US20040198618A1 - High stability, high lubricity, low toxicity, high biodegradability drilling fluid - Google Patents
High stability, high lubricity, low toxicity, high biodegradability drilling fluid Download PDFInfo
- Publication number
- US20040198618A1 US20040198618A1 US10/785,317 US78531704A US2004198618A1 US 20040198618 A1 US20040198618 A1 US 20040198618A1 US 78531704 A US78531704 A US 78531704A US 2004198618 A1 US2004198618 A1 US 2004198618A1
- Authority
- US
- United States
- Prior art keywords
- drilling fluid
- fluid
- fischer
- product
- isoparaffins
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012530 fluid Substances 0.000 title claims abstract description 108
- 238000005553 drilling Methods 0.000 title claims abstract description 75
- 231100000053 low toxicity Toxicity 0.000 title description 3
- 150000001336 alkenes Chemical class 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims description 32
- 229930195733 hydrocarbon Natural products 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000006297 dehydration reaction Methods 0.000 description 11
- 238000004821 distillation Methods 0.000 description 11
- 230000018044 dehydration Effects 0.000 description 10
- -1 fatty acid esters Chemical class 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002453 autothermal reforming Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 231100000402 unacceptable toxicity Toxicity 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
Definitions
- the present invention relates to drilling fluids derived from the products of a Fischer-Tropsch synthesis. More particularly, the invention relates to base fluids, and drilling fluids produced therefrom, having high stability, lubricity, and biodegradability while also having low toxicity. The invention further relates to processes of producing and using the drilling fluids.
- Drilling fluids are well known for use in oil and gas well drilling operations.
- crude, diesel and mineral oils were used as base fluids in formulating drilling fluids.
- Such oil based drilling fluids however, have unacceptable toxicity and persistence, or non-biodegradability. Toxicity and persistence issues are especially critical in offshore drilling operations.
- Pseudo-oil based drilling fluids are also well known wherein the base fluids are fatty acid esters or synthetic hydrocarbons.
- Such synthetic hydrocarbons have included polyalphaolefins, linear alphaolefins, internal olefins, and mixtures thereof as well as linear and branched paraffins and mixtures thereof.
- Synthetic olefinic and paraffinic base fluids produced by oligomerizing low carbon number hydrocarbons are well known but are expensive to produce. Similarly, ester base fluids are expensive to produce. 161 The cost of drilling fluids may be reduced by use of Fisher-Tropsch synthesis to produce paraffinic base fluids. Paraffinic drilling fluids, however, generally do not have adequate low temperature properties for use in offshore and cold weather drilling operations.
- One approach to the low temperature issue incorporates multi-methyl branched isoparaffins or isoparaffins with branches of higher carbon number than methyl into the paraffinic base fluid.
- Such paraffinic base fluids contain C 10 -C 24 n-paraffins and isoparaffins, with an iso to normal ratio ranging from 0.5:1 to 9:1. Greater than 50% of the total isoparaffin content are mono-methyl branched isoparaffins and about 30% are multi-methyl substituted.
- a similar approach to the low temperature issue involves formulation of a drilling fluid containing a mixture of n-paraffins and isoparaffins wherein at least 90% of the isoparaffins are mono- or poly-methyl branched isomers.
- a base fluid of a mixture of linear and branched alphaolefins with the linear to branch ratio ranging from 1:1 to 5:1 is used.
- the olefins may be produced from high temperature Fischer-Tropsch synthesis.
- High temperature Fischer-Tropsch synthesis results in primarily internal branching of the branched hydrocarbons.
- drilling fluids are not wholly biodegradable resulting in increased persistence.
- drilling fluids composed of olefins are easily oxidizable and, therefore, must be stored under a nitrogen blanket to provide a reasonable shelf life. Even with nitrogen padding, olefinic drilling fluids cannot be stored for periods as long as paraffinic drilling fluids. Therefore, the cost of using olefinic drilling fluids is increased by both its special storage requirements and loss of oxidized product.
- a base fluid which may be used for drilling fluid formulation.
