MAKE-UP MATERIALS AND ADDITIVES 造浆材料与处理剂

1. Principles of Drilling Fluids 钻井液工艺原理 Chapter6 MAKE-UP MATERIALS AND ADDITIVES 造浆材料与处理剂 Prof. Dr. XiuhuaZheng E-mail: Xiuhuazh@cugb.edu.cn Exploration Dept. School of Engineering and Technology, China University of Geosciences(Beijing) 中国地质大学(北京)工程技术学院勘查教研室

2. Answers 压差 地层孔隙（裂隙） 渗透率 滤液 初失水 压差卡钻 泥饼中的水分 粒径及粒径分布 孔隙度 静失水和动失水 Test for §5 • Pore or fracture in formation • permeability • filtrate • mud spurt • differential sticking • water retained in the cake • Particle size and particle distribution • porosity • static and dynamic filtration

3. 无机处理剂 • 加重剂 • 碳酸钠 • 粘土改性 • 沉淀作用 • 络合作用 • 氢氧化钙 • 氯化钠 • 聚磷酸钠 • 螯合作用 Glossary for §6 • Inorganic agents • Weighting Materials • Sodium carbonate • clay beneficiation • precipitation • complexing • Calcium hydroxide • Potassium chloride • sodium polyphosphates • sequestration

4. 单体 非离子 阴离子或负电性 阳离子或正电性 碳化合物 有机胶质材料 降失水 稳定粘土 乳化剂 润滑剂 Glossary for §6 • Monomer • non-ionic • anionic or negatively charged • cationic or positively charged • compounds of carbon • Organic colloidal materials • reduce filtration • stabilize clays • emulsifiers • lubricants

5. Contents Water(水) Bentonite(膨润土) Materials to Increase Density(加重材料) Inorganic Chemical Additives(无机处理剂) Polymers(聚合物)

6. 1. Water • Water affects the drilling fluid properties in various aspects, such as the yield of Bentonite, the pH value.

7. 第二类分类方法是按其在钻井液中所起的作用或功能分类。我国钻井液标准化委员会根据国际上的分类法，并结合我国的具体情况，将钻井液配浆材料和处理剂共分为以下16类，即(1)降滤失剂(Filtration Reducer)；(2)增粘剂(Viscosifier)；(3)乳化剂(Emulsifier)使油水乳化产生乳状液；(4)页岩抑制剂(Shale lnhibitor)；(5)堵漏剂(Lost Circulation Material)；(6)降粘剂(Thinner)；(7)缓蚀剂(Corrosion lnhibitor)；(8)粘土类(Clay)；(9)润滑剂(Lubricant)；(10)加重剂(Weighting Agent)；(11)杀菌剂(Bactericide)；(12) 消泡剂(Defoamer)；(13)泡沫剂(Foaming Agent)；(14)絮凝剂(Flocculant)；（15)解卡剂(Pipe-Freeing Agent)；(16)其它类(Others)等。

8. 配浆水 • 水是配制各种钻井液时不可缺少的基本组分。在水基钻井液中，水是分散介质，大多数处理剂均通过溶解于水而发挥其作用；在油包水乳化钻井液中，水(通常是含CaCl2或NaCl的盐水)是分散相。甚至在泡沫钻井流体中，水也是不可缺少的连续相。 • 在钻井液工艺中，根据水中可溶性无机盐含量的多少，一般将配浆水分为以下三类：含盐量较少(总盐度低于1%)的淡水，含盐量较多的盐水和含盐量达饱和的饱和盐水，与之相应的钻井液分别称做淡水钻井液、盐水钻井液和饱和盐水钻井液。 • 此外，常将含Ca 2+、Mg2+较多的水称为硬水，钻探用水多为软水，钙离子1.5-3.0 meq/L。

9. 膨润土是水基钻井液的重要配浆材料：为具有蒙脱石的物理化学性质，含蒙脱石不少于85％的粘土矿物。一般要求1t膨润土至少能够配制出粘度为15mPa·s的钻井液16m3。膨润土是水基钻井液的重要配浆材料：为具有蒙脱石的物理化学性质，含蒙脱石不少于85％的粘土矿物。一般要求1t膨润土至少能够配制出粘度为15mPa·s的钻井液16m3。 钠膨润土的造浆率一般较高，而钙膨润土则需要通过加入纯碱（Na2CO3）使之转化为钠膨润土后方可使用。 目前我国将配制钻井液所用的膨润土分为三个等级：一级为符合API标准的钠膨润土；二级为改性土，经过改性符合OCMA标准要求；三级为较次的配浆土，仅用于性能要求不高的钻井液。 2.Bentonite(膨润土)

10. 2.1 Mining and Processing(开采与加工) • Bentonite deposits are normally exploited by quarrying(采石). Extracted bentonite is distinctly solid, even with a high moisture content of approximately 30%. • The material is initially crushed and, if necessary, activated with the addition of soda ash (Na2CO3). Bentonite is subsequently dried (air and/or forced drying) to reach the moisture content of approximately 15%. • According to the final application, bentonite is either sieved (granular form) or milled (into powder and superfine powder form). • For special applications, bentoniteis purified by removing the associated gangue minerals, or treated with acids to produce acid activated bentonite (bleaching earths), or treated with organics to produce organoclays.

