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Zheng Xiuhua, Ma Xiaochun

Drilling Fluids

(第一版)

Zheng Xiuhua, Ma Xiaochun Drilling Fluids ( 第一版 ) 2010 地质出版社 1

2010

地质出版社

内容提要

本书参考国内外钻/完井液专著、石油/泥浆服务技术手册、科技论文等编写而成,系统

介绍了钻井液的基本原理、钻井液材料和钻井液体系,同时介绍了钻/完井液技术的最新进

展。全书分为十章,主要内容包括钻井液概述、钻井液性能及其测试、粘土矿物及胶体化学、

钻井液流变和水力性能,钻井液滤失性能、钻井液材料和处理剂、水基钻井液体系、孔壁稳

定与漏失、固相控制、钻井液技术新进展。本书为开设钻井液,特别是采用双语教学的大专

院校提供了一本很好的英文教材。

Abstract

This book was accomplished referred many literatures on drilling/completion fluids, such as monographs, technique manuals from petroleum/mud service companies and published articles,

both domestic and abroad. This book introduced systematically the principles of drilling fluids, make-up materials, additives and drilling fluids systems. This book is divided into ten chapters, i.e., the INTRODUCTION TO DRILLING FLUIDS, THE PROPERTIES AND EVALUATI ON OF DRILLING FLUIDS, CALY MINERALOGY AND THE COLLOD CHEMISTRY OF DRILLING FLUID, RHEOLOGY AND HYDRAULICS, MAKE- UP MATERIALS AND

ADITIVES,

FOR

CIRCULATION,

DRILLING FLUID. This book tries to provide the students, especially in bilingual language a teaching book.

WATER- BASE DRILLING FLUID SYSTEM,

SOLID

CONTROL,

and

SOME

UP

HOLE STABILTY AND LOSS

TECHNOLOGIE S

TO DATE

前言

随着油气勘探开发井和矿产资源勘探孔变得原来越深和越来越复杂,基础工程勘察领域

越来越广,要求钻井液分多样,性能可调,以满足各种钻井情况。

As attempts are made to drill deeper and consequently more hazardous wells to exploit petroleum and mineral resources, the dr illing fluid is expected to have physical and chemical properties that enable it to contend with a greater variety of well conditions. The satisfactory performance of these more complex functions has required that the composition of the fluid become more varied and its properties more subject to control. 最初钻井液的功能只是携带岩屑,现在已经公认钻井液是钻井成功的主要因素之一,同 时也与钻进效率和钻进成本有直接关系。因此,钻井液组分、性能和功用及其设计与维护至 关重要。

The fluid us ed in rotary drilling, once regarded only as a means of bringing rock cuttings to the surface, is now recognized as one of the major factors involved in the s uccess or failure of the drilling operation. In addition to lifting the cuttings, the drilling fluid must perform other, equally important functions directed toward the efficiency and cost. For this reason, the composition of the drilling fluid and its res ulting properties and their design and maintenance are significant . 勘查与技术工程的学生就业涵盖了石油工程、矿产勘查、资源勘探、工程勘察等工程领 域,钻井液是该专业的主修课程之一。 随着我国工程在国际市场上占有份额的增加,有的 毕业生被派往国外做技术负责;同时,有一部分学生深造攻读硕士和博士学位,有很多参与 国际交流的机会;另外,有许多国外大学提出了联合培养合作意向;还有,我国高等教育部 为提高学生素质、培养国际意识和交流能力,在外语教学投入了很多力量,学生也投入了大 量精力。以上这些因素要求,在有条件的情况下开设双语教学,使学生培养使用英语的习惯, 学以致用,认识英语只是一种交流工具。

The employment of students majored Prospection and Engineering nowadays covers many engineering fields, e.g. petroleum engineering, mineral survey, resource exploration and project investigation, etc., for which drilling fluid is one of the main subjects they major. And the following factors, i.e. 1) some are sent abroad as engineers as the international project growth; 2)some purse master and doctor degrees, for which they have more opportunities to international programs; 3)some universities proposed cooperation for high education; 4) the students have already learned English for many years under many supports of the Education Ministry, demonstrate that it is significant and possible to have some curricula in bilingual under some conditions, to help students to know that English is just a communication tool. 本书为开设钻井液双语教学提供教材。以英语形式书写,专业词汇在括号中用英语标注。 钻井液双语教学理念是利用英语学习专业知识,通过教学首先要掌握钻井液专业知识和专业 技能,同时了解专业知识的英文表达。专业知识为教学根本,英语只是一种语言,在某种程 度上更严谨地阐述科学原理。

This book tries to provide a teaching book of drilling fluids which is lectured in bilingual language. It is written in English, and the speciality words are translated to Chines in bracket. The teaching aim is firstly to convey speciality knowledge and skills, along with their expression in English. 考虑有些学生阅读英文专业文献较少,开始学习时会有困难。在学习中将采取以下几点 措施确保教学质量和效果。第一点也是最重要的一点是:“万事开头难”,要求学生有信心而 且能够坚持。第二点是配置与英文教材内容基本一致的中文教材,同时开设实验课,采用中

文实验指导书。第三点将采取循序渐进的教学方法,开始时专业术语将分别以英文和中文同

时讲授。

Considering that some students may read few English specialty literatures, it will be a bit difficult to start. Some measures shall be taken to assure the teaching quality and results. The first and the most important one is for students, i.e. Be Confident and Persevere. Nothing is easy to start. The second one is to facilitate it with Chinese specialty literature, in which the contents are consistent with the teaching contents in English, along with experiments in Chinese. The third one is to go ahead it gradually, namely the terms will be presented at the beginning both in English and Chinese. 本书由郑秀华主编,马孝春统稿。内容由中国地质大学(北京)工程技术学院勘查教研 室讨论制定,由《钻井液工艺原理》双语教学团队共同编写。

The book is edited by Prof. Dr. Xiuhua Zheng and collated by Prof. Dr. Xiaochun Ma. The contents of this book is organized by the Prospection and Technology Institute, School of Engineering and Technology, China University of Geosceicens(Beijing), co-edited by the teaching group for drilling fluids.

致谢

本书出版得到了中国地质大学(北京),工程技术学院和教研室与相关领部门及其领导 的鼓励和支持。 本书的编写过程中得到了很多人的帮助,包括德国柏林工业大学 Helmut Wolff 教授,他 最早向作者提供了钻井液原本教材。中国石油勘探开发研究院的樊世忠教授,他为作者提供 了许多他珍藏多年的文献资料,包括一些外国公司的泥浆技术手册。中国石油大学的鄢捷年 教授,在本书的编写过程中,作者参考了鄢捷年教授的教材。感谢研究生们,他们是王彬、 程金霞、尹文斌、李纯、詹美萍、陈立敏、刘选朋、刘翠娜、张志亮等,他们为本书的编写 作了许多繁琐而细微的工作。还有许多未能详尽提及的人,他们为本书做出了很大贡献。在 此一并表示感谢!

Acknowledgement

The authors appreciate CUGB, School and Institute for their encouragement and support. The authors acknowledge Prof. Dr. Helmut Wolf of Technolgy University of Berlin, Germany who provided many literatures for drilling fluids in English, Prof. Shizhong Fan who dedicated his collection for drilling fluids in English, and Prof. Jienia n Yan whose teaching book has been referred. The authors thank many undergraduated students, i.e. Bin Wang, Jinxia Cheng, Wenbin Yin, Chun Li, Meiping Zhan, Limin Chen, Xuanpeng Liu, Cuina Liu, Zhiliang Zhang, etc., along with many unnamed above. The Author would like to express her many thank to his son and his husband, especially his son, who is now in his 2 nd year of high school. He supported his mother with his effort for his school work.

About the Authors

Xiuhua Zheng holds B.S and M.S. in Exploration Engineering from Changchun Geology College, which is now the Geosciences Center of Jilin University and a Ph.D. degree in Geotechnique from China University of Geosciences(Beijing). She finished her thesis on foaming agents and applications for well drilling, and her dissertation was about underbalanced drilling and its optimization. She worked on fracturing fluids and drilling fluids for coal bed methane at Exploration Engineering Institute from 1990 to 1993. She has engaged herself in teaching and researching in the fields of drilling and completion fluids, geothermal energy since she came to university in 1993. She has published more than 40 papers, edited or co -edited 4 books published publicly and 1 teaching books used at university, and holds 2 patents.

郑秀华,于原长春地质学院,现吉林大学地学部,获探矿工程学士和硕士学位,于中国 地质大学(北京)获地质工程博士学位。她的硕士论文涉及泡沫剂及其在钻井中的应用,博 士论文则为欠平衡钻井及其优化设计。她于 1993 年在探矿工程研究所负责煤层气压裂液和 钻井液的研究,后调入中国地质大学(北京)从事钻/完井液和地热的教学与研究工作,发 表 40 多篇论文,主编或参编 4 本公开发表教材,1 本校内教材,并获 2 项专利。

The address:

郑秀华,博士、教授 中国地质大学(北京)工程技术学院 北京市海淀区学院路 29

100083

Tel.: 010-82321976

Fax: 010-82321976

Mobile: (86) 15911062856

E-mail: xiuhuazh@cugb.edu.cn zxhbobby@hotmail.com

Prof. Dr. Xiuhua Zheng School of Engineering and Technology China University of Geosciences (Beijing) 29 Xueyuan Road Beijing, 100083 P.R.China Tel.: 010-82321976 Fax: 010-82321976

Mobile: (86) 15911062856

E-mail: xiuhuazh@cugb.edu.cn zxhbobby@hotmail.com

Contents

CHAPTER 1

INTRODUCTION TO DRILLING FLUIDS

8

1.1 The Definition of Drilling Fluids(钻井流体定义)

8

1.2 The

Well Circulation System(钻井循环系统)

8

1.3 The Principal Functions(主要功能)

9

1.4 Properties of Drilling Fluids(钻井液性能)

12

1.5 Principal Components of Drilling Fluids(钻井液主要成分)

13

1.6 Drilling Fluid Design and Selection(钻井液的设计与选择)

14

CHAPTER 2

THE PROPERTIES AND EVALUATION OF DRILLING FLUIDS

15

2.1

Density(密度) or Mud Weight(比重)

15

2. 2 Viscosity and Gel Properties(粘度和凝胶性能)

16

2.3 API FiltrationAPI 失水)

19

2.4 Determination of Gas, Oil, and Solids Content(水、油与固相含量的测定)

20

2.5 Bentonite Content of Mud

21

2.6 The API Sand Test(含砂量)

22

2.7 Hydrogen Ion Concentration (pH 值的确定)

23

2.8 Filtrate Analysis(滤液分析)

23

2.9 Resistivity(电阻)

28

2.10 Electrical Stability of Emulsions (乳状液的电稳定性)

29

2.11 Treatment of Make-up Water ( 配浆水的处理)

29

2.12 Pilot Testing

30

CHAPTER 3

CLAY MINERALOGY AND THE COLLOID CHEMISTRY OF DRILLING

FLUIDS

32

3.1

Characteristics of Colloidal Systems( 胶体特性)

32

3.2

Clay Mineralogy(粘土矿物学)

34

3.3

The Colloidal Chemistry of Clay Minerals(粘土胶体化学)

44

3.4

Interactions of Components in Drilling Fluids( 钻井液中各种组分之间的作用)

57

CHAPTER 4

RHEOLOGY AND HYDRAULICS OF DRILLING FLUIDS

59

4.1 Rheology(流变学)

59

4.2 Rheological Models(流变模式)

61

4.3 Measurement of Rheological Properties (流变特性的测量)

69

4.4 Pressure Drop Modeling(压降模型)

69

4.5 Rheologieal Properties Required for Optimum Performance(流变特性与优化钻井)74

4.6 The Importance of Hole Stability( 稳定孔壁的重要性)

77

CHAPTER 5

THE FILTRATION PROPERTIES OF DRILLING FLUIDS

80

5.1 Filtration and Filtration Procedures(失水和失水过程)

80

5.2 The Static Filtration and Affecting Factors(静滤失及其影响因素)

81

5.3 The Filter Cake(滤饼)

85

5.4 Dynamic Filtration(动失水)

90

CHAPTER 6

MAKE-UP MATERIALS AND ADDITIVES FOR DRILLING FLUIDS

92

6.1 Water()

92

6.2 Bentonite(膨润土)

92

6.3 Materials to Increase Density(加重材料)

 

94

6.4 Inorganic Chemical Additives(无机处理剂)

98

6.5 Polymers(聚合物)

100

CHPATER 7

WATER BASE DRILLING FLUID

 

118

7.1 Classification of Bentonite Drilling Fluid Systems(膨润土钻井液体系分类)

118

7.2 Deflocculants Used in Dispersed Systems

 

119

7.3 Dispersed Non-Inhibited Systems(分散非抑制体系)

 

122

7.4 Dispersed

Inhibited Systems(分散型抑制体系)

 

123

7.5 Non-inhibited Systems(不分散非抑制性体系)

Non-Dispersed

 

129

7.6 Inhibited Systems(不分散抑制体系)

Non-Dispersed

132

CHAPTER 8

PROBLEMS RELATED TO DRILLING FLUIDS

138

8.1 Borehole stability(井壁稳定)

138

8.2 Loss Circulation(井漏)

142

8.3 Drilling String Sticking(卡钻)

146

CHAPTER 9

SOLDI

CONTROL

153

9.1 Solid Contained in Drilling Fluid( 钻井液中的固相)

 

153

9.2 Contents and Purposes of Solid Control(固控的内容和目的)

157

9.3 Solid Control Equipment(固控设备)

158

9.4 Arrangement of Solids Control Equipment System(固控设备体系组合的原则)

167

9.5 Evaluation of Efficiency of Solids Control Equipemnt(固控设备效率评价)

 

169

CHAPTER 10 THE NEW DRILLING FLUID TECHNOLOGY

 

175

10.1

Silicate Drilling

Fluid(硅酸盐钻井液)

 

175

10.2

Mixed

Metal Hydroxide(正电胶钻井液)

177

10.3

Polyol

Technology Systems(聚合醇钻井液)

178

10.4

Micro-bubble (Aphron) Drilling Fluid(可循环微泡沫钻井液)

 

179

10.5

Formate Drilling Fluid(甲酸盐钻井液)

 

181

10.6

Non-Invasive Drilling Fluid(无侵害钻井液)

183

10.7

High-performance

Water-Based

Drilling

Fluid-Polymeric

Amine

Drilling

Fluid

(HPWBM-聚胺钻井液)

187

References

190

CHAPTER 1

INTRODUCTION TO DRILLING FLUIDS

This chapter introduces, 1) The Definition of Drilling Fluid; 2) The Well Circulation System; 3) Functions of the Drilling Fluid; 4) Properties of drilling fluids; 5)Principal Components of Drilling Fluids; 6) Drilling Fluid Selection.

