CN110090847B - 一种含硫化矿物废石的快速风化成土方法 - Google Patents
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Abstract
本发明公开一种含硫化矿物废石的快速风化成土方法,属于矿区生态修复领域。本发明所述方法为利用硫氧化菌对含硫化矿物废石进行液淋洗或浸泡,保持硫氧化菌与废石的充分接触与氧化氛围;废石中硫化矿物被硫氧化菌氧化溶出,导致废石结构强度下降,随后对废石进行破碎、粉碎、过筛,粒径超标废石继续进行生物氧化浸出与破碎,粒径达标废石颗粒则认为形成粗砂土,可用于矿区封场闭库。本发明针对多石少土矿区封场闭库所存在的异地取土成本高、生态破坏严重等问题,通过生物风化与物理风化相结合,实现矿区废石的原位快速风化成土,有效解决了传统封场闭库过程所产生取土困难、取土及装卸运输成本高、生态破坏严重的问题。
Description
技术领域
本发明涉及一种含硫化矿物废石的快速风化成土方法,属于矿区生态修复领域。
背景技术
矿山开采完毕后,按国家要求需要进行覆土封场闭库。但对于多石少土地区,土壤资源匮乏,异地取土进行封场闭库存在土壤获取困难、取土及装卸运输成本高、取土地区生态环境被破坏等问题。因此,寻求一种废石原位快速风化成土方法就显得尤为迫切。
国内矿区矿石成分构成多以硫化矿为主,其开采过程所排放的废石之中多含有硫化矿物。自然界中土壤是岩石的风化产物,本发明提出通过人为强化岩石的生物风化与物理风化过程,加速矿区废石的风化成土过程,即利用硫氧化菌对硫化矿物的生物氧化溶出,降低废石结构强度,并辅以机械破碎、粉碎,促进废石风化为砂土,从而实现快速风化成土。此外,硫氧化菌增殖及凋亡产生的生物量也可为风化成土提供有机组分,提高砂土的肥力。
申请公布号CN 106833797A的发明专利公开了一种高硫分煤矿分段堆浸脱硫的工艺。该方法通过筑堆-酸平衡-脱无机硫-浸出液中和-脱有机硫的步骤进行。该工艺存在使用硫酸进行酸平衡,导致药剂成本较高、破碎预处理导致能耗较高;本发明无硫酸等药剂消耗,采用硫氧化菌对硫化矿物氧化溶出,导致废石的疏松度上升、结构强度下降,降低了废石破碎难度与成本。
申请公布号CN 105964390A的发明专利公开了一种铜矿废石综合利用方法及系统,将铜矿废石进行粉碎后依次进行多级浮选、磁选,后将次级尾矿用氧化亚铁硫杆菌、氧化硫硫杆菌、嗜酸异养菌中的一种或多种进行浸出,提高了铜的回收率。该方法在硫氧化菌浸出之前进行破碎,能耗高;使用浮选药剂,对后续微生物产生毒害作用;而本专利利用硫氧化菌溶出硫化矿物,使废石强度下降后,再进行破碎,降低了破碎难度和能耗;不添加浮选药剂,避免了其对微生物的毒害作用。
发明内容
针对多石少土矿区封场闭库的异地取土及生态破坏问题,本发明提出了一种含硫化矿物废石的快速风化成土方法,通过硫氧化菌氧化废石中的硫化矿物,降低了废石强度,实现了堆存废石的原位快速风化成土。
本发明通过以下技术方案实现:
一种含硫化矿物废石的快速风化成土方法,具体包括以下步骤:
(1)用硫氧化菌菌液对含硫化矿物废石堆进行淋洗或浸泡,浸泡为常规方法,例如堆浸、槽浸、桶式浸出、振动浸出和搅拌浸出。
(2)将空气或氧气连续注入废石堆,保证硫氧化菌与废石的充分接触与传质,并保持氧化氛围;
(3)对硫氧化菌氧化后的废石进行搅拌或振动破碎、粉碎。
(4)对破碎、粉碎后的废石过筛,粒径超标废石重复步骤(1)~(4),粒径达标废石颗粒则认为形成粗砂土,可用于矿区封场闭库。
优选的,本发明步骤(1)中硫氧化菌为嗜酸硫杆菌属、钩端螺旋菌属、嗜酸菌属、硫化叶菌属、金属球菌属、嗜酸热类球菌属、铁质菌属、硫化杆菌属中的一种或以任意比例混合的混合菌。
优选的,本发明步骤(1)中所述硫氧化菌菌液浓度为1×103~1×109cfu/mL,菌液的pH为1.0-5.0,温度为10-85℃,氧化还原电位为100-900 mV,淋洗或浸泡时间为3-120天。
