的流失,并提供微生物大量生存场所。
将活化后的煤矸石和其它配料混合均匀,混合物在20~50℃的陈化罐中陈化4~20天,室温下干化至含水率为18%~35%后粉碎为粒度小于0.5mm颗粒,即得煤矸石营养土。
本发明优点:
1、本发明将堆存的煤矸石固废破碎磨细至砂粒、粉粒、黏粒比例相同煤矸石颗粒,其中较细的粉粒和黏粒组成结构已进行了适当的破坏,通过浮选工艺回收有价元素的同时也使水溶性的重金属转移到液相中;并且低粒径矸石颗粒在浮选和活化过程中有利于硅、铝、钙等成分的进一步活化,浮选时添加的分散剂也阻碍了活化过程中细微颗粒的聚集,提供了有利的活化条件;
2、本发明使用低热值褐煤对煤矸石颗粒进行活化并提供养分,腐殖酸和硫化物在密闭的活化罐中能进一步对煤矸石颗粒进行解离并释放更多的有效硅钙铝成分,大量的腐殖酸能持续性地与释放的重金属元素发生络合作用降低营养土的潜在污染风险;
3、本发明所提供的营养土配方合理并具有较强的推广性,所制备的营养土性质稳定并能持续性地维持良好的理化性质。实现煤矸石有价元素再选,同时可减少企业的煤矸石处理成本和带来的环境污染。
附图说明
图1为本发明工艺流程示意图;
图中:1-破碎磨细装置;2-浮选设备;3-循环泵;4-进药充气装置;5-进料口;6-脱水干燥装置;7-搅拌装置;8-活化罐;9-陈化罐。
具体实施方式
下面通过实施例对本发明作进一步详细说明,但本发明保护范围不局限于所述内容;实施例中发酵污泥来源于生活污水处理厂所产生的活性污泥,在60℃下好氧发酵10天,使用时含水率为37%。
实施例1:如图1所示,煤矸石原料(成分如表1所示)在破碎磨细装置1中进行筛分和破碎,获得粒径0.05~0.75mm的中砂粒、粒径0.002~0.05mm的粉粒、粒径<0.002mm的黏粒,将三级筛分出的矸石颗粒等比例混合,绝干混合后颗粒密度为2300kg/m3,混合物与软水混合成含25%混合物的浆料,浆料通过进料口5进入到浮选设备2中,搅拌2分钟后,通过进药充气装置4加入1.0 kg/t的钛元素捕获剂油酸钠和0.3kg/t的分散剂水玻璃,搅拌1分钟后,再通过进药充气装置4充入0.25m3/h的空气,在此条件下浮选10分钟后刮取泡沫层,其TiO2的含量增大至13.76%;浮选设备下层浆料通过管道排入脱水干燥装置6中,上层浆料通过循环泵3泵入浮选设备内继续分选;进入脱水干燥装置6中处理后的煤矸石含水率降至28%,脱水后浆料与腐殖酸含量为34%的褐煤按重量比1:0.4的比例在搅拌装置7中混合均匀,进入活化罐8中活化14天。将活化后产物75%、发酵污泥14%、草木灰6%、锯末2%、钙镁磷肥3%混合均匀后在陈化罐9中25℃下陈化15天,风干粉碎后得到的营养土理化性质如表2所示,其中主要污染物重金属Cd的有效浓度由1.63mg/kg降低至0.44mg/kg;
表1 煤矸石化学成分分析
表2 营养土理化指标分析
实施例2:将成分如表3所示的煤矸石原料在破碎磨细装置1中进行破碎和筛分,获得粒径0.05~0.75mm的中砂粒、粒径0.002~0.05mm的粉粒、粒径<0.002mm的黏粒,将三级筛分出的矸石颗粒等比例混合,绝干混合后颗粒密度为2161kg/m3,混合物与软水混合成含30%煤矸石的浆料,浆料通过进料口5进入到浮选设备2中,与实施例一循环的上层浆料混合搅拌2分钟后,通过进药充气装置4中加入1.0 kg/t的钛元素捕获剂油酸钠和0.3 kg/t的分散剂水玻璃,搅拌1分钟后,再通过进药充气装置4充入0.25m3/h的空气,在此条件下浮选10分钟后刮取泡沫层,泡沫层TiO2的含量为9.79%。浮选设备中的所有浆料通过管道排入脱水干燥装置6中,使其含水率降至32%,脱水后产物与腐殖酸含量为41%的褐煤按重量比1:0.25的比例在搅拌装置7中混合均匀,进入活化罐8中活化14天,将活化后产物80%、发酵污泥11%、草木灰3%、锯末3%、钙镁磷肥3%混合均匀后,在陈化罐9中35℃陈化15天,风干粉碎后得到的营养土理化性质如表4所示,其中主要污染物重金属Cd的有效浓度由1.77mg/kg降低至0.35mg/kg;
