CN106335969A - 一种高含聚稠油污水处理剂 - Google Patents

一种高含聚稠油污水处理剂 Download PDF

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CN106335969A
CN106335969A CN201610912794.8A CN201610912794A CN106335969A CN 106335969 A CN106335969 A CN 106335969A CN 201610912794 A CN201610912794 A CN 201610912794A CN 106335969 A CN106335969 A CN 106335969A
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陈洪杰
杜彦敏
瞿江英
李天俊
唐伟华
罗沿予
王清玲
万龙
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China Petroleum and Chemical Corp
Petroleum Engineering Technology Research Institute of Sinopec Zhongyuan Oilfield Co
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
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    • C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
    • C08G65/3346—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur having sulfur bound to carbon and oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

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Abstract

本发明涉及一种高含聚稠油污水处理剂，属油田用化学剂及制备技术领域。一种高含聚稠油污水处理剂，含有式(1)所示结构通式的聚合物M：其中：R1为‑H、‑CH3、‑CH2CH3中的一种，m＝5‑7，n＝6‑15。本发明的有益效果是：本发明利用聚合物M和絮凝剂的协同作用，使高含聚稠油污水高效破乳絮凝，使得水质满足标准SY/T5329‑2012《碎屑岩油藏注水水质指标及分析方法》中相关要求；本发明合成工艺简便，加注浓度小，成本低，无污染。

Description

一种高含聚稠油污水处理剂
技术领域
本发明涉及一种高含聚稠油污水处理剂，属油田用化学剂及制备技术领域。
背景技术
在采用火烧油层等热采方式开发稠油区块的过程中，一般要加注催化剂、降粘剂、增效剂或其它表面活性剂等，采出液经破乳、除油等工艺处理后，分离的污水一般含油较高，呈黑色浑浊状，污水中高含聚合物，上层部分易乳化，一般采用先破乳再絮凝的方法进行处理。常用的稠油污水破乳剂，如环氧氯丙烷-二甲胺系列聚合物、二甲基二烯丙基氯化铵系列聚合物、PAMAM树形分子型破乳剂、丙烯酸改性高分子破乳剂、聚醚类高分子破乳剂以及二元或多元复配物等，常用的油田污水絮凝剂有聚合氯化铝和聚合硫酸铝，助凝剂有聚丙烯酰胺和活化硅酸等。以上聚合物破乳剂除油率一般大于90％，其中对悬浮物去除效果最好的丙烯酸改性高分子破乳剂可使悬浮物含量控制在15mg/L以下，但处理后水质仍达不到SY/T5329-2012《碎屑岩油藏注水水质指标及分析方法》对油田污水水质回注或回用的要求。
ZL200710175374.7公开了一种稠油污水破乳剂，由重量百分比为70％的工业废酸和30％的聚合氯化铝混配后加入稠油污水，将pH值调至7.0左右，按质量浓度1-3mg/L加入聚丙烯酰胺实现稠油污水破乳和油水分离，该体系对于普通稠油污水处理时，含油量可降至1mg/L以下，悬浮物含量可降至2mg/L以下，但对于热采高含聚合物的稠油污水处理时，含油量和悬浮物含量均达不到标准回注要求。
ZL200910244127.7公开了一种稠油污水破乳剂，由长链烷基聚酰胺-胺和长链烷基芳基磺酸按质量比60-90:40-10复配而成，在现场破乳温度下，90分钟内脱水率可达70％以上，但该体系对于高含聚合物的稠油污水破乳率较低而不能达到标准回注要求，同时该破乳剂成本较高，难以工业化应用。
ZL201010131017.2公开了一种油田含聚污水的高效生物处理方法，处理工艺如下：含聚污水经气浮工艺处理后，采用厌氧工艺进行生物强化，通过微生物将有机聚合物分解成低分子无机化合物，水力停留时间为24-36小时，出水再采用好氧工艺进行强化，水力停留时间10-14小时，再经过滤后进入二沉池即完成污水处理，该技术使污水含油量控制在20mg/L以下，悬浮物含量控制在30mg/L以下，达不到标准回注要求。该生物处理工艺前期设备投资较高，对于小规模污水处理系统吨均污水处理成本也较高，且该工艺系统存在腐蚀问题。
发明内容
本发明的目的是为了克服现有技术存在的高含聚稠油污水经破乳絮凝后达不到标准回注或回用的难题，提供一种高含聚稠油污水处理剂。
本发明通过以下技术方案加以实现：
一种高含聚稠油污水处理剂，含有式(1)所示结构通式的聚合物M：
其中：R1为-H、-CH3、-CH2CH3中的一种，m＝5-7，n＝6-15。
该聚合物分子量为845-1451。
一种高含聚稠油污水处理剂，由聚合物M、絮凝剂和助凝剂按以下质量百分比混合而成：聚合物M 40-60％，絮凝剂1.2-4.0％，助凝剂0.0005-0.001％，余量为水。
所述的絮凝剂为聚合氯化铝或聚合硫酸铝。
所述的助凝剂为聚丙烯酰胺或活化硅酸。
本发明的有益效果是：本发明利用聚合物M和絮凝剂的协同作用，使高含聚稠油污水高效破乳絮凝，使得水质满足标准SY/T5329-2012《碎屑岩油藏注水水质指标及分析方法》中相关要求；本发明合成工艺简便，加注浓度小，成本低，无污染。
具体实施方式
下面结合具体制备例和实施例对本发明做进一步说明。
制备例1
在带搅拌器的反应釜中加入10g甲醇、6g聚醚胺、1.6g高碳醇和1.5g(R)-3-氯苯基环氧乙烷，搅拌均匀后，加入0.01g二氯二茂钛，在80℃、0.5MPa条件下搅拌反应1h，然后加入1g亚硫酸氢钠，调整温度至70℃，压力0.1MPa，搅拌反应0.5h，然后降至常温常压，即得高含聚稠油污水破乳剂M1，其化学反应结构式如下所示：
制备例2
在带搅拌器的反应釜中加入20g乙醇、8g聚醚胺、2g高碳醇和2g 3-溴苯基环氧乙烷，搅拌均匀后，加入0.05g二氯二茂锆，在100℃、1MPa条件下搅拌反应4h，然后加入1.5g亚硫酸钠，调整温度至90℃，压力0.3MPa，搅拌反应3h，然后降至常温常压，即得高含聚稠油污水破乳剂M2，其化学反应结构式如下所示：
制备例3
在带搅拌器的反应釜中加入18g二甲苯、7g聚醚胺、1.8g高碳醇和1.8g 3-溴苯基环氧乙烷，搅拌均匀后，加入0.03g二氯二茂钛，在90℃、0.8MPa条件下搅拌反应2h，然后加入1.2g亚硫酸钠，调整温度至80℃，压力0.2MPa，搅拌反应2h，然后降至常温常压，即得高含聚稠油污水破乳剂M3，其化学反应结构式如下所示：
实施例1
取40g聚合物M1加入聚合氯化铝1.2g，聚丙烯酰胺0.0005g，水58.8g，常温常压下混合均匀即得稠油污水破乳絮凝剂，参考Q/SH 0236-2008《原油破乳剂技术要求》和Q/ZY0858-2000《油田污水处理用净水剂技术条件》等标准进行含聚稠油污水的破乳絮凝试验，加量为100ppm时，处理后污水含油量从319mg/L降至3.8mg/L，悬浮物含量从186mg/L降至1.9mg/L。
实施例2
取60g聚合物M2加入聚合氯化铝4g，活化硅酸0.001g，水36g，常温常压下混合均匀即得稠油污水破乳絮凝剂，参考Q/SH 0236-2008《原油破乳剂技术要求》和Q/ZY 0858-2000《油田污水处理用净水剂技术条件》等标准进行含聚稠油污水的破乳絮凝试验，加量为100ppm时，处理后污水含油量从319mg/L降至4.2mg/L，悬浮物含量从186mg/L降至1.8mg/L。
实施例3
取50g聚合物M3加入聚合硫酸铝2.5g，聚丙烯酰胺0.0008g，水47.5g，常温常压下混合均匀即得稠油污水破乳絮凝剂，参考Q/SH 0236-2008《原油破乳剂技术要求》和Q/ZY0858-2000《油田污水处理用净水剂技术条件》等标准进行含聚稠油污水的破乳絮凝试验，加量为100ppm时，处理后污水含油量从319mg/L降至3.5mg/L，悬浮物含量从186mg/L降至1.8mg/L。
实施例4～9步骤与实施例1、2或3相同，具体配方见表1：
表1实施例4～9配方成分(单位：g)
将实施例4～9得到的高含聚稠油污水处理剂用稠油含聚污水进行试验，试验方法参考标准同上，药剂加注浓度均为100ppm，试验结果如下表：
表2实施例4～9高含聚稠油污水处理剂的室内试验结果
从实验结果来看，分离后未处理的污水水质较差，经本发明实施例4～9配方处理后，水质平均含油量3.4mg/L，悬浮物平均含量1.8mg/L，主要指标可达到SY/T5329-2012《碎屑岩油藏注水水质指标及分析方法》中相关要求，从试验现象来看，处理后水质界面整齐，水质透明，可直接进行回注。