1.1 The Definition of Drilling Fluids(钻井流体定义)

The term drilling fluid(钻井液)encompasses all of the compositions used to aid the production and removal of cuttings from a borehole in the earth. This broad definition purposely places no restriction on the type of tools employed nor on the objective. Some specific examples of the application of drilling fluids are: water() poured into the hole while boring a foundation footing with an auger; air(空气) introduced to blow cuttings from a blast hole; mud(泥浆) made twice as heavy as water to control tectonic forces in mineral exploration; foam(泡沫) as a conveyor of cuttings from a hole being drilled for water in glacial drift; bentonite slurry(膨润土 泥浆) employed to maintain a stable wall while excavating a cutoff trench; and a mixture of emulsifier(乳化剂)s, stabilizers(稳定剂), gellants(胶凝剂) and sealants(封堵剂) in an oil base(油基) used to drill for corrosive gases at temperatures above 260. Drilling fluids

technology is potentially useful in all types of earth excavation. Drilling Fluid Technology involves the sciences of geology, chemistry, and physics, and the skills and applications of engineering. Its goal is the utilization of available equipment and materials to attain at lowest cost the desired objective of earth excavation.

1.2 The Well Circulation System(钻井循环系统)

A schematic of the well circulatory system is shown in Figure1-1. The mud pump draws mud in through the suction line from the mud pits and sends it out to the discharge line. The discharge line carries the mud into the standpipe, which runs vertically up one leg of the derrick. The mud exits the standpipe into a strong, flexible, reinforced rubber hose called the rotary hose or Kelly hose. The rotary hose joins the swivel at the gooseneck. From the swivel, the mud flows down through the kelly (or top drive), into the drillstring, mud motor (if present), and the rest of the BHA. Mud emerges from the drill pipe at the bottom of the borehole where the drill bit is grinding away at the rock formation. Now the mud begins the re turn trip to the surface carrying the pieces of rock, called cuttings, which have been scraped off the formation by the bit, up the annulus, and out of the mud return line . The return line deposits the mud over a vibrating screen called the shale shaker. The shale shaker screens out the larger cuttings and, in some cases, dumps the cuttings into the reserve pit; however, offshore, and in environmentally sensitive areas, the shale shaker dumps the cuttings into a receptacle. At the end of this process, clean mud drains back into the mud tanks (sometimes passing through de-gassers first). Some of the cuttings are taken to be examined by geologists for clues about what is going on deep down inside the well.

Fig. 1-1 The well circulation system 1.3 The Principal Functions( 主要功能 ) The rotary drilling

Fig. 1-1 The well circulation system

1.3 The Principal Functions(主要功能)

The rotary drilling process and the principal functions of the drilling fluid are related to the mechanical processes of drilling a hole and to reactions with the formations.

1.3.1 Removal of cuttings(携带岩屑) from the bottom of the hole

One of the most important functions of the drilling fluid is to efficiently remove the freshly drilled cuttings(岩屑) from the bit and transport them in the annular space between the drill pipe

and the hole to the surface, where they can be removed. The ability of the f luid to achieve this objective is dependent to a degree on the annular

velocity(环空流速), which is the speed at which the fluid is pumped up the annulus of the well. For the cuttings to move up the well the annular velocity should be greater than the slip velocity (滑动速度) of the cuttings. Slip velocity is basically the rate at which a cutting will settle

through a moving fluid and is dependent on the size, shape and density of the cutting, and on the flow properties of the fluid. Viscosity(粘度), is the resistance of the fluid to flow and considerably influences the carrying capacity(携屑能力) of the fluid. There is an upper limit to the annular velocities achievable due

to limitations of the capacity of the pumps, and due to hole erosion. When these limitations are reached the viscosity of the fluid has to be increased. The density(密度) of the fluid has a buoyant effect on the cutting particle so that an increase

in density will also increase the carrying capacity.

1.3.2 To suspend (悬浮)cuttings and weighting material when circulation is interrupted

The fluid should have the property to form a reversible gel structure(凝胶结构) when it is

stationary, so that the cuttings and weighting material(加重材料) remain suspended. The

structuring should be reversible so that re circulation can be easily established. The cuttings should also be easily removed at the surface by the solids removal equipment.

1.3.3 Control subsurface pressures

The formations are composed of solids of varying porosity(孔隙度), where the pores are filled with liquids or gases. The rock and pore fluids(孔隙流体) are under pressure arising from

the rocks overlying them and from movements of the earth's crust. The column of drilling fluid in the hole will exert a hydrostatic pressure(静液压力) proportional to the depth of the hole and

the density of the fluid. This pressure is used to control the flow of gas, oil or water from the pores and makes an important contribution to the stability of the well bore. The flow of the drilling fluid during circulation and movement of the drill string in and out of the hole creates pressure differentials(压差)that are functions of the flow properties of the fluid and the rate of circulation or speed of drill pipe movement . These pressure effects also have to be taken into account when calculating pressures on the formation.

1.3.4 Isolate the fluids from t he formation

Because of safety considerations, the hydrostatic pressure exerted by the drilling fluid in the well is usually designed to be greater than the pressures existing in the formation. If this were not so, the well could blow out(井喷) if the bit penetrated porous rocks containing brines or

hydrocarbons. Under these conditions the drilling fluid will try and penetrate the rock as a whole fluid, or will form filter cakes(滤饼) and the filtrate will penetrate materials have to be

incorporated in the drilling fluid to minimise these effects. Whole Fluid Loss(全孔漏失): There may be highly permeable or fractured formations that will allow the entry of whole drilling fluid if there is a pressure imbalance. The solids that are normally in the fluid may not be lar ge enough to bridge the passages and formation sealing agents, commonly called lost circulation materials(堵漏材料)are added.

Filtrate Loss(滤液漏失): The components in the drilling fluid are chosen so that it is difficult to filter. The solids in the mud form a thin low permeability filter cake that will reduce the amount of fluid permeating into the pore spaces. The filtration properties(滤失特性) of drilling fluids are measured under carefully

controlled conditions and can be adjusted by controlling the type and quantity of colloidal material and by special additives. It has been repeatedly shown in the field that a low fluid loss has reduced drilling problems. Conversely, a high fluid loss mud can deposit a thick filter cake on the walls of the hole. This will restrict the passage of tools and will allow excessive amounts of filtrate(滤液)

to pass into the formation which may give rise to bore hole instability.

1.3.5 Cool and lubricate the bit and drill string(冷却和润滑钻头和钻具)

During the drilling operation, a considerable amount of heat is generated by the frictional forces of the rotating bit and drill string. This heat cannot be totally absorbed by the formation and

must be conducted away by the drilling fluid. In addition, the current trend towards even deeper and hotter holes places increased importance on this function. A vast amount of this heal is lost on the surface, with a relatively cool drilling fluid being returned back down the hole. Lubrication is obtained through the deposition of a slick wall cake, and through the use of various, specially formulated additives. Additions of diesel or crude oil may also prove beneficial,

but this practice is becoming less common due to ecological restrictions.

1. 3.6 Support part of the weight of the drill and casing string(支撑钻杆和套管部分重量) The natural buoyancy of a drilling fluid aids in supporting part of the weight of the drill string or the casing string. The degree of buoyancy is proportional to the fluid density. Any increase in fluid density creates an increase in the buoyancy factor, and reduces the load on the surface equipment. The importanc e of this particular function becomes more apparent as depths increase.

1.3.7 Maximise penetration rates(提高机械钻速)

The drilling fluid is so intimately involved in the drilling process that it is inevitable that a wide range of fluid properties will influence the rate of penetration, apart from the mechanical considerations, such as the type of bit, weight on the bit and rate of rotation. Fluid properties, such as low viscosities at high shear rates, low solids, high fluid loss and lower densities than are required to balance pore pressure, all contribute to faster penetration rates. It can be seen that some of the properties, such as high fluid loss and under balance fluid densities are contradictory to the properties required for a stable hole, and a compromise must be reached.

1.3.8 Control corrosion rates(控制腐蚀速率)

The fluid should be non-corrosive to the drill pipe, casing and drilling equipment. Additives

may be used that will specifically give protection, particularly in the highly corrosive environments of hydrogen sulphide and carbon dioxide.

1.3.9 Protect the formation(保护地层)

The drilling fluid will come into intimate contact with the formations being drilled. If a stable hole is to be obtained, then interactions between the fluid and the formations should be minimal. For example, if a salt section is t o be drilled, then the aqueous phase should be saturated with salt, to prevent wash-outs occurring. Some shale(泥页岩)formations are sensitive to fresh water (水敏) and undergo significant changes in mechanical properties that may result in an enlarged hole or bore hole collapse. An oil based fluid or an inhibited water based fluid(抑制性水基钻井 液) should be used to protect these formations.

The porous zones that contain gas or oil should be penetrated with a fluid that will not irreversibly seal the porous passages w hen the hydrostatic pressure is lowered in order to evaluate the zone.

1.3.10 Secure maximum hole information(保证钻孔信息完全)

An important objective in drilling a well is to secure the maximum amount of information about the types of formations being penetrated and the fluids or gases in the pores. This information is obtained by analysis of the cuttings, dissolved gases or oil, and by electric logging technology. The cuttings should be well preserved and not disintegrated and should be transported up the hole efficiently, so that the sample is representative of the depth at which it originated. It should be possible to easily separate and analyse gases or oil dissolved in the fluid. Also the fluid

should have a defined resistivity so that satisfactory electric well logs can be obtained.

1.3.11 Transmit hydraulic energy to tools and bit(向钻具和钻头传递水力能)

Hydraulic energy provides power to mud motor(泥浆马达) for bit rotation and for MWD

(measurement while drilling 随钻测井) and LWD (logging while drilling 随钻测井) tools.

Hydraulic programs base on bit nozzles sizing for available mud pump horsepower to optimize jet impact at bottom well.

1.3.12 Facilitate cementing and completion(有助于注水泥和完井)

Cementing is critical to effective zone and well completion. During casing run, mud must remain fluid and minimize pressure surges, so fracture induced lost circulation does not occur. Mud should have thin, slick filter cake, wellbore with no cuttings, cavings or bridges.

1.3.13 Minimize impact on environment(减少环境影响)

Mud is, with varying degree, toxic. It is also difficult and expensive to dispos e of in an environmentally-friendly manner.

1.4 Properties of Drilling Fluids(钻井液性能)

The large number of functions that have to be performed has inevitably led to the formulation of complex systems, with at least some of the complexity arising from the dif ferent environments encountered in various geological situations. The dominant properties that should be controlled follow from the functions of the fluid.

1.4.1 Density(密度)

The correct drilling fluid density is dependent on the down hole formation pressures. Strong, competent formations may be drilled with air, but over-pressured shales and high pressure formations may require a fluid with a specific gravity of up to 3.0. The density is adjusted by soluble salts or by the addition of solids, termed weighting agents.

1.4.2 Viscous or flow properties(粘度或流动性能)

These will be dependent on the depth of the hole and the annular velocities obtainable. In the upper hole, water alone may be sufficient, but at greater depths more viscous fluids are required. Deep wells, angled wells, high penetration rates and high temperature gradients all create conditions requiring close attention to the flow properties.

1.4.3 Fluid loss control(漏失控制)

This is a fundamental property of the drilling fluid and becomes important when porous formations are being drilled, particularly when those formations may contain gas or oil. Special

consideration may have to be given to the high temperature and high pressure fluid loss in particular conditions.

1.4.4 Formation protection(保护地层)

The chemistry and composition of the fluid must be such that there is minimal interaction with

the formation. Zones of salt, anhydrite (CaSO 4 ) dolomite, limestone, shale and sand may be encountered. Each zone differs in its chemical and mechanical properties and each may require different and special drilling fluid properties.

1.4.5

Temperature tolerance(抗温性)

Temperatures increase with depth quite rapidly in certain areas. The additives and properties must be chosen so that they are stable at the down-hole temperatures.

1.4.6 The other related properties

The Determination pH value and alkalinity, filtrate analysis, liquids and solids content, methylene blue test(亚甲基蓝实验) for Cation Exchange Capacity(阳离子交换容量) and

bentonite content, sand content, electrical conductivity, lubricity, electrical stability of emulsions, corrosiveness.

