Non-toxic, inexpensive synthetic drilling fluid
Abstract
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Expired 10 July 2016, 10.2 years ago.
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21 claims: 9 independent, 12 dependent
- 1A wellbore fluid comprising:(I) a non-toxic base fluid;and (II) at least, one additive selected from the group consisting of emulsifiers, wetting agents, viscosifiers, weighting agents, fluid loss control agents, proppants for use in hydraulically fracturing subterranean formations, and particulate agents for use in forming a gravel pack;wherein the base fluid is a synthetic hydrocarbon mixture, which hydrocarbon mixture comprises at least 2 hydrocarbons containing a consecutive number of carbon atoms and is selected from the group consisting of: (A) a hydrocarbon mixture having a pour point greater than -30°C and a cetane index greater than 50, comprising (i) at least 90 weight percent total paraffins selected from n-paraffins and iso-paraffins, wherein n-paraffins constitute at least 10, weight percent and iso-parrafins constitute at least 50 weight percent;(ii) at least 95 weight percent hydrocarbons containing 11 or more carbon atoms;(iii) greater than 5 weight percent hydrocarbons containing 18 or more carbon atoms;(iv) 1 or less weight percent naphthenics;and (v) 0.1 or less volume percent aromatics;and (B) a hydrocarbon mixture comprising (i) at least 90 weight percent n-paraffins;and (ii) at least 95 weight percent hydrocarbons containing 10 or more carbon atoms.
- 20Use of a wellbore fluid as defined in any one of claims 1-19 as a drilling fluid in a method for drilling a borehole in a subterranean formation, wherein the method comprises the steps of:(A) rotating a drill at the bottom of the borehole;and (B) introducing said drilling fluid into the borehole to pick up drill cuttings and to carry at least a portion of the drill cuttings out of the borehole.
Independent claims9
80 paragraphs in 9 sections, as filed
0001The present invention relates to wellbore fluids (more specifically synthetic fluid-based wellbore fluids) and systems and processes for using them in a subterranean formation in oil and gas recovery operations.
0002While drilling fluids employing synthetic fluids (such as polyalphaolefin- and ester-based drilling fluids) as the base fluid are capable of achieving 96 hour LC<sub>50</sub> Mysid shrimp (<i>Mysidopsis bahia</i>) bioassay test results greater than 100,000 ppm, their commercial use has been severely restricted because of the high cost of the synthetic fluids.
SUMMARY OF THE INVENTION
0003Accordingly, there is a need for a drilling fluid which employs an inexpensive, non-toxic synthetic fluid as the base fluid. The present invention satisfies this need by providing a wellbore fluid comprising (a) at least one drilling fluid additive (e.g., an emulsifier, a viscosifier, a weighting agent, and an oil-wetting agent) and (b) an inexpensive, non-toxic base fluid. In one embodiment of the invention, the base fluid is a synthetic hydrocarbon mixture having a pour point greater than -30°C ans a cetane index greater than 50, and comprising (i) at least 95 weight percent hydrocarbons containing 11 or more carbon atoms, (ii) greater than 5 weight percent hydrocarbons containing 18 or more carbon atoms, (iii) at least 50 weight percent isoparaffins and at least 10 weight percent n-paraffins, (iv) at least 90 weight percent total paraffins, (v) at least 2 hydrocarbons containing a consecutive number of carbon atoms, (vi) 1 or less weight percent naphthenics, and (vii) 0.1 or less volume percent aromatics. (This synthetic fluid is referred to hereinafter as the "isoparaffin synthetic fluid.")
0004In another embodiment, the synthetic fluid comprises (1) at least 95 weight percent hydrocarbons containing 10 or more carbon atoms and (2) at least 90 weight percent n-paraffins. (This synthetic fluid is referred to hereinafter as the "n-paraffin synthetic fluid.") The n-paraffins usually also contain (i) less than about 10 weight percent naphthenics and (ii) less than about 0.1 volume percent aromatics.
0005Typically, both the isoparaffin and n-paraffin synthetic fluids contain (i) less than 1 weight percent sulfur, (ii) less than 1 weight percent nitrogen, and (iii) less than 1 weight percent oxygenated compounds.
0006The cost of the synthetic fluids employed in the present invention is comparable to that of diesel because the synthetic fluids are made by reacting inexpensive raw materials (e.g., H<sub>2</sub> and CO) on a massive scale designed to supply synthetic substitutes for gasoil and/or kerosene produced at conventional oil refineries. In contrast, polyalphaolefins and esters are made by polymerizing or reacting expensive raw materials on a small or moderate scale.
0007Because prior toxicity studies have shown that aromatics, sulfur, nitrogen, and oxygenated compounds can be toxic, the low or substantially non-existent concentrations of these materials in the synthetic fluids used in the present invention is very desirable. In addition, the fluids employed in the present invention which are in fact made synthetically are also desirable in view of anticipated environmental regulations which may restrict the off-shore discharge of non-aqueous-base drilling fluids to those drilling fluids using a synthetically produced base fluid.
0008The present invention further provides for the use of the afore-mentioned wellbore fluid as a drilling fluid in a method for drilling a borehole in a subterranean formation.
0009The present invention also provides for the use of the afore-mentioned wellbore fluid for treating a well.
0010A drilling system and a method for drilling a borehole are also described herein. The drilling system comprises (a) at least one subterranean formation, (b) a borehole penetrating a portion of at least one of the subterranean formations, (c) a drill bit suspended in the borehole, and (d) the above drilling fluid located in the borehole and proximate the drill bit. The drilling method comprises the steps of (a) rotating a drill bit at the bottom of the borehole and (b) introducing the aforesaid drilling fluid into the borehole (i) to pick up drill cuttings and (ii) to carry at least a portion of the drill cuttings out of the borehole.
DETAILED DESCRIPTION OF THE INVENTION
0011At least 95 weight percent of the isoparaffin synthetic drilling fluid is composed of compounds containing 11 or more, and more commonly 12 or more, carbon atoms. Also, the isoparaffin synthetic fluid consists of greater than 5, typically greater than 10, more typically greater than 15, even more typically greater than 20, and most typically greater than 25, weight percent compounds containing more than 17 carbon atoms. In fact, compounds containing 18 or more carbon atoms can constitute about 30, 35, 40, 45, or even 50 or more weight percent of the isoparaffin synthetic fluid. In addition, the isoparaffin synthetic fluid can contain isoparaffin, naphthenic, aromatic, sulfur, nitrogen, oxygenate, and total paraffin compounds in concentrations independently set forth in the following Table I. <tables id="tabl0001" num="0001"><table frame="bottom"><title><u style="single">TABLE I</u></title><tgroup cols="8" colsep="0"><colspec colnum="1" colname="col1" colwidth="23mm" /><colspec colnum="2" colname="col2" colwidth="24mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="18mm" /><colspec colnum="5" colname="col5" colwidth="20mm" /><colspec colnum="6" colname="col6" colwidth="22mm" /><colspec colnum="7" colname="col7" colwidth="19mm" /><colspec colnum="8" colname="col8" colwidth="29mm" colsep="1" /><thead><row><entry namest="col1" nameend="col8" align="center" valign="top">Isoparaffin Synthetic Fluid Composition</entry></row><row><entry rowsep="0" align="center">Isoparaffin<sup>a</sup>,</entry><entry rowsep="0" align="center">Naphthenic<sup>b</sup>,</entry><entry rowsep="0" align="center">Aromatic<sup>c</sup>,</entry><entry rowsep="0" align="center">Sulfur<sup>d</sup>,</entry><entry rowsep="0" align="center">Nitrogen<sup>e</sup>,</entry><entry rowsep="0" align="center">Oxygenate<sup>f</sup>,</entry><entry rowsep="0" align="center">Total. Paraffin<sup>g</sup>,</entry><entry rowsep="0" align="center">Normal Paraffin<sup>h</sup>,</entry></row><row><entry align="center" valign="top">wt%</entry><entry align="center" valign="top">wt%</entry><entry align="center" valign="top">v%</entry><entry align="center" valign="top">wt%</entry><entry align="center" valign="top">wt%</entry><entry align="center" valign="top">wt%</entry><entry align="center" valign="top">wt%</entry><entry align="center" valign="top">wt%</entry></row></thead><tbody><row rowsep="0"><entry align="center">≥ 50</entry><entry>≤ 1</entry><entry>≤ 0.1</entry><entry>≤ 1</entry><entry>≤ 1</entry><entry>≤ 1</entry><entry>≥ 90</entry><entry /></row><row rowsep="0"><entry align="center">≥ 55</entry><entry>≤ 0.5</entry><entry>≤ 0.5</entry><entry>≤ 0.5</entry><entry>≤ 0.5</entry><entry>≤ 0.5</entry><entry>≥ 91</entry><entry>≥ 10</entry></row><row rowsep="0"><entry align="center">≥ 60</entry><entry>≤ 0.1</entry><entry>≤ 0.01</entry><entry>≤ 0.1</entry><entry>≤ 0.1</entry><entry>≤ 0.1</entry><entry>≥ 92</entry><entry>≥ 15</entry></row><row rowsep="0"><entry align="center">≤ 65</entry><entry>≤ 0.05</entry><entry>≤ 0.005</entry><entry>≤ 0.05</entry><entry>≤ 0.05</entry><entry>≤ 0.05</entry><entry>≥ 93</entry><entry>≥ 20</entry></row><row rowsep="0"><entry align="center">≤ 70</entry><entry>≤ 0.01</entry><entry>≤ 0.001</entry><entry>≤ 0.01</entry><entry>≤ 0.01</entry><entry>≤ 0.01</entry><entry>≥ 94</entry><entry>≥ 25</entry></row><row rowsep="0"><entry align="center">≤ 75</entry><entry>≤ 0.005</entry><entry>≤ 0.0005</entry><entry>≤ 0.005</entry><entry>≤ 0.005</entry><entry>≤ 0.005</entry><entry>≥ 95</entry><entry>≥ 30</entry></row><row rowsep="0"><entry align="center">≤ 80</entry><entry>≤ 0.001</entry><entry>≤ 0.0001</entry><entry>≤ 0.001</entry><entry>≤ 0.001</entry><entry>≤ 0.001</entry><entry>≥ 96</entry><entry>≥ 35</entry></row><row rowsep="0"><entry align="center">≤ 85</entry><entry>≤ 0.0005</entry><entry /><entry>≤ 0.0005</entry><entry>≤ 0.0005</entry><entry>≤ 0.0005</entry><entry>≥ 97</entry><entry>≥ 40</entry></row><row rowsep="0"><entry align="center">≤ 90</entry><entry>≤ 0.0001</entry><entry /><entry>≤ 0.0001</entry><entry>≤ 0.0001</entry><entry>≤ 0.0001</entry><entry>≥ 98</entry><entry>≤ 45</entry></row><row rowsep="0"><entry /><entry /><entry /><entry /><entry /><entry /><entry>≥ 99.5</entry><entry /></row></tbody></tgroup><tgroup cols="8" rowsep="0"><colspec colnum="1" colname="col1" colwidth="23mm" /><colspec colnum="2" colname="col2" colwidth="24mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="18mm" /><colspec colnum="5" colname="col5" colwidth="20mm" /><colspec colnum="6" colname="col6" colwidth="22mm" /><colspec colnum="7" colname="col7" colwidth="19mm" /><colspec colnum="8" colname="col8" colwidth="29mm" /><tbody><row><entry namest="col1" nameend="col8" align="justify">a. As determined by UMT 407-90. b. As determined by UTM 407-90. c. As determined by ASTM D 5186. d. As determined by ASTM D 2622. e. As determined by ASTM D 4629. f. As determined by UTM D 484. g. As determined by UMT 407-90. h. As determined by UMT 407-90.</entry></row></tbody></tgroup></table></tables>
0012The pour point of the isoparaffin synthetic fluid (as determined by ASTM D 97) is commonly greater than -30°C (-22°F), more commonly greater than -25°C (-13°F), even more commonly greater than -20°C (-4°F), and most commonly greater than -15°C (5°F). Usually, the pour point of the isoparaffin synthetic fluid is less than 6°C (43°F), preferably less than 3°C (37°F), more preferably less than 0°C (32°F), and most preferably less than -3°C (27°F).