Claims (4)

1.一种高含聚稠油污水处理剂，其特征在于：含有式(1)所示结构通式的聚合物M：
其中：R1为-H、-CH3、-CH2CH3中的一种，m＝5-7，n＝6-15。
2.一种高含聚稠油污水处理剂，其特征在于：由聚合物M、絮凝剂和助凝剂按以下质量百分比混合而成：聚合物M 40-60％，絮凝剂1.2-4.0％，助凝剂0.0005-0.001％，余量为水。
3.根据权利要求2所述的一种高含聚稠油污水处理剂,其特征在于：所述的絮凝剂为聚合氯化铝或聚合硫酸铝。
4.根据权利要求2所述的一种高含聚稠油污水处理剂,其特征在于：所述的助凝剂为聚丙烯酰胺或活化硅酸。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1117026A (zh) * 1995-07-03 1996-02-21 石油大学(北京) 多功能污水处理剂及其制备方法
CN1335269A (zh) * 2000-07-24 2002-02-13 中国石油化工股份有限公司 一种复合型含油废水絮凝剂
CN102153181A (zh) * 2010-11-25 2011-08-17 中国海洋石油总公司 一种用于废弃钻井液的乳化油去除剂及其制备方法
CN102887580A (zh) * 2011-07-21 2013-01-23 克拉玛依奥克化学有限公司 一种高矿化度稠油污水除油净水剂及制备方法
CN105692780A (zh) * 2016-02-24 2016-06-22 中国海洋石油总公司 一种含聚污水处理用清水剂复配体系

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1117026A (zh) * 1995-07-03 1996-02-21 石油大学(北京) 多功能污水处理剂及其制备方法
CN1335269A (zh) * 2000-07-24 2002-02-13 中国石油化工股份有限公司 一种复合型含油废水絮凝剂
CN102153181A (zh) * 2010-11-25 2011-08-17 中国海洋石油总公司 一种用于废弃钻井液的乳化油去除剂及其制备方法
CN102887580A (zh) * 2011-07-21 2013-01-23 克拉玛依奥克化学有限公司 一种高矿化度稠油污水除油净水剂及制备方法
CN105692780A (zh) * 2016-02-24 2016-06-22 中国海洋石油总公司 一种含聚污水处理用清水剂复配体系

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