第33卷 第2期
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油田化学
复合型缓蚀剂的研究
王 勇, 龚金海, 鲍如兵, 刘从箐
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(1中原石油勘探局勘察设计研究院2宝鸡石油机械有限责任公司成都装备制造公司
3西南油气田分公司采气工程研究院工程技术监督中心)
王 勇等. 复合型缓蚀剂的研究. 钻采工艺, 2010, 33(2):105-107
摘 要:用不同的有机胺化学原料进行交联合成, 然后用防垢剂和杀菌剂复配研制的FH -01复合缓蚀剂具有缓蚀、防垢和杀菌综合性能。经室内评价, 针对现场污水介质的缓蚀率为71. 3%~85. 5%, 杀菌率大于等于90%, 防垢率81. 8%, 且具有酸化缓蚀效果。经现场实验, 投加该复合缓蚀剂后, 油井产出液中的总铁含量下降达27. 1~86. 4%。
关键词:合成; 复合; 缓蚀剂; 防垢; 杀菌
中图分类号:TE 357 文献标识码:A DO I :10. 3969/. j iss n. 1006-768X . 2010. 02. 033
追求一剂多用是采油化学剂的发展方向。中原油田勘察设计研究院研究的复合缓蚀剂, 旨在研究一种针对中原油田产出液, 具有杀菌、防垢和缓蚀多种功能的复合型缓蚀剂。这样不仅能有效解决药剂使用的配伍性问题, 而且在抑制腐蚀的同时能起到防止系统结垢和控制细菌生长的作用, 节省药剂费用和投加药剂的人力物力。经过一年的努力, 成功地研制出了F H -01复合缓蚀剂。
行多效复配研究。1. 缓蚀剂的室内合成
在研究过程中, 优先考虑缓蚀剂分子的空间结构, 选择几种含氮元素的有机化合物进行合成研究。由于含氮有机化合物大多是油溶性, 因此必须适当增加其水溶性。增加水溶性可以采用聚合环氧乙烷的方法, 但聚合环氧乙烷的条件比较苛刻(必须用高压反应釜, 而且常温下呈气态的环氧乙烷必须用专用钢瓶装运, 运输和贮存比较困难), 因此本课题采用将已聚合好的环氧乙烷产品(聚氧乙烯醚) 与含氮有机化合物交联的办法增加其水溶性。
缓蚀剂单剂合成采用的主要合成原料见表1。
一、复合缓蚀剂的室内研究
复合缓蚀剂的研究分两步进行, 第一步先进行缓蚀剂的室内合成研究, 第二步用合成的缓蚀剂进
缓蚀剂合成条件的选择采用正交实验法进行技
术路线设计。在合成反应中, 交联剂的选择是至关重要的因素。由于含氮有机化合物大多含有活泼氢元素, 交联反应都是通过该活泼氢进行的, 因此合成原料对水分含量的要求十分严格。原料中不得含有
任何水分, 因为水分子也含有活泼氢元素, 交联剂会优先与水分子发生反应。
设计的交联反应是在室温下进行的。反应是放热反应。经过缓蚀率评价, 初步确定了缓蚀剂单体的基本配方。
收稿日期:2009-03-04; 修回日期:2010-03-01
作者简介:王勇(1974-), 工程师, 1997年毕业于华东理工大学腐蚀与防护专业。地址:(457001) 河南省濮阳市中原路189号中原石油
, :0393-, , E m l j y w @co m
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M ar . 2010
2. 复合缓蚀剂的复配
将合成的缓蚀剂单体与防垢剂和杀菌剂进行复配, 经过反复实验和评价, 选择具有良好协同效应的组分构成F H -01复合缓蚀剂的最终配方。最终确定的复合缓蚀剂配方见表2。
表2 F H -01复合缓蚀剂原料组成表
缓蚀剂单体复合缓蚀剂
杂环胺
芳香胺
脂肪多元胺有机胺杀菌剂
聚氧
交联剂
乙烯醚增效剂
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测试采用三电极体系, 甘汞电极为参比电极, 大面积铂电极为辅助电极, 工作电极为铁电极, 铁电极工作表面为1 1c m 的正方形。扫描电位为-1~2v , 扫描速度为0. 01v /s。每次实验前, 电极表面都要用1200目砂纸打磨光滑, 并去脂, 并放入三电极体系中稳定1h 后在测试。
在NaC l 溶液中加入F H -01后负移了腐蚀电位, 故在N a C l 溶液中FH -01主要是抑制阴极过程。
在NaC l 溶液中加入F H -01后对应电流均大幅度下降。表明F H -01的缓蚀作用明显。根据电流降低值计算, F H -01在N aC l 溶液中的缓蚀率为84. 2%(见图1) 。
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缓蚀剂氨基羧酸
单体盐防垢剂
3. FH -01复合缓蚀剂的室内缓蚀效果评价
F H -01复合缓蚀剂的外观呈浅黄色水溶性液体, 密度为1. 04g /cm , p H 值为9。
