Deposition behavior of barium sulfate in microchannel reactors

doi:10.11949/j.issn.0438-1157.20171257

Abstract

Abstract:

Fouling of barium sulfate is often observed and difficult to clean up in the process of petroleum production. Barium sulfate deposition of simulated oilfield water in the microchannel reactor was studied by varying tube length, flow rate, concentration and temperature. Barium concentration and pressure drop in each microchannel section were obtained by flame atomic absorption and differential pressure method, respectively. The results show that the rate and amount of barium sulfate deposition in the microchannel increased with increase of tube length, flow rate, and concentration, which deposition rate was increased nonlinearly. With temperature increase, ion diffusion in the microchannel accelerated and deposition rate of barium sulfate increased. However, a slight rise of temperature did not change concentration of barium sulfate significantly and hence deposition amount of barium sulfate was increased very little. SEM morphology of barium sulfate in both inlet and outlet verified impacts of different factors on deposition and crystallization in the microchannel. Deposition of barium sulfate in pipeline is not just a simple homogeneous sedimentary process, as a result of influence of crystal nucleation. The barium sulfate crystal formation has two regular stages of nucleation and crystal growth.

Key words: microchannel, barium sulfate, crystallization, nucleation, deposition

摘要：

硫酸钡是石油生产过程中经常遇到的难以清除的垢。在微通道反应器内对硫酸钡沉积行为进行较详细的研究。采用火焰原子吸收法和压差法分别测量钡浓度变化和微通道管段间的压力变化，考察微通道管长、流量、浓度及温度等因素对模拟油田水在微通道反应器内硫酸钡沉积行为的影响。实验结果表明，随着管路增长、流量增大、浓度增加，微通道中硫酸钡的沉积速率加快，沉积量增多，且呈非线性增加趋势，而温度升高使得微通道管路中离子扩散加快，硫酸钡沉积速率增大，但由于温度的小幅度升高并没有使硫酸钡溶度积发生明显变化，因此硫酸钡沉积量增加较少。采用扫描电镜观察管道内进出口处硫酸钡的结垢形态，验证了不同因素对管路沉积情况和结晶形态的变化。研究得出受结晶成核的影响，管道内硫酸钡的沉积结垢并非均匀简单的沉积过程，其晶粒形成可分为两个阶段，即成核阶段和晶体生长阶段。

关键词: 微通道, 硫酸钡, 结晶, 成核, 沉积

CLC Number:

TE19

ZHANG Baodan, YANG Bei, YANG Suohe, SU Mingyue, HE Guangxiang, GUO Xiaoyan, JIN Haibo. Deposition behavior of barium sulfate in microchannel reactors[J]. CIESC Journal, 2018, 69(4): 1461-1468.

张宝丹, 杨贝, 杨索和, 苏明月, 何广湘, 郭晓燕, 靳海波. 微通道反应器内硫酸钡沉积行为[J]. 化工学报, 2018, 69(4): 1461-1468.