- the base fluid includes at least about 5 wt % olefins, at least about 5 wt % n-paraffins and between about 2 and 50 wt % branched paraffins wherein substantially all of the branch groups are monomethyl and wherein the ratio of terminal monomethyl branching to internal monomethyl branching is at least about 1:1.5.
- a drilling fluid is provided wherein the drilling fluid contains between about 2 and about 90 wt % olefins, between about 5 and about 90 wt % n-paraffins and between about 0 and about 10 wt % oxygenates.
- Yet another embodiment of the invention provides a process for producing a drilling from a light Fischer-Tropsch liquid.
- C x refers to a hydrocarbon compound having predominantly a carbon number of x.
- C x may be modified by reference to a particular species of hydrocarbons, such as, for example, C 5 olefins.
- the term means an olefin stream comprised predominantly of pentenes but which may have impurity amounts, i.e. less than about 10%, of olefins having other carbon numbers such as hexene, heptene, propene, or butene.
- C x+ refers to a stream wherein the hydrocarbons are predominantly those having a hydrocarbon number of x or greater but which may also contain impurity levels of hydrocarbons having a carbon number of less than x.
- C 15+ means hydrocarbons having a carbon number of 15 or greater but which may contain impurity levels of hydrocarbons having carbon numbers of less than 15.
- C x -C y where x and y are numbers greater than zero, refers to a mixture of hydrocarbon compounds wherein the predominant component hydrocarbons, collectively about 90% or greater by weight, have carbon numbers between x and y inclusive.
- C 5 -C 9 hydrocarbons means a mixture of hydrocarbon compounds which is predominantly comprised of hydrocarbons having carbon numbers between 5 and 9 inclusive, but may also include impurity level quantities of hydrocarbons having other carbon numbers.
- high lubricity means having a wear scar of average diameter of about ⁇ 0.46 mm at 60° C. tested in accordance with ASTM Standard D-6079-02 entitled “Standard Test Method for Evaluating Lubricity of Diesel Fuels by the High-Frequency Reciprocating Rig.”
- high stability and “high oxidative stability” mean having a total solids ⁇ 1.5 mg/100 ml tested in accordance with ASTM Standard D-22-74-Ola entitled “Standard Test Method for Oxidation Stability of Distillate Fuel Oil (Accelerated Method).” Note that these methods are being applied herein to the analysis and characterization of synthetic products although the standards refer expressly to petroleum derived products.
- Embodiments of the drilling fluid of the invention contain a base fluid having from about 5 to about 90 wt % linear alpha- and internal olefins, from about 5 to about 20 wt % isoparaffins, from about 5 to about 90 wt % n-paraffins and from about 0 to about 10 wt % oxygenates.
- the base fluid for the drilling fluid of such embodiments may be obtained from a Fischer-Tropsch synthesis using synthesis gas as a feed stock.
- production of the drilling fluid from a base fluid produced by the Fischer-Tropsch synthesis and subsequent processing as described herein is desirable as it results in a product having the desirable olefin and paraffin contents.
- the base fluid composition may be otherwise produced while yet retaining the remaining advantages of the invention.
- some embodiments of the base and drilling fluids of the invention are not produced by Fischer-Tropsch synthesis.
- a Fischer-Tropsch conversion system for converting hydrocarbon gases to liquid or solid hydrocarbon products using autothermal reforming includes a synthesis gas unit, which includes a synthesis gas reactor in the form of an autothermal reforming reactor (ATR) containing a reforming catalyst, such as a nickel-containing catalyst.
- a stream of light hydrocarbons to be converted, which may include natural gas, is introduced into the reactor along with oxygen (O 2 ).
- the oxygen may be provided from compressed air or other compressed oxygen-containing gas, or may be a pure oxygen stream.
- the ATR reaction may be adiabatic, with no heat being added or removed from the reactor other than from the feeds and the heat of reaction.
- the reaction is carried out under sub-stoichiometric conditions whereby the oxygen/steam/gas mixture is converted to syngas.
- Fischer-Tropsch systems are described in U.S. Pat. Nos. 4,973,453; 5,733,941; 5,861,441; 6,130,259, 6,169,120 and 6,172,124, the disclosures of which are herein incorporated by reference.