缓蚀剂的评价方法是依据SY /T5273-2000 油田产出水用缓蚀剂性能评价方法 进行的。该标准是用产出水作评价介质, 将缓蚀剂按预定浓度加入水介质中(同时做一个不加缓蚀剂的空白对比实验), 然后在介质中挂入钢片, 通过钢片的腐蚀情况来判断缓蚀剂的效果。由于许多油井和干线都投加缓蚀剂, 因此在联合站或计量站取产出水进行评价时, 评价介质(产出水) 中已含有一定量的缓蚀剂成分。这样会产生两个问题:一是介质中残留的缓蚀剂成分与实验过程中加入的缓蚀剂可能存在不相容性, 二是介质中残留的缓蚀剂成分使实验中的空白腐蚀降低, 直接影响实验结果。也就是说, 评价介质不具有腐蚀性, 就不能对缓蚀剂进行有效评价。
为了科学评价缓蚀剂的缓蚀效果, 经过与采油厂技术部门结合, 根据现场腐蚀的实际状况和缓蚀剂评价的实际经验确定了缓蚀剂评价的井号, 用单井介质对F H -01复合缓蚀剂进行缓蚀剂评价。同时, 采用20%的盐酸介质, 在50 实验条件下, 评价了FH -01复合缓蚀剂的酸化缓蚀效果。见表3。
表3 FH -01复合缓蚀剂的主要性能指标废水介质的缓蚀率文留13-14井卫城18-14井文明寨325井马寨164井防垢率
85. 5%79. 2%77. 4%71. 3%81. 8%
20%盐酸, 50 的缓蚀率1. 0%1. 5%2. 0%2. 5%杀菌率
98. 8%98. 9%99. 0%99. 0%90%
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二、复合缓蚀剂的现场实验
现场实验效果主要采用实验前后介质监测的方法进行评价。即通过监测实验前后总铁、钙离子含量和细菌含量的变化分别确定其缓蚀率、防垢率和杀菌率。
F H -01复合缓蚀剂的现场实验分别在中原油田采油一厂七区和采油三厂明二区进行。实验过程中共监测了15口油井的介质变化情况。实验前现场使用的是ZSY92-1缓蚀剂。1. 采油一厂的现场实验
图2是采油一厂203-36井投加F H -01复合缓蚀剂后的总铁含量的变化趋势图。
4. F H -01复合缓蚀剂的电化学评价
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采油一厂203-36井总铁含量较高。通过投加F H -01复合缓蚀剂并监测总铁含量变化, 可以发现, 油井的总铁含量下降了56. 0%。图2由于在投加FH -01复合缓蚀剂之前这些油井一直使用ZSY92-1缓蚀剂, 因此相当于FH -01复合缓蚀剂的缓蚀效果比ZSY92-1缓蚀剂提高了27. 1%~56. 0%。
从侧14-35井未加药的空白数据可以看出, 该井的总铁含量基本无变化, 这从另一个侧面证明了F H -01复合缓蚀剂的缓蚀效果十分明显。
通过监测产出液中钙离子的变化来判断FH -01复合缓蚀剂的防垢效果是我们现场实验方案中的一种设想。经监测发现, 采油一厂七区的油井产出液中钙离子无明显变化。后来经研究分析, 如果钙离子的变化在有限的1个月实验期内出现明显变化趋势的话, 系统的结垢将是十分惊人的。因此, 用监测钙离子变化的方法不能有效地判断药剂的防垢效果。
细菌监测结果表明, 投加FH -01后, 油井产出液的细菌含量普遍较低, 大多数时候不含SRB 和TGB , 偶尔检测到细菌的存在, 其含量也比较低。相对来讲, 没有投加F H -01复合缓蚀剂的侧14-35井检测出细菌含量的次数较多。由此看来, F H -01复合缓蚀剂对SRB 和TGB 细菌有较好的杀灭作用。2. 采油三厂的现场实验
图3是采油三厂WM C144井投加F H -01复合
剂后总铁含量的变化趋势图。
与采油一厂一样, 油井产出液中钙离子的含量无明显变化, 说明用监测钙离子变化的方法不能有效地判断药剂的防垢效果。同样, 投加F H -01复合缓蚀剂后, 油井产出液的细菌含量普遍都比较低, 大多数时候不含SRB 和TGB , 偶尔检测到细菌的存在, 其含量也比较低。说明F H -01复合缓蚀剂对SRB 和TGB 细菌有较好的杀灭作用。
三、结论
(1) 用不同的有机胺化学原料进行交联合成, 然后用防垢剂和杀菌剂复配研制的复合缓蚀剂F H -01具有缓蚀、防垢和杀菌综合效果。经室内评
价, 针对现场废水介质的缓蚀率为71. 3%~85. 5%, 杀菌率大于等于90%, 防垢率81. 8%。
(2) 经电化学评价, FH -01复合缓蚀剂对盐水介质具有良好的缓蚀效果, 电化学评价缓蚀率为84. 2%, 且具有良好的成膜性能。
(3) 在20%的盐酸介质中, 50 实验条件下, F H -01复合缓蚀剂用量为2. 0%时, 其缓蚀率达到99%以上, 可以作为盐酸酸洗缓蚀剂或油水井酸化缓蚀剂使用。
(4) 现场应用试验表明, F H -01复合缓蚀剂具有优良的缓蚀效果。与中原油田目前应用的ZSY92-1缓蚀剂相比, 投加F H -01复合缓蚀剂后, 油井产出液中的总铁含量一般下降达43. 5%~56. 0%。(5) 用监测钙离子变化的方法不能有效地判断药剂的防垢效果。目前还只能通过室内试验的方法来定量评价药剂的防垢效果。
(6) 投加F H -01复合缓蚀剂后, 油井产出液的细菌含量普遍较低, 大多数时候不含SRB 和TGB , 偶尔检测到细菌的存在, 其含量也比较低, 表明F H -01复合缓蚀剂具有较好的杀菌效果。
参考文献
[1]赵福麟. 采油化学[M].山东东营:石油大学出版社,
1989.
