CN101597119B - 石油石化给水节水污水回用水系统集成方法 - Google Patents
石油石化给水节水污水回用水系统集成方法 Download PDFInfo
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- CN101597119B CN101597119B CN2008100728920A CN200810072892A CN101597119B CN 101597119 B CN101597119 B CN 101597119B CN 2008100728920 A CN2008100728920 A CN 2008100728920A CN 200810072892 A CN200810072892 A CN 200810072892A CN 101597119 B CN101597119 B CN 101597119B
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- 239000011901 water Substances 0.000 title claims abstract description 130
- 239000010865 sewage Substances 0.000 title claims abstract description 33
- 239000003208 petroleum Substances 0.000 title claims abstract description 15
- 238000005516 engineering processes Methods 0.000 title abstract description 15
- 239000003921 oils Substances 0.000 claims abstract description 32
- 239000011499 joint compounds Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 238000005188 flotation Methods 0.000 claims abstract description 22
- 239000000126 substances Substances 0.000 claims abstract description 20
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 19
- 238000000034 methods Methods 0.000 claims abstract description 18
- 230000002401 inhibitory effects Effects 0.000 claims abstract description 14
- 239000003570 air Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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- 239000000463 materials Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound 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- 229920001469 poly(aryloxy)thionylphosphazenes Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound 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[O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound 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- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound 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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound 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OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound 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Classifications
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Abstract
Description
石油石化给水节水污水回用水系统集成方法
技术领域
[0001] 本发明涉及石化的污水处置及水资源综合利用技术,尤其是污水回用水系统的处 置,特别适合石油石化给水节水污水回用水系统集成方法。
背景技术
[0002] 石油化工企业,用水量大、污水排放多,环境污染;而污水净化成本高,加重企业负 担;提高循环冷却水的浓缩倍率,减少新鲜水的取用量等,都是行业的难题及攻关点。2002 年废水排放总量达33. 7亿吨,占全国工业废水排放总量的17. 8%。尽管节水减排工作取得 了些成效,但是我国石油化工行业每年污水排放量仍达8亿吨以上,而目前污水回用率仅 为 30%。
[0003] 石化污水处理与循环利用已有相似研究结果,如代秀兰等人对石化废水有一定的 抗冲击负荷能力,但二级处理不运行或没有处理效果,只通过微电解很难保证处理水质达 标;纪轩、姚春深等人研究归纳出在二沉池出水高中低浊度三种状况下,系统对浊度和COD 的去除规律及过滤周期、水头损失和絮凝剂投量等参数的变化规律;张东曙、高廷耀等人研 究介绍分析了混凝沉淀对COD的去除情况,比较了流沙过滤与纤维束过滤的处理效果;李 航宇、张英等人研究了以超滤膜+反渗透的双膜法处理经过预处理的石化废水再生利用的 中试;李善仁、高廷耀等人研究了采用悬浮填料生物膜法、混凝沉淀、快速砂滤和低电压电 场杀菌工艺,获得了好的试验结果;刘继凤研究了石化废水二级生化处理后采用絮凝氧化 膜分离等工艺的处理方法;郭文静等人介绍了活性炭吸附法、高级氧化法、膜分离法生物回 用技术等用于高级处理的情况;但研究集中于单个功能单元的强化处理或部分功能单元的 研究,欠缺系统研究。
[0004] 本项目致力于石油石化给水节水污水回用水系统的处置研究,着眼于选择适合该 系统的运行科学性、合理性,把握关键点,产生新型的集成技术,将石油化工行业污水经过 深度处置回用于循环冷却水,并提高循环冷却水的浓缩倍率,减少新鲜水的取用量,降低废 水的排放量,达到节能减排的目的。
发明内容
[0005] 本发明的目的在于:采用石油石化给水节水污水回用水系统集成方法,将石油化 工行业污水经过深度处置回用于循环冷却水,并提高循环冷却水的浓缩倍率,减少新鲜水 的取用量;水经处置全部循环利用,实现零排污,实现了绿色节能目标;经测试水质达到 GB50050-95《工业循环冷却水处理设计规范》的标准,也同时为企业带来了丰厚的经济效益。
[0006] 本发明的目的是这样实现的:石油石化给水节水污水回用水系统集成方法,包括 科学给水与过程节水、污水治理回用、循环调控三大系统,系统由除油、浮选;生化、生物过 滤处置;深度预处置;污泥、浮渣处置;膜处置;循环利用单元构成:
[0007] 除油、浮选:污水经格栅井去除大块杂质,添加除油剂3_5ppm至隔油池分离颗粒物,去除浮油进入调节池;经溶气气浮过程时,系统控制投放混凝剂30-50mg/L,去浮渣、乳 化油和悬浮物;
