油田污水精细过滤腹膜材料粉煤灰改性研究
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摘要
以粉煤灰为腹膜材料的精细过滤装置处理油田污水时,粉煤灰中含有的CaO、MgO等成分易导致滤后水结垢,影响油田回注水的品质。为此,本课题设计了一套完整的粉煤灰改性工艺,并对粉煤灰进行改性实验研究。
在研究粉煤灰的理化性质和粉煤灰中成分盐酸浸出热力学反应的基础上,提出了酸溶除杂——碱热合成沸石的改性方法,即:在初步实验的基础上,通过HCl溶解粉煤灰中的杂质成分,然后通过碱热合成法,使得粉煤灰沸石化,从而实现粉煤灰的改性。通过改性后粉煤灰助滤过滤实验,并对滤后水进行结垢预测,结果显示改性粉煤灰不但没有增加滤后水中的Ca~(2+)、Mg~(2+)等结垢离子,还使得这些离子含量有所降低,粉煤灰改性比较成功。
通过实验对影响酸浸除去粉煤灰中杂质成分的因素进行了研究,主要包括:酸浓度、液固比、酸溶温度和酸溶时间。确定了粉煤灰酸溶实验最佳参数:酸浓度为2.5mol/L,液固比为4:1mL/g,酸溶温度为90℃和酸洗时间为1h。并进一步研究了改性粉煤灰对Ca~(2+)的吸附特性,结果显示:改性粉煤灰对Ca~(2+)有较好的吸附能力,即使中性条件下表观吸附量也可达到55.60 mg/g,并且吸附速度相当快,20 min即可达到平衡。
为了使改性后粉煤灰作为腹膜材料在污水处理中能取得最佳过滤效果,进行了改性粉煤灰过滤特性实验,确立了最佳的预涂参数,即在粉煤灰粒径范围为15 m~20 m、预涂厚度为2.5mm和过滤速度为预涂速度的2倍的条件下,粉煤灰预涂层过滤特性曲线最好。
论文研究成果不仅对于降低腹膜材料成本具有巨大经济意义,并且实现了以废治废、环保节能的目的,获得巨大的社会效益与环境效益。
When oilfield sewage is filtered by precision filter coating with fly ash, filtered water is easily scaled due to CaO and MgO contained in fly ash, and affects qulity of injection water. In order to deal with this problem, the project designs a complete suite of fly ash modification technology, and carries out fly ash modification experiment.
Base on research of physicochemical property of fly ash and thermodynamics reaction of HCl and fly ash, the project carry out acid-soluble and alkali-heating modifcation mothed. on the basis of experiments, use HCl dissolve impurity composition contained in fly ash, and then change fly ash into zeolite by alkali-heating method, and realize the modification of fly ash. The scaling prediction result of oilfield sewage filtered by modified fly ash indicated that calcium and magnesian ions contents in filtered water decreased instead of increase, which proved that the modification method of fly ash is success.
This article mainly researched influence factors of removing impurity elements contained in fly ash, such as: acid concentration, solid-to-liquid ratio, acid-soluble temperature and acid-soluble time, and confirmed that the best parameters: acid concentration is 2.5mol/L, solid-to-liquid ratio is 4:1, acid-soluble temperature is 90℃and acid-soluble time is 1h. And research on adsorption characteristic of modified fly ash to calcium ion was carried out, and the result indictated that modified fly ash has preferable adsorption ability to calcium ion, even if in neutral condition adsorption amount can reach to 55.60 mg/g, and adsorption speed is very fast and would reach equilibrium in 20min.
In order to acquire the best filtering effect when the modified fly ash is used to precoating material to deal with oilfield sewage, filtration characteristics experiment of modified fly ash is carried out, and the best precoating parameters are confirmed, when grain diameter scale of the fly ash is from 15 m to 20 m, precoating thickness is 2.5mm and filtration speed is twice than precoating speed, filtration characteristics curve shape of fly ash is best.