11. http://www.ima-eu.org/en/eubaindex.htm

12. Bentonite Qualities: • Calcium-Bentonite (non-activated Bentonite): Bentonite that is predominantly occupied by Ca 2+ or Mg 2+-ions in the intermediate layers. • Activated Bentonite: Bentonite whose initial composition of Ca 2+ -ions in the intermediate layer has been replaced with Na+-ions in a technical process (alkali-activation). • Natural Sodium-Bentonite(usually Wyoming-Bentonite, but also found in other locations): Bentonite predominantly occupied by Na 2+-ions in the intermediate layers. Ca 2+ or Mg 2+ -ions can also occur commonly in Na-bentonite in varying concentrations. • OrganophilicBentonite (organoclays): Bentonite whose cations in the intermediate layers have been replaced by polar organic molecules (e.g. alkylammoniumions). They are hydrophobic and can swell in organic solvents. • Acid Activated Bentonite: Bentonite whose structure has been partially dissolved by treatment with acids. Depending on degree of activation, original Ca 2+, Mg 2+, and Na +cations are mostly removed, and part of Al, Fe, Mg, Si from the lattice are dissolved. Acid activated bentonite exhibits high surface area > 200 m 2/g and large micropore volume.

13. API Bentonite Table 6-1 Bentonite Requirement for API Specification 1lb/ft2=47.8803Pa

14. Approximate Amounts for some Applications

16. 膨润土逐渐分散在淡水中致使泥浆的粘度、切力不断增加的过程称为造浆，在添加主要处理剂之前的预水化膨润土浆常称做原浆或基浆。几乎在所有室内实验中，首先都要进行原浆的配制。由于蒙脱石含量和阳离子交换容量各不相同，来自不同产地的膨润土，其造浆效果往往有很大差别。几种典型粘土造浆的曲线如图6-1所示。

17. 造浆率(Yield of Clay) • 常将每吨粘土能配出表观粘度为15mPa·s的钻井液体积称做粘土的造浆率(Yield of Clay)。通常配浆土的质量是以造浆率来衡量的。从图6-1还可看出，配制1m315mPa·s的钻井液只需57kg怀俄明优质膨润土，如使用低造浆率粘土，则需570kg，两者的用量为1:10。经换算，用1 t优质膨润土可配制出表观粘度为15mPa·s的泥浆约16m3，而1t低造浆率粘土只能造浆约1.6 m3，相差亦近10倍。使用优质膨润土配浆，泥浆密度仅为1.03～1.04g／cm3时，表观粘度即可达到10～15 mPa·s；而使用低造浆率粘土配浆，泥浆密度必须增至1.35~1.40g／cm3时，其表观粘度才能达到同样的数值。因此，尽可能选用优质膨润土配浆，对减少体系中的固相含量，提高钻速有着重要的意义。

18. 22.5g 土+350ml水， 符合API标准，求造浆率？

19. 纯碱（Na2CO3）？ • 配制原浆时，还需加入适量纯碱，以提高粘土的造浆率。纯碱的加入量依粘土中钙离子的含量而异，可通过小型试验确定。一般约为配浆土质量的5％。加入纯碱的目的是除去粘土中的部分钙离子，将钙质土转变为钠质土，从而使粘土颗粒的水化作用进一步增强，分散度进一步提高。因此，在原浆中加入纯适量碱后，一般会使表观粘度增大，滤失量减小。如果随着纯碱加入滤失量反而增大，则表明纯碱加过量了(?)。

20. 配制一定密度泥浆所需的膨润土及水量可由下式求得: • mc--所需膨润土的质量，t ； • --膨润土密度，g／cm3； • Vm--所配制原浆的体积，m3； • --原浆密度，g／c m3； • Vw--所需水量，m3。

21. 2.3 Beneficiated and Super-Yield Bentonite（粘土改性提高造浆率） • Terms such as peptized（胶溶）, beneficiated and extra-high yield describe bentonites to which organic polymers(有机聚合物) (and sometimes also soda ash) have been added during processing. These products made with Western bentonite in America are useful as starting or spud muds（开孔泥浆）, in low-solids muds（低固相泥浆）, and in applications where cost of transportation is extremely high. Less than half as much of such a material is needed compared to the amount of API-specification bentonite.