0013The flash point of the isoparaffin synthetic fluid (as determined by the Cleveland Open Cup method) is at least 65.6°C (150°F), typically at least 71.1°C (160°F), more typically 76.7°C (170°F), even more typically at least 82.2°C (180°F), and most typically at least 85°C (185°F). Usually, the . flash point of the isoparaffin synthetic fluid is less than 121.1°C (250°F), more typically 118.3°C (245°F) or less, even more typically 115.6°C (240°F) or less, and most 112.8°C (235°F) or less.
0014As measured by ASTM D 93, the flash point of the isoparaffin synthetic fluid is at least 65.6°C (150°F), typically at least 71.1°C (160°F), more typically 76.7°C (170°F), even more typically at least 82.2°C (180°F), and most typically at least 85°C (185°F), but usually less than 115°C (239°F), more typically 110°C (230°F) or less, even more typically 105°C (221°F) or less, and most 100°C (212°F) or less.
0015The isoparaffin synthetic fluid frequently has an initial boiling point (as determined by ASTM D 86) of at least 160°C (320°F), more frequently at least 165°C (329°F), even more frequently at least 170°C (338°F), and most frequently at least 175°C (347°F) or even at least 180°C (356°F). In addition, the isoparaffin synthetic fluid commonly has a final boiling point (as determined by ASTM D 86) of at least 340°C (644°F), more commonly at least 345°C (653°F), even more commonly at least 350°C (662°F), and most commonly at least 351°C (663.8°F). Furthermore, the final boiling point of the isoparaffin synthetic fluid is typically 375°C (707°F) or less, more typically 370°C (698°F) or less, even more typically 365°C (689°F) or less, and most typically 360°C (680°F) or less.
0016The viscosity of the isoparaffin synthetic fluid at 40°C (104°F) (as measured by ASTM D 445) is ordinarily between 1 to 10 centistokes (cst) Preferably, the viscosity of the isoparaffin synthetic fluid at 40°C (104°F) is less than 6, more preferably less than 5, even more preferably less than 4.5, and most preferably less than 4, cst, where 1 cst corresponds to 1×10<sup>-6</sup> m<sup>2</sup>/sec.
0017At 15°C, the isoparaffin synthetic fluids commonly have an API gravity greater than 40°, more commonly greater than 42°, even more commonly greater than 44°, and most commonly greater than 46°.
0018The cetane index (as determined by ASTM D 976) is generally greater than 60, preferably greater than 62, more preferably greater than 64, even more preferably greater than 66, and most preferably greater than 68. In fact, the cetane index is frequently at least about 70, 71, 73, 74, 75, 76, about 77 or more.
0019An isoparaffin synthetic fluid commercially available from MDS(Malaysia) typically has the properties set forth in the following Table II. <tables id="tabl0002" num="0002"><table frame="all"><title>TABLE II</title><tgroup cols="5" rowsep="0"><colspec colnum="1" colname="col1" colwidth="67mm" /><colspec colnum="2" colname="col2" colwidth="19mm" /><colspec colnum="3" colname="col3" colwidth="15mm" /><colspec colnum="4" colname="col4" colwidth="14mm" /><colspec colnum="5" colname="col5" colwidth="25mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col5" align="center">Typical Properties of MDS(Malaysia) Isoparaffin Synthetic Fluid</entry></row><row rowsep="1"><entry /><entry namest="col2" nameend="col4" align="center">Value</entry><entry /></row><row rowsep="1"><entry>Property</entry><entry align="center">Typical</entry><entry align="center">Max</entry><entry align="center">Min</entry><entry align="center">Test Method</entry></row></thead><tbody><row><entry>Density at 15°C, kg/m<sup>3</sup></entry><entry align="right">738</entry><entry align="right">790</entry><entry /><entry>ASTM D 1298</entry></row><row><entry>ASTM Color</entry><entry align="right">0</entry><entry align="right">2.0</entry><entry /><entry>ASTM D 1500</entry></row><row><entry>Distillation Range, °C</entry><entry /><entry /><entry /><entry>ASTM D 86</entry></row><row><entry>IBP</entry><entry align="right">201</entry><entry /><entry align="right">175</entry><entry /></row><row><entry>5%</entry><entry align="right">219</entry><entry /><entry /><entry /></row><row><entry>50%</entry><entry align="right">271</entry><entry /><entry /><entry /></row><row><entry>90%</entry><entry /><entry align="right">350</entry><entry /><entry /></row><row><entry>95%</entry><entry align="right">353</entry><entry /><entry /><entry /></row><row><entry>FBP</entry><entry align="right">358</entry><entry align="right">360</entry><entry /><entry /></row><row><entry>Sulphur, ppm</entry><entry align="right">0</entry><entry align="right">500</entry><entry /><entry>ASTM D 1266</entry></row><row><entry>Cetane Index</entry><entry align="right">75</entry><entry /><entry align="right">70</entry><entry>ASTM D 976</entry></row><row><entry>Flash Point, °C</entry><entry align="right">88</entry><entry /><entry align="right">68</entry><entry>ASTM D 93</entry></row><row><entry>Pour Point, °C</entry><entry align="right">-7</entry><entry /><entry /><entry>ASTM D 97</entry></row><row><entry>Cloud Point, °C</entry><entry align="right">-2</entry><entry /><entry /><entry>ASTM D 2500</entry></row><row><entry>CFPP, °C</entry><entry align="right">-3</entry><entry /><entry /><entry>IP 309</entry></row><row><entry>Kinematic Viscosity at 25°C, cSt (10<sup>-6</sup>m<sup>2</sup>/sec)</entry><entry align="right">4.3</entry><entry /><entry /><entry>ASTM D 445</entry></row><row><entry>Aromatics, %v</entry><entry align="right"><0.1</entry><entry /><entry /><entry>ASTM D 5186</entry></row><row rowsep="1"><entry>API Gravity at 15°C, °</entry><entry align="right">48.75</entry><entry /><entry /><entry /></row></tbody></tgroup></table></tables>
0020An interesting characteristic of the isoparaffin synthetic fluid described in above Table II is that mono- and poly-methyl isomers typically constitute at least about 90, more typically at least about 92, even more typically at least about 94, and most typically at least about 96, weight percent of the C11 or less isoparaffinic content of the isoparaffin synthetic fluid. In fact, the mono- and poly-methyl isomers of isoparaffins containing 11 or less carbon atoms can constitute 97, 98, or even 99, weight percent of the isoparaffin hydrocarbons having up to 11 carbon atoms. In other words, for the isoparaffin synthetic fluid reported in Table II, isoparaffins whose branched moieties contain more than one carbon atom (e.g., have an ethyl, propyl, butyl, or larger substituent group) constitute a negligible portion of the total amount of isoparaffins containing 11 or less carbon atoms.
0021Two other isoparaffin synthetic fluids commercially available from MDS(Malaysia) typically have the properties set forth in the following Table III. <tables id="tabl0003" num="0003"><table frame="all"><title>TABLE III</title><tgroup cols="4" rowsep="0"><colspec colnum="1" colname="col1" colwidth="68mm" /><colspec colnum="2" colname="col2" colwidth="24mm" /><colspec colnum="3" colname="col3" colwidth="24mm" /><colspec colnum="4" colname="col4" colwidth="28mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col4" align="center">Typical Properties of Other MDS(Malaysia) Isoparaffin Synthetic Fluids</entry></row><row rowsep="1"><entry /><entry namest="col2" nameend="col3" align="center">Value</entry><entry /></row><row rowsep="1"><entry>Property</entry><entry align="center">Fluid A</entry><entry align="center">Fluid B</entry><entry>Test Method</entry></row></thead><tbody><row><entry>Density at 15°C, kg/m<sup>3</sup></entry><entry>738.8</entry><entry>784.2</entry><entry>ASTM D 1298</entry></row><row><entry>ASTM Color</entry><entry><0.5</entry><entry><0.5</entry><entry>ASTM D 1500</entry></row><row><entry>Distillation Range, °C</entry><entry /><entry /><entry>ASTM D 86</entry></row><row><entry>IBP</entry><entry>207.1</entry><entry>217.4</entry><entry /></row><row><entry>FBP</entry><entry>351.4</entry><entry>353.8</entry><entry /></row><row><entry>Sulphur, ppm</entry><entry>>50</entry><entry>>50</entry><entry>ASTM D 1266</entry></row><row><entry>Cetane Index</entry><entry>77.5</entry><entry>75.5</entry><entry>ASTM D 976-91</entry></row><row><entry>Flash Point, °C</entry><entry>86</entry><entry>97</entry><entry>ASTM D 93-90</entry></row><row><entry>Pour Point, °C</entry><entry><0</entry><entry><0</entry><entry>ASTM D 97-87</entry></row><row><entry>Kinematic Viscosity at 40°C, cSt (10<sup>-6</sup> m<sup>2</sup>/sec)</entry><entry>3.4</entry><entry>3.5</entry><entry>ASTM D 445</entry></row><row rowsep="1"><entry>Aromatics, %v</entry><entry><0.1</entry><entry><0.1</entry><entry>UV method</entry></row></tbody></tgroup></table></tables>
0022Another isoparaffin synthetic fluid, which is commercially available from Sasol, has the properties shown in the following Table IV. <tables id="tabl0004" num="0004"><table frame="all"><title>TABLE IV</title><tgroup cols="3" rowsep="0"><colspec colnum="1" colname="col1" colwidth="59mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><colspec colnum="3" colname="col3" colwidth="24mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col3" align="center">Typical Sasol Brand Isoparaffin Synthetic Fluid Properties</entry></row><row rowsep="1"><entry>Property</entry><entry>Value</entry><entry>Test Method</entry></row></thead><tbody><row><entry>Density at 20°C, kg/l</entry><entry>0.778-0.785</entry><entry>ASTM D 1298</entry></row><row><entry>Color, Saybolt</entry><entry>+30</entry><entry>ASTM D 156</entry></row><row><entry>Distillation Range at 101.3kPals</entry><entry /><entry>ASTM D 1078</entry></row><row><entry>IBP, °C</entry><entry>200 min.</entry><entry /></row><row><entry>FBP, °C</entry><entry>250 max.</entry><entry /></row><row><entry>Sulphur, %mass</entry><entry><0.01</entry><entry>ASTM D 2622</entry></row><row><entry>Flash Point (closed cup at 101.3kPa), °C</entry><entry>77</entry><entry>IP 170</entry></row><row><entry>Kinematic Viscosity<sup>1</sup> at 40°C</entry><entry>1.6-2.1</entry><entry>ASTM D 445</entry></row><row><entry>Aromatics, %mass</entry><entry>1 max.</entry><entry>GC</entry></row><row><entry>Water, %mass</entry><entry>0.01</entry><entry>ASTM D 1744</entry></row><row><entry>Acidity, mgKOH/G</entry><entry>0.01</entry><entry>ASTM D 3242</entry></row><row><entry>Ash, %mass</entry><entry>0.01</entry><entry>ASTM D 482</entry></row><row rowsep="1"><entry>Ionol content, mg/kg</entry><entry>900-1100</entry><entry>GC</entry></row></tbody></tgroup><tgroup cols="3" rowsep="0"><colspec colnum="1" colname="col1" colwidth="59mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><colspec colnum="3" colname="col3" colwidth="24mm" /><tbody><row><entry namest="col1" nameend="col3" align="justify"><sup>1</sup> Centistoke (cst), where 1 cst = 1 × 10<sup>-6</sup> m<sup>2</sup>/sec.</entry></row></tbody></tgroup></table></tables>
0023When the isoparaffin synthetic fluids are employed as the base fluid in a drilling mud, the base oil generally contains less than 1, preferably less than about 0.9, more preferably less than 0.8, even more preferably less than about 0.7, and most preferably less than about 0.6, weight percent polar activator (e.g., polar ether alcohols). In fact, the concentration of polar activators in the base fluid is commonly less than about 0.5, more commonly less than about 0.4, even more commonly less than about 0.3, and most commonly less than about 0.2, weight percent. In addition, the base fluid can contain less than about 0.1, 0.05, 0.01, 0.005, 0.001, weight percent polar activator or even be totally devoid of any polar activator. Furthermore, when the base fluid is the isoparaffin synthetic fluid, the entire drilling mud usually contains less than 1, preferably less than about 0.75, more preferably less than 0.5, even more preferably less than about 0.25, and most preferably less than about 0.1, weight percent polar activator. In fact, in such instances the drilling mud can contain less than about 0.05, 0.01, 0.005, 0.001, weight percent polar activator or be entirely devoid of any polar activator.