1.5 Principal Components of Drilling Fluids(钻井液主要成分)

Drilling fluids can be classified on the basis of a principal component. These components are (1) water, (2) oil, and (3) gas. Frequently two-and sometimes all three-of these fluids are present at the same time, and each contributes to the properties of the drilling fluid. This general classification is shown in Table 1-1.

Table 1-1 Classification of Drilling Fluids According to Principal Constituent

Gas

Water

Oil

Dry gas: Air, natural gas, exhaust gas, combustion gas

Fresh water:

Oil: Diesel or crude

Mist: Droplets of water or mud carried in the air stream

Foam: Air bubbles surrounded by

a film of water containing a

foam-stabilizing surfactant

Stable Foam: Foam containing film-strengthening materials, such

as organic polymers and bentonite

Solution: True and colloidal, i.e., solids do not separate from water on prolonged standing. Solids in solution with water include:

1. Salts, e.g., NaCl, CaCl 2

2. Surfactants, e.g., detergents, flocculants

3. Organic

cellulosic and acrylic polymers

colloids,

e.g.,

Emulsion:

 

An

oily

liquid

maintained

in

small

droplets

in

water

by

an

emulsifying

agent,

e.g.,

diesel

oil

and

a

film-stabilizing surfactant

Mud: A suspension of solids (e.g., clays, barite, small cuttings) in any of the above liquids, with chemical additives as required to modify properties

Oil mud: A sable oil-base drilling fluid contains:

1. Water-emulsifying agents

2. Suspending agents

3. Filtration-control agents

Contains

formations drilled

cuttings

from

the

May contain barite to raise density

When the principal constituent is a liquid (water or oil), the term mud is applied to a suspension of solids in the liquid. Water muds and oil muds are thus characterized. The presence of both liquids together results in an emulsion(乳化液 ), provided there is agitation and the

presence of a suitable emulsifying agent. The chemical nature of the emulsifying agent determines whether that oil is emulsified in the water (usually called an oil emulsion mud), or whether the water is emulsified in the oil (usually called an invert emulsion).

1.6 Drilling Fluid Design and Selection(钻井液的设计与选择)

The task of selecting the proper fluids for each particular situation is the job of the mud engineer, who is educated in the functions and propert ies of drilling fluids, and who acquires in the field an expertise to choose the right fluids for the right applications, keeping in mind the restrictions of expense, time, and performance. Drilling fluids ranging widely in composition and properties are a vailable for selection. Density of the drilling fluid, which is often the determining factor in the selection, can vary from the density of air to two-and-one half times the density of water, as is illustrated in Fig.1-2.

times the density of water, as is illustrated in Fig.1-2. Fig. 1-2 Drilling fluids can be

Fig. 1-2 Drilling fluids can be prepared ranging in density from that of air to 2 1/2 times that of water

1.6.1 Mud Selection Among the many factors to consider when choosing a drilling fluid are the wells design, anticipated formation pressures and rock mechanics, formation chemistry, the need to limit damage to the producing formation, temperature, environmental regulations, logistics, and economics. To meet these design factors, drilling fluids offer a complex array of interrelated properties.

Five basic properties are usually defined by the well program and monitored during drilling:

rheology, density, fluid loss, solids content and chemical properties. For any type of drilling fluid, all five properties may, to some extent, be manipulated by using additives. However, the resulting chemical properties of a fluid depend largely on the type of mud chosen. And this choice rests on the type of well, the nature of the formation to be drilled and the environmental circumstances of the well. Exercise One

The definition of drilling Fluids

Functions of the drilling Fluids

Principal components of drilling fluids

Properties related to the effective functions of the drilling fluids

CHAPTER 2

THE PROPERTIES AND EVALUATION OF

DRILLING FLUIDS

This chapter introduces Drilling Fluid Properties related to its performances: 1) Density; 2) Mud solid and liquid content; 3) Bentonite Content of Mud; 4) T he API Sand content; 5) Viscosity; 6) Gel strength; 7 ) API filtration; 8) pH determination.

2.1 Density(密度 ) or Mud Weight(比重)

Density(密度 ), or Mud Weight (比重 ) is weight per unit of volume. Once the density is determined it may be expressed in any convenient unit; for example, in pounds per gallon (lb/gal or ppg), pounds per cubic foot (lb/ft3), Specific Gravity (SG) (g/cm3), or in pressure gradient as pounds per square inch per 1, 000 feet(psi/1,000 ft) of mud in the hole. The latter unit is most convenient because it may be readily used to calculate the hydrostatic head of the mud column for any depth of hole in the same units in which the pump pressure and the reservoir or formation fluid pressure are calculated. This facilitates control when excessive formation pressure or lost circulation is encountered. The c onversion factors are as follows:

3

(g/cm 3 ) =

lb

/

gal

/

gal

ft

8.33 62.3

lb

lb

/

Specific Gravity (SG)

Mud gradient in psi/ft =

lb

/

ft

3

SG0.433

144 19.24

Mud gradient in kg/cm 2 /m = SG0.1

2-1

2-2

2-3

The mud balance (Fig.2-1) provides the most convenient way of obtaining a precise volume. It consists of a supporting base, a cup, a lid, and a graduated arm carrying a sliding weight. A knife edge on the arm rests on the supporting base.

A knife edge on the arm rests on the supporting base. Fig.2-1. Mud Balance 1-Arm; 2-Knife;

Fig.2-1. Mud Balance 1-Arm; 2-Knife; 3-Cup; 4-Lid of the cup; 5-Calibration tank; 6-sliding weight(rider); 7- Base; 8- Fulcrum

The procedure for measuring the density of the mud is as follows:

a. Set up the instrument base so that it is approximately level.

b. Fill the clean, dry cup with the mud to be weighed.

c. Place the lid on the cup m ud seat it firmly but slowly with a twisting motion. Be sure

some mud runs out of the hole in the cap.

d. With the hole in the cap covered with a finger, wash or wipe all mud from the outsid e of the cup and arm.

e. Set the knife on the fulcrum and move the sliding weight along the graduated arm until the cup and arm are balanced.

f. Read the density of the mud at the left-hand edge of the sliding weight. Make appropriate corrections when a range extender is used.

g. Read the result to the nearest scale division, in lb/gal, lb/ft 3 , SG, or psi/1,000 ft of depth.

Wash the mud from the cup immediately after each use. It is absolutely essential that all parts

of the mud balance be kept clean if accurate res ults are to be obtained. Example 1:

If the mud reading is 1.20 SG, then it equals 10.0 lb/gal= 74.8 lb/ft 3 = 519 psi/1,000 ft of depth.

Calibrating the Mud Balance:

a. Fill the cup with pure water.

b. Replace the lid and wipe dry.

c. Set the sliding weight at 8.33 and set the knife edge of the balance on the fulcrum.

d. If the weight and cup do not balance in level position, add or remove shot as required, or

adjust the calibration screw at the end of the arm. Shot may be added or removed by removing the screw in the s hot chamber at the end of the graduated arm.

e. If clear water gives a reading less than 8.3, add the difference between 8.3 and the reading to the mud weight when the test is made, vice versa. Example 2:

If clear water weighs 8.1 lb/gal, and the mud reading immediately afterward is 10.5, then adding 0.2 to 10.5 gives 10.7 lb/gal as the correct weight.

Density and Pressure Control(密度与压力控制). The formation pressure must be properly controlled in drilling process therefore downhole troubles such as blowout, loss of circulation, formation collapse and stuck pipe can be avoided, the bearing formations effectively protected and the drilling operations accomplished safely and smoothly.

2. 2 Viscosity and Gel Properties(粘度和凝胶性能)

2.2.1 Marsh Funnel(马氏漏斗) The Marsh Funnel is useful on the drilling rig, where it enables the crew to periodically report the consistency(粘度/稠度) of the mud, so

that significant changes may be noted by the mud engineer. It consists of a funnel and a measuring cup (Fig.2-2), and gives an empirical value for the consistency of the mud. The test procedure is to fill the funnel to the level of the screen and to then observe the time (in seconds) of efflux of 946ml (1quart).The

number obtained depends partly on the effective viscosity at the rate of shear prevailing in the orifice, and partly on the rate of gelation. The

time of efflux of fresh water at 213 is 26 0.5 seconds.

of gelation . The time of efflux of fresh water at 21  3 ℃ is

Fig.2-2

Marsh Funnel

2.2.2 Direct-Indicating Viscometers(直读式粘度计) These instruments are a form of concentric cylinder viscometer that enables the variation of shearing stress(剪切应力) with shear rate(剪切速率) to be observed. The essential elements are shown in Figure 2-32-4. A bob suspended from a spring(弹簧) hangs concentrically in an outer cylinder(外筒).

The test procedure is to lower the assembly to a prescribed mark(刻线) in a cup of mud, and the outer cylinder rotated(旋转) at a constant speed. The viscous drag(粘滞力) of the mud turns the bob until balanced by the torque in the spring. The deflection(偏转角) of the bob is read from a calibrated dial(刻度盘、标度盘) on the top of the instrument, which thus provides

a measure of the shear stress at the surface of the bob.

a measure of the shear stress at the surface of the bob. Fig.2-3 Schematic diagram of

Fig.2-3 Schematic diagram of the direct indicating viscometer. The deflection in degrees of the bob is read from the graduated scale on the dial

of the bob is read from the graduated scale on the dial Fig.2-4 Fann direct indicating

Fig.2-4 Fann direct indicating viscometer

The 6 speed viscometer is a motor driven rotational-type viscometer. For measurements, a mud is contained in the annular space between two cylinders. The outer cylinder, or rotor sleeve (转子套筒), is driven by a motor and can rotate at a designed constant RPM. The rotation of the rotor sleeve in the mud produces a torque on the inner cylinder(内筒,浮筒), or bob. A torsion spring(扭力弹簧) restrains the movement of the bob, and an attached graduated dial indicates it s displacement(位移), l dial reading=5.11 dynes/cm 2 shear stress. The viscometer has 6 rotational speeds -- 3 rpm, 6 rpm, 100 rpm, 200 rpm, 300 rpm and 600 rpm, 1rpm= 1.703s -1 . Gel Strength: el strength at 10 seconds G 10" and that at 10 minutes G 10' can be measured by the following steps:

a. Using the same sample in the viscometer cup as in PV and YP measurements, stir the sample at 600 rpm for 10 seconds.

b. Let the sample to stand undisturbed for 10 sec. Turn on the viscometer at 3 rpm and take

the maximum reading attained

1

2

3

in Pa.

3

as initial gel strength(初切) G l0" in

lb/100 ft

2

, or

c. Restir the mud sample for 10 seconds at 600 rpm and wait for 10 minutes. Start the

viscometer at 3 rpm and record the maximum reading attained

(终切) G 10' in

lb/100 ft

2

, or

1

2

3 in Pa.

2.2.3 Calculation of Parameters

3

as final gel strength

2.2.3.1 Bingham Model-Plastic Viscosity,

p

, Yield Point,

0

, and Apparent Viscosity,

a

:

0.511( , mPa ) s

p

0

600

300

300

p

(cp)

0.511(2

300

600

a

1

600

2 ,

mPa s

(cp)

), Pa

At other rotor speeds, the apparent viscosity,

a

300

N

N ,

mPa s

(cp)

a

2.2.3.2 Power Law Model-Flow Behavior Index, n

n

3.32lg(

 

600

/

300

)

, is given by:

and Consistency Index,

K

:

2-4

2-5

2-6

2-7

2-8

K (0.511

300

n

)/511 ,Pas

n

2-9

Example 3:

A mud sample in a rotational viscometer equipped with a standard torsion spring gives a dial reading of 46 when operated at 600 rpm and a dial reading of 28 when operated at 300 rpm. Compute the apparent viscosity of the mud at each rotor speed. Also compute the plastic viscosity and yield point. Solution:

Use of Eq. 2-6 for the 300-rpm dial reading gives :

a

300

N

300(28)

N 300

28 cp

(mPas)

Similarly, use of Eq. 2-6 for the 600-rpm dial reading gives

a

300(46)

600

23

cp

(mPas)

Note that the apparent viscosity does not remain constant but decreases as the rotor speed is increased. This type of non-Newtonian behavior is shown by essentially all drilling muds. The plastic viscosity of the mud can be computed using Eq. 2-4:

P

600

300

46

28

18 cp

(mPas)

The yield point can be computed using Eq. 2-5:

  

0

300

p

28

18

10

lbf

/100

ft

2

0.511

300

p

Pa

2.3 API FiltrationAPI 失水)

API(美国石油学会) filtration can be measured using API filtration press (Fig.2-5 Low

Pressure filter tester 低压失水仪 ) under a pressure of 100 1.0psi(690 6.9kPa)

applied

with nitrogen gas and a proper 9 cm filter paper. The measurement procedure can be done as follows:

a. Be sure each part of the cell is clean and dry, and that the gaskets(密封圈) are not

distorted or worn. Pour the sample of mud into the cell and complete the assembly with the filter paper in place.

b. Place a dry graduated cylinder under the drain tube to receive the filtrate(滤出液). Close the relief valve and adjust the regulator so that a pressure of

100 1.0psi(690 6.9kPa)

the time of pressure application.

is set up in 30 seconds or less. The test period begins at

c. Begin timing with timer. At the end of 30 minutes, read the volume of filtrate. Shut off the flow through the pressure regulator and open the relief valve carefully. The time interval, if other than 30 minutes, shall be reported.

d. Report the volume of filtrate in cubic centimeters (to 0.1cm 3 ) as the API filtrate. Report at the start of the test the mud temperature. Save the filtrate for appropriate chemical testing if necessary.

e. Disassemble the cell, discard the mud, and use extreme care to save the filter paper with a minimum of disturbance to the cake. Rinse the filter cake on the paper with a gentle stream of water, or with diesel oil in the case of oil mud. Measure the thickness of the filter cake, and report the thickness in millimeters.

f. Describe the quality of the mud cake using simple technical words.

the quality of the mud cake using simple technical words. Fig.2-5 Low Pressure filter tester Example

Fig.2-5 Low Pressure filter tester

Example 4:

Using the following data obtained using an HTHP filter press, determine the spurt loss and API water loss.