The research results not only lower cost of filter aid and have great economic significance, but also have achieved goal of using waste treat waste and save energy and protect the environment, and aquired great social and enviromental benefit.
在研究粉煤灰的理化性质和粉煤灰中成分盐酸浸出热力学反应的基础上,提出了酸溶除杂——碱热合成沸石的改性方法,即:在初步实验的基础上,通过HCl溶解粉煤灰中的杂质成分,然后通过碱热合成法,使得粉煤灰沸石化,从而实现粉煤灰的改性。通过改性后粉煤灰助滤过滤实验,并对滤后水进行结垢预测,结果显示改性粉煤灰不但没有增加滤后水中的Ca~(2+)、Mg~(2+)等结垢离子,还使得这些离子含量有所降低,粉煤灰改性比较成功。
通过实验对影响酸浸除去粉煤灰中杂质成分的因素进行了研究,主要包括:酸浓度、液固比、酸溶温度和酸溶时间。确定了粉煤灰酸溶实验最佳参数:酸浓度为2.5mol/L,液固比为4:1mL/g,酸溶温度为90℃和酸洗时间为1h。并进一步研究了改性粉煤灰对Ca~(2+)的吸附特性,结果显示:改性粉煤灰对Ca~(2+)有较好的吸附能力,即使中性条件下表观吸附量也可达到55.60 mg/g,并且吸附速度相当快,20 min即可达到平衡。
为了使改性后粉煤灰作为腹膜材料在污水处理中能取得最佳过滤效果,进行了改性粉煤灰过滤特性实验,确立了最佳的预涂参数,即在粉煤灰粒径范围为15 m~20 m、预涂厚度为2.5mm和过滤速度为预涂速度的2倍的条件下,粉煤灰预涂层过滤特性曲线最好。
论文研究成果不仅对于降低腹膜材料成本具有巨大经济意义,并且实现了以废治废、环保节能的目的,获得巨大的社会效益与环境效益。
When oilfield sewage is filtered by precision filter coating with fly ash, filtered water is easily scaled due to CaO and MgO contained in fly ash, and affects qulity of injection water. In order to deal with this problem, the project designs a complete suite of fly ash modification technology, and carries out fly ash modification experiment.
Base on research of physicochemical property of fly ash and thermodynamics reaction of HCl and fly ash, the project carry out acid-soluble and alkali-heating modifcation mothed. on the basis of experiments, use HCl dissolve impurity composition contained in fly ash, and then change fly ash into zeolite by alkali-heating method, and realize the modification of fly ash. The scaling prediction result of oilfield sewage filtered by modified fly ash indicated that calcium and magnesian ions contents in filtered water decreased instead of increase, which proved that the modification method of fly ash is success.
This article mainly researched influence factors of removing impurity elements contained in fly ash, such as: acid concentration, solid-to-liquid ratio, acid-soluble temperature and acid-soluble time, and confirmed that the best parameters: acid concentration is 2.5mol/L, solid-to-liquid ratio is 4:1, acid-soluble temperature is 90℃and acid-soluble time is 1h. And research on adsorption characteristic of modified fly ash to calcium ion was carried out, and the result indictated that modified fly ash has preferable adsorption ability to calcium ion, even if in neutral condition adsorption amount can reach to 55.60 mg/g, and adsorption speed is very fast and would reach equilibrium in 20min.
In order to acquire the best filtering effect when the modified fly ash is used to precoating material to deal with oilfield sewage, filtration characteristics experiment of modified fly ash is carried out, and the best precoating parameters are confirmed, when grain diameter scale of the fly ash is from 15 m to 20 m, precoating thickness is 2.5mm and filtration speed is twice than precoating speed, filtration characteristics curve shape of fly ash is best.
The research results not only lower cost of filter aid and have great economic significance, but also have achieved goal of using waste treat waste and save energy and protect the environment, and aquired great social and enviromental benefit.