0024With respect to the n-paraffin synthetic fluid, at least 95 weight percent of the n-paraffin synthetic drilling fluid is composed of compounds containing 10 or more carbon atoms. Typically, at least 95 weight percent of the n-paraffin synthetic drilling fluid is composed of compounds containing 11 or more, more typically 12 or more, even more typically 13 or more, and most typically 14 or more carbon atoms. Usually, the n-paraffin synthetic fluid contains less than 5, more commonly less 3, even more commonly less than 2, and most commonly less than 1, weight percent of compounds containing 18 or more carbon atoms. In addition, the n-paraffin synthetic fluid can contain n-paraffin, iso-paraffin, naphthenic, aromatic, sulfur, nitrogen, and oxygenate compounds in concentrations independently listed in the following Table V. <tables id="tabl0005" num="0005"><table frame="bottom"><title><u style="single">TABLE V</u></title><tgroup cols="7" colsep="0"><colspec colnum="1" colname="col1" colwidth="22mm" /><colspec colnum="2" colname="col2" colwidth="24mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="18mm" /><colspec colnum="5" colname="col5" colwidth="20mm" /><colspec colnum="6" colname="col6" colwidth="24mm" /><colspec colnum="7" colname="col7" colwidth="24mm" colsep="1" /><thead><row><entry namest="col1" nameend="col7" align="center" valign="top">N-paraffin Synthetic Fluid composition</entry></row><row rowsep="0"><entry align="center" valign="top">N-paraffin<sup>a</sup>,</entry><entry align="center" valign="top">Naphthenic<sup>b</sup>,</entry><entry align="center" valign="top">Aromatic<sup>c</sup>,</entry><entry align="center" valign="top">Sulfur<sup>d</sup>,</entry><entry align="center" valign="top">Nitrogen<sup>e</sup>,</entry><entry align="center" valign="top">Oxygenates<sup>f</sup>,</entry><entry align="center" valign="top">Isoparaffins<sup>g</sup>,</entry></row><row><entry align="center" valign="top">wt%</entry><entry align="center" valign="top">wt%</entry><entry align="center" valign="top">v%</entry><entry align="center" valign="top">wt%</entry><entry align="center" valign="top">wt%</entry><entry align="center" valign="top">wt%</entry><entry align="center" valign="top">wt%</entry></row></thead><tbody><row rowsep="0"><entry align="center">≥ 90</entry><entry>≤ 10</entry><entry>≤ 0.1</entry><entry>≤ 1</entry><entry>≤ 1</entry><entry>≤ 1</entry><entry align="right">≤ 10</entry></row><row rowsep="0"><entry align="center">≥ 91</entry><entry>≤ 5</entry><entry>≤ 0.05</entry><entry>≤ 0.5</entry><entry>≤ 0.5</entry><entry>≤ 0.5</entry><entry align="right">≤ 9</entry></row><row rowsep="0"><entry align="center">≥ 92</entry><entry>≤ 1</entry><entry>≤ 0.01</entry><entry>≤ 0.1</entry><entry>≤ 0.1</entry><entry>≤ 0.1</entry><entry align="right">≤ 8</entry></row><row rowsep="0"><entry align="center">≥ 93</entry><entry>≤ 0.5</entry><entry>≤ 0.005</entry><entry>≤ 0.05</entry><entry>≤ 0.05</entry><entry>≤ 0.05</entry><entry align="right">≤ 7</entry></row><row rowsep="0"><entry align="center">≥ 94</entry><entry>≤ 0.1</entry><entry>≤ 0.001</entry><entry>≤ 0.01</entry><entry>≤ 0.01</entry><entry>≤ 0.01</entry><entry align="right">≤ 6</entry></row><row rowsep="0"><entry align="center">≥ 95</entry><entry>≤ 0.05</entry><entry>≤ 0.0005</entry><entry>≤ 0.005</entry><entry>≤ 0.005</entry><entry>≤ 0.005</entry><entry align="right">≤ 5</entry></row><row rowsep="0"><entry align="center">≥ 96</entry><entry>≤ 0.01</entry><entry>≤ 0.0001</entry><entry>≤ 0.001</entry><entry>≤ 0.001</entry><entry>≤ 0.001</entry><entry align="right">≥ 4</entry></row><row rowsep="0"><entry align="center">≥ 97</entry><entry>≤ 0.005</entry><entry /><entry>≤ 0.0005</entry><entry>≤ 0.0005</entry><entry>≤ 0.0005</entry><entry align="right">≥ 3</entry></row><row rowsep="0"><entry align="center" /><entry>≤ 0.001</entry><entry /><entry>≤ 0.0001</entry><entry>≤ 0.0001</entry><entry>≤ 0.0001</entry><entry align="right">≤ 2</entry></row><row rowsep="0"><entry align="center" /><entry>≤ 0.0005</entry><entry /><entry /><entry /><entry /><entry align="right">≤ 1</entry></row><row><entry align="center" /><entry>< 0.0001</entry><entry /><entry /><entry /><entry /><entry align="center" /></row></tbody></tgroup><tgroup cols="7" rowsep="0"><colspec colnum="1" colname="col1" colwidth="22mm" /><colspec colnum="2" colname="col2" colwidth="24mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="18mm" /><colspec colnum="5" colname="col5" colwidth="20mm" /><colspec colnum="6" colname="col6" colwidth="24mm" /><colspec colnum="7" colname="col7" colwidth="24mm" /><tbody><row><entry namest="col1" nameend="col7" align="justify">a. As determined by UTM 407-90. b. As determined by UTM 407-90. c. As determined by ASK D 5186. d. As determined by ASK D 2622. e. As determined by ASTM D 4629. f. As determined by UTM 484. g. As determined by UTM 407-90.</entry></row></tbody></tgroup></table></tables>
0025The pour point of the n-paraffin synthetic fluid (as determined by ASTM D 97) is commonly greater than -30°C (-22°F) and more commonly greater than -25°C (-13°F). Frequently, the pour point of the n-paraffin synthetic fluid is less than 10°C (50°F), more frequently less than 9°C (48.2°F), even more frequently less than 8°C (46.4°F), and most frequently less than 7°C (44.6°F).
0026The flash point of the n-paraffin synthetic fluid (as determined by ASTM D 93) is typically at least 65°C (149°F), more typically at least 70°C (158°F), even more typically at least 75°C (167°F), and most typically at least 80°C (176°F). The n-paraffin synthetic fluids can have even higher flash points, such as at least 85°C (185°F), 90°C (194°F), 95°C (203°F), or at least 100°C (212°F) or higher.
0027The n-paraffin synthetic fluid frequently has an initial boiling point (as determined by ASTM D 86) of at least 190°C (374°F), more frequently at least 200°C (392°F), even more frequently at least 210°C (410°F), and most frequently at least 220°C (428°F). Even higher initial boiling points, such as 230°C (446°F), 240° (464°F), or 250°C (482°F) or more, are not unusual for the n-paraffin synthetic fluids.
0028The viscosity of the n-paraffin synthetic fluid at 40°C (104°F) (as measured by ASTM D 445) is ordinarily between 1 to 10 cst. Preferably, the viscosity of the n-paraffin synthetic fluid at 40°C (104°F) is less than 5, more preferably less than 4, even more preferably less than 3, and most preferably less than 2 cst, where 1 cst corresponds to 1 × 10<sup>-6</sup> m<sup>2</sup>/sec.
0029At 15°C, the n-paraffin synthetic fluids commonly have an API gravity greater than 45°, more commonly greater than 50°, even more commonly greater than 50.5°, and most commonly greater than 51°.