- the Fischer-Tropsch reaction for converting syngas which is composed primarily of carbon monoxide (CO) and hydrogen gas (H 2 ) may be characterized by the following general reaction:
- Non-reactive components such as nitrogen may also be included or mixed with the syngas. This may occur in those instances where air or some other non-pure oxygen source is used during the syngas formation.
- the syngas is delivered to a synthesis unit, which includes a Fischer-Tropsch reactor (FTR) containing a Fischer-Tropsch catalyst.
- Fischer-Tropsch catalysts may be used in carrying out the reaction. These include cobalt, iron, ruthenium as well as other Group VIIIB transition metals or combinations of such metals, to prepare both saturated and unsaturated hydrocarbons.
- a non-iron catalyst may be used.
- the F-T catalyst may include a support, such as a metal-oxide support, including silica, alumina, silica-alumina or titanium oxides.
- a Co catalyst on transition alumina with a surface area of approximately 100-200 m 2 /g is used in the form of spheres of 50-150 ⁇ m in diameter.
- the Co concentration on the support may also be 15-30%.
- Certain catalyst promoters and stabilizers may be used.
- the stabilizers include Group IIA or Group IIIB metals, while the promoters may include elements from Group VIII or Group VIIB.
- the Fischer-Tropsch catalyst and reaction conditions may be selected to be optimal for desired reaction products, such as for hydrocarbons of certain chain lengths or number of carbon atoms.
- any of the following reactor configurations may be employed for Fischer-Tropsch synthesis: fixed bed, slurry reactor, ebullating bed, fluidizing bed, or continuously stirred tank reactor (CSTR).
- CSTR continuously stirred tank reactor
- a slurry bed reactor is used.
- the FTR may be operated at a pressure of 100 to 500 psia and a temperature of 375° F. to 500° C.
- the reactor gas hourly space velocity (“GHSV”) may be from 1000 to 8000 hr ⁇ 1 .
- Syngas useful in producing a Fischer-Tropsch product useful in the invention may contain gaseous hydrocarbons, hydrogen, carbon monoxide and nitrogen with H 2 /CO ratios from about 1.8 to about 2.4.
- the hydrocarbon products derived from the Fischer-Tropsch reaction may range from methane (CH 4 ) to high molecular weight paraffinic waxes containing more than 100 carbon atoms.
- An overhead product stream is recovered from the FTR and may be separated into tail gas and light Fischer-Tropsch liquid (“LFTL”) products in a cold separator. The LFTL stream may then be distilled to yield a hydrocarbon product of primarily C 13 -C 22 olefins and paraffins.
- the C 13 -C 22 distillation cut may be used directly as the base fluid.
- Low levels of C 13 ⁇ hydrocarbons may be present in the C 13 -C 22 cut provided such levels do not cause the drilling fluid to exceed current regulatory limits.
- C 13 ⁇ hydrocarbons may be present in amounts between about 0.01 and 10 wt %. The presence of such small amounts of C 13 ⁇ hydrocarbons permits incorporation of a wider distribution of C 13+ hydrocarbons, particularly C 16+ hydrocarbons, for improved lubricity.
- the hydrocarbon number distribution is such as to result in a drilling fluid pour point below about 10° C.
- Embodiments of the base fluid contains from about 5 to about 90 wt % linear alpha- and internal olefins.
- the olefin content may provide the mixture with lower pour-point, better surface activity, better lubricity and better adherence to metal.
- the Fischer-Tropsch product will have approximately 5% alpha and internal olefin content.
- Concentration of olefins may be undertaken, for example, by one or more of the following known techniques: (1) molecular sieve separation of olefins and paraffins, such as UOP's OLEX® process, and (2) distillation of paraffins away from individual C X cuts.
- the base fluid may contain between about 5 to about 95 wt % paraffins. Of the total paraffin content from about 3 to about 20 wt % are isoparaffins. Substantially all of the isoparaffins are terminal monomethyl species. As used herein, the terminal species include 2- and 3-methyl branched. The presence of monomethyl isoparaffins improves low temperature properties, such as pour point, as well as lubricity and viscosity. Moreover, because the isoparaffins are predominantly terminally branched, the paraffin content of the base fluid is substantially wholly biodegradable. Using the Fischer-Tropsch synthesis described herein, about 5 wt % terminal methyl branched paraffins are produced in the LFTL.