References 33

[1]	徐军, 陶荣德, 李养池, 等. 油田结垢机理及阻垢剂评价方法探讨[J]. 广州化工, 2013, 41(16):18-19. XU J, TAO R D, LI Y C, et al. Oilfield scale formation mechanism and evaluation methods of scale inhibitors[J]. Guangzhou Chemical Industry, 2013, 41(16):18-19.
[2]	王亭沂. 油田污水结垢问题及防垢技术研究进展[J]. 中国科技信息, 2009, 2:29-30. WANG T Y. Oilfield sewage scaling problems and research advance of antiscale technology[J]. China Science and Technology Information, 2009, 2:29-30.
[3]	王守虎, 张明霞, 陆小兵, 等. 长庆超低渗透油藏华庆油田硫酸钡锶垢的防治[J]. 石油天然气学报, 2011, 33(5):269-270. WANG S H, ZHANG M X, LU X B, et al. The prevention of the scale about barium sulfate and strontium in the oilfield of Huaqing in the ultra-low permeability reservoir in Changqing[J]. Journal of Oil and Gas Technology, 2011, 33(5):269-270.
[4]	房伟. 高含钡条件下硫酸钡防垢剂的研究及室内评价[J]. 内蒙古石油化工, 2012, 12:1-3. FANG W. Indoor evaluation and research of barium sulfate anti-scaling agent with high barium[J]. Inner Mongolia Petrochemical Industry, 2012, 12:1-3.
[5]	廖辉, 唐善法, 吴振宇, 等. 钙垢阻垢剂的制备及复配性能[J]. 化工生产与技术, 2013, 20(6):33-35. LIAO H, TANG S F, WU Z Y, et al. Preparation and mixing properties of calcium scale inhibitor[J]. Chemical Production and Technology, 2013, 20(6):33-35.
[6]	OLAJIRE A A. A review of oilfield scale management technology for oil and gas production[J]. Journal of Petroleum Science and Engineering, 2015, 135:723-737.
[7]	古昕, 刘宏芳, 齐公台, 等. 油田注入水硫酸钡动态结垢机理研究[J]. 工业水处理, 2011, 31(6):39-42. GU X, LIU H F, QI G T, et al. Dynamic scaling mechanisms of BaSO4 from oilfield injected water[J]. Industrial Water Treatment, 2011, 31(6):39-41.
[8]	刘振, 王丽玲. 冷指实验研究碳酸钡结垢规律[J]. 当代化工, 2014, 43(2):194-197. LIU Z, WANG L L. Research on rule of barium carbonate scaling by cold finger experiment[J]. Contemporary Chemical Industry, 2014, 43(2):194-197.
[9]	徐志明, 张一龙, 王景涛, 等. 两种阴离子对析晶污垢沉积的影响[J]. 化工学报, 2015, 66(6):2268-2272. XU Z M, ZHANG Y L, WANG J T, et al. Effect of two kinds of anions on crystallization fouling deposition[J]. CIESC Journal, 2015, 66(6):2268-2272.
[10]	徐志明, 韩志敏, 王景涛, 等. 圆形楞涡流发生器结构对矩形通道内CaSO4污垢沉积特性的影响[J]. 化工学报, 2015, 66(12):4815-4822. XU Z M, HAN Z M, WANG J T, et al. Effect of flute structure of circular vortex generators on CaSO4 fouling deposition characteristics in rectangular channel[J]. CIESC Journal, 2015, 66(12):4815-4822.
[11]	KHORMALI A, PETRAKOV D G, MOEIN M J A. Experimental analysis of calcium carbonate scale formation and inhibition in waterflooding of carbonate reservoirs[J]. Journal of Petroleum Science and Engineering, 2016, 147:843-850.
[12]	靳海波, 杨贝, 杨索和, 等. 油田注水系统中毛细管内硫酸钡结垢动力学分析[J]. 中国石油大学学报(自然科学版), 2015, 39(5):157-162. JIN H B, YANG B, YANG S H, et al. Scaling kinetics of barium sulfate in the capillary of the oilfield injected water[J]. Journal of China University of Petroleum(Edition of Natural Science), 2015, 39(5):157-162.
[13]	PIEPER M, AMAN S, TOMAS J. Agglomeration kinetics of submicron barium sulfate precipitates[J]. Chemical Engineering Science, 2012, 77:228-234.
[14]	FAN C F, KAN A T, ZHANG P, et al. Scale prediction and inhibition for oil and gas production at high temperature/high pressure[R]. SPE 130690, 2012, 17(2):379-392.
[15]	BUKUAGHANGIN O, SANNI O, KAPUR N, et al. Kinetics study of barium sulphate surface scaling and inhibition with a once-through flow system[J]. Journal of Petroleum Science and Engineering, 2016, 147:699-706.