[2]赵福麟. 采油用剂[M].山东东营:石油大学出版社,
1997.
[3]郭稚狐. 缓蚀剂及其应用[M ].武汉:华中工学院出版
社, 1987.
(编辑:包丽屏)
采油三厂WM C 144井投加F H -01复合缓蚀剂后, 每个周期总铁含量的峰值出现明显的下降趋势。通过对总铁含量周期性峰值的变化进行计算, 加入FH -01复合缓蚀剂后, 油井的总铁下降了43. 5%~86. 4%。
V o. l 33N o . 2M ar . 2010DR I LL ING &PRODU CT I ON TEC HNOLOGY
Si chuan
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leu m U ni versi ty , X i ngdu D i stri ct 610500, Chengdu C it y , Prov i nce , P . R. Chi na
M obil e :+86-[1**********]E -mai:l zeng w ei 3069@126. com
O I L DISPLACE MENT PROPERTY OF HYDROP HOBI -C ALLY ASSOCI ATI NG POLYACRYLA M I DE
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LU Hongsheng , FE NG Yu j un and C AO W e i pi ng (1. Chengdu I nstit ute ofO rganic Che m i stry , Chi nese A cade my Science ; 2. Instit ute of Che m istry and Che m i cal Eng i neeri ng , South west Pe -tro l eu m U niversit y) , DPT 33(2), 2010:94-96, 110
Abstrac t :H ydrophobi call y assoc i ati ng polyacry l am i de (HA-P AM ) and po l yacry l a m i de(P AM ) were i nvesti gated f or enhance oil recovery at sm i ul ated Ch i nese ma j or o il reservo i r . It i ndicated t hat HAPAM has better oil di spl ace m ent propert y than that of P AM. W hen the i nj ected vo l u me o f po l y m er so l ution was 0. 4~0. 5PV, the i ncreased e fficiency o f enhance oil recovery i s about 2~4%.The effect o fHAPA M concentrati on on enhance o il recovery is very obv-i
ous when the HAP AM concentration was lo w er t han 2000mg /L. But when t he HAPAM concentrati on reached 2000m g /L, t he a mplifica -tion o f recovery ratio woul d sl ow up . HAPA M coul d a l so exhi bit be-t ter ther m al stab ilit y and sa lt resi st ance t han PAM. The displ ace ment pressure and o il di splace m ent effici ency were i ncreased w it h the i n -creasi ng ofHAPA M i nj ected vo l u me .
K ey words :hydrophobica ll y assoc i ati ng po l yacryla m ide , po l y -acry l am i de , o il displ ace men, t recovery ratio , t her m al st abili ty , salt resi stance
LU Hongsheng (doctor , lecturer ), born i n 1979, i s engaged i n t he research on o ilfi e l d che m istry treat ment fl uid .
Add :Chengdu Instit ute o fO rganic Che m i stry , Chi nese A cade -my Sc i ence , Chengdu C i ty 610041, S i chuan Prov i nce , P . R. Ch i na M obil e :+86-[1**********] E -mai:l shhl u @163. com SYNTHESI S AND EVALUATI ON OF THE ULTRA -H I GH TE MPERATURE LOSS ADDI TI VE F LA 240USED F OR DR I LL I NG FLUI D
111
W A NG Zhong hua , WANG Xu , ZHOU L equn and WU 2
Lan (1. D r illi ng Technology R esearch Institut e o f Zhongyuan O il Expl orati on Bureau ; 2. CC DC Sa f ety , Env iron m en, t Quali ty Super -v i si on&T esti ng Research Instit ute), DPT 33(2), 2010:97-100
Abstrac t :T aki ng acry l a m ide , acry l oyloxy l oxy is obut y ls ulfoni c ac i d , N, N-dm i ethy l acry la m i de and acry lic as base m ateri a, l the copoly m er ultra -hi gh te mperat ure loss add i ti ve FLA240used f or drilli ng fl ui d was synthesi zed by redox i nitati on . The struct ure and t her ma l st ability of FLA 240w ere researched by usi ng i nfrared spec -troscopy and t her m al ana l ysis , its anti-te mperat ure mechanis m was a ls o analyzed , t he perf or m ances of FLA 240drilli ng fl ui dsw ere eva-l ua t ed i n laboratory . The results s howed tha, t FLA240had very good t her ma l stab ility and co mpati bl eness , and it had better fl u i d loss characteristics i n fresh w ater , bri ne and saturated br i ne drilli ng fl u -i d . A fter the 240 ultra -h i gh te mperature ag i ng , it can bett er
3
control the filter loss o f dr illi ng fl uid . In the density o f 2. 25g /cm sat urated br i ne drilli ng fl ui d , when t he FLA240w as i ncreased fro m 1. 0%t o 4. 0%,filtration of h i gh -te mperature and h i gh pressure drilli ng fl uid can reduced fro m 110mL to 6mL .
K ey words :drilli ng fl ui d , flui d l oss additi ve , copoly m er , ultra -h i gh te m perature , synthesi s
W A NG Zhonghua (professorial senior engi neer ), graduated from Che m i stry Depart m ent o f Zheng z hou Un i versit y i n 1985, i s a chief eng i neer ofD rilli ng Technol ogy R esearch Instit ute of Zhongyuan O ilExpl orati on Bureau , is engaged i n t he research on fi ne chem i cal eng i neeri ng and o ilfiel d che m istry .
