CN109336350A - 含油污泥热解处理及其残渣生物腐植酸绿色修复工艺 - Google Patents
含油污泥热解处理及其残渣生物腐植酸绿色修复工艺 Download PDFInfo
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Abstract
含油污泥热解处理及其残渣生物腐植酸绿色修复工艺，将粉碎后的含油污泥和循环固体热灰从旋转反应器前端加入，搅拌混合、快速加热、汽化热解；热解油气经过气固分离器分离的热解油气进入分馏塔得到馏分油或合成原油以及塔底油，热解渣通过返料控制器进入煅烧流化床与热流化空气混合燃烧加热，在煅烧流化床顶部经过二级气固分离，大中颗粒热灰通过循环管返回旋转反应器，细小颗粒灰流入降温罐作为残渣外排，烟气经过空气预热器后外排；通过风机加压后的空气经过空气预热器加热后流入煅烧流化床底部作为热流化空气；冷却后的残渣用腐植酸物质进行重金属脱毒和团粒化，恢复土壤自我修复和种植功能。
Description
1.技术领域
本发明提供的含油污泥热解处理及其残渣生物腐植酸绿色修复工艺，涉及污染土壤的净化治理，尤其涉及含油污泥的修复。
2.背景技术
含油污泥是指混入原油、各种成品油、渣油等重质油的泥土，形成了一种极其难以处理的含油污泥。油田在油气生产过程中都会产生一定量的含油污泥，主要来自两个方面：一是原油从地层中携带至地面，在各类容器、大罐和回收水池等地面设施中淤积，需定期清理的污泥；二是油井作业、集输油管道穿孔和盗油产生的落地污泥。含油污泥对人体有害，对植物、水体生物有害，蒸发在空气中的油气能刺激皮肤、眼睛及呼吸器官，使土地失去植物生长的功能，处理和修复困难。由于油田含油污泥的物理化学性质十分复杂，使得含油污泥极难分离和处理，是石油及石油化工工业的主要污染物之一。含油污泥按照《按照国家危险废物名录》属于HW08危险废弃物，面对这令人头疼的油泥，企业处理含油污泥的手法以前主要为掩埋和焚烧两种办法。
掩埋就是将含油污泥找个地方挖个坑，做好防渗透后埋起来，这种方法会占用大量的土地，且容量有限。而焚烧法就是将含油污泥进行高温焚烧，这种方法可实现废物减量并焚毁污染物质，还可回收一部分热量。但缺陷在于需要消耗大量燃料，运行成本高。
含油污泥热解处理技术是指在加热的情况下，将含油污泥中的重质油类分解成带挥发性的低碳烃类燃料、合成原油和固体碳等，被认为是最有工业化前景的处理技术。目前开发的基本是以外加热的旋转窑反应器为主的含油污泥热解处理技术，减量化和资源化效果十分明显。但是升温速率低和反应时间长从而导致液收低、处理规模难以大型化、热解残渣中含有较高的石油烃和重金属，残渣的无害化利用成为了制约该技术工业化推广应用的瓶颈。
腐植酸是动、植物的残骸经过微生物的分解和转化以及地球物理化学的一系列过程而形成的一类大分子有机弱酸混合物，保持了各种结构成分的自然状态和生物活性及其丰富的官能团，如芳香环、共轭双键、羟基、羧基、酚羟基、羰基等，能够刺激和促进微生物群的繁殖和生长，加速多环芳烃降解，促进土壤团粒化，保墒保肥增温，提高作物抗逆性和产量，协助消除土壤多环芳烃、络合固定重金属的优势，是来源广、绿色低成本的环境修复材料。
因此,含油污泥高效热解和残渣无害化处理，实现含油污泥无害化、减量化和资源化，成为当前含油污泥处理的重点和热点。
3.发明内容
本发明的目的是为了克服现有含油污泥热解技术的不足而发明的一种含油污泥热解处理及其残渣生物腐植酸绿色修复工艺，通过含油污泥内混式固体热载体快速热解提高液收、热解残渣流化床煅烧彻底脱出石油烃、分级分离的大中颗粒用作循环热载体和细小颗粒外排生物腐植酸绿色修复实现无害化利用的技术措施耦合，实现含油污泥无害化、减量化和资源化处理。
本发明的技术方案：