[16]	杨欢, 罗跃, 苑慧莹, 等. 油田集输管道内流动流体结垢动力学研究[J]. 油田化学, 2016, 33(2):351-356. YANG H, LUO Y, YUAN H Y, et al. Fouling kinetics model of flowing fluid in oil gathering pipeline[J]. Oilfield Chemistry, 2016, 33(2):351-356.
[17]	JIN H B, YANG B, YANG S H, et al. An experimental and modeling study of barite deposition in one-dimensional tubes[J]. Journal of Petroleum Science and Engineering, 2015, 125:107-116.
[18]	BEDRIKOVETSKY P G, LOPES JR R P, ROSARIO F F, et al. Oilfield scaling(Ⅰ):Mathematical and laboratory modelling[R]. SPE 81127, 2003.
[19]	BEDRIKOVETSKY P G, GLADSTONE P M, LOPES Jr R P, et al. Oilfield scaling(Ⅱ):Productivity index theory[R]. SPE 81128, 2003.
[20]	BEDRIKOVETSKY P G, LOPES JR R P, GLADSTONE P M, et al. Barium sulphate oilfield scaling:mathematical and laboratory modeling[R]. SPE 87457, 2004.
[21]	李洪建, 余先政, 周文静, 等. 硫酸钡结垢动力学瞬态模型研究[J]. 西南石油大学学报(自然科学版), 2017, 39(5):178-184. LI H J, YU X Z, ZHOU W J, et al. Study on transient dynamic model of barium sulfate scale formation[J]. Journal of Southwest Petroleum University(Science & Technology Edition), 2017, 39(5):178-184.
[22]	KIM T, BAI C, CHO Y. A study of CaCO3 fouling with a microscopic imaging technique[J]. International Journal of Heat and Mass Transfer, 2002, 45(3):597-607.
[23]	张博丽. 火焰原子吸收光谱法测定硫酸钡中的游离钡[J]. 无机盐工业, 2012, 44(2):60-61. ZHANG B L. Determination of free barium in barium sulphate by atomic absorption spectrometry[J]. Inorganic Chemicals Industry, 2012, 44(2):60-61.
[24]	杨贝, 赵月龙, 焦玉海, 等. 富氧天然气火焰原子吸收光谱法测定油田水中的钡含量[J]. 石油化工, 2013, 42(12):1393-1397. YANG B, ZHAO Y L, JIAO Y H, et al. Measuring barium content in oil field water by oxygen-enriched gas flame atomic absorption spectrometry[J]. Petrochemical Technology, 2013, 42(12):1393-1397.
[25]	BOAK L S, Al-MAHROUQI H, MACKAY E J. What level of sulfate reduction is required to eliminate the need for scale-inhibitor squeezing[R]. SPE 95089, 2005.
[26]	BOAK L. S, SORBIE K S. The kinetics of sulfate deposition in seeded and unseeded tests[R]. SPE 100513, 2006.
[27]	BEDRIKOVETSKY P G, MACKAY E, MONTEIRO R P, et al. Injectivity impairment due to sulfate scaling during PWRI:analytical model[R]. SPE 100512, 2006.
[28]	CARAGEORGOS T, MAROTTI M, BREDRIKOVETSKY P G. A new method to characterize scaling damage from pressure measurements[R]. SPE 112500, 2008.
[29]	YU J G, LIU S W, CHENG B. Effects of PSMA additive on morphology of barite particles[J]. Journal of Crystal Growth, 2005, 275:572-579.
[30]	李雪娇. 硫酸钡结垢影响因素及化学阻垢实验研究[D]. 南充:西南石油大学, 2015:37-39. LI X J. The factors affecting barium sulfate scaling and the experimental research on chemical inhibitors[D]. Nanchong:Southwest Petroleum University, 2015:37-39.
[31]	BLOUNT C W. Barite solubilities and thermodynamic quantities up to 300℃ and 1400 bars[J]. American Mineralogist, 1977, 62:942-957.
[32]	MAVREDAKI E, NEVILLE A, SORBIE K S. Initial stages of barium sulfate formation at surfaces in the presence of inhibitors[J]. Crystal Growth & Design, 2011, 11:4751-4758.
[33]	钱惠娟, 朱明亮, 罗忠贵, 等. 油田硫酸钡结垢过程影响因素研究[J]. 油气田环境保护, 2017, 36(8):89-92. QIAN H J, ZHU M L, LUO Z G, et al. Research on the influence factors of barium sulfate scaling process in oilfield[J]. Environmental Protection of Oil & Gas Fields, 2017, 36(8):89-92.