Add :D rilli ng Technol ogy R esearch Instit ute of Zhongyuan O il Expl orati on Bureau , 59Zhongyuan Road , Puyang C it y 457001, Henan P rovi nce , P . R . Ch i na
Te:l +86-393-4899235 E -mai:l z peb w z h @126. co m RES EARC H ON SY NTHESI S OF FLU I D LOSS ADDI -TI VE PADA M OF A MPH I PR OT I C P OLY MER DRI LL I NG FLUI DS
1, 22
YANG Ji nrong and MA X i pi ng (1. G all D ng
Co mpany; 2. Sout hwest Petroleu m U ni versi ty), DPT 33(2), 2010:
101-104
Abstract :An amphi proti c tetrapo l y m er (acryla m ide /dmi ethy l di -a ll y l am m oniu m chlori de/2-acry l a m i do-2-m et hyl propane su-l fon i c acid/methyl acry li c aci d) (PADAM ) has been synt hesized through orthogona l desi gn by free radica l poly m er i zati on i n aq ueous so l uti on usi ng ox i dation-reducti on-i nitiati on s yste m as acti vator i n the paper . T he aff ecti on o fm onomer m i xture concentrati ons , initia -ti ng agen, t mono m er m olar ratio and reacti on tm i e on mo l ecular we i ght and properties o f P ADAM w ere di scussed , t he mo l ecular structures were verifi ed by i nfrared s pectroscopy , t he flui d loss con -trol abili ty and t he i nhi biti on abilit y of PADAM i n drilli ng fl ui dswere eva l uated . The results i ndicated that t he productw it h cert a i n molecu -l ar para m eter had good anti -sal, t anti -high te mperat ure and the a -bility o f flui d l oss control and i nhi b i ti on . The PADAM i s a ki nd o f a mph i proti c copoly m erw ith bot h fl u i d loss control and i nh i bition ab i -l it y i n fac. t
K ey words :a mph i proti c pol ymer , synthesi s , salt resistancy , dr illi ng flui ds , fl ui d loss additi ve , i nhi biti ve
YANG Ji nrong (senior e ngineer ), is worki ng i n G reat W a ll D rilli ng Co mpany and study i ng f or his doctor s degree i n South west P etro l eu m U ni versity .
Add :G reatW allD rilli ng Co mpany , 101A nli Road , Chaoyang D istr i ct 100101, Be iji ng , P . R. Chi na RESEARCH ON CO MPOSI TE C ORR O SI ON I N H I B I TOR
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WANG Yong , GONG Ji nha i , B AO Rubi ng and L I U Con -3
gqin (1. Zhongyuan O ilfiel d Survey and D esi gn R esearch Insti tute ; 2. Bao ji Petro l eu m M achi nery Co . , L td . Chengdu Equi p m entM anu -fact uri ng Company ; 3. Eng i neeri ng Supervisi on Center of G as Pro -ducti on Research I nstit ute , Sout h w estO il/gasF i eld Co . ) , DPT 33(2), 2010:105-107
Abstract :Composite corrosion i nh i bit or F H -01, synt hesized by a m i ne , sca l e i nh i bitor and bacterici de , possesses t he effi cacy o f corrosion i nh i biti on , anti scale and disi nfecti on . The l aboratory i nd-i
cated t ha, t i n t he medi u m ofwaste water , rate of co rrosion i nhi b iti on was 71. 3%~85. 5%, sterilize ra t e was above 90%, and rate o f scale i nh i bition was 81. 8%.Even it can be used as ac i dul a t e corro -si on i nhi bitor . The res ults of fi eld experm i ent showed t ha, t after addi ng corrosion i nh i bit or F H -01, iron content o f the oilw ell liqui d was descended by 27. 1%~86. 4%.
K ey words :s ynt hesis , co mposite corrosion i nhi bitor , ant-i scale , disi nf ecti on
WANG Yo ng (e ngineer ), graduated fro m Huadong Un i versit y of Sc i ence and Eng i neer i ng i n 1997, i s engaged i n the research on o ilfiel d anticorrosion eng i neeri ng .
Add :ZhongyuanO ilfi eld Survey and D esi gn Research Insti tute , Puyang C i ty 457001, Henan Provi nce , P. R . Chi na
T e:l +86-393-4822135E -mai :l z yshywy @163. com STUDY ON A MODIFIED POLYVI NYL ALC OHOL AN -T I -SLOUGH I NG A GENT S HENG X i n and YU L ibi n (Tuha D rilli ng T echno l ogy R e -search Institut e , C NPC W est D rilli ng Co mpany ) , DPT 33(2), 2010:108-110
Abstract :A ne w ly anti -sloughi ng agent w as developed through modif y i ng t he po l yv i nyl alcoho. l The results showed that t he m od i fi ed po l yvi nyl a l coho l anti-sl oughi ng agent had strong i nh i b-i
ti ve , coul d effecti ve l y reduce t he friction coeffi c i ent of dr illi ng fl u i d , and m i prove the rheo l ogical propert y and water loss of drilli ng fl u i d . Furt her m ore , it is no-t ox i c and b i odegradable .
K ey words :polyv i ny l alcoho, l anti -sl ough i ng agen, t perfor m -ance eva l ua ti on , tox i c it y , biodegradati on S HENG X i n , born i n 1973, is superintendent o f O ilfi e l d Che m i stry Research Instit ute o f Tuha D rilli ng T echno l ogy R esearch Instit ute , bei ng engaged i n t he research on drilli ng fl ui d techno l ogy .