优选的,本发明步骤(1)中所述淋洗过程的淋洗速率为1-40L/(h∙m2),淋洗时间为3-120天,每天淋洗1-24h。
优选的,本发明步骤(2)中所述空气或氧气连续注入废石堆,保持液相中溶解氧浓度为2-10mg/L。
优选的,本发明充氧过程还可以补加二氧化碳或碳酸盐,保持液相中碳氮比(C/N)为:3:1-5:1。
优选的,本发明控制步骤(2)所述液相中钾离子浓度为0.25-3.0g/L、磷酸根浓度为0.5-1.5g/L、镁离子浓度为0.1-1.5g/L、钙离子浓度为0.01-0.1g/L;这些营养物质有利于细菌氧化活性、加速含硫化矿物废石风化成土过程,并为后续植物生长奠定基础。
本发明所述硫氧化菌菌液,是指按常规方法和培养基培养的硫氧化菌,根据废石中钾离子、磷酸根、镁离子、钙离子的含量调整硫氧化菌菌液中钾离子、磷酸根、镁离子、钙离子浓度的浓度,使步骤(2)中钾离子浓度为0.25-3.0g/L、磷酸根浓度为0.5-1.5g/L、镁离子浓度为0.1-1.5g/L、钙离子浓度为0.01-0.1g/L。
优选的,本发明控步骤(4)中所述过筛废石粒径≤ 5 mm。
本发明步骤(3)中,搅拌或振动目的在于破碎、粉碎废石;搅动、振动破碎过程可通过机械搅拌、空气搅拌、振动泵振动、碾压设备碾压实现。
本发明所述含硫化矿物废石为坑道采掘废石、露天开采的剥离的废石、煤矸石。
本发明的原理:
硫氧化菌吸附于废石表面和细小孔隙中,氧化金属离子、硫化矿物、硫化氢、及元素硫,生成硫酸和金属硫酸盐溶液;硫氧化菌分泌有机酸促使废石进一步分解;硫氧化菌死亡残体,附着于废石表面,为含硫化矿物废石风化成土进一步提供有机质,含硫化矿物废石的氧化分解过程如下:
2H2S+O2+硫氧化菌=2H2O+2S+能量(3)
MeS+1/2O2+2H+=Me2++S0+H2O
Fe2++1/4O2+H+=Fe3+ +H2O
MeS+2Fe3+=Me2++S0+2Fe2+
2S+3O2+2H2O+硫氧化菌=2H2SO4+能量(4)
6CO2+6H2O+能量(3)(4) 酶=C6H12O6+6O2
MS+O2+H2SO4=H2O+MSO4
MS+2O2=MSO4
本发明的有益效果在于:
本发明所述方法解决了传统封场闭库过程中取土困难的问题;节约了异地取土及装卸运输费用;避免了取土所产生的生态破坏;实现了矿区堆存废石的原位快速风化成土。
附图说明
图1为本发明的工艺流程图。
具体实施方式
下面结合具体实施例本发明作进一步的详细说明,但本发明的保护范围并不限于所述内容。
实施例1
一种硫化镍矿开采废石的快速风化成土方法,具体包括以下步骤:
(1)某硫化镍矿开采过程中,堆置大量含有硫化铁、硫化铜、硫化锰的废石,购买硫杆菌纯菌种配制成浓度为109cfu/mL的菌液,控制菌液pH为5.0,温度为25℃,氧化还原电位:300mV;
(2)以3L/(h∙m2)的淋洗速率,用步骤(1)中的菌液淋洗废石堆,每日淋洗24h,使废石与菌液充分接触,淋洗过程中将氧气连续注入废石堆,保持液相中溶解氧浓度为2mg/L,并补充二氧化碳,保持液相中碳氮比(C/N)为:5:1,为微生物代谢提供氧气和碳源;控制液相中钾离子浓度为0.25-3.0g/L、磷酸根浓度为0.5-1.5g/L、镁离子浓度为0.1-1.5g/L、钙离子浓度为0.01-0.1g/L。此过程中硫氧化菌氧化废石中残留的硫化铁、硫化铜、硫化锰,生成金属硫酸盐溶液和硫酸,废石结构强度下降,每3天回流淋洗液继续淋洗废石。
每处理3天,对硫氧化菌氧化后的废石进行搅拌或振动破碎、粉碎,连续处理30天后,经过孔径为5mm的筛网筛选,粒径小于5mm的颗粒质量占总质量的80%,上述结果说明本实施例所述方法可以加速硫化镍矿开采废石的风化成土过程。
实施例2