Time(min)

1.0

Filtrate Volume(cm 3 )

6.5

7.5

14.2

Solution:

The spurt loss of the cell can be obtained by extrapolating to zero time using the two data points given:

14.25  6.5 6.5  1  2.07 cm 3 7.5  1
14.25
 6.5
6.5
1
2.07
cm
3
7.5
 1

However, since the standard API filter press has twice the cross-sectional area of the HTHP filter press, the corrected spurt loss is 4.14 cm 3 . The 30-min filtrate volume can be computed using Eq. 2-10.

V 30 = 2(V 7.5 - V sp ) + V sp = 2(14.2-2.07)+2.07 = 26.33 cm 3 Adjusting for the effect of filter press cross -sectional area, an API water loss of 52.66 cm 3 at the elevated temperature and pressure of the test can be obtained.

2. 4 Determination of Gas, Oil, and Solids Content (水、油与固相含量的测定)

Solids contained in drilling fluid include bentonite, weighting materials and drilled solids (drilled cuttings of formation rocks or formation detritus derived from sloughing or collapse). Weighting materials have higher density (usually>4.0g/cm 3 ) and are called high-density solids, and bentonite and drilled solids have lower density (usually<2.7g/cm 3 ) and are called low-density solids. Weighting materials and bentonite are useful solids and drilled solids are useless or harmful solids. 2.4.1 Gas Content A measure of the amount of gas or air entrained in a mud may be obtained by diluting the mud substantially, stirring to release the gas, weighing the gas-free mud, and then back-calculating the

density of the gas -free mud without dilution. For example, if

1

is the density of the gas-cut

mud,

2 the density after diluting 1 volume of mud with 1 volume of water and removing the

gas,

3

the density of the gas-free, undiluted mud, and

w

volume fraction of gas in the original mud, then:

1

(1

)

x

3

1

the density of water, and x is the

2-11

2

(1

x

)

3

 

1

w

2 x

Solving for x from the above equations:

3

x

2

 

2

1

w

2

may then be calculated from either of the first two equations.

2-12

2-13

2.4.2

Oil and Solids Content

2.4.2 Oil and Solids Content Fig.2-6 Retort for determining oil and water content of muds The

Fig.2-6 Retort for determining oil and water content of muds

The volume fractions of oil, water, and solids in a mud are determined in a retort such as that shown in Figure 2-6. It is important that any air or gas entrained on the mud be removed before retorting; otherwise, the

solids content will be in considerable error. Removal of gas by substantial dilution is undesirable because of the loss of accuracy involved, especially with low-solids muds. Gas may often be removed by adding

a defoamer such as aluminum stearate(硬脂酸铝), or

a high molecular weight alcohol, plus a thinner if necessary to break the gel. If, as indicated by the dilution test described above, this procedure fails to remove all the gas, a vacuum should be applied.

Portable hand vacuum pumps are available for use in the field. Retorting involves placement of a precise volume of mud in a steel container, and heating it in the retort until no more distillate collects in the graduated cylinder. The volume of oil and water are read in the graduated cylinder, and their sum s ubtracted from the volume of the mud sample to obtain the volume of solids. The method is rather inaccurate with low solids muds because the result depends on the difference between two large numbers. If the mud contains substantial amounts of salt, the volume occupied by the salt must be subtracted from the volume of solids. The volume of salt (as NaCl) in the mud may be estimated with sufficient accuracy by multiplying the grams of chloride per 100 cm 3 of filtrate (determined by titration) by 0.6 and by the volume fraction of water in the mud.

2.5 Bentonite Content of Mud

A rapid estimate of the amount of montmorillonite present in a mud or clay can be obtained by means of the methylene blue test. This test measures the amount of methylene blue dye adsorbed by the clays, w hich is a function of their cation exchange capacity. Since montmorillonite has a

much larger cation exchange capacity than other clay minerals, the test has come to be regarded as

a measure of the amount of montmorillonite present.

2.5.1 Methylene Blue Test and Cation Exchange Capacity Equipment and Regents:

a. Methylene blue solution: 3.20 g pure grade methylene blue

liter.

C

16

H

18

N SCl

3

3

H O

2

per

b. Hydrogen peroxide: 3 % solution.

c. Dilute sulfuric acid: approximately 5N (13.9 ml 36 N H 2 SO 4 diluted in 100 ml with deionized water).

d. 250 ml Erlenmeyer flask with rubber stopper.

e.

Serological pipettes: one 1 ml and one 5 ml.

f. Burette: 10 ml.

g. Graduated cylinder: 50 ml.

h. Hot plate.

i. Stirring rod.

j. Filter paper.

Procedure

a. Add 2 ml of mud (or suitable volume of mud that requires 2-10 ml of methylene blue reagent) to 10 ml of water in the 250

ml of methylene blue reagent) to 10 ml of water in the 250 ml Erlenmeyer flask.

ml Erlenmeyer flask. Add 15 ml of 3 %

hydrogen peroxide and 0.5 ml of dilute

sulfuric acid. Boil gently for 10 minutes. Dilute to about 50 ml with distilled water.

Fig. 2-7 Procedure of methylene blue test and determination of the end point

b. Add methylene blue solution (1 ml=0.01 milliequivalents) from the pipette to the flask. After each 0.5 ml of methylene blue is titrated into the flask, swirl the contents of the flask for about 30 seconds. While the solids are still suspended, remove one drop of liquid with a stirring rod and place the drop on the filter paper. The end point is reached when

the dye appears as a greenish - blue ring surrounding the dyed solids.

c. When the blue tint spreading from the spot is detected, shake the flask an additional

minute and place another drop on the filter paper. If the blue ring is again evident, the end point has been reached. If the ring does not appear or the ring appears temporarily and disappears soon, continue as before until a drop taken after shaking two minutes shows

the blue ring firmly evident (see Fig. 2-7).

d. Report the cation exchange capacity of the mud as the methylene blue

Fig.2-8
Fig.2-8

Srandard

sand sieve

API

capacity, calculated as follows:

Methylene blue capacity

No.of ml of methylene blue

No.of ml of mud

3

, cm /cm

3

2-14

2.5.2 Bentonite Content of Mud Some chemical addit ives such as CMC, polyacrylates, lignites and lignosulfonates added in mud for treatments may have methylene blue behavior. In order to eliminate the interference of these additives, a prior treatment with hydrogen peroxide is needed to conduct. If other m ethylene blue adsorptive materials are not present in significant amounts, the bentonite content of the mud can be estimated as follows:

Bentonite content of mud in kg/m 3 =14.25×methlylene blue capacity

2-15

2.6 The API Sand Test(含砂量)

The sand content is a measure of the amount of particles lager than 200 mesh present in a mud. Even though it is called a sand test, the test defines the size, not the composition, of the particles. The test is conveniently made in the apparatus shown in Fig.2 -8. The mud is first diluted by adding mud and water to the respective marks inscribed on the glass tube. The mixture is then

shaken and poured through the screen in the upper cylinder, and then washed with water till clean. The material remaining on the screen is then backwashed through the funnel into the glass tube and allowed to settle, and, finally, the gross volume is read from the graduations on the bottom of the tube.

2.7 Hydrogen Ion Concentration (pH 值的确定)

The significant influence of the hydrogen ion concentration on the properties of drilling fluids has long been recognized and has been the subject of numerous studies. Hydrogen ion concentration is more conveniently, expressed as pH, which is the logarithm of the reciprocal of the hydrogen ion concentration in gram mols per liter. Thus, in a neutral solution the hydrogen ion

(H + ) and the hydroxyl ion (

OH

) concentrations are equal, and each is equal to 10 -7 . A pH of 7 is

neutral. A decrease in pH below 7 shows an increase in acidity (h ydrogen ions), while an increase in pH above 7 shows an increase in alkalinity (hydroxyl ions). Each pH unit represents a ten-fold change in concentration. Two methods for the measurement of pH are in common use: (1) a colorimetric method(比色 法) using paper test strips impregnated with indicators, and (2) an electrometric method using a

glass electrode instrument. Colorimetric Method(比色法). Paper test strips impregnated with organic dyes which develop colors characteristic of the pH of the liquid with which th ey come in contact afford a simple and convenient method of pH measurement. The rolls of indicator paper are dispensed from a dispenser which has the reference comparison colors mounted on its sides. Test papers are available in both a wide -range type, which permits estimation of pH to 0.5 unit, and a narrow -range type, which permits estimation to 0.2 unit of pH. The test is made by placing a strip of the paper on the surface of the mud (or filtrate), allowing it to remain until the color has stabilized (us ually less than 30 seconds), and comparing the color of the paper with the color standards. High concentrations of salt in the sample may alter the color developed by the dyes and cause the estimate of pH to be unreliable. Glass Electrode pH Meter(玻璃电极 pH 计). When a thin membrane of glass separates two solutions of differing hydrogen-ion concentrations, an electrical potential difference develops that can be amplified and measured. The pH meter consists of: (1) a glass electrode_ made of a thin-walled bulb of special glass within which is sealed a suitable electrolyte and electrode; (2) the reference electrode, a saturated calomel cell; (3) means of amplifying the potential difference between the external liquid (mud) and the glass electrode; and (4) a meter r eading directly in pH units. Provision is made for calibrating with standard buffer solutions and for compensating for variations in temperature. A special glass electrode (less affected by sodium ions) should be used in measuring the pH of solutions containing high concentrations of sodium ions (high salinity or very high pH).

2.8 Filtrate Analysis(滤液分析)

Some chemical tests are made on mud filtrates to determine the presence of contaminants, such as salt or anhydrite, or to assist in the control of mud properties; for example, the test for

alkalinity in h igh p H muds. The same tests can be applied to make-up waters, which in some areas contain dissolved salts which materially affect mud treatment. The equipment generally used for

filtrate analysis includes automatic burette, reagent bottle, dropper bottler, casserole, graduated cylinder, graduated pipette, and glass stirring rod.

2.8.1 Alkalinity Determinations(碱度测定)

Because the pH scale is logarithmic , the alkalinity of a high pH mud can vary a considerable amount with no measurable change in pH. In highly alka line systems analysis of the mud filtrate to determine the alkalinity yields more significant results than pH measurement. The procedure for the alkalinity test P f is:

a.

Measure one or more cubic centimeters of fresh filtrate into a 125-ml Erlenmeyer flask or casserole.

b.

Add 2 to 3 drops of phenolphthalein indicator solution. If no color develops, P f is 0. If a pink color develops-

c.

Add 0.02 normal (N/50) sulfuric acid from an automatic burette or a pipette, stirring continuously, until the sample turns from pink to colorless. If the sample is so colored with chemicals that this end point is masked, the end point is then taken when the pH drops to 8.3 using the glass electrode pH meter. The number of cubic centimeters of 0.02

normal (N/50) sulfuric acid divided by the cubic centimeters of sample taken is called the "P" alkalinity of the filtrate (P f ).

d.

To the sample which has been titrated to the "P" end point, add 2 or 3 drops of methyl orange indicator solution. Add standard acid drop by drop from the pipette w hile stirring until the color of the solution changes from orange to pink. Record as "M," the total volume of acid, in cubic centimeters, used to reach the methyl orange end point, including that of the "P" end point. If the sample is so colored that the change in color is not evident, the end point is taken when the pH drops to 4.3, as measured with the glass electrode pH meter.

e.

Report the methyl orange alkalinity of the filtrate, M f , as the total cubic centimeters of 0.02 normal acid per cubic centimeter of filtrate required to reach methyl orange end point.

2.8.2

Lime Content Estimation(石灰含量测定)

Some knowledge of the amount of excess lime present is of considerable value as an aid in

controlling the properties of a lime- treated mud. An estimation of lime content can be made based on alka lin ity titrations of the filtrate and of the whole mud. The titration of the mud must be made rapidly to permit titration of calcium hydroxide and sodium hydroxide without interference from calcium carbonate. The procedure for estimating the lime content is:

a. Measure one cc of mud into a casserole and dilute to about 50 cc with distilled water. A veterinary syringe is satisfactory for measuring even very thick mud, while a pipette m ay be used for thinnner muds.

b. Add 2 to 3 drops of phenolphthalein indicator solution. A pink color develops.

c. Add 0.02 normal (N/50) sulfuric acid rapidly from a burette or pipette, stirring continuously, until the sample first turns from pink to the color of the mud. The number of cubic centimeters of 0.02 N acid divided by the cubic centimeters of sample taken is called the P alkalinity of the mud (P m ).

d.