Add :T uha D rilli ng Technology R esearch Institut e , Shans han 838202; X i njiang , P . R . China
M o b ile :+86-[1**********]E -mai :l l kh54321@si na . co m
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油田化学
复合型缓蚀剂的研究
王 勇, 龚金海, 鲍如兵, 刘从箐
1
1
2
3
(1中原石油勘探局勘察设计研究院2宝鸡石油机械有限责任公司成都装备制造公司
3西南油气田分公司采气工程研究院工程技术监督中心)
王 勇等. 复合型缓蚀剂的研究. 钻采工艺, 2010, 33(2):105-107
摘 要:用不同的有机胺化学原料进行交联合成, 然后用防垢剂和杀菌剂复配研制的FH -01复合缓蚀剂具有缓蚀、防垢和杀菌综合性能。经室内评价, 针对现场污水介质的缓蚀率为71. 3%~85. 5%, 杀菌率大于等于90%, 防垢率81. 8%, 且具有酸化缓蚀效果。经现场实验, 投加该复合缓蚀剂后, 油井产出液中的总铁含量下降达27. 1~86. 4%。
关键词:合成; 复合; 缓蚀剂; 防垢; 杀菌
中图分类号:TE 357 文献标识码:A DO I :10. 3969/. j iss n. 1006-768X . 2010. 02. 033
追求一剂多用是采油化学剂的发展方向。中原油田勘察设计研究院研究的复合缓蚀剂, 旨在研究一种针对中原油田产出液, 具有杀菌、防垢和缓蚀多种功能的复合型缓蚀剂。这样不仅能有效解决药剂使用的配伍性问题, 而且在抑制腐蚀的同时能起到防止系统结垢和控制细菌生长的作用, 节省药剂费用和投加药剂的人力物力。经过一年的努力, 成功地研制出了F H -01复合缓蚀剂。
行多效复配研究。1. 缓蚀剂的室内合成
在研究过程中, 优先考虑缓蚀剂分子的空间结构, 选择几种含氮元素的有机化合物进行合成研究。由于含氮有机化合物大多是油溶性, 因此必须适当增加其水溶性。增加水溶性可以采用聚合环氧乙烷的方法, 但聚合环氧乙烷的条件比较苛刻(必须用高压反应釜, 而且常温下呈气态的环氧乙烷必须用专用钢瓶装运, 运输和贮存比较困难), 因此本课题采用将已聚合好的环氧乙烷产品(聚氧乙烯醚) 与含氮有机化合物交联的办法增加其水溶性。
缓蚀剂单剂合成采用的主要合成原料见表1。
一、复合缓蚀剂的室内研究
复合缓蚀剂的研究分两步进行, 第一步先进行缓蚀剂的室内合成研究, 第二步用合成的缓蚀剂进
缓蚀剂合成条件的选择采用正交实验法进行技
术路线设计。在合成反应中, 交联剂的选择是至关重要的因素。由于含氮有机化合物大多含有活泼氢元素, 交联反应都是通过该活泼氢进行的, 因此合成原料对水分含量的要求十分严格。原料中不得含有
任何水分, 因为水分子也含有活泼氢元素, 交联剂会优先与水分子发生反应。
设计的交联反应是在室温下进行的。反应是放热反应。经过缓蚀率评价, 初步确定了缓蚀剂单体的基本配方。
收稿日期:2009-03-04; 修回日期:2010-03-01
作者简介:王勇(1974-), 工程师, 1997年毕业于华东理工大学腐蚀与防护专业。地址:(457001) 河南省濮阳市中原路189号中原石油
, :0393-, , E m l j y w @co m
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M ar . 2010
2. 复合缓蚀剂的复配
将合成的缓蚀剂单体与防垢剂和杀菌剂进行复配, 经过反复实验和评价, 选择具有良好协同效应的组分构成F H -01复合缓蚀剂的最终配方。最终确定的复合缓蚀剂配方见表2。
表2 F H -01复合缓蚀剂原料组成表
缓蚀剂单体复合缓蚀剂
杂环胺
芳香胺
脂肪多元胺有机胺杀菌剂
聚氧
交联剂
乙烯醚增效剂
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测试采用三电极体系, 甘汞电极为参比电极, 大面积铂电极为辅助电极, 工作电极为铁电极, 铁电极工作表面为1 1c m 的正方形。扫描电位为-1~2v , 扫描速度为0. 01v /s。每次实验前, 电极表面都要用1200目砂纸打磨光滑, 并去脂, 并放入三电极体系中稳定1h 后在测试。
在NaC l 溶液中加入F H -01后负移了腐蚀电位, 故在N a C l 溶液中FH -01主要是抑制阴极过程。
在NaC l 溶液中加入F H -01后对应电流均大幅度下降。表明F H -01的缓蚀作用明显。根据电流降低值计算, F H -01在N aC l 溶液中的缓蚀率为84. 2%(见图1) 。
2
缓蚀剂氨基羧酸
单体盐防垢剂
3. FH -01复合缓蚀剂的室内缓蚀效果评价
F H -01复合缓蚀剂的外观呈浅黄色水溶性液体, 密度为1. 04g /cm , p H 值为9。