[0008] 生化、生物过滤处置:水经厌氧生化系统,流化床生化系统含鼓风曝气系统,投加 生物促生剂0. 5-4mg/L ;经涡涡气浮,去除有机物、重金属和脱磷除氮;
[0009] 深度预处置:水经二沉池、滤池、中转水池、生物滤池、中高压溶气气浮、生物碳塔、 过滤,去除悬浮物和胶体;经超滤前投加杀菌剂l_5ppm,控制微生物繁殖与污堵;
[0010] 污泥、浮渣处置:将溶气气浮、涡涡气浮浮渣经浮渣池与隔油池、二沉池的污泥浓 缩,投放脱水剂^-3ang/L,干化回收;
[0011] 膜处置:水脱盐采用反渗透专用装置,包括压力容器与膜;专用药剂用量为阻垢 剂3-5mg/L ;杀菌剂3-5mg/L ;清洗剂按制水量的3_5%,即100m3/h使用3_5吨,水入产品 水池;
[0012] 循环利用:循环水系统采用示踪技术的智能监控,在PH值常态范围时,阻垢缓蚀 剂的投加量15-20mg/l时,浓缩倍率为5. 0-6. 0 ;加之投放微生物灭菌剂50_120mg/L,循环 水全部利用。
[0013] 所述的集成方法,除油、浮选的除油剂为阳离子有机聚合物;混凝剂为工业废水专 用剂。
[0014] 所述的集成方法,生化、生物过滤处置,采用生物接触氧化、生物膜BF、序批式活性 污泥法SBR、膜生物反应器MBR、A/0。
[0015] 所述的集成方法,生化、生物过滤处置投加的生物促生剂为酶;微量元素、维生素、 天然荷尔蒙;促生素-细胞分裂素;有机物、盐类和重金属。
[0016] 所述的集成方法,污泥、浮渣处置投加脱水剂为阳离子聚丙烯酰胺。
[0017] 所述的集成方法,膜处置使用的阻垢剂、杀菌剂、清洗剂为膜专用;阻垢剂、杀菌剂 连续投加;清洗剂的使用1次/月。
[0018] 所述的集成方法,循环利用时投加的阻垢缓蚀剂为专用,满足循环水浓缩倍率的 要求。
[0019] 所述的集成方法,系统使用的水灭菌剂为氧化性杀菌剂、非氧化性杀菌剂和复合 杀菌剂。
[0020] 本发明的石油石化给水节水污水回用水系统集成方法,将科学给水与过程节水、 污水治理回用、循环调控三大系统进行整合改造,大大提升了系统的全面性,安全性。发明 采用生物碳塔新装置;多级浮选除胶体装置;过滤采用低成本耐用滤池;系统浮选、生化、 反渗透阶段选用了高端化学处置,保证去除率,安全稳定性,运行的出水水质;系统智控全 面,实现了循环水利用的高效能,为行业的技术进步作出了新贡献。
[0021] 本发明的集成方法的流程揭示技术的全面性与创新性。
[0022] 本发明的集成方法,包括除油、浮选;生化、生物过滤处置;深度预处置;污泥、浮 渣处置;膜处置;循环利用等:除油、浮选:污水经格栅井去除大块杂质,添加阳离子有机聚 合物3-5ppm至隔油池分离颗粒物去除浮油进入调节池,水经溶气气浮处置,系统控制投放 工业废水专用混凝剂30-50mg/L,去浮渣、乳化油和悬浮物;生化、生物过滤处置:采用生物 膜BF,膜生物反应器处置,水经厌氧生化系统,流化床生化系统含鼓风曝气系统,投加的生 物促生剂0. 5-4mg/L为酶,微量元素、维生素、天然荷尔蒙等,促生素-细胞分裂素,有机物、盐类和重金属,经涡涡气浮,去除有机物、重金属和脱磷除氮;深度预处置:水经二沉池、滤 池、中转水池、生物滤池、中高压溶气气浮、生物碳塔、过滤,去除悬浮物和胶体,经超滤前投 加杀菌剂l_5ppm,控制微生物繁殖与污堵;污泥、浮渣处置:将溶气气浮、涡涡气浮浮渣经 浮渣池与隔油池、二沉池的污泥浓缩,投加阳离子聚丙烯酰胺脱水剂^_3aiig/L,干化回收; 膜处置:水脱盐采用反渗透专用装置,包括压力容器与膜,专用药剂用量为阻垢剂3-5mg/L 和杀菌剂3-5mg/L,连续投加,清洗剂按制水量的3-5%,即IOOm3A使用3_5吨,1次/月, 获得产品水;循环利用:循环水系统采用示踪技术的智能监控,在PH值常态范围时,阻垢缓 蚀剂的投加量15-20mg/l时,浓缩倍率为5. 0-6. 0,加之投放微生物杀菌剂50_120mg/L,循 环水全部利用;该系统采用的水杀菌剂为氧化性杀菌剂、非氧化性杀菌剂和复合杀菌剂。