Determine the P alkalinity of the filtrate (P f ) according to the method given in the preceding section.

e. Calculate the lime content as follows:

0.26 (P m -F w P f )=equivalent calcium hydroxide (lb/bbl)

Where:

P m = cc 0.02 N acid for P of mud P f = cc 0.02 N ac id for P of filtrate F w = volume fraction of water in mud

2-16

2.8.3 Salt Concentration (Chloride) Test The salt or chloride test is very significant in areas where salt can contaminate the drilling fluid. Salt tests are among the means of detecting these flows. When the chloride content exceeds

6,000 ppm, it may be necessary to alter the mud program. The test is made on a portion of the original filtrate, or on the sample from the alkalinity test to which a pinch of calcium carbonate has been added. The chloride content test procedure follows:

a. Measure a sample of any convenient volume, from one cc to 10 cc, into the casserole and dilute to about 50 cc with distilled water.

b. Add a few drops of phenolphthalein indicator. If a pink color develops, add sulfuric acid until it completely disappears. If phosphates have been added in large quantities, add 10 to 15 drops of calcium acetate solution.

c. Add four or five drops of potassium chromate indicator to give the sample a bright yellow

color.

d. Add standard silver nitrate solution a drop at a time, stirring continuously. The end point of the titration is reached when the sample first changes to orange or brick-red.

Calculate the chloride (Cl) content as follows:

Cl content in mg per liter or ppm

cc of silver nitrate

1,000

cc of sample

If in the standard solution, 1 cc=1 mg Cl, or 4.7910 g of AgNO 3 per liter (0.0282 N)

or

Cl content in mg per liter or ppm

ccof silver nitrate

10,000

ccof sample

If in the standard solution, 1 cc=10 mg Cl, or 47.910 g of AgNO 3 , per liter (0.282 N)

The above method of calculation assumes no change in density of the filtrate with increasing salt concentration. Therefore, the results are correctly expressed in mg per liter but not in ppm. To express the concentration in ppm or percent by weig ht, use the following:

mg per liter

ppm

percent by wt

density of sol., g per mg cc per liter

,(

10 000 density of sol., g per cc

2-17

2-18

In addition to common salt, which is sodium chloride, salt beds and brines often contain t he chlorides of calcium and magnesium. The testing method described determines the amount of "chloride ion" present. The result can be expressed in terms of sodium chloride, or salt, by

multiplying by 1.65.

2.8.4 Preservative Concentration(防腐剂含量)

Some knowledge of the amount of preservative present in a mud for the prevention of fermentation of starch is necessary. Because paraformaldehyde is frequently used alone and because it is the major constituent of many proprietary preservatives, a method of estimating the

formaldehyde content of the mud filtrate is given below.

a. Measure 3 cc of filtrate into a casserole or test tube. Add 2 drops of phenolphthalein indicator solution. If the sample remains colorless, it is acid, and 0.02 normal (N/50) sodium hydroxide solution should be added drop-by-drop with agitation until a faint pink color develops. Then add 0.02 normal (N/50) sulfuric acid drop-by-drop to discharge the color.

b. If the filtrate becomes colored with the first addition of phenolphthale in, add the sulfuric

acid dropwise until the color is just dispelled.

c. To the neutralized f iltrate add one c c of 4.0 percent sodium sulfite solution. A red color will develop.

d. After approximately 30 sec, titrate using a 10 cc pipette with a 0.02 normal (N/50) sulfuric acid until the sample is a very faint pink. Record the amount of acid in cubic centimeters.

e. Repeat the above procedure (3 and 4) using distilled water instead of mud filtrate.

f. Subtract the cubic centimeters of acid required for the blank determination (5) from the

cubic centimeters used for Step 4 and multiply by 0.07 to find the formaldehyde content in lb per bbl. Preservation test kits equipped only with dropper bottles are widely used for preservative content determination. If the test is carefully made, the resulting values will be in substantial agreement with those found by the above procedure. It should be noted that a sodium sulfite solution deteriorates readily and if older than 30 days should be replaced with fresh solution. The

solution is prepared by dissolving 4 g of sodium sulfite in l00 cc of distilled water.

2.8.5 Tests for Hardness and Calcium Concentration

By "hard water" we mean water containing dissolved calcium and magnesium salts. The

common evidence of har dness in water is the difficulty of producing a lather in it with soap. As is well understood, drilling clays have low "yields" when mixed in hard water. The harder the water, the more bentonite it takes to make a satisfactory gel mud. While in extreme cases it has been found economical to treat the water chemically before using it for mixing mud, this is not generally true. Frequently, however, where there is a choice of two or more sources of water for the rig, it may be desirable to make a simple test to select the softer of the two. All field men are familiar with the effects on the mud when anhydrite, calcium sulfate, or "gyppy" formations are drilled. Likewise, calcium salts are picked up in dril ling cement plugs and sometimes in penetrating sections of limy shale. Any extensive calcium contaminatio n results in abnormally high water loss and fast gel rate. Two methods of testing for calcium are given below. Calcium Sulfate. Some knowledge of the calcium sulfate content is necessary th e proper maintenance of gyp muds. Determination of the calcium sulfate content of a mud may be made by the Versenate test using the following procedure:

a. Add 5 cc of mud to 245 cc of distilled water. Stir the mixture for 15 minutes and then

filter through hardened filter paper. Discard the cloudy portion of filtrate.

b. Titrate l0 cc of the clear filtrate to the Versenate end point as described in Versenate Test for Hardness.

c. Titrate 1 cc of f iltrate of the original mud to the Versenate end point.

d. Report the calcium sulfate content in lb/bbl, calculated as follows:

Total calcium sulfate, lb/bbl= 2.38 V t Undissolved calcium sulfate, lb/bbl = 2.38 V t - 0.48 V f F w Where: V t = cc of Versenate solution to titrate 10 cc of the filtrate of the diluted mud V f = cc of Versenate solution to titrate 1 cc of filtrate of the original mud F w = Volume fraction of water in the mud

Estimation of Calcium by Oxalate. When c ontamination by calcium salts is suspected, the relative amount present can be estimated by a simple test, as follows:

a. Place from 2 to 4 cc of filtrate in a test tube or other convenient clean container.

b. Add about one cc of dilute ammonium oxalate solution.

c. The calcium present will be precipitated out of solution and will appear as a milky, w hile

precipitate in the sample. Since this test does not give the calcium content in parts per million, it is general practice to record the calcium content as "trace," "show," "light," and "heavy" calcium concentration. Versenate Test for Hardness:

a. To approximately 50 cc of distilled water in a titration dish add about 2 cc of Har dness Buffer Solution and 5 to 10 drops (0.25 cc to 0.50 cc) of Hardness Indicator Solution. If a red color develops, indicating hardness in the distilled water, add Hardness Titrating Solution (1 cc equivalent to 20 milliequlvalents per liter using 1 cc sample) dropwise until the water first turns to blue. Do not include this volume of titrating s olution in calculating hardness of the sample in Step 4.

b. Measure 1 or more cc of sample into the casserole. A pink to wine red color, depending upon the color of the sample, will develop if calcium or magnesium is present.

c. Add Hardness Titrating Solution, stirring continuously, until the sample first turns blue.

d. The total hardness is calculated as follows:

cc of titrating solution

20

cc of titrating cc of sample solution

cc of sample

1000

ppm of calcium and magnesium as CaCO

Mg)

milliequiv alents per liter of (Ca

Versenate Test for Calcium:

3

a. To approximately 50 cc of distilled water in a tit rat ing dish add about a pinch of CalVer I I. Then add 1 cc of Calcium Buffer Solution. If a wine red color develops indicating calcium in the distilled water, add hardness titrating solution, 1 cc equivalent to 20 ppm, using 1 cc sample, until a blue color appears. Do not include this volume of titrating solution in calculating calcium of the sample in Step 4.

b. Measure 1 cc of sample into the titrating dish. A wine red color will appear if calcium is present.

c.

Add hardness titrating solution until the water turns blue.

d. The calcium is determined as follows:

ccof titrating solution

20

ccof sample

milliequiv alents per liter of (Ca)

e. To determine Mg present subtract equivalents per liter of Ca obtained from equivalents per liter total hardness (Ca + Mg) determined by Versenate Test for Hardness above. Estimation of Sulfate by Barium Chloride. Acidified barium chloride solution can be used

to estimate the sulfate content in a manner similar to that in the use of ammonium oxalate solution for the estimation of calcium, thus:

a. Place from 2 to 4 cc of filtrate in a casserole, beaker, or test tube.

b. Add a few drops of barium chloride solution.

c. Any sulfates present will appear in the sample as a milky, white precipitate.

The terms "trace,' "show,' "light ," and "heavy" are to indicate the relative seriousness of the contamination. A more accurate determination of the amount of sulfate can be made in the field with a photo cell apparatus. All of the ions commonly encountered in water may be tested with the device.

The Photo Tester. In the photo tester a prefocused beam of light passes through a sample bottle containing the sample and the reagent and falls on a photoelectric cell. This generates a small electric current which can be measured by a microammeter. The current thus measured is referred to a calibration chart to show the amount of a given ion present.

2.9 Resistivity(电阻)

Control of the resistivity of a mud and mud filtration while drilling may be desirable to permit better evaluation of formation characteristics from electric logs. T he determination of resistivity is essentially the measurement of resistance to electrical current flow through known sample configuration. Measured resistance converted to resistivity by use of a cell constant. The constant is fixed by the configuration of the sample the cell and is determined by calibration with stand ard solutions of known resistivity. The resistivity is expressed in ohmmeters. Equipment. The measurement of electrical resistivity of the mud and mud filtrate requires:

a. A calibrated resistivity cell.

b. An instrument or apparatus for measuring the resistance of the sample in the cell.

c. A thermometer for measuring the sample temperature.

Any type of cell and instrumentation w hich is sufficiently accurate to permit determination of resistivity within 5 percent of the cor rect value may be used. If the instrument indicates the sample resistance is ohms, the cell constant must be known. The resistivity in ohmmeters is obtained by multiplying the resis tance in ohms , by the cell constant in square meters per meter. If the instrument is a type of direct-reading resistivity meter, the cell constant has been adjusted to a particular value or accounted for in the electrical circuit of the meter. Such an instrument measures

the sample resistance and converts it to resistivity so that the reading is taken directly as ohmmeters. For all instruments, the manufacturers' instructions for current source, calibration, measurement, and calculation should be followed. Procedure . Fill the clean, dry resistivity cell with freshly stirred mud or with filtrate. Be sure

that no air or gas is entrained in the sample. Connect the cell to the measuring instrument. Meas ure the resistance in ohms, and using the cell constant or calibration char t, convert to resistivity; or measure the resistivity directly with a direct-indicating resistivity meter. Measure the temperature of the sample to the nearest degree F. Report the mud resistivity R m or filtrate resistivity R mf in ohmmeters to the nearest 0.01 ohmmeter. Report the sample temperature in degrees F. Clean the resistivity cell. Scrub with a brush and detergent solution if necessary. Rinse the cell thoroughly with distilled water and allow it to dry.

2.10 Electrical Stability of Emulsions (乳状液的电稳定性)

The electrical stability test indicates the stability of emulsions of water in oil. Equipment. The emulsion tester consists of a reliable circuit using a source of variable ac current, or dc current in portable units, connected to strip electrodes. The voltage imposed across the electrodes can be increased until a predetermined amount of current flows. The measure of emulsion breakdown is indicated by current flow. Relative stability is indicated as the voltage at breakdown point. Procedure. Insert the probe (electrodes) into the drilling fluid to be tested. Choose the voltage range multiplier applicable. Increase the voltage across the electrode until the instrument indicates emulsion breakdown. Record the voltage reading as an electrical stability number. Report the temperature of the sample in degrees F.

2.11 Treatment of Make-up Water (配浆水的处理)

In areas where only hard water is available for mixing mud, the yield of the clay can be increased and the water loss decreased by removing the dissolved calcium and magnesium. Soda ash is added to form a precipitate of calcium carbonate while caustic soda will be required to precipitate magnesium as the hydroxide. The quantity of soda ash and caustic needed to soften the water can be estimated from the hardness found by the Versenate titration, as follows:

Lb Lb of of sodaash sodium hydroxide per bblof per water bblof 0.014 water   me/l 0.018 of Ca me/1 ion of mg

Where: me/l is the milliequivalent per liter Treatment with soda ash alone will not remove all of the hardness from a water containing a high concentration of bicarbonate. The alkalinity of such waters must be raised to allow complete removal of calcium by soda ash. The bicarbonate content of the water can be calculated from the alkalinity determined according to the procedure given in "Alkalinity Determin ation." The estimation of hydroxide, carbonate, and bicarbonate is made from these relations:

Let:

P = cc 0.02N H 2 SO 4 required for phenolphthalein end point M = total cc 0.02N H 2 SO 4 required for methyl orange end point Then when:

P = zero, the alkalinity is due to bicarbonate alone P = M, the alkalinity is due to hydroxide alone 2P > M, the alkalinity is due to a mixture of carbonate and hydroxide 2P < M, the alkalinity is due to a mixture of carbonate and bicarbonate

The results may be expressed as:

a. Total Alkalinity

M20 = milliequivalents of total alkalin ity per liter

b. Carbonate Alkalinity

(a) If hydroxide is present,

(M

(M

- P)

- P)

 

40 = milliequivalents of carbonate alkalinity per liter 1200 = parts per million of carbonate (CO 3 )

(b)

If hydroxide is absent,

P

40 = milliequivalents of carbonate alkalinity per liter

P

1200 = parts per million of carbonate (CO 3 )

c. Hydroxide Alkalinity -

- M)

d. Bicarbonate Alkalinity

(2P

(2P

M)

  

20 = milliequivalents of hydroxide alka linity per liter

340 = parts per million of hydroxide (OH)

(M - 2P)

(M - 2P)

20 = milliequivalents of bicarbonate alkalinity (HCO 3 ) per liter

1220 = parts per million

of bicarbonate (HCO 3 )