引文
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[2]李亚峰,孙凤海,牛晚扬等.粉煤灰处理废水的机理及应用[J].矿业安全与环保,2001,18(2):30-34
[3]王福元,吴正严.粉煤灰利用手册第二版[M].北京:中国电力出版社,2004
[4]张信.改性粉煤灰处理含磷废水研究[D],山东:山东大学,2006
[5]吕梁,侯浩波.粉煤灰性能与利用[M].北京:中国电力出版社,1998
[6]韩怀强,蒋挺大.粉煤灰利用技术[M],北京:化学工艺出版社.2001
[7]李亚峰,杨辉,赵红.粉煤灰处理废水的理论与实践[M].工业用水与废水,1999,3(13):1-3
[8]李剑超,褚君达,右华丽等.粉煤灰在废水处理中的最新应用研究[J].电力环境保护,2001,17(4):40-42
[9]于衍真.粉煤灰混凝剂性能研究[J].环境科学学报,1998,18(4),431-433
[10]郑礼胜,王士龙,颜世柱.用粉煤灰处理含镍废水的实验研究[J].粉煤灰,1998,(6):15-17
[11]郑礼胜,王士龙,陆文武等.用粉煤灰处理含铬废水的实验研究[J].粉煤灰综合利用,1997,(2):38-41
[12] P.Ricou, et al. Removal of Cu2+, Zn2+, and Pb2+ by adsorption onto fly ash and fly ash/lime mixing. Wat.Sc.Tech, 1999, 39(10):239-242
[13] Sen Asit K, et al. Adsorption of Mercury(Ⅱ) by coal fy ash. Water Research. 1987, 21(8): 885
[14]阎存仙.粉煤灰处理含磷废水的研究[J].上海环境科学,2000,19(1):77-78
[15]赵建夫.粉煤灰用于去除氟化物的实验研究[J].粉煤灰综合利用,1990,(2):3-5
[16]马志毅.用粉煤灰处理含氟废水的研究[J].中国环境科学,1991,(6):460-463
[17]周珊,杜冬云.改性粉煤灰处理含油废水的实验研究[J].化学与生物工程,2005,(3):43-45
[18] Kumar S, et al. Removal of Phenols By Assorption on Fly ash J Chem Tech Brotechnol, 1987, 37(4):281-290
[19]齐广才.用粉煤灰处理含酚、胺类废水[J].延安大学学报(自然科学版),2002,21(3):43-45
[20]邵颖.活化粉煤灰对弱酸性艳绿GS吸附性能的研究[J].工业水处理.1997,17(1): 21-23.27
[21]阎存仙.粉煤灰对燃料废水的脱色研究[J].环境污染与防治,2000,22(5):3-5
[22]肖羽堂.利用电厂粉煤灰处理染料中间体废水[J].环境工程,1998,16(2):30-33
[23]梁天民.用粉煤灰处理造纸制药废水的研究[J].粉煤灰综合利用,1993,(3):40-42
[24]李亚峰.粉煤灰处理废水的理论与实践[J].工业用水与废水,1999,30(3):1-3
[25]于晓彩,徐微,辛泽.粉煤灰改性处理啤酒废水的研究[J].环境保护科学,2005,31 (129) :43-45
[26]于晓彩,王恩德等.改性粉煤灰处理造纸废水的研究[J].东北大学学报2003,24(8):814-816
[27]相会强.改性粉煤灰去除抗生素废水色度的研究[J].粉煤灰综合利用,2005(1):41-42
[28]胡巧开,揭武.改性粉煤灰对二甲酚橙的吸附研究[J].上海化工,2006,31(9):5-8
[29]阮燕,吴定燕,高琼英.粉煤灰的颗粒组成与磨细灰的火山灰活性[J].粉煤灰综合利用,2001,(2):28-30.