[0023] 本发明的集成方法达到绿色节能目标:污水经处理全部循环利用,实现零排污; 水处理达到GB50050-95《工业循环冷却水处理设计规范》的标准;采用反渗透处理,水质含 盐量降低明显优于普通的补充水,降低了循环水系统的化学药剂的投加量,同比降低10% 以上;降低了含磷化学品的危害,降低有机物、COD、油、氨氮、SS、挥发酚、硫化物等对环境的 污染。
[0024] 综上所述,发明的石油石化给水节水污水回用水系统集成方法,工艺娴熟、科学, 可操作性强,技术实施后,每年处理污水量按80万吨计算,节约新鲜水60万吨,利润增加额 76. 35万元,减轻企业负担,减少排污量,保护环境。以新疆境内的大型化工企业的6400万 吨污水处理采用该发明技术,每年可节约新鲜水4800万吨以上,减少6400万吨的污水外 排,利润增加额为6108万元,技术应用推广前景广阔,社会和经济效益都非常显著。
附图说明
[0025] 图清晰的示意了本发明集成方法流程:包括科学给水与过程节水、污水治理回用、 循环调控三大系统,由除油、浮选;生化、生物过滤处置;深度预处置;污泥、浮渣处置;膜处 置;循环利用单元构成。
具体实施方式
[0026] 下面结合实施方案对本发明作进一步描述。石油石化给水节水污水回用水系统集 成方法的实施例如下:
[0027] 实施例1
[0028] 系统运行中技术关键点控制:
[0029] 溶气气浮,投加高效的工业废水专用混凝剂强化混凝效果,提高乳化油和悬浮物 的去除;
[0030] 生化处置依据来水,投加生物促生剂/解毒剂/活性磷/营养剂,强化处理效果, 为后续处理减轻负荷;
[0031] 生物碳塔是过滤和反渗透系统不发生悬浮物和有机物污堵的重要屏障,可在生物 碳塔前增加中高压溶气气浮装置,去除水中悬浮物和有机胶体,确保生物碳塔正常工作。
[0032] 控制过滤后的微生物的繁殖与污堵,使用反渗透系统专用杀菌剂,产品属铵盐非 氧化性杀菌剂,可有效防止微生物的滋生。
[0033] 控制和防止反渗透系统结垢,须在精滤器前加入阻垢剂;使用的反渗透专用阻垢剂,有极佳的兼容性、溶解性、稳定性,不与铁铝氧化物及硅化合物凝聚形成不溶物和电中 性等特点,其进水PH值5-10范围有效;可允许进水侧铁的浓度达8. Oppm、浓水侧允许SW2 290ppm,在不加酸条件下LSI最大允许值为2. 8 ;采用专用的软件输入水质情况就可获得最 佳的投加量。
[0034] 实施例2
[0035] 提高循环冷却水的浓缩倍率:
[0036] 冷却水在循环使用过程中由于不断蒸发浓缩,水中的有害离子成倍增加,再加上 冷却塔在室外长年受阳光照射,风吹雨淋,灰尘、杂物的飘落,会产生腐蚀、结垢生物粘泥滋
生等危害。
[0037] 结垢危害:指水中溶解或悬浮的无机物,由于受热等因素,而沉积在金属的表面, 主要成分有碳酸钙和腐蚀产物二种,使用了阻垢缓蚀剂,有效控制结垢危害。
[0038] 腐蚀危害:循环冷却水造成的腐蚀,主要以溶解氧腐蚀为主,腐蚀输水管线、水冷 设备减少使用寿命,防治抗锈瘤的产生,使用了阻垢缓蚀剂,有效控制腐蚀危害。
[0039] 生物粘泥危害:生物粘泥主要由细菌及藻类等微生物的分泌产物粘附了水中悬浮 杂质而形成,生物粘泥的产生会导致传热效率下降,列管堵塞,增加局部腐蚀等危害。调控 水温、PH、溶解氧和投加杀菌灭藻剂等可有效控制生物粘泥危害。
[0040] 其它离子的危害:系统的金属管线还会因为氯离子和硫酸根离子的存在而引起危 害,α—和SO/—均属强腐蚀性离子,特别是氯离子由于其半径小,容易穿透钝化膜表面的细 孔而产生点蚀现象,另在有污垢存在时,氯离子可依靠其穿透力进入垢下与1¾2+反应生成 FeCl2jFeCl2进一步水解生成狗(OH)2和HCL,导致腐蚀区溶液呈酸性,使金属的腐蚀速度加 快,所以冷却水中氯离子的允许浓度应根据设备的材质、结构而确定;SO/—的存在有利于硫 酸盐还原菌的滋生和繁殖,并还原生成硫化氢,促进冷却水系统金属的腐蚀;由于集成技术 的合理性,有效控制其危害。