A simple treatment, adequate for most hard make-up waters, is to add enough caustic soda to raise the pH to 9 and then add soda ash equivalent to the total calc ium and caustic soda equivalent to the magnesium. The hydroxide, carbonate, and bicarbonate values determined as in the foregoing represent a proper type of water analysis. The application of these procedures to the usual mud filtrate is,

however, of

with other soluble components, such as treating

agents, do not permit quantitative determinations of carbonate and bicarbonate by simple titration.

doubtful validity becaus e reactions

2.12 Pilot Testing

Certain suggestions as to pilot testing procedures will be helpful as a guide in determining the appropriate treatment to condition a mud. For example, confusion can be avoided by recording the results of pilot tests in field units. An addition of one gram of material to a 350 cc sample of mud is equivalent to an addition of one pound of material per barrel of mud. Additions of liquids can be made as percent by volume and recorded as barrels of liquid per 100 bbl of original mud. It is important when making pilot tests to consider the order and manner in winch materials will be added under field conditions. Considerable variation in results can be obtained by first adding a material as a dry solid and then adding it in solution, or by adding a clay before a chemical thinner as compared to adding it afterward. The order of addition should always be indicated when recording pilot test results. It is convenient to have solutions with water of materials which are normally added through the chemical barrel. A caus tic -quebrac ho solution, for example, can be prepared by dissolving 35 g of caustic soda and 35 g of dry quebracho in a convenient quantity of water and then adding more

water to make 350 cc of solution. In a pilot test, 10 cc of this solution added to 350 cc of mud is equivalent to adding 1 lb of caustic soda and 1 lb of quebracho per barrel of mud, along with 3 percent by volume of water. Mixing of a pilot-test sample is also quite important. There is no simple method of duplicating closely the mixing which the mud receives in the course of circulation. Experience has indicated some very general rules when using a high-speed mixer, such as:

a. Stir 5 min when adding liquids or inert solids .

b. Stir 15 min when adding solids which need only to be dispersed.

c. Stir slowly for 30 min (or stir and allow to stand) when adding materials which undergo hydration or enter into chemical reactions which take place slowly.

d. Take care to avoid excessive stirring. High-speed shearing may alter the properties of a mud; consequently, the untreated mud should be stirred and tested in the same way as the treated samples.

Even though muds of the same type will perform in a somewhat similar manner, at no time will two field muds have exactly the same composition. Pilot testing is therefore frequently helpful in predicting the response of a field mud to a particular treatment or to a particular contamination. In many complex mud systems, however, pilot testing chemical additives without proper heat aging may give misleading values. It is most important to conduct a thorough mud check, evaluate the condition of the mud based on the values obtained, and add treating materials with the know ledge of exactly why each material is added.

Discussion

1. Discuss the relationships between drilling fluid properties and the drilling operation.

2. How does density affect hole stability and penetrate rate?

3. How does rheology affect the drilling operation?

4. How about the other properties, such as filtration properties, solid contents, pH value, etc.?

CHAPTER 3

CLAY MINERALOGY AND THE COLLOID

CHEMISTRY OF DRILLING FLUIDS

Anyone concerned with drilling fluids technology should have a good basic knowledge of clay mineralogy(粘土矿物学), as clay provides the colloidal base of nearly all aqueous muds(水 基泥浆), and is also used in oil-based drilling fluids(油基泥浆) . Drill cuttings from

argillaceous formations become incorporated in the drilling fluid, and profoundly change its properties. The stability of the borehole depends to a large extent on interactions between the drilling fluid and exposed shale formations. Interactions between the mud filtrate(滤液) and the clays present in producing horizons(生产层) may restrict productivity of the w ell if the wrong

type of mud is used. All of these point out the need for the knowledge of clay mineralogy. The drilling fluid technologist should have a basic knowledge of colloid chemistry(胶体化 学) as well as clay mineralogy, because clays form colloidal su spensions(胶体悬浮液) in water, and also because a number of organic colloids(有机胶体) are used in drilling muds.

In this chapter it will summarize briefly those aspects of clay mineralogy and colloid chemistry which affect drilling fluid technology.

3.1 Characte ristics of Colloidal Systems (胶体特性)

Colloids are not, as is sometimes supposed, a specific kind of matter. They are particles whose size falls roughly between that of the smallest partic les that can be seen with an optical microscope and that of true molecules, but they may be of any substance. Actually, it is more correct to speak of colloidal systems, since the interactions between two phases of matter is an essential part of colloidal behavior. Colloidal systems may consist of solids dispersed in liquids (e.g., clay suspensions 粘土悬浮液 ), liquid droplets dispersed in liquids (e.g., emulsions-乳状液 ), or solids dispersed in gases (e.g., smoke-尘雾 ). In this chapter, we shall only

be concerned with solids dispersed in water. One characteristic of aqueous colloidal s ystems is that the particles are so small that they are kept in suspension indefinitely by bombardment of water molecules, a phenomenon known as the Brownian movement.(布朗运动). The erratic movements of the particles can be seen by light

reflected off them when they are viewed against a dark background in the ultramicroscope. Another characteristic of colloidal systems is that the particles are so small that properties like viscosity and sedimentation velocity are controlled by surface phenomena(表面现象). Surface phenomena occur because molecules in the surface layer are not in electrostatic balance(电荷平 衡); i.e., they have similar molecules on one side and dissimilar molecules on the other, whereas

molecules in the interior of a phase have similar molecules on all sides. Therefore, the su rface carries an electrostatic charge(静电荷), the size and sign of which depends on the coordination of the atoms(原子配位) on both sides of the interface. Some substances, notably clay minerals, carry an unusually high surface potential(表面能) because of certain deficiencies in their atomic

structure, which will be explained later. The greater the degree of subdivision(分散度) of a solid, the greater will be its surface area per unit weight, and therefore the greater will be the influence of the surface phenomena. For example, a cube with sides one mm long would have a total surface area of 6 mm 2 . If it were

subdivided into cubes with one micron sides (1 micron =

1

10

3 mm) there would be 10 9 cubes,

each with a surface area of

6

10

6

mm 2 , and the total surface area would be

610 610

6

3

Subdivided again into milli-micron cubes, the total surface area would be

mm 2 ,

mm 2 .

or

6

square meters. The ratio of surface area per unit weight of particles is c alled the specific surface(比表面). Thus if a 1 cm 3 cube were divided into micron sized cubes, the specific surface would be

6  10 6 / 2.7  2.7. Figure 3-1
6
 10
6 / 2.7
2.7.
Figure
3-1

2.2

10 mm

shows

6

2

/ g

2

2.2m / g

, assuming the specific gravity of the cube to be

m / g , assuming the specific gravity of the cube to be Fig. 3-1 Specific

Fig. 3-1

Specific surface of cubes. Assuming specific gravity of 2.7

surface

versus cube size. To put the values in perspective, the size of various particles, expressed in equivalent spherical radii

(esr-等效球形半径), are shown at the top.

specific

The esr

of

a particle is

the radius

of

a

sphere

that

would

have

the

same

sedimentation rate as the particle. The

esr

may be determined

by

applying

Stokes'

Law

(see

Chapter

3)

to

the

measured

sedimentation rate.

 

The division between colloids and silt; shown in Figure 3-1, is arbitrary and indefinite, because colloidal activity depends (a) on specific surface, which varies with particle shape, and (b) on surface potential, which varies with atomic

structure. A large proportion of the solids in drilling muds fall in the silt size range. These particles are

derived either from natural silts picked up from the formation, from larger particles comminuted by the action of the bit, or from barite added to raise the density. Particles in this size fraction are commonly called the inert solids( 惰性材料) , but the term is relative, and when pres ent in high

enough concentrations, the inert solids exercise a considerable influenc e on the viscous properties of the mud. Colloids, on the other hand, usually constitute a small proportion of the total solids, but exercise a relatively high influence on mud properties because of their high degree of activity. They may be divided in two classes: (a) clay minerals, and (b) organic colloids, such as starch(淀 粉), the carboxycelluloses(羧基纤维素), and the polyacrylamide derivatives((聚丙烯酰胺衍 生物). These substances have macro-molecules(高分子), or are long-chain polymers(长链聚合 物), whose size gives them colloidal properties.

3.2 Clay Mineralogy(粘土矿物学)

3.2.1 Introduction

The group of minerals classed as clays play a central role in many areas of drilling fluid technology. The clay group can be described chemically as aluminium silicates(硅铝酸盐).

Since the elements that constitute the clays account for over 80% of the mass of the earth (aluminium 8.1%, silicon 27.7% and oxygen 46.6%) it can be readily realised that every stage of drilling a hole brings contact with the clays(粘土).

The most common formations that are drilled are clays and shales, where the type and quantity of c lay minerals present is one of the most important features that determine the chemical and mechanical properties of the rock(岩石的化学和力学性质). The selection of the drilling fluid is often related to the reactions between the fluid and the rock, as these can inf luence the stability of the bore hole. Thus, an understanding of clay chemistry is important in the selection of a drilling fluid system and bore hole stability(井壁稳定性).

Clays are often used to derive the viscous flow properties of the fluids. Clays, such as bentonite(膨润土) and attapulgite(绿坡缕石), are added purposely and formation clays are entrained in the circulating fluid. A large range of chemicals, including those described as "mud

conditioning chemicals", are added to control the viscous properties. A full understanding of the chemistry of those chemicals and the clays will enable the engineer to control the fluid properties more effectively. Most reservoir sandstones(砂岩) contain some clay minerals. These may react with the fluids that contact them in suc h a way as to completely block the formation. Again the structures and reactions of clays are important in the design of fluids that may be in contact with the production zone.

3.2.2 Basic features(基本特征)

There are a number of features of the clay minerals that distinguish them as a group. The most important one is the chemical analysis which shows them to be composed essentially of silica(二

氧化硅), alumina(氧化铝), water and frequently with appreciable quantities of iron(铁) and magnesium(镁) and lesser quantities of sodium(钠) and potassium. Other properties, such as

fine size, large surface area and chemical reactivity of the surface, are related to the structural details. 3.2.2.1 Fundamental building units(基本构造单元) There are two simple building units from which the different clay minerals are constructed. Octahedral layer(八面体层) .This unit consists of two sheets of closely packed oxygens or hydroxyls in which aluminium, iron or magnesium ions(铝离子和镁离子) are embedded in

octahedrat coordination. When aluminium is present , only two thirds of the possible positions are filled to balance the structure, which is the gibbsite structure. Al (OH) 3 . When magnesium is present, all the positions are filled and the structure is brucite, Mg (OH) 2 . Often in clays, this layer

contains more than one metal ion. See

Figure 3-2.
Figure 3-2.
Fig. 3-2 Diagrammatic sketch of (a) single octahedral unit, and (b) the sheet structure of

Fig. 3-2 Diagrammatic sketch of (a) single octahedral unit, and (b) the sheet structure of the octahedral units

Tetrahedral layer(四面体层). In each tetrahedral unit(四面体单元), a silicon atom(硅 原子 ) is located in the centre of a tetrahedron, equidistant from four oxygen atoms, or hydroxyls,

if needed to balance the structure. The silica(二氧化硅) tetrahedral groups are arranged to form a hexagonal network, which is

repeated infinitely to form a sheet of composition, Si 4 O 6 (OH) 4 ,

viewed from above in

3-3. The sheet is

See Figure

Figure 3
Figure 3

-4 to show the hexagonal network with a "hole " in the centre.

the hexagonal network with a "hole " in the centre. Fig. 3-3 Diagrammatic sketch of (a)

Fig. 3-3 Diagrammatic sketch of (a) a single silica tetrahedron, and (b) the sheet structure of silica tetrahedrons

and (b) the sheet structure of silica tetrahedrons Fig. 3-4 The silica chain viewed from above

Fig. 3-4 The silica chain viewed from above arranged in a hexagonal network

It is the different combinations of these units and modification of the basic structure that give rise to the range of clay minerals with different properties. The two units are the alumina octahedral sheet and the silica tetrahedral sheet. 3. 2.2.1 Structures of clay minerals(粘土矿物的结构) The fundamental units of tetrahedral sheets and octahedral sheets can combine with the hydroxyl group of the tetrahedral layer contributing to the octahedral layer. Different combinations and chemical modification have given rise to over 26 different clay mlnerals(粘土矿物).

The clay minerals are built up by different ratios of silica layer to octahedral layer. The largest group is the 2:1 layer, there are also 2:1:1 minerals and 1:1 minerals. The most important clay

minerals of interest to the drilling fluid engineer are kaolin, mica, illite, montmorillonite, sepiolite, attapulgite and chlorite.

Examples of these structures are summarised in

Table 3-1
Table 3-1

and in

Figure 3-5.
Figure 3-5.
structures are summarised in Table 3-1 and in Figure 3-5. Fig.3-5 Schematic representation of the structure

Fig.3-5 Schematic representation of the structure of the principal clay minerals

Before the structures of the clay minerals can be discussed in any detail, the two mec hanisms by which electrical charges(带电) may be developed on the clay surfaces, must be described. 3.2.3 Charges on clay surfaces(粘土表面的电荷) Charges on clay surfaces arise from two mechanisms. One is related to the structure of the clay and is a characteristic of the particular mineral. The other arises from the broken edges. 3.2.3.1 Isomorphous substitution(同晶取代) The idealised combinations of tetrahedrat and octahedral sheets give a structure in which the charges are balanced. However, if a metal ion is replaced by an ion of lower charge valency, a negative charge is created. For example, in the tetrahedral layer(四面体层) , silica may be

replaced by iron, or in the octahedral layer aluminium may be replaced by magnesium . The negative charge on the clay lattice is neutralised by the adsorption of a cation(吸附阳离子). This gives rise to the important property of the clays known as cation exchange capacity(CEC,阳离子 交换容量 ), because the ions of one type may be exchanged with ions of the same or different type.