22. 3. Materials to Increase Density(加重材料) • 加重材料(Weighting Material)又称加重剂，由不溶于水的惰性物质经研磨加工制备而成。为了对付高压地层和稳定井壁，需将其添加到钻井液中以提高钻井液的密度。加重材料应具备的条件是自身的密度大，磨损性小，易粉碎；并且应属于惰性物质，既不溶于钻井液，也不与钻井液中的其它组分发生相互作用。 • 钻井液的常用加重材料有以下几种：(1)重晶石粉(Barite-4.2 )；(2)石灰石粉(Limestone-2.7~2.9) ；(3)铁矿粉 (Hematite-4.9~5.3)和钛铁矿粉(Ilmenite-4.5~5.1) (4)方铅矿粉(Galena-7.4~7.7) 。 2.30 1.68 3.0

23. Materials to Increase Density

24. Fig. 6-1 Effect of specific gravity of weighting material on the solids concentration of weighted muds Figure 6-1 shows the effect of the specific gravity of the weighting material on the solids concentration of weighted muds（加重泥浆）. For example, the solid content of mud weighted to 19.0 lb/gal (2.28 g/cm3) with material having a specific gravity of 4.2 is 39.5% by volume, as compared with 30% by volume for a material of 5.2 specific gravity.

25. Barite Requirements for APl Specification • Specific gravity: 4.20, minimum • Wet screen analysis: • Residue on U.S. Sieve (ASTM) no. 200: 3.0% maximum • Residue on U.S. Sieve (ASTM) no. 325: 5.0% minimum • Soluble alkaline earth metals as calcium: 250 ppm, maximum

26. Calculation of Weighting Materials（加重材料的计算） 基本公式：

27. No limitation to the final fluid volume 1）加重后体积没有限制，则：

28. With limitation to the final fluid volume 2）加重后体积有限制，加重前必须排掉，则：

29. Dilution with water before weighting 根据： 推出：

30. 4. Inorganic Chemicals无机处理剂

31. 无机处理剂在钻井液中的作用机理 • 无机处理剂都是水溶性的无机碱类和盐类，其中多数可提供阳离子和阴离子，也有一些与水形成胶体或生成络合物。它们在钻井液中的作用机理可归纳为以下方面： • 1．离子交换吸附 • 2．调控钻井液的pH值 • 3．沉淀作用 • 4．络合作用 • 5．与有机处理剂生成可溶性盐 • 6．抑制溶解的作用

32. Sodium carbonate, Na2CO3碳酸钠 • Sodium carbonate turns Ca-Bentonite to Na-Bentonite through cation exchange and precipitation(沉淀作用), clay beneficiation(粘土改性)i.e.: • Sodium carbonate can be used when the muds are invaded by Ca2+ by precipitation,

33. Sodium hydroxide, NaOH氢氧化钠 • Used in water muds • to raise pH; • to solubilizelignite(褐煤), lignosulfonate（木质素磺酸盐）and tannin（单宁）substances; • to counteract corrosion, and • to neutralize hydrogen sulfide（硫化氢） • Concentration 0.6~11 kg/m3

34. Calcium oxide, CaO and Calcium hydroxide, Ca(OH)2 • Calcium hydroxide, Ca(OH)2, Produced by adding calcium oxide to water ； • 0.16% solubility of CaO; • Used in lime muds（石灰泥浆）, high-calcium-ion muds, and for the removal of soluble carbonates.

35. Calcium sulfate, CaSO4 • CaSO4, anhydrite（无水石膏）; CaSO4.2H2O, gypsum（熟石膏）, white of colorless crystals or powder with 2.31-2.32 g/cm3 density. • Slightly soluble in water with about 0.2% solubility. • Source of calcium ions in gyp muds. • Concentration 2 to 8 lb/ bbl (6 to 23 kg/m3).

36. Calcium chloride, CaCl2 • Calcium chloride, CaCl2, CaCl2.6H2O; white deliquescent crystals (75% solubility), granules, lumps, flakes with 1.68g/cm3 density. • Used in hole-stabilizing oil muds; • in calcium-treated muds, • in the preparation of dense salt solutions for completion and workover, and for lowering the freezing point of water muds. • Concentration ranges from 10 to 200 lb/bbl (28 to 570 kg/m3).

37. Sodium chloride, NaCl • Sodium chloride, NaCl, table salt, halite(岩盐), rock salt; white crystals with 2.20 g/cm3. • Used as produced or as prepared brine in completion（完井液）and workover（修井液）operations; • to saturate water before drilling rock salt; • to lower freezing point of mud; • to raise the density (as a suspended solid) and • act as a bridging agent in saturated solutions, and • in hole-stabilizing oil muds. Concentration 10 to 25 lb/bbl (30 to 360 kg/m3).