含油污泥热解处理及其残渣生物腐植酸绿色修复工艺，将粉碎后的含油污泥从内混式的旋转反应器前端的顶部加入，与前端顶板的上部侧面加入的循环固体热灰在旋转反应器中搅拌混合、快速加热、汽化热解；含尘的热解油气从旋转反应器末端的顶部流出并进入气固分离器，热解渣从旋转反应器末端的底部流出并通过返料控制器进入煅烧流化床底部；经过气固分离器分离的热解油气进入分馏塔得到馏分油或合成原油以及塔底油，固体灰通过返料控制器流入煅烧流化床底部，塔底油返回与含油污泥混合；热解渣和固体灰在煅烧流化床内与热流化空气混合燃烧加热，在煅烧流化床顶部经过二级气固分离，大中颗粒热灰通过循环管返回旋转反应器，细小颗粒灰流入降温罐作为残渣外排，烟气经过空气预热器后外排；通过风机加压后的空气经过空气预热器加热后流入煅烧流化床底部作为热流化空气；冷却后的残渣用腐植酸物质进行重金属脱毒和团粒化，恢复土壤自我修复和种植功能。
其中，含油污泥和循环热灰的比例为2:10，旋转反应器转速为0.2-1200转/分钟，旋转反应器末端的油气出口温度为400-650℃，旋转反应器固体停留时间为0.002-20分钟。
煅烧流化床操作温度为600-1050℃，流化气速0.02-18米/秒。
残渣与腐植酸物质混合均匀，进行重金属原位还原和络合固化脱毒，腐植酸促使土壤团粒化包裹阻断颗粒内重金属的渗出与迁移；陈化2天以上后，将脱毒残渣再与半焦菌肥混合均匀，利用微生物菌群持续产生的活性腐植酸实现永久还原与固定，恢复土壤自我修复和种植功能。
腐植酸物质为腐植酸、腐植酸钾、腐植酸钠或生物质热解油等中的一种或多种，其中生物质热解油为农林废弃物快速热解液体产品或气化过程生成的生物油。
粉碎机为球磨机、圆锥破碎机、齿辊式破碎机、反击式破碎机，冲击式破碎机、锤式破碎机、旋回式破碎机、复合式破碎机、液压破碎机、深腔破碎机、辊式破碎机、西蒙斯圆锥破碎机、液压圆锥破碎机、颚式破碎机等中的一种；
残渣修复治理时，半焦微生物群修复剂用量为3-10公斤/立方土，腐殖酸物质用量为5-40 公斤/立方土，氮肥和磷肥比例为5-10:1，氮肥施用量0.05-0.2公斤/立方土。
按照上述方案进行实施、试验，证明本发明含油污泥热解处理高效清洁、残渣修复方法合理、操作简便安全，生产成本低，质量好，效率高，实现含油污泥无害化、减量化和资源化的同时，残渣原位脱毒和重金属固定，杜绝二次污染和治理反弹，改善自然环境，修复快，效果好，修复后的土壤能够正常种植各种农作物，治理费用低，适用范围广泛，提高了经济社会效益，很好地达到了预定目的。
4.附图说明
附图1为本发明含油污泥热解处理及其残渣生物腐植酸绿色修复工艺流程示意图。
附图的设明如下：
1、粉碎机 2、旋转反应器 3、顶板 4、油气出口 5、气固分离器 6、分馏塔 7、热解渣出口 8、返料控制器 9、煅烧流化床、10、一级分离器 11、二级分离器 12、冷却器 13、残渣改性修复器 14、空气预热器 15.风机
下面结合附图和实施例来详述本发明的工艺特点。
5.具体实施方式
实施例1，
将含油15％的污泥通过圆锥破碎机(1)粉碎后，从内混式的旋转反应器(2)前端的顶部加入，与前端顶板(3)的上部侧面加入的循环固体热灰在旋转反应器(2)中搅拌混合、快速加热、汽化热解；含尘的热解油气从旋转反应器(2)末端的顶部油气出口(4) 流出并进入气固分离器(5)，热解渣从旋转反应器(2)末端的底部热解渣出口(7)流出并通过返料控制器(8)进入煅烧流化床(9)底部；经过气固分离器(5)分离的热解油气进入分馏塔(6)得到馏分油或合成原油以及塔底油，固体灰通过返料控制器(8)流入煅烧流化床(9)底部，塔底油返回与含油污泥混合；热解渣和固体灰在煅烧流化床(9)内与热流化空气混合燃烧加热，在煅烧流化床(9)顶部经过一级分离器(10)气固分离，大中颗粒热灰通过循环管返回旋转反应器(2)，烟气进二级分离器(11)再次气固分离；细小颗粒灰流入降温罐(12)作为残渣外排，烟气经过空气预热器(14)后外排；通过风机 (15)加压后的空气经过空气预热器(14)加热后流入煅烧流化床(9)底部作为热流化空气；冷却后的残渣在残渣改性修复器(13)用腐植酸物质进行重金属脱毒和团粒化，恢复土壤自我修复和种植功能。
其中，含油污泥和循环热灰的比例为2:10，旋转反应器(2)转速为0.2-1200转/分钟，旋转反应器(2)末端的油气出口温度为400-650℃，旋转反应器(2)固体停留时间为0.002-20 分钟。