0030Typical properties for some commercially available n-paraffin synthetic fluids are shown in the following Tables VI and VII. <tables id="tabl0006" num="0006"><table frame="all"><title>TABLE VI</title><tgroup cols="4" rowsep="0"><colspec colnum="1" colname="col1" colwidth="44mm" /><colspec colnum="2" colname="col2" colwidth="25mm" /><colspec colnum="3" colname="col3" colwidth="25mm" /><colspec colnum="4" colname="col4" colwidth="24mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col4" align="center">Typical Properties Of MDS(Malaysia) Brand N-paraffin Synthetic Fluids</entry></row><row rowsep="1"><entry>Property</entry><entry>Sarapar 103</entry><entry>Sarapar 147</entry><entry>Test Method</entry></row></thead><tbody><row><entry>Saybolt Color</entry><entry>+30</entry><entry>+30</entry><entry>ASTM D 156</entry></row><row><entry>Bromine Index, mgBr/100g</entry><entry>8</entry><entry>6</entry><entry>ASTM D 2710</entry></row><row><entry>Sulphur, ppm</entry><entry>0</entry><entry>0</entry><entry>ASTM D 5120</entry></row><row><entry>Carbon Distribution, %mass</entry><entry /><entry /><entry /></row><row><entry>nC9</entry><entry>0</entry><entry>0</entry><entry /></row><row><entry>nC10</entry><entry>9</entry><entry>0</entry><entry /></row><row><entry>nC11</entry><entry>30</entry><entry>0</entry><entry /></row><row><entry>nC12</entry><entry>29</entry><entry>0</entry><entry /></row><row><entry>nC13</entry><entry>27</entry><entry>4</entry><entry /></row><row><entry>nC14</entry><entry>1</entry><entry>25</entry><entry /></row><row><entry>nC15</entry><entry>0</entry><entry>24</entry><entry /></row><row><entry>nC16</entry><entry>0</entry><entry>22</entry><entry /></row><row><entry>nC17</entry><entry>0</entry><entry>16</entry><entry /></row><row><entry>nC18</entry><entry>0</entry><entry>4</entry><entry /></row><row><entry>nC19</entry><entry>0</entry><entry>0</entry><entry /></row><row><entry>n-Paraffin content, %mass</entry><entry>96</entry><entry>95</entry><entry /></row><row><entry>Average Molecular Mass</entry><entry>167</entry><entry>213</entry><entry /></row><row><entry>Density at 15°C, kg/m<sup>3</sup></entry><entry>750</entry><entry>775</entry><entry>ASTM D 4052</entry></row><row><entry>Distillation Range, °C</entry><entry /><entry /><entry>ASTM D 86</entry></row><row><entry>IBP</entry><entry>190</entry><entry>250</entry><entry /></row><row><entry>FBP</entry><entry>230</entry><entry>280</entry><entry /></row><row><entry>Flash Point, °C</entry><entry>75</entry><entry>110</entry><entry>ASTM D 93</entry></row><row><entry>Pour Point,°C</entry><entry>-20</entry><entry>5</entry><entry>ASTM D 97</entry></row><row><entry>Viscosity at 25°C, mm/s</entry><entry>1.7</entry><entry>3.3</entry><entry>ASTM D 445</entry></row><row rowsep="1"><entry>API Gravity at 15°C, °</entry><entry>57.17</entry><entry>51.08</entry><entry /></row></tbody></tgroup></table></tables><tables id="tabl0007" num="0007"><table frame="none"><title><u style="single">TABLE VII</u></title><tgroup cols="6" colsep="0"><colspec colnum="1" colname="col1" colwidth="53mm" /><colspec colnum="2" colname="col2" colwidth="23mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="23mm" /><colspec colnum="5" colname="col5" colwidth="17mm" /><colspec colnum="6" colname="col6" colwidth="28mm" /><thead><row><entry namest="col1" nameend="col6" align="center" valign="top">Typical Properties of Sasol Brand N-paraffin Synthetic Fluids</entry></row><row><entry rowsep="0" align="center" valign="top" /><entry namest="col2" nameend="col5" align="center" valign="top">Paraffins</entry><entry rowsep="0" align="center" valign="top" /></row><row><entry rowsep="0" align="center" valign="top" /><entry align="center" valign="top">Light</entry><entry align="center" valign="top" /><entry align="center" valign="top">Heavy</entry><entry align="center" valign="top" /><entry align="center" valign="middle">Test Method</entry></row><row><entry valign="top">Property</entry><entry valign="top">Specification</entry><entry valign="top">Typical</entry><entry valign="top">Specification</entry><entry valign="top">Typical</entry><entry /></row></thead><tbody><row rowsep="0"><entry>n-Paraffins, %mass</entry><entry align="center">92 min.</entry><entry align="center">93</entry><entry align="center">92 min.</entry><entry align="center">93</entry><entry>Sasol 11.28/83</entry></row><row rowsep="0"><entry>Aromatics, %mass</entry><entry align="center">0.5 max.</entry><entry align="center"><0.1</entry><entry align="center">0.5 max.</entry><entry align="center"><0.1</entry><entry>Sasol 5.107/92</entry></row><row rowsep="0"><entry>Bromine Index, mgBr/100g</entry><entry align="center">20 max.</entry><entry align="center"><10</entry><entry align="center">20 max.</entry><entry align="center"><10</entry><entry>ASTM D 2710-89</entry></row><row rowsep="0"><entry>Sulphur, ppm</entry><entry align="center">5 max.</entry><entry align="center"><1</entry><entry align="center">5 max.</entry><entry align="center"><1</entry><entry>ANTEK 1.211/92</entry></row><row rowsep="0"><entry>Acidity, mg KOH/g</entry><entry align="center">0.02max.</entry><entry align="center"><0.01</entry><entry align="center">0.02max.</entry><entry align="center"><0.01</entry><entry>ASTH D 3242</entry></row><row rowsep="0"><entry>Ash, %mass</entry><entry align="center">0.03max.</entry><entry align="center"><0.01</entry><entry align="center">0.03max.</entry><entry align="center"><0.01</entry><entry>ASTH D 482</entry></row><row rowsep="0"><entry>Saybolt Color</entry><entry align="center">+30 min.</entry><entry align="center">+30</entry><entry align="center">+25 min</entry><entry align="center">+30</entry><entry>ASTM D 156</entry></row><row rowsep="0"><entry>Carbon Distribution, %mass</entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry>Sasol 11.28/83</entry></row><row rowsep="0"><entry>C 9 and lighter</entry><entry align="center">0.5 max.</entry><entry align="center"><0.1</entry><entry align="center" /><entry align="center" /><entry /></row><row rowsep="0"><entry>C10</entry><entry align="center">4-10</entry><entry align="center">5</entry><entry align="center" /><entry align="center" /><entry /></row><row rowsep="0"><entry>C11</entry><entry align="center">30-38</entry><entry align="center">35</entry><entry align="center" /><entry align="center" /><entry /></row><row rowsep="0"><entry>C12</entry><entry align="center">29-37</entry><entry align="center">32</entry><entry align="center" /><entry align="center" /><entry /></row><row rowsep="0"><entry>C13</entry><entry align="center">23-30</entry><entry align="center">28</entry><entry align="center" /><entry align="center" /><entry /></row><row rowsep="0"><entry>C14 and heavier</entry><entry align="center">0.5 max.</entry><entry align="center">0.2</entry><entry align="center" /><entry align="center" /><entry /></row><row rowsep="0"><entry>C13 and lighter</entry><entry align="center" /><entry align="center" /><entry align="center">0.5 max.</entry><entry align="center">3.5</entry><entry /></row><row rowsep="0"><entry>C14 and heavier</entry><entry align="center">0.5 max.</entry><entry align="center">0.2</entry><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry>C13 and lighter</entry><entry align="center" /><entry align="center" /><entry align="center">0.5 max.</entry><entry align="center">3.5</entry><entry align="center" /></row><row rowsep="0"><entry>C14-C17</entry><entry align="center" /><entry align="center" /><entry align="center">95 min.</entry><entry align="center">96</entry><entry align="center" /></row><row rowsep="0"><entry>C18 and heavier</entry><entry align="center" /><entry align="center" /><entry align="center">1 max.</entry><entry align="center">0.3</entry><entry align="center" /></row><row rowsep="0"><entry>Boiling Range, °C</entry><entry align="center" /><entry align="center">192-226</entry><entry align="center" /><entry align="center">254-287</entry><entry align="center" /></row><row rowsep="0"><entry>Pour Point, °C</entry><entry align="center" /><entry align="center"><0</entry><entry align="center" /><entry align="center">3</entry><entry align="center" /></row><row rowsep="0"><entry>Flash Point, °C</entry><entry align="center" /><entry align="center">70</entry><entry align="center" /><entry align="center">114</entry><entry align="center" /></row><row rowsep="0"><entry>Average Molecular Mass</entry><entry align="center" /><entry align="center">163</entry><entry align="center" /><entry align="center">219</entry><entry align="center" /></row><row rowsep="0"><entry>Density at 25°C, kg/l</entry><entry align="center" /><entry align="center">0.744</entry><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry>API Gravity at 25°C, °</entry><entry align="center" /><entry align="center">58.43</entry><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry>Viscosity at 40°C, cst (10<sup>-6</sup>m<sup>2</sup>/sec)</entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center">2.4</entry><entry align="center" /></row></tbody></tgroup></table></tables>
0031The synthetic fluids employed in the wellbore fluids of the present invention are typically prepared by the Fischer-Tropsch process and various modifications thereof (especially the Shell Middle Distillate Synthesis process). See, for example, <nplcit id="ncit0001" npl-type="s"><text>Sie et al., Catalysis Today, 8:371-394 (1991)</text></nplcit>; <nplcit id="ncit0002" npl-type="s"><text>van der Burgt et al., Petroleum Review, pages 204-209 (April 1990</text></nplcit>);<nplcit id="ncit0003" npl-type="s"><text> Oil & Gas Journal, pages 74-76 (February 17, 1986</text></nplcit>); <nplcit id="ncit0004" npl-type="s"><text>Eilers et al., Catalysis Letters, pages 253-270 (1990</text></nplcit>); <nplcit id="ncit0005" npl-type="s"><text>Bartholomew, Catalysis Letters, pages 303-316 (1990</text></nplcit>); <nplcit id="ncit0006" npl-type="s"><text>Gregor, Catalysis Letters, pages 317-332 (1990</text></nplcit>); <nplcit id="ncit0007" npl-type="s"><text>Dry, Journal of Organometallic Chemistry, 372:117-127 (1989)</text></nplcit>; <nplcit id="ncit0008" npl-type="s"><text>Dry, Applied Industrial Catalysis, 2:167-213 (1983)</text></nplcit>; and <nplcit id="ncit0009" npl-type="s"><text>Dry, Hydrocarbon Processing, pages 121-124 (August 1982</text></nplcit>). In general, the Fischer-Tropsch process entails reacting carbon monoxide and hydrogen over a catalyst (e.g., iron, ruthenium, or cobalt) to produce products which, in the absence of secondary transformations, are highly linear. When desired, some or all of the linear products are subjected to a conversion process (such as the Shell Middle Distillate Synthesis Process) where (a) olefins present in the Fischer-Tropsch product are hydrogenated, (b) small amounts of oxygen-containing compounds, mainly primary alcohols, are removed, (c) the Fischer-Tropsch product is hydroisomerized, and (d) the n-paraffins are hydrocracked to isoparaffins of a desired chain length and/or boiling range.
0032Due to the manner in which they are synthesized, the synthetic fluids are composed of hydrocarbons containing a consecutive number of carbon atoms (i.e., a mixture of hydrocarbons where the carbon atom content of the individual hydrocarbons is C<sub>n</sub>, C<sub>n+1</sub>, C<sub>n+2</sub>, C<sub>n+3</sub>, etc. and n is a whole number.) The synthetic fluids are composed of at least 2, more commonly at least 3, even more commonly at least 4, and most commonly at least 5 hydrocarbons containing a consecutive number of carbon atoms. In fact, some synthetic fluids contain at least 6, 7, 8, 9, or 10 or more hydrocarbons having a consecutive number of carbon atoms.
0033The synthetic fluids are commercially available from Sasol in South Africa and Shell Middle Distillate in Malaysia and are preferably the fraction which has a boiling range similar to gasoils and/or kerosenes produced at conventional petroleum refineries.
0034Optionally, one or more pour point depressants are employed in the synthetic fluids to lower their pour point. Typical pour point depressants include, but are not limited to, ethylene copolymers, isobutylene polymers, polyaklylnaphthalenes, wax-aromatic condensation products (e.g., wax-naphthalene condensation products, phenol-wax condensation products), polyalkylphenolesters, polyalkylmethacrylates, polymethacrylates, polyalkylated condensed aromatics, alkylaromatic polymers, iminodiimides, and polyalkylstyrene. (The molecular weights for polyaklylnaphthalenes, polyalkylphenolesters, and polyalkylmethacrylates range from about 2,000 to about 10,000.) Because they are non-toxic, ethylene copolymers and isobutylene polymers are the preferred pour point depressants.
0035Up to about 1 weight percent pour point depressant is employed. (As used herein, the weight percent of the pour point depressant is based upon the weight of the synthetic fluid, i.e., it is the weight of the pour point depressant divided by the weight of the synthetic fluid, the quotient being multiplied by 100%.) Preferably, the pour point depressant is employed in a concentration of 0.005 to about 0.5, more preferably about 0.01 to about 0.4, and most preferably about 0.02 to about 0.3, weight percent.
0036When employed, the pour point depressant is preferably mixed with the synthetic fluid and the resulting composition is then combined with any additional additives as described below.
0037One or more surfactants (e.g., emulsifiers, wetting agents), viscosifiers, weighting agents, fluid loss control agents, and shale inhibiting salts are also optionally used in the wellbore fluid of the present invention. (As used herein, the term "surfactant" means a substance that, when present at low concentration in a system, has the property of adsorbing onto the surfaces or interfaces of the system and of altering to a marked degree the surface or interfacial free energies of those surfaces (or interfaces). As used in the foregoing definition of surfactant, the term "interface" indicates a boundary between any two immiscible phases and the term "surface" denotes an interface where one phase is a gas, usually air.) Because the wellbore fluids of the present invention are intended to be non-toxic, these optional ingredients, like the synthetic fluid, are preferably also non-toxic.
0038Exemplary emulsifiers include, but are not limited to, fatty acids, soaps of fatty acids, and fatty acid derivatives including amido-amines, polyamides, polyamines, esters (such as sorbitan monoleate polyethoxylate, sorbitan dioleate polyethoxylate), imidaxolines, and alcohols.
0039Typical wetting agents include, but are not limited to, lecithin, fatty acids, crude tall oil, oxidized crude tall oil, organic phosphate esters, modified imidazolines, modified amidoamines, alkyl aromatic sulfates, alkyl aromatic sulfonates, and organic esters of polyhydric alcohols.