The cation exchange capacity arising from substitutions within the lattice structure does not vary with pH. It is an important characteristic of the clays and varies from mineral to mineral, as shown

in Table 3-1.

Table 3-1

Summary of Structure and Properties of the most common clay minerals

Properly

Kaolin

Mica

Mint

Attap *

Chlorite

Layer Type

1:1

2:1

2:1

2:1

2:1:1

Crystal Structure

Sheet

Sheet

Sheet

Sheet

Sheet

Particle Shape

Hexagonal plate

extensive plates

flake

needle

plate

Particle Size Microns

5-0.5

Large sheets to 0.5

2-0.1

1-0.1

5-0.1

Surface Area BET-N 2 -M 2 /g BET-H 2 O- M 2 /g

15-25

50-110

30-80

200

140

200-800

Cation Exchange

3-15

10-40

80-150

15-25

10-40

Capacity meq/100g

Viscosity in Water

Low

Low

High

High

Low

Effect of Salts

Flocculates

Flocculates

Flocculates

Little or none

Flocculates

mont=montmoriionite ,

* attap=attapulgite

This property is often used to characterise clays, shales and drilling fluid and is determined by measurement of the adsorption of a cationic dye, methylene blue(亚甲基蓝). The result is quoted

as the milli-equivalents of dye adsorbed per l00g of dry clay. The pattern of isomorphous substitution varies in the different minerals in the following aspects:

a)

tetrahedral or octahedral substitution

b)

extent of substitution

c)

the nature of the exchanged cations, i.e. Na, K or Ca

The replaceability of cations depends on a number of factors such as:-

- effect of concentration

- population of exchange sites

- nature of anion

- nature of cation

-

nature of clay miner al

This large number of variables creates a complex system to analyse. It has been shown that different ions have different attractive forces for the exchange sites. The relative replacing power of cations is generally Li + <Na + <K + <Mg ++ <Ca ++ <H + . Thus at equal concentrations, calcium will displace more sodium than sodium will displace calcium. If the concentration of the replacing cation is increased , then the exchanging power of that cation is also increased. For example, high concentrations of potassium can replace calcium. Als o, in some minerals such as mica, potassium is particularly strongly adsorbed and net easily replaced, except by hydrogen(氢).

The potassium can be leached out by acid. This is related to particular properties of the clay mineral which will be discussed later. 3.2.3.2 Broken edge charges(破损边缘的电荷) When a clay sheet is broken, the exposed surface will create unbalanced groups of charges on the surface. Some of the newly exposed groups have the structure of silica, a weak acid. and some have the structure of alumina or magnesia, a weak base. Therefore, the charge on the edge will

vary according to the pH of the solution, as shown in

Figure 3-6.
Figure 3-6.
Fig. 3-6 pH dependent charges on the broken edges of Clay crystals Thus at low

Fig. 3-6 pH dependent charges on the broken edges of Clay crystals

Thus at low pH values, the broken edges are more positive and at high pH the edges are more negative. One of the reasons for the pH values of drilling fluid to be kept on the alkaline side is to ensure that the clay particles are only negatively charged so that electrostatic interactions are kept at a minimum. Chemical treatment of drilling fluids is often aimed at a reaction with the groups on the broken edges. Since the edge surface is created by grinding or breaking down the clays, chemical treatment costs can be minimised by ensuring that the formation clays are removed as cuttings, rather than broken down at the bit into finer sized particles.

3.2.4 Clay mineral groups(粘土矿物组) There are published lists of over 400 mineral and rock names to describe clay minerals. We will restrict our attention only to a few minerals that are most common and most applicable to drilling fluid technology.

3.2.4.1 Kaolin(高岭土)

to drilling fluid technology. 3.2.4.1 Kaolin (高岭土) Fig.3-7 Diagrammatic sketch of structure of Kaolin Kaolin is

Fig.3-7 Diagrammatic sketch of structure of Kaolin

Kaolin is composed of a single tetrahedral sheet and a single dioctahedral alumina sheet, combined so that the tips of the oxygen atoms of the silica tetrahedra and the oxygen and hydroxyl layer of the octahedral layer, form one layer. A diagrammatic sketch of the 1:1 structure is given in

Figures 3-5 and 3-7

.

The charges within the structure are balanced and there are very few lattice substitutions. Very strong hydrogen bonding(氢键结合) exists between successive layers of the basic building units,

so that no swelling occurs, and the natural crystals consist of about 100 unit layers stacked one upon the other. The clay platelets are charged mainly due to the broken edge charges, which are sensitive to the pH of the suspension. The slurries are low viscosity because of the non-swelling structure of the clay.

 

The origin of the clay is often hydro-thermal alteration of feldspars, or from volcanic ash,

particularly under acid conditions Extensive deposits of pure clay are found in Georgia. US.A. and Cornwall. The characteristics of fine particle size , whiteness and low viscosity are exploited in

various industries, such as paper making and ceramics.

 

The clay is extensively found in shales and marine deposits. There is a tendency towards alteration to illite and chlorite at greater depth (age). Kaolin can be found in sandstone reservoirs in a diagenetic form, known as Dickite. 3.2.4.2 Micas(云母)

form, known as Dickite. 3.2.4.2 Micas (云母) Fig.3-8 Diagrammatic sketch of structure of Muscovite Micas

Fig.3-8 Diagrammatic sketch of structure of Muscovite

Micas are a 2:1 lattice type mineral, where two silica units sandwich an octahedrat layer, as

shown in

The two important features of micas are that the ion replacement is mainly in the tetrahedral layer, where silicon is replaced by aluminium or iron, and that the charge deficiency is balanced by potassium ions. In well crystallised micas, about one in four of the silicon atoms are replaced by aluminium. The role of potassium in the mica structure will be discussed in some detail because it is fundamental to an understanding of borehole stabilisation using potassium chloride brine. The main characteristics of a cation will be the number of charges they carry and the diameter of the ions. It will be seen that the smaller the s phere and the greater the number of charges, so the charge density will be higher.

Figures 3-5 and

3-9.

A high charge density will, in turn, attract polar water molecules more strongly.

Table 3-
Table 3-

2 lists

the diameters of common cations in the dehydrated and hydrated state.

Table 3-2

Ionic radii of ions before and after hydration

 

Aton

Dehydrated lon Diameter

 

Hydrated lon Diame

ter

 

A(埃)

 

A(埃

Na-Sodium

1.90

5.5-11.2

 

K-Potassium

2.66

4.64-7.6

Cs-Cesium

3.34

4.6-7.2

Mg-Magnesium

1.30

21.6

Ca-Calcium

1.90

19.0

A range is given because different techniques for measuring the ion diameter give rise to different values. It can be seen that the potassium ion has a small diameter and, as a consequence,

can fit neatly into the hexagonal holes in the silica layer and very effect ively neutralise the charge deficiency in that layer. Thus successive sheets are strongly bound together and a non-expanding structure is produced. Muscovite mica(白云母 ) is dioctahedral, i.e. only two thirds of the possible octahedral

positions are occupied.

chemical composition is K 2 O, 11.8%, SiO 2 , 45%, Al 2 O 3 , 38.5%, H 2 O, 4.5%. The biotite micas(

云母) are trioctahedral with the octahedral positions populated mostly by Mg 2+ , Fe 2+ and/or Fe 3+ .

It is important that in the well crystallised micas, no imperfections in the regularity of stacking

occur. The mica used for lost circulation material is of this type. The illite(伊砾石) clay minerals differ from the well crystallised micas in several possible

ways. The micas found in sedimentary shale sections would normally be classed as illite. There is less substitution of Al 3+ for Si 4+ and the net unbalance charge deficiency is reduced from 2 per unit cell to about 1.3 per unit cell. The potassium ions between the unit layers may be partially replaced by other cations, possibly Ca 2+ , Mg 2+ or H + . Thus, the illite or mica may react with potassium ions and be stabilised to some extent. The smectites often degrade to micas or illites through reaction with potassium ions. Mica or illite concentrations tend to increase with age and depth.

The structural formula is (OH) 4 K 2 (Si 6 Al 2 )Al 4 O 2 O,

and the theoretical

Fig.3-9 Diagrammatic sketch of the structure of Montmorillonite-Bentonite 3.2.4.3 Montmorillonite (蒙脱石)

Fig.3-9 Diagrammatic sketch of the structure of Montmorillonite-Bentonite

3.2.4.3 Montmorillonite(蒙脱石) Montmorillonite is the major clay mineral in "bentonite(膨润土 )", or "fresh water gel", and is

the most common mineral in a group of minerals called the smectites. A diagram of the structure is

given in

The essential feature that gives rise to the expandable structure is that the ionic substitutions are mainly in the octahedral layer. Thus, the charge is in the centre of the layer, so that the cations that are associated with the mineral to balance the ionic charge are unable to approach the negative charge sites close enough to completely lose the ionic character of the cation or the mineral surface. This residual ionic character provides the attractive force for the adsorption of polar molecules, such as water, between the unit sheets. The unique properties of montmorillonite are due to the very large surface area available when

the clay expands and hydrates fully to just single sheets.

3 gives the surface areas for

kaolin, illite and montmorillonite determined by adsorption of a non-polar molecule, nitrogen, and polar water molecules. It will be seen that only montmorillonite has the greater available area to the polar adsorbent. The full potential area is not available in these experiments, as the theoretical surface ar ea of montmorillonite on dispersion to nearly unit cell dimensions, is 800 M 2 /g.

Figures 3-5 and 3-9.

Table 3-
Table 3-

Table 3-3 Surface areas of clay samples determined by nitrogen and water vapour adsorption

Sample

Surface Area M 2 /g

Water Area

Nitrogen

Water

Nitrogen Area

Na Bentonite

38

203 + /250

5.3/6.6

Kaokinite

16

12 + /12

0.8

Illite

56

52 + /82

0.9/1.5

The swelling behaviour is most dependent on the type of cation in the exchangeable sites. This

will be discussed in terms of sodium and calcium, since these are the most common soluble ions.

A monovalent cation(单价阳离子), such as sodium, can associate with a charge deficient area

such that dispersion in water will create separated sheets.

A divalent cation(二价阳离子), such as calcium, cannot effectively associate with two negative

charge centres on one sheet, and thus must bind two sheets together. Contact with water can cause swelling and mechanical dispersion may separate a sheet, but the ulimate surface area available, and the volume of closely associated water, will be considerably lower than with the sodium

system. These different hydration patterns are illustrated in

Figures 3-10 and 3-11.

hydration patterns are illustrated in Figures 3-10 and 3-11. Fig. 3-10 Hydration of Calcium Montmorillonite Fig.

Fig. 3-10 Hydration of Calcium Montmorillonite

and 3-11. Fig. 3-10 Hydration of Calcium Montmorillonite Fig. 3-11 Hydration of Sodium Montmorillonite Natural

Fig. 3-11 Hydration of Sodium Montmorillonite

Natural bentonite occurs as the calcium form. The deposit in Wyoming is fairly unique in that

it is predominantly in the sodium form and thus hydrates and expands more fully. This clay is

preferred as a drilling mud additive because the desired viscosity is obtained at low concentrations. The calcium clays are often chemically treated with sodium carbonate to partially convert them to

the sodium form. Expandable montmorillonite can exist in substantial quantities in shales as the result of volcanic ash falling into a marine environment. The shales show the expected reaction to water in that the clay expands, and the high surface area gives a plastic, sticky cutting when being drilled. The clays are often termed "Gumbo" clays.

3.2.4.4 Sepiolite (海泡石)and Attapulgite(绿坡缕石)

(海泡石) and Attapulgite (绿坡缕石) Fig. 3-12 Schematic structure of Sepiolite and Attapulgite

Fig. 3-12 Schematic structure of Sepiolite and Attapulgite

The clay minerals, sepiolite and attapulgite, are used to viscosify salt water based drilling

fluids and are similar in structure. A diagram of the structures is given in

Attapulgite consists of double silica chains running parallel to the long axis, The chains form a network of strips which are joined together along the edges . The upper and lower parts of each chain are held together by aluminium, and/or magnesium, in octahedral coordination. The overall structure resembles a channelled wall where every second brick is missing. Diagrammatic

In sepiolite the chains are

representations of attapulgite and sepiolite are given in formed from two silica chains to give wider channels.

Figure 3-12.

Figure3-12.

Attapulgite derives three unusual characteristics from its unique structure. First, because the structure consists of three-dimensional chains it cannot swell like clays such as montmorillonite which have a sheet structure. Second, there is a cleavage plane along the long axis, parallel to the silica chains, so that the mineral crystals have a needle-like shape, typically 1 micron long and

0.01 micron wide. Third, the mineral has a high

capacity for water, where some is held

loosely onto the surface and some is bond strongly in the channels and is referred to as "zeolitic(沸 石)" water.

