水合物抑制剂的合成及在超深水钻井液中的应用

刘书杰; 徐一龙; 张宇飞; 储跃康; 岳前升; 赵庆美

doi:10.12358/j.issn.1001-5620.2024.05.002

水合物抑制剂的合成及在超深水钻井液中的应用

doi: 10.12358/j.issn.1001-5620.2024.05.002

刘书杰^{1, 2,},
徐一龙^{1, 2},
张宇飞³,
储跃康⁴,
岳前升⁴,
赵庆美^4, ,

1.
中海油海南能源有限公司, 海口 570311
2.
中海石油(中国)有限公司海南分公司, 海口 570311
3.
中海油田服务股份有限公司油田化学研究院, 河北燕郊 065201
4.
长江大学化学与环境工程学院, 湖北荆州 420023

基金项目: 国家重点研发计划“3000 m级深海油气钻探关键技术与装备研究”（2022YFC2806500）。

详细信息

作者简介:
刘书杰，博士，现在主要从事海洋油气钻探开发。E-mail：liushj@cnooc.com.cn。

通讯作者:
赵庆美，E-mail：qingmeizhao123@163.com.cn。

中图分类号: TE254.4
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- HTML全文浏览量: 94
- PDF下载量: 90
- 被引次数: 0
出版历程
- 收稿日期: 2024-03-14
- 修回日期: 2024-04-23
- 刊出日期: 2024-11-07

Synthesis of a Hydrate Inhibitor and Its Application in Drilling Fluids for Ultra-Deep Water Drilling

LIU Shujie^{1, 2
,},
XU Yilong^{1, 2},
ZHANG Yufei³,
CHU Yuekang⁴,
YUE Qiansheng⁴,
ZHAO Qingmei^{4
, ,}

1.
Cnooc Hainan Energy Co. LTD, Haikou , Hainan 570311
2.
Cnooc (China) Co., Ltd. Hainan branch, Haikou , Hainan 570311
3.
Oilfield Chemistry Research Institute, China Oilfield Service Co., LTD., Yanjiao, Hebei 065201
4.
Yangtze University, College of Chemistry and Environmental Engineering, Jingzhou,Hubei 420023

摘要

摘要: 天然气水合物的生成危及钻采作业的安全进行，研发性能优异的动力学抑制剂（KHI）与热力学抑制剂复配对抑制超深水条件水合物生成具有重要意义。选用4-丙烯酰吗啉与N-乙烯基吡咯烷酮共聚，合成不同单体配比动力学抑制剂ACN，采用单因素法优化合成条件，采用红外、扫描电镜、凝胶渗透色谱仪等分析产品；采用甲烷水合物模拟测试法（MHS）、四氢呋喃抑制性能评价法(THF)评价抑制性能；优选最佳ACN产品及加量并与其它KHI产品对比，复配适用于超2000 m窄密度窗口钻井液抑制剂，并配制钻井液。研究发现以1%的AIBN为引发剂，反应温度65 ℃，反应时间6 h为其最佳合成条件，确定2%ACN（4∶6）抑制效果最佳；确定该抑制剂复配方案为2%ACN+1%KHI-1+35%乙二醇+5%NaCl，该抑制剂密度1.078 g/cm³，THF法−25 ℃测其初始结晶时间为32 min；钻井液密度为1.150 g/cm³，高温高压滤失量小于17 mL，滚动回收率大于82%，满足该研究钻井液相关性能要求。
- 天然气水合物 /
- 超深水钻井液 /
- 抑制性能 /
- 4-丙烯酰吗啉
Abstract: In ultra-deep water drilling, the formation of natural gas hydrates aways endanger the safety of drilling and production. The development of excellent kinetic hydrate inhibitors (KHI) which are compounded with thermodynamic is of great importance to the effective inhibition of gas hydrates in ultra-deep water drilling. Using 4-acryloyl morpholine and N-vinylpyrrolidone to copolymerize in different molar ratios to produce kinetic gas hydrate inhibitor ACNs. The reaction conditions are optimized through single-factor method, the reaction products are analyzed by IR, SEM and gel permeation chromatograph, and the properties of the products are evaluated by methane-hydrate simulation (MHS) test and tetrahydrofuran (THF) inhibition performance test. Through the evaluation and test, the best ACN is selected, and is compared with other KHIs. The best ACN is then compounded with thermodynamic gas hydrate inhibitors to produce a gas hydrate inhibitor for use in drilling fluids for drilling in areas with water depth of more than 2,000 m and with narrow safe drilling windows. XXXX found in studies that the best ACN can be obtained when AIBN is used as the reaction initiator and let the monomers react under 65 ℃ for 6 h, and 2% ACN (4∶6) has the optimum inhibition. The formulation of the gas hydrate inhibitor is 2%ACN + 1%KHI-1 + 35%glycol + 5%NaCl. The density of the gas hydrate inhibitor is 1.078 g/cm³, and the initial crystallization time of the gas hydrate inhibitor measured at −25 ℃with THF method is 32 min. The drilling fluid tested has a density of 1.150 g/cm³, a high temperature high pressure filtration rate of less than 17 mL, and a percent shale cuttings recovery in hot rolling test of greater than 82%, satisfying the relevant requirements for the drilling fluid.
- Natural gas hydrate /
- Ultra-deep water drilling fluid /
- Inhibitive capacity /
- 4-acrylyl morpholine

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图 1 抑制剂CAN的分子式

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图 2 不同引发剂加量对引发效果的影响

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图 3 反应时间对抑制剂ACN产率的影响

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图 4 反应温度对数均分子量及起黏时间的影响

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图 5 抑制剂ACN的红外谱图

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图 6 抑制剂ACN的SEM图

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图 7 THF法测ACN抑制效果

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图 8 高压釜内压力随时间变化曲线

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图 9 高压反应釜中水合物图片

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表 1 ACN与其它KHI对比及复配

抑制剂种类	ρ/ g·cm⁻³	结晶诱导时间/min	结晶凝固时间/min	P_{24 h} 保留率/%
纤维素	0.999	27	30	59.6
丝氨酸	1.000	24	27	50.3
果胶	0.999	28	74	87.3
ACN(4∶6)	0.999	78	84	94.1
KHI-1	1.001	160	171	97.3
KHI-2	1.000	72	76	91.1
KHI-3	0.999	65	69	89.7
KHI-4	1.001	39	58	78.5
2%ACN+1%KHI-1	1.002	201	233	97.8
2%ACN+1%KHI-2	1.001	75	82	94.0

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表 2 NaCl加量对复配体系性能的影响

NaCl/ %	ρ/ g·cm⁻³	结晶诱导时间/min	结晶凝固时间/min
0	1.046	26	27
1	1.051	23	25
2	1.057	26	27
3	1.064	28	29
4	1.071	31	32
5	1.078	32	34
6	1.085	44	45
7	1.090	70	75
10	1.103	87	92

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表 3 钻井液的性能评价

NaCl/ %	ρ/ g·cm⁻³	AV/ mPa·s	PV/ mPa·s	YP/ Pa	FL/mL		滚动回收率/%
NaCl/ %	ρ/ g·cm⁻³	AV/ mPa·s	PV/ mPa·s	YP/ Pa	API	HPHT	滚动回收率/%
3	1.10	10.5	8.5	2.0	5.4	16.2	82.3
5	1.15	10.5	8.0	2.5	5.8	16.8	82.5
7	1.18	10.5	8.0	2.5	5.6	16.7	82.9

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参考文献(14)

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