0040Exemplary weighting agents include, but are not limited to barite, iron oxide, gelana, siderite, and calcium carbonate.
0041Common shale inhibiting salts are alkali metal and alkaline-earth metal salts. Calcium chloride and sodium chloride are the preferred shale inhibiting salts.
0042Exemplary viscosifiers include, but are not limited to, organophilic clays (e.g., hectorite, bentonite, and attapulgite), non-organophilic clays (e.g., montmorillonite (bentonite), hectorite, saponite, attapulgite, and illite), oil soluble polymers, polyamide resins, and polycarboxylic acids and soaps. (As used herein, the term "non-organophilic clay" means a clay which has not been amine-treated to convert the clay from water-yielding to oil-yielding.)
0043Illustrative fluid loss control agents include, but are not limited to, asphaltics (e.g., asphaltenes and sulfonated asphaltenes), amine treated lignite, and gilsonite. For drilling fluids intended for use in high temperature environments (e.g., where the bottom hole temperature exceeds about 204.4°C (400°F)), the fluid loss control agent is preferably a polymeric fluid loss control agent. Exemplary polymeric fluid loss control agents include, but are not limited to, polystyrene, polybutadiene, polyethylene, polypropylene, polybutylene, polyisoprene, natural rubber, butyl rubber, polymers consisting of at least two monomers selected from the group consisting of styrene, butadiene, isoprene, and vinyl carboxylic acid. Individual or mixtures of polymeric fluid loss control agents can be used in the wellbore fluid of this invention.
0044For drilling fluids intended for use in high temperature environments (e.g., where the bottom hole temperature exceeds about 204.4°C (400°F)), it is desirable to use the synthetic fluid as the base material in conjunction with the formulations and materials disclosed in <patcit id="pcit0001" dnum="US786034A" dnum-type="L"><text>U.S. patent applications Serial No. 07/786,034</text></patcit> and Serial <patcit id="pcit0002" dnum="US08268801B"><text>No. 08/268,801</text></patcit>.
0045General drilling fluid formulations are set forth in the following Table VIII: <tables id="tabl0008" num="0008"><table frame="all"><title>TABLE VIII</title><tgroup cols="3" rowsep="0"><colspec colnum="1" colname="col1" colwidth="43mm" /><colspec colnum="2" colname="col2" colwidth="21mm" /><colspec colnum="3" colname="col3" colwidth="24mm" /><thead valign="top"><row rowsep="1"><entry>Ingredient</entry><entry>Typical</entry><entry>More Typical</entry></row></thead><tbody><row><entry align="center">Synthetic fluid, volume %<sup>a</sup></entry><entry align="center">25-85</entry><entry align="center">40-60</entry></row><row><entry align="center">Surfactant (active), ppb<sup>b</sup></entry><entry align="center">0.5-40</entry><entry align="center">3-25</entry></row><row><entry align="center">kg/m<sup>3</sup></entry><entry align="center">2.86-57.2</entry><entry align="center">2.86-28.6</entry></row><row><entry align="center">Water, volume %<sup>a</sup></entry><entry align="center">up to 45</entry><entry align="center">1-20</entry></row><row><entry align="center">Weighting agent, ppb</entry><entry align="center">up to 700</entry><entry align="center">150-600</entry></row><row><entry align="center">kg/m<sup>3</sup></entry><entry align="center">up to 2002</entry><entry align="center">429-1716</entry></row><row><entry align="center">Polymer viscosifier, ppb</entry><entry align="center">0.05-15</entry><entry align="center">0.1-6</entry></row><row><entry align="center">kg/m<sup>3</sup></entry><entry align="center">0.143-42.9</entry><entry align="center">0.286-17.16</entry></row><row><entry align="center">Organophilic clay, ppb</entry><entry align="center">up to 15</entry><entry align="center">0.1-6</entry></row><row><entry align="center">kg/m<sup>3</sup></entry><entry align="center">up to 42.9</entry><entry align="center">0.286-17.16</entry></row><row><entry align="center">Shale inhibiting salt, ppb</entry><entry align="center">up to 60</entry><entry align="center">5-30</entry></row><row><entry align="center">kg/m<sup>3</sup></entry><entry align="center">up to 171.6</entry><entry align="center">143-85.8</entry></row><row><entry align="center">Lime<sup>c</sup>, ppb</entry><entry align="center">up to 30</entry><entry align="center">1-20</entry></row><row><entry align="center">kg/m<sup>3</sup></entry><entry align="center">up to 85.8</entry><entry align="center">2.86-57.2</entry></row><row><entry align="center">Fluid loss control agent, ppb</entry><entry align="center">up to 30</entry><entry align="center">2-20</entry></row><row rowsep="1"><entry align="center">kg/m<sup>3</sup></entry><entry align="center">up to 85.8</entry><entry align="center">5.72-57.2</entry></row></tbody></tgroup><tgroup cols="3" rowsep="0"><colspec colnum="1" colname="col1" colwidth="43mm" /><colspec colnum="2" colname="col2" colwidth="21mm" /><colspec colnum="3" colname="col3" colwidth="24mm" /><tbody><row><entry namest="col1" nameend="col3" align="justify">a. Volume percent is based on the total volume of the drilling fluid. b. The pounds per barrel (ppb) is based upon the final composition of the drilling fluid. c. As used in the specification and claims, the term "lime" means quicklime (CaO), quicklime precursors, and hydrated quicklime (e.g., slaked lime (Ca(OH)<sub>2</sub>)).</entry></row></tbody></tgroup></table></tables>
0046The properties (e.g., synthetic fluid to water ratio, density, etc.) of the wellbore fluids of the invention can be adjusted to suit any drilling operation. For example, the drilling fluid is usually formulated to have a volumetric ratio of synthetic fluid to water of about 100:0 to about 40:60 and a density of about 0.9 kg/l (7.5 pounds per gallon (ppg)) to about 2.4 kg/l (20 ppg). More commonly, the density of the drilling fluid is about 1.1 kg/l (9 ppg) to about 2.3 kg/l (19 ppg).
0047The drilling fluids are preferably prepared by mixing the constituent ingredients in the following order: (a) synthetic fluid, (b) emulsifier, (c) lime, (d) fluid loss control agent, (e) an aqueous solution comprising water and the shale inhibiting salt, (f) organophilic clay (when employed), (g) oil wetting agent, (h) weighting agent, (i) non-sulfonated polymer, (j) sulfonated polymer (when employed), and (k) non-organophilic clay (when employed).
EXAMPLES
0048The following examples (which are intended to illustrate and not limit the invention defined by the claims) demonstrate the preparation of exemplary drilling fluids within the scope of the present invention (Examples 1-7), show the results obtained from an analysis of an isoparaffin synthetic fluid sample (Example 8), document initial and aged rheological properties of a drilling fluid which employs the isoparaffin synthetic fluid sample as the base fluid (Example 9), and compare the toxicity of two drilling fluids which solely differ in that the base fluid of one is the isoparaffin synthetic fluid sample and the base fluid of the other is the dimer of 1-decene (a commercially used, non-toxic base fluid).
EXAMPLES 1-6
Preparation Of Drilling Fluids
0049Six drilling fluids (3 lab barrels per drilling fluid formulation, with each lab barrel containing about 350 ml) having a density of about 2.16 kg/l (about 18 ppg) and within the scope of the present invention are formulated by sequentially adding ingredients in the order set forth in Table A. After the addition of each ingredient, the resulting composition is mixed for the indicated mixing time prior to adding a subsequent ingredient to the composition. <tables id="tabl0009" num="0009"><table frame="none"><title><u style="single">TABLE A</u></title><tgroup cols="9" colsep="0"><colspec colnum="1" colname="col1" colwidth="23mm" /><colspec colnum="2" colname="col2" colwidth="24mm" /><colspec colnum="3" colname="col3" colwidth="13mm" /><colspec colnum="4" colname="col4" colwidth="13mm" /><colspec colnum="5" colname="col5" colwidth="13mm" /><colspec colnum="6" colname="col6" colwidth="13mm" /><colspec colnum="7" colname="col7" colwidth="13mm" /><colspec colnum="8" colname="col8" colwidth="13mm" /><colspec colnum="9" colname="col9" colwidth="34mm" /><thead><row><entry namest="col1" nameend="col2" rowsep="0" align="left" valign="top" /><entry namest="col3" nameend="col8" align="center" valign="top">Examples</entry><entry morerows="1" align="center" valign="top">Mixing Time, minutes</entry></row><row><entry namest="col1" nameend="col2" align="left" valign="top">Component</entry><entry align="center" valign="top">1</entry><entry align="center" valign="top">2</entry><entry align="center" valign="top">3</entry><entry align="center" valign="top">4</entry><entry align="center" valign="top">5</entry><entry align="center" valign="top">6</entry></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Synthetic fluid, ml</entry><entry align="char" char=".">164.5</entry><entry align="char" char="." charoff="42">164.5</entry><entry align="char" char="." charoff="42">164.5</entry><entry align="char" char="." charoff="42">164.5</entry><entry align="char" char="." charoff="42">164.5</entry><entry align="char" char="." charoff="42">164.5</entry><entry align="center" /></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Primary emulsifier, ml</entry><entry align="char" char=".">8.5</entry><entry align="char" char="." charoff="42">8.5</entry><entry align="char" char="." charoff="42">8.5</entry><entry align="char" char="." charoff="42">8.5</entry><entry align="char" char="." charoff="42">8.5</entry><entry align="char" char="." charoff="42">8.5</entry><entry align="center" /></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Lime, g</entry><entry align="char" char=".">8.0</entry><entry align="char" char="." charoff="42">8.0</entry><entry align="char" char="." charoff="42">8.0</entry><entry align="char" char="." charoff="42">8.0</entry><entry align="char" char="." charoff="42">8.0</entry><entry align="char" char="." charoff="42">8.0</entry><entry align="center" /></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Fluid loss control agent, g</entry><entry align="char" char=".">10.0</entry><entry align="char" char="." charoff="42">10.0</entry><entry align="char" char="." charoff="42">10.0</entry><entry align="char" char="." charoff="42">10.0</entry><entry align="char" char="." charoff="42">10.0</entry><entry align="char" char="." charoff="42">10.0</entry><entry align="center">20</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Brine solution</entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center">10</entry></row><row rowsep="0"><entry /><entry>CaCl<sub>2</sub>, g</entry><entry align="char" char=".">12.1</entry><entry align="char" char="." charoff="42">12.1</entry><entry align="char" char="." charoff="42">12.1</entry><entry align="char" char="." charoff="42">12.1</entry><entry align="char" char="." charoff="42">12.1</entry><entry align="char" char="." charoff="42">12.1</entry><entry align="center" /></row><row rowsep="0"><entry /><entry>Water, ml</entry><entry align="char" char=".">23.8</entry><entry align="char" char="." charoff="42">23.8</entry><entry align="char" char="." charoff="42">23.8</entry><entry align="char" char="." charoff="42">23.8</entry><entry align="char" char="." charoff="42">23.8</entry><entry align="char" char="." charoff="42">23.8</entry><entry align="center" /></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Organophilic clay, g</entry><entry align="char" char=".">1.0</entry><entry align="char" char="." charoff="42">2.0</entry><entry align="char" char="." charoff="42">3.0</entry><entry align="char" char="." charoff="42">2.0</entry><entry align="center">2.0</entry><entry align="center">1.0</entry><entry align="center">20</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Oil wetting agent, ml</entry><entry align="char" char=".">6.0</entry><entry align="char" char="." charoff="42">6.0</entry><entry align="char" char="." charoff="42">6.0</entry><entry align="char" char="." charoff="42">6.0</entry><entry align="char" char="." charoff="42">6.0</entry><entry align="char" char="." charoff="42">6.0</entry><entry align="center">10</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Weighting Agent, g</entry><entry align="char" char=".">572</entry><entry align="char" char="." charoff="42">572</entry><entry align="char" char="." charoff="42">572</entry><entry align="char" char="." charoff="42">572</entry><entry align="char" char="." charoff="42">572</entry><entry align="char" char="." charoff="42">572</entry><entry align="center">20</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Styrene-butadiene polymer, g</entry><entry align="char" char=".">0</entry><entry align="char" char="." charoff="42">0</entry><entry align="char" char="." charoff="42">0</entry><entry align="char" char="." charoff="42">0</entry><entry align="char" char="." charoff="42">0</entry><entry align="char" char="." charoff="42">2.0</entry><entry align="center">10</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Polystyrene, g</entry><entry align="char" char=".">3.0</entry><entry align="char" char="." charoff="42">3.0</entry><entry align="char" char="." charoff="42">3.0</entry><entry align="char" char="." charoff="42">4.0</entry><entry align="char" char="." charoff="42">2.0</entry><entry align="char" char="." charoff="42">3.0</entry><entry align="center">10</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Bentonite, g</entry><entry align="char" char=".">3.0</entry><entry align="char" char="." charoff="42">3.0</entry><entry align="char" char="." charoff="42">3.0</entry><entry align="char" char="." charoff="42">2.0</entry><entry align="char" char="." charoff="42">4.0</entry><entry align="char" char="." charoff="42">3.0</entry><entry align="center">35</entry></row></tbody></tgroup></table></tables>
EXAMPLE 7
Preparation Of Drilling Fluid
0050An invert emulsion drilling fluid is prepared by (a) initially agitating about 240 ml of a synthetic fluid for about 1 minute using a blender and (b) then sequentially adding the following ingredients (with continuous mixing for about one minute after the addition of each material): (i) about 6 g of a primary emulsifier; (ii) about 8 g of lime (calcium hydroxide); and (iii) about 4 g of a fluid-loss preventing agent.