38. Potassium chloride, KCl • Potassium chloride, KCl, sylvite(钾盐), potash（苛性钾）; colorless or white crystals with 1.98 g/cm3 density. • Shale inhibitor（页岩抑制剂）. • Primary source of potassium ions for potassium-polymer muds(钾盐聚合物泥浆). • Concentration 2 to 60 lb/bbl (6 to 170 kg/m3).

39. Sodium dichromateNa2Cr2O7.2H2O • Sodium dichromate, Na2Cr2O7.2H2O; red-orange crystals with 2.35 g/cm3 density. • Used as constituent of chrome lignosulfonate（木素磺算铬）and chrome lignite compositions for increased thermal stability, and • to inhibit corrosion in salty muds. • Concentration 0.1 to 2lb/bbl (0.3 to 6 kg/m3).

40. The sodium polyphosphates（聚磷酸钠） • The sodium polyphosphates（聚磷酸钠） are very effective deflocculants（抗絮凝剂）for clays in fresh water and Fig.6-3 Schematic representation of a polyphosphate molecule adsorbed on clay crystal edge by bonding with exposed aluminum atoms were among the first thinners for mud. • The glassy polyphosphates effectively soften hard water by forming soluble complexes（可溶性络合物）with calcium and magnesium ions. This action, called sequestration（螯合作用）, is applied in dispersing bentonite for filtration reduction（降失水）.

41. Sodium acid pyrophosphate（焦磷酸钠）,SAPP, Na2H2P2O7 • Sodium tetraphosphate（四磷酸钠）, Na6P4O13 • Sodium hexametaphosphate（六偏硫酸钠）, (NaPO3)6

42. Fig.6-2 Schematic representation of a polyphosphate molecule adsorbed on clay crystal edge by bonding with exposed aluminum atoms

43. 硅酸钠 • 硅酸钠(Sodium Silicate)俗名水玻璃或泡花碱。分子式为Na2O·nSiO4，式中n称为水玻璃的模数，即二氧化硅与氧化钠的分子个数之比。n值越大，碱性越弱。n值在3以上的称为中性水玻璃，n值在3以下的称为碱性水玻璃。 • 硅酸盐钻井液是防塌钻井液的类型之一 。 • 水玻璃是一种堵漏剂。

44. 混合金属层状氢氧化物 • 混合金属层状氢氧化物(Mixed Metal Layered Hydroxide Compounds，简称为MMH)由一种带正电的晶体胶粒所组成，常称为正电胶。目前，其产品有溶胶、浓胶和胶粉等三种剂型。实验表明，该处理剂对粘土水化有很强的抑制作用，与膨润土和水所形成的复合体具有独特的流变性能。

45. 5. Polymers(聚合物)

46. Organic polymer（有机聚合物） • composed of a number of repeating or similar units, or groups of atoms (called monomers单体) consisting primarily of compounds of carbon（碳化合物）. • Organic colloidal materials（有机胶质材料）are used in drilling fluids to reduce filtration（降失水）, stabilize clays（稳定粘土）, flocculate drilled solids（絮凝固相）, increase carrying capacity（提高携岩能力）, and (incidentally) to serve as emulsifiers（乳化剂） and lubricants（润滑剂）.

47. Classification • Some, such as the starches（淀粉）and guar gum（胍胶）, occur naturally, and are ready for use after slight processing. • Others, such as xanthan gum（黄原胶）, employ natural processes in their production. • Still other polymers, such as derivatives of the starches and gums, and sodium carboxymethylcellulose, might be called semi-synthetic(半合成). • Antoherclass of petrochemical derivatives（石化产品）, such as the polyacrylates and ethylene oxide polymersis purely synthetic.

48. Glossary about polymer • The repeating units (monomers) that make up the polymer may be the same, or two or more monomers may be combined forming copolymers（共聚物）. • Structurally, the polymer may be linear(线性) or branched（支链）. • and these structures, either linear, branched, or both, may be cross-linked（交联）, i.e., tied together by covalent bonds（共价键）. • Furthervariations(变异) in the structure of polymers exist because of the possibility of combining two monomers in several different ways. • The structure may coil（卷曲） or uncoil, depending upon its environment.

50. Critical examination of the factors for selection of polymers（选用聚合物的影响因素） • Among the factors affecting performance are the effects of shear conditions, temperature, dissolved salts and alkaline materials, microorganisms, and time of use on the polymer. • If the application takes place in completion operations, both the solubility of the polymer in acids and the possible plugging action（堵塞）of the polymer on the productive formation must be considered. • Other factors involved are ease of handling and mixing, possible environmental effects, and cost of the polymer.