- Concentration of isoparaffins may be increased by one or more of the following techniques: (1) molecular sieve separation of linear and branched paraffins, such as UOP's OLEX® process, and (2) isomeric distillation of isoparaffin.
- Embodiments of the base fluid contain between about 0 and about 10 wt % oxygenates.
- the oxygenates are principally primary alcohols.
- Other oxygenates, including aldehydes, ketones, carboxylic acids and esters and di-esters of carboxylic acids are also present in small amounts.
- Oxygenate content in the C 13 -C 22 cut of the Fischer-Tropsch reaction product ranges from between about 0.5 to about 5.0 wt %.
- Low levels of oxygenates in the drilling fluid from between about 0 and about 10 wt % provide improved lubricity.
- oxygenates may assist in emulsification in invert drilling muds.
- Oxygenate control may be used on the C 13 -C 22 cut of the Fischer-Tropsch product stream.
- a base fluid is produced by vaporizing a product stream and passing the vaporized product over an activated alumina catalysts to dehydrate alcohols to corresponding olefins. The conversion of the alcohol content of the product stream occurs according to the following reaction:
- the LFTL, C 13 -C 22 or other product stream may be vaporized at a temperature from about 400° F. to about 800° F. and then passed over one or more dehydration beds containing activated treated alumina or silica-alumina.
- the dehydration beds are packed beds. Essentially all of the primary and internal alcohols present in the vaporized stream are dehydrated to their corresponding olefins, with conversion rates of at least 95%.
- Dehydration reaction temperature may range from between about 400° and 800° F.
- the vaporized feed for the dehydration unit may be superheated prior to being fed into the dehydration beds or alternatively, may be heated within packed beds.
- the LHSV of packed beds may range from about 0.10 hr ⁇ 1 to about 2.0 hr ⁇ 1 .
- Reaction pressure may be maintained by the pressure of the accumulator and must be such to vaporize all of the dehydration feed. Typically, the pressure may range from between about 0 psia to about 100 psig.
- a moving bed of alumina or silica-alumina catalyst may be used. Fluidized beds, slurry beds or ebullating beds may be used with continuous batch or semi-batch catalyst removal and regeneration. The catalyst may be removed by one of these methods and regenerated by passing a mixture of nitrogen and oxygen or air at elevated temperatures over the catalyst.
- Alumina catalysts useful for the dehydration of alcohols include, for example, gamma-alumina, theta-alumina, pacified alumina, and activated alumina.
- High surface area aluminas are particularly useful in the invention and include those aluminas having a surface area of about 100 m 2 /gm or greater.
- alumina useful in the integrated Fischer-Tropsch process include, for example, S-400, which has a surface area of about 335 m 2 /gm, and DD-470, which has a surface area of about 375 m 2 /gm.
- S-400 ad DD-470 are alumina catalysts made and sold by Alcoa.
- Alumina catalysts for use in the integrated Fischer-Tropsch process generally contain at least about 90 wt % Al 2 O 3 , oxides of silicon and iron present in amounts of less than about 0 wt %, and oxides of sodium present in an amount of less than about 1 wt %.
- the alumina catalysts are generally supplied as substantially spherical particles having diameter from about 1 ⁇ 8 to about 1 ⁇ 4 inch.
- molecular sieve or zeolitic molecular sieve forms of the alumina or silica-alumina catalysts may be used.
- silico alumino phosphate (“SAPO”) molecular sieves may be used in the packed beds.
- SAPO molecular sieves contain a 3-dimensional microporous crystal structure having 8, 10, or 12 membered ring structures. The ring structures can have an average pore size ranging from between about 3.5 angstroms to about 15 angstroms.
- Other silica-containing zeolitic molecular sieve catalysts, such as ZSM-5 may be used in the dehydration bed.
- the aqueous and organic phases may be separated. Such dehydration process may further be used to increase the olefin content of the product stream to be used to produce the base fluid.