0051Subsequently, about 39 ml of fresh water is added to the above mixture and the resulting composition is mixed for about ten minutes. Then, about 11 g of an amine-treated bentonite is added and the resulting mixture is agitated for about 15 minutes.
0052Thereafter, the following materials are added in sequence, with about 5 minutes of mixing after the addition of each of the materials: (i) about 2 g of a secondary emulsifier; (ii) about 210 g of powdered barite (a non-toxic weighting agent); (iii) about 24 g of calcium chloride dihydrate (to provide salinity to the water phase without water wetting the barite); and (iv) about 20 g of a powdered clay (composed of about 35 weight percent smectite and about 65 weight percent kaolinite) to simulate drilled formation particles.
EXAMPLE 8
Analysis of Isoparaffin Synthetic Fluid Sample
0053Analytical results obtained from the analysis of an isoparaffin synthetic fluid sample from Shell Malaysia by gas chromatography are reported in the following Tables B-D. <tables id="tabl0010" num="0010"><table frame="all"><title>TABLE B</title><tgroup cols="2" rowsep="0"><colspec colnum="1" colname="col1" colwidth="28mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col2" align="center">Carbon Number Distribution Results</entry></row><row rowsep="1"><entry align="center">Carbon Number</entry><entry align="center">Weight Percent off</entry></row></thead><tbody><row><entry align="right">8</entry><entry align="char" char="." charoff="12">0.31</entry></row><row><entry align="right">9</entry><entry align="char" char="." charoff="12">0.41</entry></row><row><entry align="right">10</entry><entry align="char" char="." charoff="12">0.84</entry></row><row><entry align="right">11</entry><entry align="char" char="." charoff="12">1.86</entry></row><row><entry align="right">12</entry><entry align="char" char="." charoff="12">4.61</entry></row><row><entry align="right">13</entry><entry align="char" char="." charoff="12">6.22</entry></row><row><entry align="right">14</entry><entry align="char" char="." charoff="12">7.13</entry></row><row><entry align="right">15</entry><entry align="char" char="." charoff="12">8.33</entry></row><row><entry align="right">16</entry><entry align="char" char="." charoff="12">8.38</entry></row><row><entry align="right">17</entry><entry align="char" char="." charoff="12">9.43</entry></row><row><entry align="right">18</entry><entry align="char" char="." charoff="12">11.04</entry></row><row><entry align="right">19</entry><entry align="char" char="." charoff="12">10.95</entry></row><row><entry align="right">20</entry><entry align="char" char="." charoff="12">10.39</entry></row><row><entry align="right">21</entry><entry align="char" char="." charoff="12">8.23</entry></row><row><entry align="right">22</entry><entry align="char" char="." charoff="12">5.95</entry></row><row><entry align="right">23</entry><entry align="char" char="." charoff="12">3.43</entry></row><row><entry align="right">24</entry><entry align="char" char="." charoff="12">1.51</entry></row><row><entry align="right">25</entry><entry align="char" char="." charoff="12">0.64</entry></row><row rowsep="1"><entry align="right">>25</entry><entry align="char" char="." charoff="12">0.34</entry></row></tbody></tgroup></table></tables><tables id="tabl0011" num="0011"><table frame="all"><title>TABLE C</title><tgroup cols="4" rowsep="0"><colspec colnum="1" colname="col1" colwidth="27mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><colspec colnum="3" colname="col3" colwidth="30mm" /><colspec colnum="4" colname="col4" colwidth="34mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col4" align="center">Paraffin Distribution Results</entry></row><row rowsep="1"><entry namest="col1" nameend="col2" align="center">Analytical Data</entry><entry namest="col3" nameend="col4" align="center">Calculated Results</entry></row><row rowsep="1"><entry align="center">Carbon Content</entry><entry align="center">n-Paraffin Wt. %</entry><entry align="center">Iso-Paraffin Wt. %</entry><entry align="center">Ratio of Iso/n Paraffin</entry></row></thead><tbody><row><entry align="right">10</entry><entry align="right">0.60</entry><entry align="char" char=".">0.24</entry><entry>0.40</entry></row><row><entry align="right">11</entry><entry align="right">1.55</entry><entry align="char" char=".">0.31</entry><entry>0.20</entry></row><row><entry align="right">12</entry><entry align="right">2.60</entry><entry align="char" char=".">2.01</entry><entry>0.773</entry></row><row><entry align="right">13</entry><entry align="right">2.83</entry><entry align="char" char=".">3.39</entry><entry>1.198</entry></row><row><entry align="right">14</entry><entry align="right">5.22</entry><entry align="char" char=".">1.91</entry><entry>0.366</entry></row><row><entry align="right">15</entry><entry align="right">4.70</entry><entry align="char" char=".">3.63</entry><entry>0.77</entry></row><row><entry align="right">16</entry><entry align="right">4.30</entry><entry align="char" char=".">4.01</entry><entry>0.949</entry></row><row><entry align="right">17</entry><entry align="right">4.69</entry><entry align="char" char=".">4.74</entry><entry>1.01</entry></row><row><entry align="right">18</entry><entry align="right">4.52</entry><entry align="char" char=".">6.52</entry><entry>1.44</entry></row><row><entry align="right">19</entry><entry align="right">3.33</entry><entry align="char" char=".">7.62</entry><entry>2.29</entry></row><row><entry align="right">20</entry><entry align="right">2.25</entry><entry align="char" char=".">8.14</entry><entry>3.62</entry></row><row><entry align="right">21</entry><entry align="right">1.53</entry><entry align="char" char=".">6.70</entry><entry>5.17</entry></row><row><entry align="right">22</entry><entry align="right">0.89</entry><entry align="char" char=".">5.06</entry><entry>5.68</entry></row><row><entry align="right">23</entry><entry align="right">0.39</entry><entry align="char" char=".">3.04</entry><entry>7.79</entry></row><row><entry align="right">24</entry><entry align="right">0.12</entry><entry align="char" char=".">1.39</entry><entry>11.58</entry></row><row><entry align="right">25</entry><entry align="right">0.03</entry><entry align="char" char=".">0.61</entry><entry>20.33</entry></row><row><entry align="right">26</entry><entry align="right">0.01</entry><entry align="char" char=".">0.33</entry><entry>33</entry></row><row><entry align="right">27</entry><entry align="right">0.00</entry><entry /><entry /></row><row><entry align="right">28</entry><entry align="right">0.00</entry><entry /><entry /></row><row rowsep="1"><entry align="right">Total</entry><entry align="right"><o ostyle="single">39.53</o></entry><entry /><entry /></row></tbody></tgroup></table></tables>
0054Based upon the results listed in Table C, the iso-paraffin/n-paraffin ratio of the isoparaffin synthetic fluid sample for compounds containing from 17 to 20 carbon atoms follows the equation y = (x-16)<sup>(0.53+0.2(x-18))</sup>, where x is the carbon number and y is the iso-paraffin/n-paraffin ratio. In addition, for compounds containing 21 to 25 carbon atoms, the iso-paraffin/n-paraffin ratio of the isoparaffin synthetic fluid sample follows the equation y = (x-21)<sup>(1.48+0.25(x-23))</sup>, where x and y are as defined above. The foregoing equations are generally accurate within ± 1 unit and even within ± 0.5 unit. <tables id="tabl0012" num="0012"><table frame="all"><title>TABLE D</title><tgroup cols="6" rowsep="0"><colspec colnum="1" colname="col1" colwidth="17mm" /><colspec colnum="2" colname="col2" colwidth="15mm" /><colspec colnum="3" colname="col3" colwidth="15mm" /><colspec colnum="4" colname="col4" colwidth="15mm" /><colspec colnum="5" colname="col5" colwidth="15mm" /><colspec colnum="6" colname="col6" colwidth="15mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col6" align="center">Percent Off To Temperature Results</entry></row><row rowsep="1"><entry /><entry namest="col2" nameend="col3" align="center">Temperature</entry><entry /><entry namest="col5" nameend="col6" align="center">Temperature</entry></row><row rowsep="1"><entry align="center">Wt% Off</entry><entry align="center">°C</entry><entry align="center">°F</entry><entry align="center">V% Off</entry><entry align="center">°C</entry><entry align="center">°F</entry></row></thead><tbody><row><entry align="char" char="." charoff="21">0.5</entry><entry align="char" char=".">150.0</entry><entry align="center">302</entry><entry align="char" char="." charoff="25">0.5</entry><entry align="char" char=".">145.6</entry><entry align="center">294</entry></row><row><entry align="char" char="." charoff="21">5.0</entry><entry align="char" char=".">207.8</entry><entry align="center">406</entry><entry align="char" char="." charoff="25">5.0</entry><entry align="char" char=".">205.6</entry><entry align="center">402</entry></row><row><entry align="char" char="." charoff="21">10.0</entry><entry align="char" char=".">222.8</entry><entry align="center">433</entry><entry align="char" char="." charoff="25">10.0</entry><entry align="char" char=".">221.1</entry><entry align="center">430</entry></row><row><entry align="char" char="." charoff="21">15.0</entry><entry align="char" char=".">237.8</entry><entry align="center">460</entry><entry align="char" char="." charoff="25">15.0</entry><entry align="char" char=".">236.7</entry><entry align="center">458</entry></row><row><entry align="char" char="." charoff="21">20.0</entry><entry align="char" char=".">253.9</entry><entry align="center">489</entry><entry align="char" char="." charoff="25">20.0</entry><entry align="char" char=".">252.8</entry><entry align="center">487</entry></row><row><entry align="char" char="." charoff="21">25.0</entry><entry align="char" char=".">260.6</entry><entry align="center">501</entry><entry align="char" char="." charoff="25">25.0</entry><entry align="char" char=".">257.8</entry><entry align="center">496</entry></row><row><entry align="char" char="." charoff="21">30.0</entry><entry align="char" char=".">272.2</entry><entry align="center">522</entry><entry align="char" char="." charoff="25">30.0</entry><entry align="char" char=".">271.7</entry><entry align="center">521</entry></row><row><entry align="char" char="." charoff="21">35.0</entry><entry align="char" char=".">281.7</entry><entry align="center">539</entry><entry align="char" char="." charoff="25">35.0</entry><entry align="char" char=".">280.0</entry><entry align="center">536</entry></row><row><entry align="char" char="." charoff="21">40.0</entry><entry align="char" char=".">289.4</entry><entry align="center">553</entry><entry align="char" char="." charoff="25">40.0</entry><entry align="char" char=".">288.9</entry><entry align="center">552</entry></row><row><entry align="char" char="." charoff="21">45.0</entry><entry align="char" char=".">298.9</entry><entry align="center">570</entry><entry align="char" char="." charoff="25">45.0</entry><entry align="char" char=".">297.2</entry><entry align="center">567</entry></row><row><entry align="char" char="." charoff="21">50.0</entry><entry align="char" char=".">304.4</entry><entry align="center">580</entry><entry