[0041] 循环冷却水的浓缩倍率一般在3以下,而国外先进水平为5. O左右,通过提高浓缩 倍率可提高节水量,详见下表。
[0042] 浓缩倍率与用水量的关系
[0043] 以IOOOOm3水为例: 单位:m3
[0044]
[0045] 通过上表可看出,随着浓缩倍率的逐步提高,用水量逐步下降,当浓缩倍率达到 5. 0时,可节约比达到83. 3 %,按照浓缩倍率由3. 0提高至5. 0来计算,同比可节约8. 33 %。
[0046] 实施例3
[0047] 药剂确定与使用
[0048] 通过水质分析、模拟试验、絮凝、静态阻垢率、旋转腐蚀挂片、动态模拟试验、微生 物试验等确定最佳的控制参数。
[0049] 控制参数:
[0050] 投加混凝剂
[0051] 确定在溶气气浮段中选用工业废水专用混凝剂,投加量为30_50mg/L。
[0052] 投加生物促生剂
[0053] 确定在生化段投加生物促生剂(BE),投加量以水的情况而定,一般为0. 5-4mg/L0 投加生物促生剂,能促使生物处理系统中微生物的新陈代谢功能达到最高,加速微生物的 繁殖,促使形成良好的菌胶团,提高微生物对有机污染物的处理效率。有效提高好氧生化系 统抗冲击能力,改善污泥结构和提高污泥沉降性能,完善污泥微生物种群,降低进水中的有 机毒物对活体微生物的毒害。
[0054] 投加剂量和方法(按照11,OOOmVD计):
[0055]
[0056] 投加生物解毒剂
[0057] 确定在生化段投加生物解毒剂(MT),滴加前稀释10〜20倍,保证了药剂在系统中 的停留时间和分散效果,去除非生物途径将毒性官能团,有利于微生物降解大分子官能团 或长链烃,并将有害化学物质转化为小分子易降解。
[0058] 投加剂量和方法如下(按照11,OOOmVD计):
[0059]
[0060] 投加补充磷营养
[0061] 原水中的磷酸盐含量一般在lmg/L以下,考虑到不能够充分满足活性污泥新陈代 谢对磷营养物质的需求,必须补充磷营养,将出水的余磷浓度控制在0. 5mg/L以下,根据废 水的特性和磷酸盐的物理化学性质投加生物活性磷。
[0062] 依据进入生化段废水COD和氨氮数据,按照11,OOOmVD计算,需要加入生物活性
磷^kg/天。[0063] 投加污泥脱水剂
[0064] 确定在污泥脱水段使用阳离子聚丙烯酰胺857BS为污泥脱水剂,投加量为30mg/L 可达到反应速度快,絮团量大的脱水效果。
[0065] 实验方法:取200ml含油污泥倒入500ml烧杯中,加30PPM阳离子聚丙烯酰胺后, 直接把污泥和药剂倒入另一个500ML的烧杯中,来回反复,记下污泥大量脱水时倒样的次 数S1,再记下污泥絮团开始散碎时的次数&。AS = S2-S1 ;AS值越大说明药剂跟污泥的 反应时间快,污泥絮团的强度大。
[0066] 投加反渗透剂
[0067] 确定采用反渗透膜装置进行脱盐处置,药剂投加量为:
[0068] 反渗透阻垢剂:PTP-0100,投加量3_5mg/L,连续投加;
[0069] 反渗透杀菌剂:MicroTreat BIO,投加量3_5mg/L,连续投加;
[0070] 反渗透清洗剂=Dimamite和High Flux,按设计制水量的3_5%,即100m3/h,投加 清洗剂1次/月,3-5吨。
[0071] 投加缓蚀阻垢剂
[0072] 确定用DL-240缓蚀阻垢剂对循环冷却水的处置,投加量15_20mg/L时,能够满足 循环水浓缩倍率5倍的要求。
[0073] 静态阻垢率试验(CaCO3沉积法GB/T 16632-1996)
[0074]
[0075] 旋转挂片腐蚀试验(GB/T 18175-2000)
[0076] 5. 0倍水样,碳钢、不锈钢、黄铜材质旋转挂片缓蚀试验数据
[0077]
[0078]
[0079] 结果表明:补充水浓缩倍数为5. 0倍时,DL-240在使用15mg/L和20mg/L投加量 时对各种材质试片的腐蚀率远小于国标规定。
[0080] 投加灭菌剂