一种煤矸石的快速风化成土方法,具体包括以下步骤:
(1)某煤矿废石堆场,堆置大量煤矸石,购买硫化叶菌纯菌种配制浓度为103cfu/mL的菌液。控制菌液pH为2.0,温度为68℃,氧化还原电位:500 mV;
(2)用步骤(1)中的菌液浸泡煤矸石,连续曝气,保持液相中溶解氧浓度为10 mg/L;控制液相中钾离子浓度为0.25-3.0g/L、磷酸根浓度为0.5-1.5g/L、镁离子浓度为0.1-1.5g/L、钙离子浓度为0.01-0.1g/L。此过程中硫氧化菌氧化煤矸石中的SO3、FeS2,生成硫酸和硫酸铁溶液,硫酸腐蚀煤矸石,煤矸石结构强度下降,每90天回流浸出液继续浸泡煤矸石。
处理90天后,对硫氧化菌氧化后的废石进行搅拌或振动破碎、粉碎,经过孔径为5mm的筛网筛选,粒径小于5mm的颗粒质量占总质量的90%,上述结果说明本实施例所述方法可以加速煤矸石的风化成土过程。
实施例3
一种辉铜矿采矿废石的快速风化成土方法,具体包括以下步骤:
(1)某辉铜矿采矿过程中,堆置大量含有Cu2S、FeS2的废石,经驯化和扩大培养,得到的硫氧化菌包括嗜酸硫杆菌属、钩端螺旋菌属、嗜酸菌属、硫化杆菌属和铁质菌属,控制硫氧化菌浓度为105cfu/mL;培养条件为pH :1.0,温度:10℃,氧化还原电位:900 mV;
(2)以40L/(h∙m2)的淋洗速率,用步骤(1)中的菌液淋洗废石,每日淋洗1h,使废石与菌液充分接触,淋洗过程中将氧气连续注入废石堆,保持液相中溶解氧浓度为4 mg/L,并补充碳酸盐,保持液相中碳氮比(C/N)为:3:1;控制液相中钾离子浓度为0.25-3.0g/L、磷酸根浓度为0.5-1.5g/L、镁离子浓度为0.1-1.5g/L、钙离子浓度为0.01-0.1g/L。此过程中硫氧化菌氧化废石中的Cu2S和FeS2,生成硫酸和金属硫酸盐溶液,硫酸腐蚀废石,废石结构强度下降;每45天回流淋洗液继续淋洗废石。
每处理45天,对硫氧化菌氧化后的废石进行搅拌或振动破碎、粉碎,连续处理135天后,经过孔径为5mm的筛网筛选,粒径小于5mm的颗粒质量占总质量的95%,上述结果说明本实施例所述方法可以加速辉铜矿采矿废石的风化成土过程。
Claims (5)
1.一种含硫化矿物废石的快速风化成土方法,其特征在于,具体包括以下步骤:
(1)用硫氧化菌菌液对含硫化矿物废石堆进行淋洗或浸泡;
(2)将空气或氧气连续注入废石堆,保持液相中溶解氧浓度为2-10mg/L,保证硫氧化菌与废石的充分接触与传质,并保持氧化氛围;充氧过程补加二氧化碳或碳酸盐,保持液相中碳氮比(C/N)为:3:1-5:1;
(3)对硫氧化菌氧化后的废石进行搅拌或振动破碎、粉碎;
(4)对破碎、粉碎后的废石过筛,粒径超标废石重复步骤(1)~(4),粒径达标废石颗粒则认为形成粗砂土,可用于矿区封场闭库;所述过筛废石粒径≤ 5 mm。
2.根据权利要求1所述方法,其特征在于:步骤(1)中硫氧化菌为嗜酸硫杆菌属、钩端螺旋菌属、嗜酸菌属、硫化叶菌属、金属球菌属、嗜酸热类球菌属、铁质菌属、硫化杆菌属中的一种或以任意比例混合的混合菌。
3.根据权利要求1所述方法,其特征在于:步骤(1)中所述硫氧化菌菌液浓度为1×103~1×109cfu/mL,菌液的pH为1.0-5.0,温度为10-85℃,氧化还原电位为100-900 mV,淋洗或浸泡时间为3-120天。
4.根据权利要求1所述方法,其特征在于:步骤(1)中所述淋洗过程的淋洗速率为1-40L/(h∙m2),淋洗时间为3-120天,每天淋洗1-24h。
5.根据权利要求1所述方法,其特征在于:控制步骤(2)所述液相中钾离子浓度为0.25-3.0g/L、磷酸根浓度为0.5-1.5g/L、镁离子浓度为0.1-1.5g/L、钙离子浓度为0.01-0.1g/L。
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