align="char" char="." charoff="25">50.0</entry><entry align="char" char=".">304.4</entry><entry align="center">580</entry></row><row><entry align="char" char="." charoff="21">55.0</entry><entry align="char" char=".">311.7</entry><entry align="center">593</entry><entry align="char" char="." charoff="25">55.0</entry><entry align="char" char=".">310.6</entry><entry align="center">591</entry></row><row><entry align="char" char="." charoff="21">60.0</entry><entry align="char" char=".">318.3</entry><entry align="center">605</entry><entry align="char" char="." charoff="25">60.0</entry><entry align="char" char=".">317.8</entry><entry align="center">604</entry></row><row><entry align="char" char="." charoff="21">65.0</entry><entry align="char" char=".">323.9</entry><entry align="center">615</entry><entry align="char" char="." charoff="25">65.0</entry><entry align="char" char=".">322.8</entry><entry align="center">613</entry></row><row><entry align="char" char="." charoff="21">70.0</entry><entry align="char" char=".">331.7</entry><entry align="center">629</entry><entry align="char" char="." charoff="25">70.0</entry><entry align="char" char=".">330.6</entry><entry align="center">627</entry></row><row><entry align="char" char="." charoff="21">75.0</entry><entry align="char" char=".">337.2</entry><entry align="center">639</entry><entry align="char" char="." charoff="25">75.0</entry><entry align="char" char=".">335.6</entry><entry align="center">636</entry></row><row><entry align="char" char="." charoff="21">80.0</entry><entry align="char" char=".">345.0</entry><entry align="center">653</entry><entry align="char" char="." charoff="25">80.0</entry><entry align="char" char=".">344.4</entry><entry align="center">652</entry></row><row><entry align="char" char="." charoff="21">85.0</entry><entry align="char" char=".">351.7</entry><entry align="center">665</entry><entry align="char" char="." charoff="25">85.0</entry><entry align="char" char=".">351.1</entry><entry align="center">664</entry></row><row><entry align="char" char="." charoff="21">90.0</entry><entry align="char" char=".">360.0</entry><entry align="center">680</entry><entry align="char" char="." charoff="25">90.0</entry><entry align="char" char=".">359.4</entry><entry align="center">679</entry></row><row><entry align="char" char="." charoff="21">95.0</entry><entry align="char" char=".">371.7</entry><entry align="center">701</entry><entry align="char" char="." charoff="25">95.0</entry><entry align="char" char=".">371.1</entry><entry align="center">700</entry></row><row rowsep="1"><entry align="char" char="." charoff="21">99.5</entry><entry align="char" char=".">399.4</entry><entry align="center">751</entry><entry align="char" char="." charoff="25">99.5</entry><entry align="char" char=".">398.9</entry><entry align="center">750</entry></row></tbody></tgroup></table></tables>
0055In addition, the gas chromatography analysis (both mass spectrometry and flame ionization detector (FID)) did not detect the presence of either aromatic or naphthenic compounds.
EXAMPLE 9
Preparation And Testing Of Isoparaffin Synthetic Fluid-Containing Drilling Fluid
0056Each of two substantially identical samples of an oil-base drilling fluid within the scope of the present invention was formulated as follows. (The isoparaffin synthetic fluid sample analyzed in Example 8 was employed as the synthetic fluid.) Ingredients were sequentially added in the order set forth below in Table E. After the addition of each ingredient, the resulting composition was mixed for the indicated mixing time prior to adding a subsequent ingredient to the composition. <tables id="tabl0013" num="0013"><table frame="all"><title>TABLE E</title><tgroup cols="3" rowsep="0"><colspec colnum="1" colname="col1" colwidth="54mm" /><colspec colnum="2" colname="col2" colwidth="12mm" /><colspec colnum="3" colname="col3" colwidth="34mm" /><thead valign="top"><row rowsep="1"><entry>Component</entry><entry /><entry align="center">Mixing Time, minutes</entry></row></thead><tbody><row><entry>Synthetic Fluid, ml</entry><entry>209</entry><entry /></row><row><entry>Imvitone brand organophilic clay, g</entry><entry>7.0</entry><entry align="center">30</entry></row><row><entry>Novamul brand emulsifier, ml</entry><entry>10.0</entry><entry /></row><row><entry>Novamod brand rheology modifier, g</entry><entry>2.0</entry><entry align="center">10</entry></row><row><entry>Lime, g</entry><entry>10.0</entry><entry align="center">10</entry></row><row><entry>Brine solution</entry><entry /><entry align="center">30</entry></row><row><entry> CaCl<sub>2</sub>, g</entry><entry>26.3</entry><entry /></row><row><entry> Water, ml</entry><entry>51.3</entry><entry /></row><row><entry>Versatrol I brand fluid loss</entry><entry /><entry /></row><row><entry>control agent, g</entry><entry>10.0</entry><entry align="center">15</entry></row><row rowsep="1"><entry>Barite, g</entry><entry>269</entry><entry align="center">30</entry></row></tbody></tgroup></table></tables>
0057One sample was used to check the initial rheological properties, and the other sample was used to test the aged rheological properties. The age-tested sample was placed into an aging bomb in the presence of about 790.8 kpascal (100 psi) nitrogen and rolled at about 176.7°C (350° F). After aging, the rheological properties of the age-tested sample were checked. Unless otherwise noted below in Table F, both the initial and age-tested rheological properties were measured at about at 48.9°C (120°F) according to procedures described in <u style="single">Recommended Practice - Standard Procedure for Field Testing Drilling Fluids</u>, API Recommended Practice 13B-2 (RP 13B-2), Second Edition, December 1, 1991, American Petroleum Institute, Washington, DC (hereinafter referred to as "API"). The measured results are set forth in Table F. <tables id="tabl0014" num="0014"><table frame="all"><title>TABLE F</title><tgroup cols="3" rowsep="0"><colspec colnum="1" colname="col1" colwidth="38mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="18mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col3" align="center">Drilling Fluid Rheological Properties</entry></row><row rowsep="1"><entry>Property</entry><entry>Initial</entry><entry>Aged</entry></row></thead><tbody><row><entry>Dial reading<sup>a</sup>,</entry><entry /><entry /></row><row><entry> 600 rpm</entry><entry>103</entry><entry>106</entry></row><row><entry> 300 "</entry><entry>74</entry><entry>61</entry></row><row><entry> 200 "</entry><entry>59</entry><entry>48</entry></row><row><entry> 100 "</entry><entry>42</entry><entry>29</entry></row><row><entry> 6 "</entry><entry>20</entry><entry>8</entry></row><row><entry> 3 "</entry><entry>18</entry><entry>7</entry></row><row><entry>Gel Strength<sup>b</sup>,</entry><entry /><entry /></row><row><entry> 10 sec, lb/100ft<sup>2</sup></entry><entry>19</entry><entry>7</entry></row><row><entry> kg/10m<sup>2</sup></entry><entry>9.3</entry><entry>3.4</entry></row><row><entry> 10 min, lb/100ft<sup>2</sup></entry><entry>23</entry><entry>37</entry></row><row><entry> kg/10m<sup>2</sup></entry><entry>11.2</entry><entry>18.0</entry></row><row><entry>PV<sup>c</sup>, cp</entry><entry>29</entry><entry>45</entry></row><row><entry> N-sec/m<sup>2</sup>(10<sup>3</sup>)</entry><entry>29</entry><entry>45</entry></row><row><entry>YP<sup>d</sup>, lb/100ft<sup>2</sup></entry><entry>45</entry><entry>16</entry></row><row><entry> kg/10m<sup>2</sup></entry><entry>22.0</entry><entry>7.8</entry></row><row><entry>HTHP fluid loss<sup>e</sup>, ml</entry><entry>2.8</entry><entry>2.8</entry></row><row><entry>ES<sup>f</sup>, volts</entry><entry>814</entry><entry>593</entry></row><row><entry>API fluid loss, ml</entry><entry>1.5</entry><entry>0</entry></row><row rowsep="1"><entry>Cake</entry><entry>0</entry><entry>0</entry></row></tbody></tgroup><tgroup cols="3" rowsep="0"><colspec colnum="1" colname="col1" colwidth="38mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="18mm" /><tbody><row><entry namest="col1" nameend="col3" align="justify">a. Dial readings were obtained using a 115-volt motor driven viscometer and measured according to the procedure described in API, pages 9-10, sections 2.4 to 2.5. b. Gel strength for 10 seconds and 10 minutes was determined in accordance with the procedure discussed in API, page 10, section 2.5, paragraphs f and g, respectively. c. PV was determined in accordance with the procedure and calculations discussed in API, page 10, sections 2.5 to 2.6. d. YP was determined in accordance with the procedure and calculations discussed in API, page 10, sections 2.5 to 2.6. e. HTHP denotes "high-temperature/high-pressure test" and was determined in accordance with the procedure discussed in API, pages 13-14, section 3. f. "ES" denotes "electrical stability" and was measured in accordance with the procedure discussed in API, pages 21-22, section 6.</entry></row></tbody></tgroup></table></tables>
<u style="single">EXAMPLE 10</u>
<u style="single">Toxicity Study</u>
0058With one modification, another drilling fluid was prepared in accordance with the protocol set forth in preceding Example 8 using the isoparaffin synthetic fluid analyzed in Example 8 as the synthetic fluid. The sole modification consisted of using about ten times the amount of each ingredient in formulating the drilling fluid. The drilling fluid was subjected to the 96 hour LC<sub>50</sub> Mysid shrimp (<i>Mysidopsis bahia</i>) bioassay test by an independent laboratory and achieved a score of about 396x10<sup>3</sup>.
EXAMPLE 11
Comparative Toxicity Study
0059With two modifications, another drilling fluid was prepared in accordance with the protocol set forth above in Example 8. One modification entailed using the dimer of 1-decene (the base synthetic fluid of Novadril brand non-toxic drilling fluid) as the synthetic fluid, and the other modification consisted of using about ten times the amount of each ingredient in formulating the drilling fluid. The drilling fluid was subjected to the 96 hour LC<sub>50</sub> Mysid shrimp (<i>Mysidopsis bahia</i>) bioassay test by the same independent laboratory employed in Example 10 and achieved a score of about 207.6x10<sup>3</sup>.
0060Since a higher numerical result obtained by the 96 hour LC<sub>50</sub> Mysid shrimp (<i>Mysidopsis bahia</i>) bioassay test is indicative of lower toxicity of the material test, comparative Examples 10-11 indicate that a synthetic fluid within the scope of the present invention is substantially less toxic than the commercially used Novadril brand synthetic fluid. The reason for this is that the number obtain by the exemplary synthetic fluid-containing drilling fluid is roughly about 1.9 times greater than that obtained by the Novadril-containing drilling fluid. In fact, the results documented in comparative Examples 10-11 are quite surprising and unexpected because conventional wisdom in the drilling fluids industry considers toxicity to increase with decreasing carbon content and the tested synthetic fluid within the scope of the present invention has a significantly higher concentration of hydrocarbons containing less than 20 carbon atoms than present in the Novadril brand synthetic fluid.