The clays have a large surface area and thus are effective viscosifying agents. Flocculation by salt water with subsequent reaggregation, will not occur with the needle shaped particles. The

sorbtive
sorbtive

needle shaped particles do not have the right shape to form an impermeable filter cake. Fluid loss control has to be achieved by the addition of other products and often small quantities of prehydrated bentonite are added. 3.2.4.5 Chlorite(绿泥石)

bentonite are added. 3.2.4.5 Chlorite (绿泥石) Fig.3-13 Diagrammatic sketch of the structure of Chlorite

Fig.3-13 Diagrammatic sketch of the structure of Chlorite

The chlorite structure consists of alternate mica-type/brucite(氢氧镁石)-type layers, where

the charge deficiencies in the mica layer are balanced by what is , in effect, a polymeric cation. The

3-13. The bonding between layer s is strong, and similar to that

found in kaolinite, thus the clay is a low viscosity type. Chlorite tends to be associated with older sediments, so that kaolin and smectites tend to be replaced by chlorite and illites.

general structure is given in

Figure
Figure

3.3 The Colloidal Chemistry of Clay Minerals(粘土胶体化学)

3.3.1 Ion Exchange(离子交换) As already mentioned, cations are adsorbed on the basal surfaces of clay crystals to compensate for atomic substitutions in crystal structure. Cations and anions are also held at the crystal edges , because the interruption of the crystal structure along the c axis results in broken valence bonds. In aqueous suspension, both sets of ions may exchange with ions in the bulk solution(基液). The exchange reaction(交换反应) is governed primarily by the relative concentration o f the

different species of ions in each phase, as expressed by the law of mass action. For example, for two species of monovalent(单价) ions, the equation may be written:

[A] c /[B] c =K[A] s /[B] s

Where [A] s and [B] s are the molecular concentrations of the two sp ecies of ions in the solution, and [A] c and [B] c are those on the clay. K is the ion exchange equilibrium constant(交换平衡常 数) , e.g., when K is greater than unity, A is preferentially adsorbed. When two ions of different valencies are present, the one with the higher valence is generally adsorbed preferentially. The order of preference usually is: H + > Ba ++ > Sr ++ > Ca ++ > Cs + > Rb + > K + > Na + > Li + , but this series does not strictly apply to all clay minerals: there may be variations. Note that hydrogen is strongly adsorbed, and therefore pH has a strong influence on the base exchange reaction. The total amount of cations adsorbed, expressed in milliequivalents per hundred grams of dry clay, is called the cation exchange capacity (CEC 阳离子交换容量). The CEC of a clay and the

species of cations in the exchange positions are a good indication of the colloidal activity of the clay. A clay, such as montmorillonite that has a high cation exchange capacity, swells greatly and forms viscous suspens ions at low concentrations of clay, particularly when sodium is in the exchange positions. In contrast, kaolinite is relatively inert, regardless of the species of exchange cations. The CEC and the species of exchange cations may be determined in laborator y by leaching the clay with excess of a suitable salt, such as ammonium acetate(醋酸铵), which displaces both the

adsorbed cations and those in the interstitial water. Then, another sample is leached with distilled water, which displaces only the ions in the interstitial water. Both filtrates are analyzed for the common exchange cations : the difference between the ionic content of the acetate and water leachates(沥出液) gives the meq of each species adsorbed on the clay, and the total meq of all

species of cations gives the CEC. A field test for the approximate determination of the CEC (but not the species of cations)

based on the adsorption of methylene blue is given

in Chapter 2.

3.3.2 Clay Swelling Mechanisms(粘土膨胀机理)

2 . 3.3.2 Clay Swelling Mechanisms (粘土膨胀机理) Fig.3-14 Diagrammatic representation of a 3 layer expanding

Fig.3-14 Diagrammatic representation of a 3 layer expanding clay lattice

All classes of clay minerals adsorb water, but smecitites take up much larger volumes than do

other classes, because of their expanding lattice. For this reason, most of the studies on clay swelling have been made with smectites, particularly with montmorillonite. Two swelling mechanisms are recognized: crystalline and osmotic. Crystalline swelling(晶体 膨胀) (sometimes called surface hydration- 表面水化 ), results from the adsorption of

mono-molecular layers of water on the basal surfaces-on both the external, and in the case of

expanding latticed clays, the inter-layer surfaces (

on the surface by hydrogen bonding to the hexagonal network of oxygen atoms, as shown in Fig.3-15. Consequently, the water molecules are also in hexagonal coordination. The next layer is similarly coordinated and bonded to the first, and so on with succeeding layers. The strength of the bonds decreases with distance from the surface, but structured water is believed to

persist to distances of 75-100

The first layer of water is held

see Fig.
see Fig.

3-14).

of 75-100 The first layer of water is held see Fig. 3-14). Fig.3-15 Crystalline swelling A

Fig.3-15 Crystalline swelling

water is held see Fig. 3-14). Fig.3-15 Crystalline swelling A from an external surface. The structured

A from an external surface.

The structured nature of the water gives it quasi-crystalline

structured nature of the water gives it quasi-crystalline 10 A of the surface has a specific

10 A of the surface has a specific

properties. Thus, water within

volume about 3% less than that of free water(compared with the specific volume of ice, which is 8% greater than that of free water.) The structured water also has a viscosity greater than that of free water. The exchangeable cations influence the crystalline water in

two ways. First, many of the cations are themselves hydrated i.e., they have shells of water molecules (exceptions are NH 4 + , K + and Na + ). Second, they bond to the crystal surface in competition with the water molecules, and thus tend to disrupt the water structure. Exceptions are Na + and Li + , which are lightly bonded and tend to diffuse away. Osmotic swelling(渗透膨胀) occurs because the concentration of cations between the layers

is greater than that in the bulk solution. Consequently, water is drawn between the layers, thereby increasing the c-spacing and permitting the development of the diffuse double layers that are discussed in the next section. Although no semi-permeable membrane is involved, the mechanism is essentially osmotic, because it is governed by a difference in electrolyte concentration. Osmotic swelling cause much larger increases in bulk volume than does crystalline swelling. For example, sodium montmorillonite adsorbs about 0.5 g water per g of dry clay, doubling the volume, in the crystalline swelling region, but about 10g water per g dry clay, increasing the volume twenty fold, in the osmotic region. On the other hand, the repulsive forces between the layers are much less in the osmotic region than in the crystalline region.

3.3.3 The Electrostatic Double Layer(扩散双电层) At the beginning of this chapter, we said that particles in colloidal suspension carried a surface charge. This charge attracts ions of the opposite sign, which are called counter ions(反离子 , and the combination is called electrostatic double layer( 双电层) . Some counter ions are not tightly held to the surface and tend to drift away, forming a diffuse ionic atmosphere(扩散离子氛)

around the particle. In addition to attracting ions of the opposite sign, the surface charge repels those of the same sign. The net result is a distribution of positive and negative ions, as shown

schematically in

and the exchangeable cations act as counter ions. The distribution of ions in the double layer results in a potential grading from a maximum at the clay surface to zero in the bulk solution, as

Fig.
Fig.

3-16. In the case of clays, the surface charge is negative, as we have seen,

shown in

Fig.
Fig.

3-17.

shown in Fig. 3-17. Fig.3-16 Diagrammatic representation of the electrical double layer Fig. 3-17 Diagram illustrating

Fig.3-16 Diagrammatic representation of the electrical double layer

Diagrammatic representation of the electrical double layer Fig. 3-17 Diagram illustrating the zeta potential The layer

Fig. 3-17 Diagram illustrating the zeta potential

The layer of cations next to the surface of the particle, known as the Stern layer, is bound to and moves with the particle, whereas the diffuse ions are independently mobile. Thus, if a clay suspension is placed in a cataphoretic cell(阳离子电泳池), the particle plus the Stern layer moves to the cathode(阴极). The potential difference from the Stern layer to the bulk of the solution is known as the zeta potential(电动电位-ξ 电位) , and is a major factor controlling the

behavior of the particle. The zeta potential is maximum, and the mobile layer(移动层) is most diffuse when the bulk

solution is pure water. Addition of electrolytes(电解液) to the suspension compresses the diffuse layer(扩散层), and reduces the zeta potential. The zeta potential decreases greatly with increase

in valenc e of the added cations, especially if low valence ions are replaced by high valence ones through base exchange, the ratio being approximately 1 to 10 to 500 for monovalent, divalent, and trivalent cations, respectively. The zeta potential is also reduced b y the adsorption of certain long-chain organic cations. In some cases, it is possible to neutralize and reverse the zeta potential. The potential difference between the surface of the particle and the bulk solution is known as the Nernst potential(热力学电位). This potential is constant, and independent of the electrolytes in solution.

3.3.4 Particles Association Clays play a significant role in drilling fluids , particularly the water based ones. They may be added intentionally to control the viscous flow properties and to provide the colloidal properties required for fluid loss control. In most cases there is a rapid build up in the circulating fluid of clays from the formation. The flow properties and fluid loss control are both modified by chemical treatment, either added intentionally or as a consequence of drilling throug h water soluble "formations", such as cement, anhydrite salt or magnesium salts. 3.3.4.1 Particle associations(粒子结合) The associations between clay particles are important as they affect important properties, such as viscosity, yield and fluid loss. The terms describing the associations are as follows:-- Deflocculated(解絮凝). A system of suspended particles is described as deflocculated, or dispersed, when there is an overall repulsive force between the particles . This is normally achieved by creating the conditions in which the particles carry the same charge. In clay systems, under alkaline conditions, this is normally a nett negative charge. Flocculated Systems(絮凝体系). A system may be described as flocculated when there are nett attractive forces for the particles and they can associate with each other, to form a loose structure. Aggregated Systems(聚结体系). The clays consist of a basic sheet structure and the crystals consist of assemblages of the sheets, one upon the other. In the swelling clay montmorillonite, the

sheets can be separated from one another by hydration forces and by mechanical shear. Thus , a clay aggregate is an assemblage of sheets, that may be disaggregated by hydration and/or mechanical shear. Sheets, or the aggregates themselves, may be flocculated or deflocculated as

shown in

Figure 3-18.

Fig. 3-18 Modes of particle association of clays Dispersed System( 分散体系 ). A system in

Fig. 3-18 Modes of particle association of clays

Dispersed System(分散体系 ). A system in which the breakdown of the aggregates is complete is called a dispersed system. Both the dispersed clays and the aggregates themselves may be flocculated or deflocculated. The clays may be regarded as sheets assembled into books , with an "edge' surface and a "face" surface. The edge may carry charges arising from broken bonds, which may be positive or negative and are dependent on pH. The face may carry pH independent negative charges. The particle associations possible are given in Figure 13.

3.3.4.2 Interparticle forces(粒间力)

The forces acting on the clay particles can be described as either repulsive forces or attractive forces. The particles approach each other due to Brownian motion. Whether they will agglomerate or not will depend on the summation of these two forces.

3.3.4.2.1 Repulsive forces(斥力) Electrical Double Layer Repulsion(双电层斥力). The clay particles have been described as small crystals that have a negatively charged surface. A compensating charge is provided by the ions in solution that are electrostatically attracted to the surface. At the same time there is a need for the ions to diffuse away from the surface, towards the bulk of the solution. The action of the two competitive tendencies results in a high concentration of ions near the surface with a gradual fall off further from the surface. The volume around the clay surface is called the The "thickness" of the layer is reduced by the addition of salt or electrolyte. The reduction in

thickness is related to the salt concentration and to the valence of the ions of opposite charge. Thus, calcium chloride will compress the double layer more effectively than sodium chloride. When two particles, each with their diffuse counter-ion atmosphere, approach each other, there is an interference that leads to changes in the distribution of ions in the double layers of both particles. A change infers that energy must be put into the system to force the particles together. In other words, there will be a repulsion between the particles that will become larger the closer the particles approach each other.

become larger the closer the particles approach each other. Figure 3-19 . Effect of salt on

Figure 3-19Effect of salt on the attractive and repulsive force between clay particles

on the attractive and repulsive force between clay particles Fig. 3-20 Diagram to illustrate the origins

Fig. 3-20 Diagram to illustrate the origins of the Van der Waals attractive forces

However, since the electric double layer can be compressed by electrolytes, then, as the electrolyte level is increased, so the particles can approach closer to each other before the

repulsive energies are significant. This is shown in

. This is a very short-term repulsion force that is generated when

contact is close enough to distort the electrons in the atoms. It resists the interpenetration of the crystal lattices.

. The polar nature of the clay surface holds one or

two layers of water tightly to the surface. Thus for the particles to approach closely to one another, energy has to be expanded to desorb the water. This repulsive energy probably becomes appreciable at particle separations of the order of 10 Angstroms or less.

3.3.4.2.2

Figure 3-19.

Born Repulsion(博恩斥力)

Desorption of Water(水的解吸附作用)

Attractive forces(引力)

Van der Waals Forces(范德华力). Van der Waals forces arise through the attraction of the spontaneous dipoles being set up due to distortion of the cloud of electrons around each atom.

This is illustrated in

decays very rapidly with distance (I/d 7 ), but for two spherical particles, the force is inversely proportional to only the third power of the distance (l/d 3 ). Thus, for a large assemblage of atoms, such as in a clay platelet, this force can be significant as it is additive. The attractive force is essentially independent of the electrolyte concentration.

3-20 (Van der Waals dipoles). For two atoms, the attractive force

Figure
Figure

3.3.5 Flocculation and Deflocculation(絮凝与反絮凝)

As

mentioned

in

the beginning

of

this chapter, colloid

particles

remain

indefinitely

in

suspension because of their extremely small size. Only if they agglomerate(聚结 ) to larger units

do they have finite sedimentation rates. When suspended in pure water, they cannot agglomerate, because of interference between the highly diffuse double layers. But if an electrolyte(电解质 ) is added, the double layers are compressed(压缩), and if enough electrolytes are added, the particles can approach each other so closed that the attractive forces predominate, and the particles agglomerate. This phenomenon is kno