缓蚀剂的评价方法是依据SY /T5273-2000 油田产出水用缓蚀剂性能评价方法 进行的。该标准是用产出水作评价介质, 将缓蚀剂按预定浓度加入水介质中(同时做一个不加缓蚀剂的空白对比实验), 然后在介质中挂入钢片, 通过钢片的腐蚀情况来判断缓蚀剂的效果。由于许多油井和干线都投加缓蚀剂, 因此在联合站或计量站取产出水进行评价时, 评价介质(产出水) 中已含有一定量的缓蚀剂成分。这样会产生两个问题:一是介质中残留的缓蚀剂成分与实验过程中加入的缓蚀剂可能存在不相容性, 二是介质中残留的缓蚀剂成分使实验中的空白腐蚀降低, 直接影响实验结果。也就是说, 评价介质不具有腐蚀性, 就不能对缓蚀剂进行有效评价。
为了科学评价缓蚀剂的缓蚀效果, 经过与采油厂技术部门结合, 根据现场腐蚀的实际状况和缓蚀剂评价的实际经验确定了缓蚀剂评价的井号, 用单井介质对F H -01复合缓蚀剂进行缓蚀剂评价。同时, 采用20%的盐酸介质, 在50 实验条件下, 评价了FH -01复合缓蚀剂的酸化缓蚀效果。见表3。
表3 FH -01复合缓蚀剂的主要性能指标废水介质的缓蚀率文留13-14井卫城18-14井文明寨325井马寨164井防垢率
85. 5%79. 2%77. 4%71. 3%81. 8%
20%盐酸, 50 的缓蚀率1. 0%1. 5%2. 0%2. 5%杀菌率
98. 8%98. 9%99. 0%99. 0%90%
3
二、复合缓蚀剂的现场实验
现场实验效果主要采用实验前后介质监测的方法进行评价。即通过监测实验前后总铁、钙离子含量和细菌含量的变化分别确定其缓蚀率、防垢率和杀菌率。
F H -01复合缓蚀剂的现场实验分别在中原油田采油一厂七区和采油三厂明二区进行。实验过程中共监测了15口油井的介质变化情况。实验前现场使用的是ZSY92-1缓蚀剂。1. 采油一厂的现场实验
图2是采油一厂203-36井投加F H -01复合缓蚀剂后的总铁含量的变化趋势图。
4. F H -01复合缓蚀剂的电化学评价
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采油一厂203-36井总铁含量较高。通过投加F H -01复合缓蚀剂并监测总铁含量变化, 可以发现, 油井的总铁含量下降了56. 0%。图2由于在投加FH -01复合缓蚀剂之前这些油井一直使用ZSY92-1缓蚀剂, 因此相当于FH -01复合缓蚀剂的缓蚀效果比ZSY92-1缓蚀剂提高了27. 1%~56. 0%。
从侧14-35井未加药的空白数据可以看出, 该井的总铁含量基本无变化, 这从另一个侧面证明了F H -01复合缓蚀剂的缓蚀效果十分明显。
通过监测产出液中钙离子的变化来判断FH -01复合缓蚀剂的防垢效果是我们现场实验方案中的一种设想。经监测发现, 采油一厂七区的油井产出液中钙离子无明显变化。后来经研究分析, 如果钙离子的变化在有限的1个月实验期内出现明显变化趋势的话, 系统的结垢将是十分惊人的。因此, 用监测钙离子变化的方法不能有效地判断药剂的防垢效果。
细菌监测结果表明, 投加FH -01后, 油井产出液的细菌含量普遍较低, 大多数时候不含SRB 和TGB , 偶尔检测到细菌的存在, 其含量也比较低。相对来讲, 没有投加F H -01复合缓蚀剂的侧14-35井检测出细菌含量的次数较多。由此看来, F H -01复合缓蚀剂对SRB 和TGB 细菌有较好的杀灭作用。2. 采油三厂的现场实验
图3是采油三厂WM C144井投加F H -01复合
剂后总铁含量的变化趋势图。
与采油一厂一样, 油井产出液中钙离子的含量无明显变化, 说明用监测钙离子变化的方法不能有效地判断药剂的防垢效果。同样, 投加F H -01复合缓蚀剂后, 油井产出液的细菌含量普遍都比较低, 大多数时候不含SRB 和TGB , 偶尔检测到细菌的存在, 其含量也比较低。说明F H -01复合缓蚀剂对SRB 和TGB 细菌有较好的杀灭作用。
三、结论
(1) 用不同的有机胺化学原料进行交联合成, 然后用防垢剂和杀菌剂复配研制的复合缓蚀剂F H -01具有缓蚀、防垢和杀菌综合效果。经室内评
价, 针对现场废水介质的缓蚀率为71. 3%~85. 5%, 杀菌率大于等于90%, 防垢率81. 8%。
(2) 经电化学评价, FH -01复合缓蚀剂对盐水介质具有良好的缓蚀效果, 电化学评价缓蚀率为84. 2%, 且具有良好的成膜性能。
(3) 在20%的盐酸介质中, 50 实验条件下, F H -01复合缓蚀剂用量为2. 0%时, 其缓蚀率达到99%以上, 可以作为盐酸酸洗缓蚀剂或油水井酸化缓蚀剂使用。
(4) 现场应用试验表明, F H -01复合缓蚀剂具有优良的缓蚀效果。与中原油田目前应用的ZSY92-1缓蚀剂相比, 投加F H -01复合缓蚀剂后, 油井产出液中的总铁含量一般下降达43. 5%~56. 0%。(5) 用监测钙离子变化的方法不能有效地判断药剂的防垢效果。目前还只能通过室内试验的方法来定量评价药剂的防垢效果。
(6) 投加F H -01复合缓蚀剂后, 油井产出液的细菌含量普遍较低, 大多数时候不含SRB 和TGB , 偶尔检测到细菌的存在, 其含量也比较低, 表明F H -01复合缓蚀剂具有较好的杀菌效果。
参考文献
[1]赵福麟. 采油化学[M].山东东营:石油大学出版社,
1989.
[2]赵福麟. 采油用剂[M].山东东营:石油大学出版社,
1997.