[0081] 确定用DIX^S工业灭菌剂对循环冷却水的微生物处置,采用冲击式人工加药,每 1月投加2-4次(夏季每月投加4次,冬季每月投加2次),每次加药剂量为100mg/L。
[0082] 采用了工业循环冷却水中粘液形成菌的测定-平皿计数法GB/T 14642. 1-93和微 生物测定,结果如下:
[0084] 注:每次投加后系统密闭运行M小时后对循环水进行置换。
[0085] 实施例4
[0086] 本发明公开了石油石化给水节水污水回用水系统集成方法,包括除油、浮选;生 化、生物过滤处置;深度预处置;污泥、浮渣处置;膜处置;循环利用的单元:除油、浮选:污 水经格栅井去除大块杂质,添加阳离子有机聚合物3-5ppm至隔油池分离颗粒物去除浮油 进入调节池,水经溶气气浮处置,系统控制投放工业废水专用混凝剂30-50mg/L,去浮渣、乳 化油和悬浮物;生化、生物过滤处置:采用生物膜BF,膜生物反应器处置,水经厌氧生化系 统,流化床生化系统含鼓风曝气系统,投加的生物促生剂0. 5-4mg/L为酶,微量元素、维生素、天然荷尔蒙等,促生素-细胞分裂素,有机物、盐类和重金属,经涡凹气浮,去除有机物、 重金属和脱磷除氮;深度预处置:水经二沉池、滤池、中转水池、生物滤池、中高压溶气气 浮、生物碳塔、过滤,去除悬浮物和胶体,水经超滤前投加杀菌剂l_5ppm,控制微生物繁殖与 污堵;污泥、浮渣处置:将溶气气浮、涡凹气浮浮渣经浮渣池与隔油池、二沉池的污泥浓缩, 投加阳离子聚丙烯酰胺脱水剂^_3aiig/L,干化回收;膜处置:水质脱盐采用反渗透专用装 置,包括压力容器与膜,专用反渗透PTP-0100阻垢剂连续投加3-5mg/L,Micr0Treat BIO杀 菌剂连续投加3-5mg/L,Dimamite和High Flux清洗剂按制水量的3_5%,即100m3/h投放, 3-5吨/月.次,获得产品水;循环利用:循环水系统采用示踪技术的智能监控,在PH值常 态范围时,专用DL-240阻垢缓蚀剂的投加量15-20mg/l时,浓缩倍率为5. 0-6. 0,加之投放 微生物杀菌剂50-120mg/L,循环水全部利用;系统采用的水杀菌剂为氧化性杀菌剂、非氧 化性杀菌剂和复合杀菌剂。
[0087] 实施例5
[0088] 本发明公开了石油石化给水节水污水回用水系统集成方法,包括除油、浮选;生 化、生物过滤处置;深度预处置;污泥、浮渣处置;膜处置;循环利用的单元:除油、浮选:污 水经格栅井去除大块杂质,添加阳离子有机聚合物4ppm至隔油池分离颗粒物去除浮油进 入调节池,水经溶气气浮处置,系统控制投放工业废水专用混凝剂40mg/L,去浮渣、乳化油 和悬浮物;生化、生物过滤处置:采用生物膜BF,膜生物反应器处置,水经厌氧生化系统,流 化床生化系统含鼓风曝气系统,投加的生物促生剂3mg/L为酶,微量元素、维生素、天然荷 尔蒙等,促生素-细胞分裂素,有机物、盐类和重金属,水经涡凹气浮,去除有机物、重金属 和脱磷除氮;深度预处置:水经二沉池、滤池、中转水池、生物滤池、中高压溶气气浮、生物 碳塔、过滤,去除悬浮物和胶体,水经超滤前投加复合杀菌剂3ppm,控制微生物繁殖与污堵; 污泥、浮渣处置:将溶气气浮、涡凹气浮浮渣经浮渣池与隔油池、二沉池的污泥浓缩,投加 阳离子聚丙烯酰胺脱水剂25mg/L,干化回收;膜处置:水脱盐采用反渗透专用装置,包括压 力容器与膜,连续投加PTP-0100阻垢剂%ig/L,连续投加MicroTreat BIO杀菌剂%ig/L, Dimamite和High Flux清洗剂按制水量的4%,即IOOm3A投放,4吨/月.次,获得产品水; 循环利用:循环水系统采用示踪技术的智能监控,在PH值常态范围时,专用DL-240阻垢缓 蚀剂的投加量18mg/L时,浓缩倍率为5. 0,加之投放微生物杀菌剂100mg/L,循环水全部利 用;系统采用的水杀菌剂为氧化性杀菌剂、非氧化性杀菌剂和复合杀菌剂。
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