煅烧流化床(9)操作温度为600-1050℃，流化气速0.02-18米/秒。
残渣与10公斤/立方土的腐植酸物质混合均匀，进行重金属原位还原和络合固化脱毒，腐植酸促使土壤团粒化包裹阻断颗粒内重金属的渗出与迁移；陈化2天以上后，将脱毒残渣再与10公斤/立方土的半焦菌肥混合均匀，同时配施0.1公斤/立方土的氮肥和0.01公斤/ 立方土的磷肥，利用微生物菌群持续产生的活性腐植酸实现永久还原与固定。原位摊平即可种植黑麦草用作生物质气化原料，15天后芳烃未检出，重金属固定率大于95％，30天内脱多环芳烃和固定重金属效果均可达到国标要求，恢复土壤自我修复和种植功能。
含油污泥热解处理及其残渣生物腐植酸绿色修复工艺的优点是通过循环热灰分级分离、大中颗粒热灰用作循环热载体、细小颗粒热灰作为残渣外排以及塔底油返回作为原料循环热解，解决了固体热解液体含灰高、油品质量差和残渣含油量高的难题，液收达到含油量的85％，残渣无油、含碳量小于1％；腐植酸和半焦菌肥结合，实现了残渣快速脱毒和永久脱毒，重金属固化脱除达到未检出。
Claims (7)
1.含油污泥热解处理及其残渣生物腐植酸绿色修复工艺，其特征是将粉碎后的含油污泥从内混式的旋转反应器前端的顶部加入，与前端顶板的上部侧面加入的循环固体热灰在旋转反应器中搅拌混合、快速加热、汽化热解；含尘的热解油气从旋转反应器末端的顶部流出并进入气固分离器，热解渣从旋转反应器末端的底部流出并通过返料控制器进入煅烧流化床底部；经过气固分离器分离的热解油气进入分馏塔得到馏分油或合成原油以及塔底油，固体灰通过返料控制器流入煅烧流化床底部，塔底油返回与含油污泥混合；热解渣和固体灰在煅烧流化床内与热流化空气混合燃烧加热，在煅烧流化床顶部经过二级气固分离，大中颗粒热灰通过循环管返回旋转反应器，细小颗粒灰流入降温罐作为残渣外排，烟气经过空气预热器后外排；通过风机加压后的空气经过空气预热器加热后流入煅烧流化床底部作为热流化空气；冷却后的残渣用腐植酸物质进行重金属脱毒和团粒化，恢复土壤自我修复和种植功能。
2.根据权利要求1所述的含油污泥热解处理及其残渣生物腐植酸绿色修复工艺，其特征在于含油污泥和循环热灰的比例为2:10，旋转反应器转速为0.2-1200转/分钟，旋转反应器末端的油气出口温度为400-650℃，旋转反应器固体停留时间为0.002-20分钟。
3.根据权利要求1所述的含油污泥热解处理及其残渣生物腐植酸绿色修复工艺，其特征在于煅烧流化床操作温度为600-1050℃，流化气速0.02-18米/秒。
4.根据权利要求1所述的含油污泥热解处理及其残渣生物腐植酸绿色修复工艺，其特征在于残渣与腐植酸物质混合均匀，进行重金属原位还原和络合固化脱毒，腐植酸促使土壤团粒化包裹阻断颗粒内重金属的渗出与迁移；陈化2天以上后，将脱毒残渣再与半焦菌肥混合均匀，利用微生物菌群持续产生的活性腐植酸实现永久还原与固定，恢复土壤自我修复和种植功能。
5.根据权利要求1所述的含油污泥热解处理及其残渣生物腐植酸绿色修复工艺，其特征在于腐植酸物质为腐植酸、腐植酸钾、腐植酸钠或生物质热解油等中的一种或多种，其中生物质热解油为农林废弃物快速热解液体产品或气化过程生成的生物油。
6.根据权利要求1所述的含油污泥热解处理及其残渣生物腐植酸绿色修复工艺，其特征在于粉碎机为球磨机、圆锥破碎机、齿辊式破碎机、反击式破碎机，冲击式破碎机、锤式破碎机、旋回式破碎机、复合式破碎机、液压破碎机、深腔破碎机、辊式破碎机、西蒙斯圆锥破碎机、液压圆锥破碎机、颚式破碎机等中的一种。
7.根据权利要求1所述的含油污泥热解处理及其残渣生物腐植酸绿色修复工艺，其特征在于中低浓度含油烃污染土壤修复治理时，半焦微生物群修复剂用量为3-10公斤/立方土，腐殖酸物质用量为5-40公斤/立方土，氮肥和磷肥比例为5-10:1，氮肥施用量0.05-0.2公斤/立方土。
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