[30]于立竟.粉煤灰的火法改性及其在废水处理中的应用[J].矿物岩石地球化学通报, 2006,25(4):343-347
[31]周珊,杜冬云.改性粉煤灰处理含油废水的实验研究[J].化学与生物工程,2005 (3):43-45
[32]曹先艳,岳钦艳.PDMDAAC改性粉煤灰处理染料废水及其最终处置[J].工业水处理, 2006,26(9):56-58
[33]王敏欣,谷庆宝.无机改性粉煤灰对模拟染料废水吸附脱色的作用[J].黑龙江矿业学院学报,2000,10(3):13-19
[34]黄继国,张永详,曹玉清等.含氟废水的粉煤灰处理实验研究[J].水文地质工程地质,2001,(4):43-44
[35]沸石分子筛,中国科学院大连化学物理研究所分子筛编著,北京科学出版社,1978
[36]徐如人.沸石分子筛的结构与合成[M].吉林大学出版社,1987
[37]童军杰,以流化床粉煤灰为原料合成系列沸石的研究[J].粉煤灰综合利用,2003 (4):12-13
[38]付克明,路迈西,朱虹.利用粉煤灰合成沸石的方法研究[J].煤炭工程.2007(1): 78-80
[39]黄翼.文209块油田结垢机理及阻除垢剂筛选研究[D] .北京:北京服装学院, 2007
[40]丁绪维.工业结晶[M].北京:清华大学出版社,1985:122～125
[41]张俐.均一相碳酸钙晶须的制备与生长机理研究[D].硕士论文
[42]姚连增.晶体生长基础[M].合肥,中国科学技术大学出版社,1995
[43]张克从,张乐惠.晶体生长[M].北京:科学出版社,1981
[44]姜同川.正交试验设计[M].山东科学技术出版社,1985
[45]童军杰.以流化床粉煤灰为原料合成系列沸石的研究[D].太原:太原理工大学, 2003
[46]中国石油天然气总公司.SY/T0600-1997.油田污水结垢趋势预测[S].中华人民共和国石油天然气行业标准
[47]丁启圣,王维一.新型实用过滤技术[M].北京:冶金工业出版社,2000.9
[48]于衍真,李国忠,傅兴华等.粉煤灰混凝剂的性能研究[J].环境科学学报,1998, (4):431～434
[2]李亚峰,孙凤海,牛晚扬等.粉煤灰处理废水的机理及应用[J].矿业安全与环保,2001,18(2):30-34
[3]王福元,吴正严.粉煤灰利用手册第二版[M].北京:中国电力出版社,2004
[4]张信.改性粉煤灰处理含磷废水研究[D],山东:山东大学,2006
[5]吕梁,侯浩波.粉煤灰性能与利用[M].北京:中国电力出版社,1998
[6]韩怀强,蒋挺大.粉煤灰利用技术[M],北京:化学工艺出版社.2001
[7]李亚峰,杨辉,赵红.粉煤灰处理废水的理论与实践[M].工业用水与废水,1999,3(13):1-3
[8]李剑超,褚君达,右华丽等.粉煤灰在废水处理中的最新应用研究[J].电力环境保护,2001,17(4):40-42
[9]于衍真.粉煤灰混凝剂性能研究[J].环境科学学报,1998,18(4),431-433
[10]郑礼胜,王士龙,颜世柱.用粉煤灰处理含镍废水的实验研究[J].粉煤灰,1998,(6):15-17
[11]郑礼胜,王士龙,陆文武等.用粉煤灰处理含铬废水的实验研究[J].粉煤灰综合利用,1997,(2):38-41
[12] P.Ricou, et al. Removal of Cu2+, Zn2+, and Pb2+ by adsorption onto fly ash and fly ash/lime mixing. Wat.Sc.Tech, 1999, 39(10):239-242
[13] Sen Asit K, et al. Adsorption of Mercury(Ⅱ) by coal fy ash. Water Research. 1987, 21(8): 885