- Other methods of oxygenate control include, for example, reaction of the alcohol content of the C 13 -C 22 cut of a Fischer-Tropsch product stream with maleic or succinic anhydride or with a carboxylic acid, such as formic acid, acetic acid, or other acids.
- the carboxylic acid esters may be retained in the stream as they are excellent lubricants which are also highly biodegradable. Both the lubricity and the biodegradability of the base fluid may be improved by converting at least a portion of the alcoholic oxygenate content to carboxylic acid esters.
- the drilling fluid may optionally include one or more surfactants (e.g., emulsifiers, wetting agents), viscosifiers, weighting agents, fluid loss control agents, and proppants. Because the drilling fluid should be non-toxic, these optional ingredients, like the base fluid, are preferably also non-toxic. Acceptable emulsifiers include, but are not limited to, fatty acids, and fatty acid derivatives including amido-amines, polyamides, polyamines, esters, imidaxiolines, and alcohols.
- Typical 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.
- Exemplary weighting agents include, but are not limited to, barite, iron oxide, gelana, siderite, calcium oxide, and calcium carbonate.
- Acceptable proppants include sand, gravel, and nut shells.
- Exemplary viscosifiers include, but are not limited to, organophilic clays, non-organophilic clays, oil soluble polymers, polyamide resins, and polycarboxylic acids and soaps.
- the base fluid constitutes from about 25 to about 85 volume percent of the total drilling fluid.
- Illustrative fluid loss control agents include, but are not limited to, asphaltics (e.g., asphaltenes and sulfonated asphaltenes), modified lignites, and polymers, such as polystyrene, polybutadiene, polyethylene, polypropylene, polybutylene, polyisoprene, natural rubber, and butyl rubber.
- the LFTL feed was introduced into a first packed distillation column and C 13 and lighter materials were distilled overhead.
- the first distillation column was operated at the following conditions: 10 psig, 480° F. feed preheat temperature, 407° F. overhead temperature, 528° F. bottoms temperature.
- the first distillation column had approximately 98 inches of Sulzer Mellapack 750Y packing.
- the bottoms of the first distillation column constituted a C 13-20+ hydrocarbon fraction, the composition of which is shown in Table 2.
- the overhead stream of the first distillation column was fed into a second packed distillation column operated at 12 psig, 370° F. overhead temperature and 437° F. bottoms temperature.
- the second distillation column had about 28 inches of Sulzer EX packing.
- An LFTL feed substantially having the composition shown in Table 1, was hydrotreated at reactor conditions of 800 psig and 550° to 590° F.
- the resulting hydrotreated stream was distilled under conditions as described in Example 1 forming a hydrotreated analog of the C 10-13 light kerosene product.
- This hydrotreated light kerosene material was analyzed on a Hewlett Packard Series II gas chromatograph with 60 m RTX 1 column with 0.32 mm diameter and 3 micron film thickness. The isomer content of this product is shown in Table 4. TABLE 5 Component Wt.
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Abstract
A drilling fluid including at least about 2 wt % olefin, at least about 5 wt % n-paraffins, and at least about 2 wt % isoparaffins, wherein the isoparaffins are substantially wholly terminal monomethyl branched is provided. A method for producing the drilling fluid, and a method for drilling a borehole using the drilling fluid are disclosed.
Description
- This application claims priority to U.S. Provisional Application Serial No. 60/449,557, filed on Feb. 24, 2003.
- Not applicable.
- Not applicable.
- The present invention relates to drilling fluids derived from the products of a Fischer-Tropsch synthesis. More particularly, the invention relates to base fluids, and drilling fluids produced therefrom, having high stability, lubricity, and biodegradability while also having low toxicity. The invention further relates to processes of producing and using the drilling fluids.