EXAMPLE 12
Additional Analysis of Isoparaffin Synthetic Fluid Samples
0061Analytical results obtained from the analysis of two additional isoparaffin synthetic fluid samples from Shell Malaysia by gas chromatography are reported in the following Table G. <tables id="tabl0015" num="0015"><table frame="all"><title>TABLE G</title><tgroup cols="5" rowsep="0"><colspec colnum="1" colname="col1" colwidth="27mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><colspec colnum="5" colname="col5" colwidth="20mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col5" align="center">Carbon Number Distribution Results</entry></row><row rowsep="1"><entry /><entry namest="col2" nameend="col5" align="center">Weight Percent Off</entry></row><row rowsep="1"><entry align="center">Carbon Number</entry><entry namest="col2" nameend="col3" align="center">Total Organics</entry><entry namest="col4" nameend="col5" align="center">N-Alkanes Only<sup>a</sup></entry></row><row rowsep="1"><entry /><entry align="center">Sample A</entry><entry align="center">Sample B</entry><entry align="center">Sample A</entry><entry align="center">Sample B</entry></row></thead><tbody><row><entry align="right">≤6</entry><entry align="right">0.02</entry><entry align="right">0.05</entry><entry align="right">0.013</entry><entry align="right">0.023</entry></row><row><entry align="right">7</entry><entry align="right">0.07</entry><entry align="right">0.14</entry><entry align="right">0.050</entry><entry align="right">0.096</entry></row><row><entry align="right">8</entry><entry align="right">0.23</entry><entry align="right">0.39</entry><entry align="right">0.161</entry><entry align="right">0.25</entry></row><row><entry align="right">9</entry><entry align="right">0.59</entry><entry align="right">0.78</entry><entry align="right">0.354</entry><entry align="right">0.42</entry></row><row><entry align="right">10</entry><entry align="right">0.93</entry><entry align="right">1.21</entry><entry align="right">0.55</entry><entry align="right">0.66</entry></row><row><entry align="right">11</entry><entry align="right">1.42</entry><entry align="right">2.15</entry><entry align="right">0.67</entry><entry align="right">1.05</entry></row><row><entry align="right">12</entry><entry align="right">5.17</entry><entry align="right">7.57</entry><entry align="right">1.96</entry><entry align="right">3.33</entry></row><row><entry align="right">13</entry><entry align="right">7.49</entry><entry align="right">10.21</entry><entry align="right">2.17</entry><entry align="right">3.17</entry></row><row><entry align="right">14</entry><entry align="right">9.22</entry><entry align="right">10.16</entry><entry align="right">3.60</entry><entry align="right">2.74</entry></row><row><entry align="right">15</entry><entry align="right">9.00</entry><entry align="right">8.99</entry><entry align="right">3.87</entry><entry align="right">2.43</entry></row><row><entry align="right">16</entry><entry align="right">9.26</entry><entry align="right">7.84</entry><entry align="right">4.35</entry><entry align="right">2.19</entry></row><row><entry align="right">17</entry><entry align="right">9.30</entry><entry align="right">8.59</entry><entry align="right">4.46</entry><entry align="right">3.01</entry></row><row><entry align="right">18</entry><entry align="right">13.45</entry><entry align="right">11.21</entry><entry align="right">5.78</entry><entry align="right">4.37</entry></row><row><entry align="right">19</entry><entry align="right">11.53</entry><entry align="right">9.83</entry><entry align="right">4.61</entry><entry align="right">3.64</entry></row><row><entry align="right">20</entry><entry align="right">7.57</entry><entry align="right">7.60</entry><entry align="right">2.95</entry><entry align="right">2.51</entry></row><row><entry align="right">21</entry><entry align="right">5.94</entry><entry align="right">5.32</entry><entry align="right">2.32</entry><entry align="right">1.76</entry></row><row><entry align="right">22</entry><entry align="right">4.50</entry><entry align="right">4.06</entry><entry align="right">1.39</entry><entry align="right">1.05</entry></row><row><entry align="right">23</entry><entry align="right">2.42</entry><entry align="right">2.33</entry><entry align="right">0.65</entry><entry align="right">0.51</entry></row><row><entry align="right">24</entry><entry align="right">1.00</entry><entry align="right">0.94</entry><entry align="right">0.27</entry><entry align="right">0.19</entry></row><row><entry align="right">25</entry><entry align="right">0.42</entry><entry align="right">0.31</entry><entry align="right">0.076</entry><entry align="right">0.037</entry></row><row><entry align="right">>25</entry><entry align="right">0.49</entry><entry align="right">0.30</entry><entry /><entry /></row><row><entry align="right">Total</entry><entry align="right"><o ostyle="single">100.02</o></entry><entry align="right"><o ostyle="single">99.98</o></entry><entry align="right"><o ostyle="single">40.254</o></entry><entry align="right"><o ostyle="single">33.436</o></entry></row><row><entry align="right">FP<sup>b</sup>,</entry><entry /><entry /><entry /><entry /></row><row rowsep="1"><entry align="right">°C(°F)</entry><entry align="right">110(231)</entry><entry align="right">106(224)</entry><entry /><entry /></row></tbody></tgroup><tgroup cols="5" rowsep="0"><colspec colnum="1" colname="col1" colwidth="27mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><colspec colnum="5" colname="col5" colwidth="20mm" /><tbody><row><entry namest="col1" nameend="col5" align="justify">a. "(N-Alkanes/TO)100%" denotes, for a given carbon number, the weight percent off of n-alkanes divided by the weight percent off of total organics, the quotient being multiplied by 100%. b. "FP" denotes flash point as determined by Cleveland Open Cup method.</entry></row></tbody></tgroup></table></tables>
0062Although the present invention has been described in detail with reference to some preferred versions, other versions are possible. For example, the synthetic fluid can also be employed as the base liquid component in other wellbore fluids. (As used in the specification and claims, the term "wellbore fluid" means a fluid used while conducting pay zone drilling, underreaming, drilling in, plugging back, sand control, perforating, gravel packing, chemical treatment, hydraulic fracturing, cleanout, well killing, tubing and hardware replacement, and zone selective operations (e.g., well completion operations) as well as a fluid employed as a packer fluid or as a spotting fluid.) In addition to the base liquid, the wellbore fluids contain one or more additional ingredients such as proppants suitable for use in hydraulically fracturing subterranean formations, particulate agents suitable for use in forming a gravel pack, viscosifiers, organophilic clays, and fluid loss control agents.
0063Common proppants suitable for use in hydraulic fracturing procedures are quartz sand grains, tempered glass beads, sintered bauxite, resin coated sand, aluminum pellets, and nylon pellets. Generally, the proppants are employed in the wellbore fluids intended for use as hydraulic fracturing fluids and are used in concentrations of roughly about 119.8 to about 1,198.3 kg/m<sup>3</sup> (1 to about 10 pounds per gallon) of the wellbore fluid. The proppant size is typically smaller than about 2 mesh on the U.S. Sieve Series scale, with the exact size selected being dependent on the particular type of formation to be fractured, the available pressure and pumping rates, as well as other factors known to those skilled in the art.
0064Typical particulate agents employed in the wellbore fluids used as gravel packing fluids include, but are not limited to, quartz sand grains, glass beads, synthetic resins, resin coated sand, walnut shells, and nylon pellets. The gravel pack particulate agents are generally used in concentrations of about 119.8 to about 2,396.5 kg/m<sup>3</sup> (1 to about 20 pounds per gallon) of the wellbore fluid. The size of the particulate agent employed depends on the type of subterranean formation, the average size of formation particles, and other parameters known to those skilled in the art. Generally, particulate agents of about 8 to about 70 mesh on the U.S. Sieve Series scale are used.
0065Illustrative viscosifiers, organophilic clays, and fluid loss control agents optionally used in wellbore fluids and their concentrations are the same as discussed above in connection with drilling fluids.
0066The wellbore fluids are prepared by combining the synthetic fluid with any additional additive (e.g., hydraulic fracturing proppants, gravel pack particulate agents, viscosifiers, fluid loss control agents, and organophilic clays). The synthetic fluid typically comprises at least about 50 weight percent of the wellbore fluid, the weight percent being based on the weight of all ingredients present in the wellbore fluid. Accordingly, wellbore fluids containing at least about 60, 70, 80, or even 90 weight percent synthetic fluid are not uncommon. (In fact, in some cases, the synthetic fluid constitutes the entire wellbore fluid.) In terms of the liquid fraction of the wellbore fluid, the synthetic fluid generally comprises from about 50 to 100 weight percent of the liquids employed in wellbore fluids. For example, the synthetic fluid can comprise at least about 60, 70, 80, or 90 weight percent of the liquid portion of the wellbore fluid.
0067The specific techniques used when employing the wellbore fluid are determined by its intended use and are analogous to methodologies employed when using prior art wellbore fluids for corresponding completion or work-over operations. For example, when the wellbore fluid is employed as a gravel packing fluid, it is typically injected into the formation in accordance with the procedure discussed in <patcit id="pcit0003" dnum="US4552215A"><text>U.S. Patent 4,552,215</text></patcit>.
0068When employed as a fracturing fluid, the wellbore fluid of the present invention is usually injected into the formation using procedures analogous to those disclosed in <patcit id="pcit0004" dnum="US4488975A"><text>U.S. Patent 4,488,975</text></patcit>; <patcit id="pcit0005" dnum="US4553601A"><text>U.S. Patent 4,553,601</text></patcit>; Howard et al., <u style="single">Hydraulic Fracturing</u>, Society of Petroleum Engineers of the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., New York, NY (1970); and <nplcit id="ncit0010" npl-type="s"><text>Allen et al., Production Operations, Well completions, Workover, and Stimulation, 3rd Edition, Oil & Gas Consultants International, Inc., Tulsa, Oklahoma (1989) (Allen), volume 2, chapter 8</text></nplcit>.
0069When employed in a perforating operation, the wellbore fluid of the present invention is used according to the methodologies disclosed in volume 1, chapter 7 of Allen, referenced above.
0070Techniques for using packer fluids and well killing fluids, such as those discussed in volume 1, chapter 8 of Allen, are also applicable to the wellbore fluid of the present invention.
0071In addition, because the synthetic fluids employed in the present invention are lubricous, they can constitute up to about 10, and preferably from about 2 to about 5, weight percent of a water-based drilling fluid. In fact, any moving parts can be lubricated with these synthetic fluids.
0072Furthermore, while the synthetic fluid is generally manufactured by the Fischer-Tropsch process and various modifications thereof, fluids meeting the specifications set forth above in Tables I-V can also be obtained by further processing various petroleum refinery products (e.g., subjecting a petroleum product to further distillation, hydroisomerization, and/or hydrocracking procedures).
Contents9
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Numbers
- Publication
- 0840769
- Application
- 969237411
Titles3
- German
- NICHTTOXISCHE, BILLIGE SYNTHETISCHE BOHRFLÜSSIGKEIT
- English
- NON-TOXIC, INEXPENSIVE SYNTHETIC DRILLING FLUID
- French
- FLUIDE DE FORAGE SYNTHETIQUE ECONOMIQUE NON TOXIQUE
Classification
- CPC, 4
- C09K8/64
- C09K8/34
- C09K8/60
- Y10S507/905
- IPC, 7
- C09K8 06
- C09K8 02
- C09K8 34
- C09K8 60
- C09K8 64
- E21B43 04
- E21B43 267
Designated states4
- Contracting states, 4
- Denmark
- United Kingdom
- Italy
- Netherlands (Kingdom of the)