[14]阎存仙.粉煤灰处理含磷废水的研究[J].上海环境科学,2000,19(1):77-78
[15]赵建夫.粉煤灰用于去除氟化物的实验研究[J].粉煤灰综合利用,1990,(2):3-5
[16]马志毅.用粉煤灰处理含氟废水的研究[J].中国环境科学,1991,(6):460-463
[17]周珊,杜冬云.改性粉煤灰处理含油废水的实验研究[J].化学与生物工程,2005,(3):43-45
[18] Kumar S, et al. Removal of Phenols By Assorption on Fly ash J Chem Tech Brotechnol, 1987, 37(4):281-290
[19]齐广才.用粉煤灰处理含酚、胺类废水[J].延安大学学报(自然科学版),2002,21(3):43-45
[20]邵颖.活化粉煤灰对弱酸性艳绿GS吸附性能的研究[J].工业水处理.1997,17(1): 21-23.27
[21]阎存仙.粉煤灰对燃料废水的脱色研究[J].环境污染与防治,2000,22(5):3-5
[22]肖羽堂.利用电厂粉煤灰处理染料中间体废水[J].环境工程,1998,16(2):30-33
[23]梁天民.用粉煤灰处理造纸制药废水的研究[J].粉煤灰综合利用,1993,(3):40-42
[24]李亚峰.粉煤灰处理废水的理论与实践[J].工业用水与废水,1999,30(3):1-3
[25]于晓彩,徐微,辛泽.粉煤灰改性处理啤酒废水的研究[J].环境保护科学,2005,31 (129) :43-45
[26]于晓彩,王恩德等.改性粉煤灰处理造纸废水的研究[J].东北大学学报2003,24(8):814-816
[27]相会强.改性粉煤灰去除抗生素废水色度的研究[J].粉煤灰综合利用,2005(1):41-42
[28]胡巧开,揭武.改性粉煤灰对二甲酚橙的吸附研究[J].上海化工,2006,31(9):5-8
[29]阮燕,吴定燕,高琼英.粉煤灰的颗粒组成与磨细灰的火山灰活性[J].粉煤灰综合利用,2001,(2):28-30.
[30]于立竟.粉煤灰的火法改性及其在废水处理中的应用[J].矿物岩石地球化学通报, 2006,25(4):343-347
[31]周珊,杜冬云.改性粉煤灰处理含油废水的实验研究[J].化学与生物工程,2005 (3):43-45
[32]曹先艳,岳钦艳.PDMDAAC改性粉煤灰处理染料废水及其最终处置[J].工业水处理, 2006,26(9):56-58
[33]王敏欣,谷庆宝.无机改性粉煤灰对模拟染料废水吸附脱色的作用[J].黑龙江矿业学院学报,2000,10(3):13-19
[34]黄继国,张永详,曹玉清等.含氟废水的粉煤灰处理实验研究[J].水文地质工程地质,2001,(4):43-44
[35]沸石分子筛,中国科学院大连化学物理研究所分子筛编著,北京科学出版社,1978
[36]徐如人.沸石分子筛的结构与合成[M].吉林大学出版社,1987
[37]童军杰,以流化床粉煤灰为原料合成系列沸石的研究[J].粉煤灰综合利用,2003 (4):12-13
[38]付克明,路迈西,朱虹.利用粉煤灰合成沸石的方法研究[J].煤炭工程.2007(1): 78-80
[39]黄翼.文209块油田结垢机理及阻除垢剂筛选研究[D] .北京:北京服装学院, 2007
[40]丁绪维.工业结晶[M].北京:清华大学出版社,1985:122～125
[41]张俐.均一相碳酸钙晶须的制备与生长机理研究[D].硕士论文
[42]姚连增.晶体生长基础[M].合肥,中国科学技术大学出版社,1995
[43]张克从,张乐惠.晶体生长[M].北京:科学出版社,1981
[44]姜同川.正交试验设计[M].山东科学技术出版社,1985
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