表3 煤矸石化学成分分析
表4 营养土理化指标分析
实施例3:将煤矸石原料(成分如表5所示)在破碎磨细装置1中进行破碎筛分,获得粒径0.05~0.75mm的中砂粒、粒径0.002~0.05mm的粉粒、粒径<0.002mm的黏粒,将三级筛分出的矸石颗粒等比例混合,绝干混合后颗粒密度为2572kg/m3,混合物与软水混合成含35%煤矸石的浆料;浆料通过进料口5进入到浮选设备2中,搅拌2分钟后,通过进药充气装置4中加入1.0 kg/t的钛元素捕获剂十二胺和0.35 kg/t的分散剂六偏磷酸钠,搅拌1分钟后再通过进药充气装置4充入0.3m3/h的空气,在此条件下浮选10分钟后刮取泡沫层,泡沫层V2O5的含量增大至48.72%。浮选设备2中所有浆料通过管道排入脱水干燥装置6中处理至含水率降至29%后,与腐殖酸含量为39%的褐煤按重量比1:0.4的比例在搅拌装置7中混合均匀,进入活化罐8中活化18天,将活化后产物70.5%、发酵污泥16%、草木灰7%、聚丙烯酰胺-粉煤灰(1:1)混合料4%、钙镁磷肥2.5%的比例混合均匀后在陈化罐9中陈化15天,风干粉碎后得到的营养土理化性质如表6所示,其中主要污染物重金属Cd的有效浓度由1.59mg/kg降低至0.13mg/kg;
表5 煤矸石化学成分分析
表6 营养土理化指标分析
Claims (10)
1.一种以煤矸石固废制备营养土的方法,其特征在于:煤矸石原料在破碎磨细装置中进行破碎和筛分,将筛分获得的不同粒径的煤矸石等比例混合,加水制成浆料,浆料通入到浮选设备中,搅拌后分别通过进药充气装置中加入浮选药剂和充气,浮选后刮取泡沫层获得含有价元素的矸石矿物;上层浆料通过循环泵泵入浮选设备内继续分选,下层浆料通过管道排入脱水干燥装置中进行脱水干燥,脱水后浆料与褐煤在搅拌装置中搅拌混合均匀后,进入活化罐中活化,活化后产物与其它配料混匀后在陈化罐中陈化,风干粉碎后得到的营养土。
2.根据权利要求1所述的以煤矸石固废制备营养土的方法,其特征在于:破碎筛分后获得粒径0.05~0.75mm的中砂粒、粒径0.002~0.05mm的粉粒、粒径<0.002mm的黏粒,绝干混合煤矸石的密度大于1400kg/m3。
3.根据权利要求1所述的以煤矸石固废制备营养土的方法,其特征在于:添加的水为软水或去离子水,加水制成质量浓度7%~40%的浆料。
4.根据权利要求1所述的以煤矸石固废制备营养土的方法,其特征在于:浮选药剂为捕获剂和/或分散剂。
5.根据权利要求1所述的以煤矸石固废制备营养土的方法,其特征在于:捕获剂为油酸钠、十二烷基硫酸钠、辛基异羟肟酸、丁基黄原酸钾、邻氨基苯酸、氨基酸、十二胺、十八胺中一种或几种,使用量为0.5~3.5 kg/t;分散剂为六偏磷酸钠、多聚磷酸钠及焦磷酸钠、水玻璃、碳酸钠中的一种,使用量为0.1~0.5 kg/t。
6.根据权利要求1所述的以煤矸石固废制备营养土的方法,其特征在于:脱水干燥装置处理后产物的含水率在40%以下。
7.根据权利要求1所述的以煤矸石固废制备营养土的方法,其特征在于:脱水后浆料与褐煤质量比为1 : 0.05~0.5,其中褐煤粒径≥60目,褐煤中腐植酸含量≥23%,混合均匀后在活化罐中活化3~21天。
8.根据权利要求1所述的以煤矸石固废制备营养土的方法,其特征在于,活化后产物和其它配料按如下重量百分比混合:活化后产物55%~85%、发酵污泥3%~20%、草木灰0.1%~15%、保水材料0.1%~4%、磷肥0.5%~4%。
9.根据权利要求8所述的以煤矸石固废制备营养土的方法,其特征在于:保水材料为半纤维素、高吸水性树脂、锯末、蛭石、聚丙烯酰胺、粉煤灰中的一种或几种,磷肥为过磷酸钙、磷矿粉、磷石膏、钙镁磷肥、磷尾矿粉、磷酸铵中的一种或几种。
10.根据权利要求9所述的以煤矸石固废制备营养土的方法,其特征在于:陈化是在20~50℃下处理4~20天,风干粉碎后含水率为18%~35%,粒度小于0.5mm。
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