[3]郭稚狐. 缓蚀剂及其应用[M ].武汉:华中工学院出版
社, 1987.
(编辑:包丽屏)
采油三厂WM C 144井投加F H -01复合缓蚀剂后, 每个周期总铁含量的峰值出现明显的下降趋势。通过对总铁含量周期性峰值的变化进行计算, 加入FH -01复合缓蚀剂后, 油井的总铁下降了43. 5%~86. 4%。
V o. l 33N o . 2M ar . 2010DR I LL ING &PRODU CT I ON TEC HNOLOGY
Si chuan
A BSTRACT 7
leu m U ni versi ty , X i ngdu D i stri ct 610500, Chengdu C it y , Prov i nce , P . R. Chi na
M obil e :+86-[1**********]E -mai:l zeng w ei 3069@126. com
O I L DISPLACE MENT PROPERTY OF HYDROP HOBI -C ALLY ASSOCI ATI NG POLYACRYLA M I DE
1, 211
LU Hongsheng , FE NG Yu j un and C AO W e i pi ng (1. Chengdu I nstit ute ofO rganic Che m i stry , Chi nese A cade my Science ; 2. Instit ute of Che m istry and Che m i cal Eng i neeri ng , South west Pe -tro l eu m U niversit y) , DPT 33(2), 2010:94-96, 110
Abstrac t :H ydrophobi call y assoc i ati ng polyacry l am i de (HA-P AM ) and po l yacry l a m i de(P AM ) were i nvesti gated f or enhance oil recovery at sm i ul ated Ch i nese ma j or o il reservo i r . It i ndicated t hat HAPAM has better oil di spl ace m ent propert y than that of P AM. W hen the i nj ected vo l u me o f po l y m er so l ution was 0. 4~0. 5PV, the i ncreased e fficiency o f enhance oil recovery i s about 2~4%.The effect o fHAPA M concentrati on on enhance o il recovery is very obv-i
ous when the HAP AM concentration was lo w er t han 2000mg /L. But when t he HAPAM concentrati on reached 2000m g /L, t he a mplifica -tion o f recovery ratio woul d sl ow up . HAPA M coul d a l so exhi bit be-t ter ther m al stab ilit y and sa lt resi st ance t han PAM. The displ ace ment pressure and o il di splace m ent effici ency were i ncreased w it h the i n -creasi ng ofHAPA M i nj ected vo l u me .
K ey words :hydrophobica ll y assoc i ati ng po l yacryla m ide , po l y -acry l am i de , o il displ ace men, t recovery ratio , t her m al st abili ty , salt resi stance
LU Hongsheng (doctor , lecturer ), born i n 1979, i s engaged i n t he research on o ilfi e l d che m istry treat ment fl uid .
Add :Chengdu Instit ute o fO rganic Che m i stry , Chi nese A cade -my Sc i ence , Chengdu C i ty 610041, S i chuan Prov i nce , P . R. Ch i na M obil e :+86-[1**********] E -mai:l shhl u @163. com SYNTHESI S AND EVALUATI ON OF THE ULTRA -H I GH TE MPERATURE LOSS ADDI TI VE F LA 240USED F OR DR I LL I NG FLUI D
111
W A NG Zhong hua , WANG Xu , ZHOU L equn and WU 2
Lan (1. D r illi ng Technology R esearch Institut e o f Zhongyuan O il Expl orati on Bureau ; 2. CC DC Sa f ety , Env iron m en, t Quali ty Super -v i si on&T esti ng Research Instit ute), DPT 33(2), 2010:97-100
Abstrac t :T aki ng acry l a m ide , acry l oyloxy l oxy is obut y ls ulfoni c ac i d , N, N-dm i ethy l acry la m i de and acry lic as base m ateri a, l the copoly m er ultra -hi gh te mperat ure loss add i ti ve FLA240used f or drilli ng fl ui d was synthesi zed by redox i nitati on . The struct ure and t her ma l st ability of FLA 240w ere researched by usi ng i nfrared spec -troscopy and t her m al ana l ysis , its anti-te mperat ure mechanis m was a ls o analyzed , t he perf or m ances of FLA 240drilli ng fl ui dsw ere eva-l ua t ed i n laboratory . The results s howed tha, t FLA240had very good t her ma l stab ility and co mpati bl eness , and it had better fl u i d loss characteristics i n fresh w ater , bri ne and saturated br i ne drilli ng fl u -i d . A fter the 240 ultra -h i gh te mperature ag i ng , it can bett er
3
control the filter loss o f dr illi ng fl uid . In the density o f 2. 25g /cm sat urated br i ne drilli ng fl ui d , when t he FLA240w as i ncreased fro m 1. 0%t o 4. 0%,filtration of h i gh -te mperature and h i gh pressure drilli ng fl uid can reduced fro m 110mL to 6mL .
K ey words :drilli ng fl ui d , flui d l oss additi ve , copoly m er , ultra -h i gh te m perature , synthesi s
W A NG Zhonghua (professorial senior engi neer ), graduated from Che m i stry Depart m ent o f Zheng z hou Un i versit y i n 1985, i s a chief eng i neer ofD rilli ng Technol ogy R esearch Instit ute of Zhongyuan O ilExpl orati on Bureau , is engaged i n t he research on fi ne chem i cal eng i neeri ng and o ilfiel d che m istry .
Add :D rilli ng Technol ogy R esearch Instit ute of Zhongyuan O il Expl orati on Bureau , 59Zhongyuan Road , Puyang C it y 457001, Henan P rovi nce , P . R . Ch i na
Te:l +86-393-4899235 E -mai:l z peb w z h @126. co m RES EARC H ON SY NTHESI S OF FLU I D LOSS ADDI -TI VE PADA M OF A MPH I PR OT I C P OLY MER DRI LL I NG FLUI DS
1, 22
YANG Ji nrong and MA X i pi ng (1. G all D ng
Co mpany; 2. Sout hwest Petroleu m U ni versi ty), DPT 33(2), 2010:
101-104
Abstract :An amphi proti c tetrapo l y m er (acryla m ide /dmi ethy l di -a ll y l am m oniu m chlori de/2-acry l a m i do-2-m et hyl propane su-l fon i c acid/methyl acry li c aci d) (PADAM ) has been synt hesized through orthogona l desi gn by free radica l poly m er i zati on i n aq ueous so l uti on usi ng ox i dation-reducti on-i nitiati on s yste m as acti vator i n the paper . T he aff ecti on o fm onomer m i xture concentrati ons , initia -ti ng agen, t mono m er m olar ratio and reacti on tm i e on mo l ecular we i ght and properties o f P ADAM w ere di scussed , t he mo l ecular structures were verifi ed by i nfrared s pectroscopy , t he flui d loss con -trol abili ty and t he i nhi biti on abilit y of PADAM i n drilli ng fl ui dswere eva l uated . The results i ndicated that t he productw it h cert a i n molecu -l ar para m eter had good anti -sal, t anti -high te mperat ure and the a -bility o f flui d l oss control and i nhi b i ti on . The PADAM i s a ki nd o f a mph i proti c copoly m erw ith bot h fl u i d loss control and i nh i bition ab i -l it y i n fac. t
K ey words :a mph i proti c pol ymer , synthesi s , salt resistancy , dr illi ng flui ds , fl ui d loss additi ve , i nhi biti ve
YANG Ji nrong (senior e ngineer ), is worki ng i n G reat W a ll D rilli ng Co mpany and study i ng f or his doctor s degree i n South west P etro l eu m U ni versity .
Add :G reatW allD rilli ng Co mpany , 101A nli Road , Chaoyang D istr i ct 100101, Be iji ng , P . R. Chi na RESEARCH ON CO MPOSI TE C ORR O SI ON I N H I B I TOR
112
WANG Yong , GONG Ji nha i , B AO Rubi ng and L I U Con -3
gqin (1. Zhongyuan O ilfiel d Survey and D esi gn R esearch Insti tute ; 2. Bao ji Petro l eu m M achi nery Co . , L td . Chengdu Equi p m entM anu -fact uri ng Company ; 3. Eng i neeri ng Supervisi on Center of G as Pro -ducti on Research I nstit ute , Sout h w estO il/gasF i eld Co . ) , DPT 33(2), 2010:105-107
Abstract :Composite corrosion i nh i bit or F H -01, synt hesized by a m i ne , sca l e i nh i bitor and bacterici de , possesses t he effi cacy o f corrosion i nh i biti on , anti scale and disi nfecti on . The l aboratory i nd-i
cated t ha, t i n t he medi u m ofwaste water , rate of co rrosion i nhi b iti on was 71. 3%~85. 5%, sterilize ra t e was above 90%, and rate o f scale i nh i bition was 81. 8%.Even it can be used as ac i dul a t e corro -si on i nhi bitor . The res ults of fi eld experm i ent showed t ha, t after addi ng corrosion i nh i bit or F H -01, iron content o f the oilw ell liqui d was descended by 27. 1%~86. 4%.
K ey words :s ynt hesis , co mposite corrosion i nhi bitor , ant-i scale , disi nf ecti on
WANG Yo ng (e ngineer ), graduated fro m Huadong Un i versit y of Sc i ence and Eng i neer i ng i n 1997, i s engaged i n the research on o ilfiel d anticorrosion eng i neeri ng .
Add :ZhongyuanO ilfi eld Survey and D esi gn Research Insti tute , Puyang C i ty 457001, Henan Provi nce , P. R . Chi na
T e:l +86-393-4822135E -mai :l z yshywy @163. com STUDY ON A MODIFIED POLYVI NYL ALC OHOL AN -T I -SLOUGH I NG A GENT S HENG X i n and YU L ibi n (Tuha D rilli ng T echno l ogy R e -search Institut e , C NPC W est D rilli ng Co mpany ) , DPT 33(2), 2010:108-110
Abstract :A ne w ly anti -sloughi ng agent w as developed through modif y i ng t he po l yv i nyl alcoho. l The results showed that t he m od i fi ed po l yvi nyl a l coho l anti-sl oughi ng agent had strong i nh i b-i
ti ve , coul d effecti ve l y reduce t he friction coeffi c i ent of dr illi ng fl u i d , and m i prove the rheo l ogical propert y and water loss of drilli ng fl u i d . Furt her m ore , it is no-t ox i c and b i odegradable .
K ey words :polyv i ny l alcoho, l anti -sl ough i ng agen, t perfor m -ance eva l ua ti on , tox i c it y , biodegradati on S HENG X i n , born i n 1973, is superintendent o f O ilfi e l d Che m i stry Research Instit ute o f Tuha D rilli ng T echno l ogy R esearch Instit ute , bei ng engaged i n t he research on drilli ng fl ui d techno l ogy .
Add :T uha D rilli ng Technology R esearch Institut e , Shans han 838202; X i njiang , P . R . China
M o b ile :+86-[1**********]E -mai :l l kh54321@si na . co m