- Drilling fluids, or drilling muds, are well known for use in oil and gas well drilling operations. In early applications, crude, diesel and mineral oils were used as base fluids in formulating drilling fluids. Such oil based drilling fluids, however, have unacceptable toxicity and persistence, or non-biodegradability. Toxicity and persistence issues are especially critical in offshore drilling operations. Pseudo-oil based drilling fluids are also well known wherein the base fluids are fatty acid esters or synthetic hydrocarbons. Such synthetic hydrocarbons have included polyalphaolefins, linear alphaolefins, internal olefins, and mixtures thereof as well as linear and branched paraffins and mixtures thereof. Synthetic olefinic and paraffinic base fluids produced by oligomerizing low carbon number hydrocarbons are well known but are expensive to produce. Similarly, ester base fluids are expensive to produce. 161 The cost of drilling fluids may be reduced by use of Fisher-Tropsch synthesis to produce paraffinic base fluids. Paraffinic drilling fluids, however, generally do not have adequate low temperature properties for use in offshore and cold weather drilling operations.
- One approach to the low temperature issue incorporates multi-methyl branched isoparaffins or isoparaffins with branches of higher carbon number than methyl into the paraffinic base fluid. Such paraffinic base fluids contain C10-C24 n-paraffins and isoparaffins, with an iso to normal ratio ranging from 0.5:1 to 9:1. Greater than 50% of the total isoparaffin content are mono-methyl branched isoparaffins and about 30% are multi-methyl substituted. A similar approach to the low temperature issue involves formulation of a drilling fluid containing a mixture of n-paraffins and isoparaffins wherein at least 90% of the isoparaffins are mono- or poly-methyl branched isomers. Although the use of Fisher-Tropsch synthesis somewhat lowers the cost of such paraffinic drilling fluids, the necessity of hydrocracking and hydroisomerization adds to the overall cost of the drilling fluid. Moreover, to sufficiently improve the low temperature properties of the paraffinic base fluids, pour point depressant additives may be required, further increasing the cost of the drilling fluid.
- In another known drilling fluid a base fluid of a mixture of linear and branched alphaolefins with the linear to branch ratio ranging from 1:1 to 5:1 is used. In this known drilling fluid the olefins may be produced from high temperature Fischer-Tropsch synthesis. High temperature Fischer-Tropsch synthesis, however, results in primarily internal branching of the branched hydrocarbons. Thus, such drilling fluids are not wholly biodegradable resulting in increased persistence. Moreover, because of the reactivity of olefins, drilling fluids composed of olefins are easily oxidizable and, therefore, must be stored under a nitrogen blanket to provide a reasonable shelf life. Even with nitrogen padding, olefinic drilling fluids cannot be stored for periods as long as paraffinic drilling fluids. Therefore, the cost of using olefinic drilling fluids is increased by both its special storage requirements and loss of oxidized product.
- Therefore, there remains a need for a further improved lower cost drilling fluid having oxidative stability, high lubricity, low toxicity, improved low temperature properties, and high biodegradability.
- In one embodiment of the invention, a base fluid which may be used for drilling fluid formulation is provided. The base fluid includes at least about 5 wt % olefins, at least about 5 wt % n-paraffins and between about 2 and 50 wt % branched paraffins wherein substantially all of the branch groups are monomethyl and wherein the ratio of terminal monomethyl branching to internal monomethyl branching is at least about 1:1.5.
- In other embodiments of the invention a drilling fluid is provided wherein the drilling fluid contains between about 2 and about 90 wt % olefins, between about 5 and about 90 wt % n-paraffins and between about 0 and about 10 wt % oxygenates.
- Yet another embodiment of the invention provides a process for producing a drilling from a light Fischer-Tropsch liquid.
- None.
- The term “Cx”, where x is a number greater than zero, refers to a hydrocarbon compound having predominantly a carbon number of x. As used herein, the term Cx may be modified by reference to a particular species of hydrocarbons, such as, for example, C5 olefins. In such instance, the term means an olefin stream comprised predominantly of pentenes but which may have impurity amounts, i.e. less than about 10%, of olefins having other carbon numbers such as hexene, heptene, propene, or butene. Similarly, the term “Cx+” refers to a stream wherein the hydrocarbons are predominantly those having a hydrocarbon number of x or greater but which may also contain impurity levels of hydrocarbons having a carbon number of less than x. For example, the term C15+means hydrocarbons having a carbon number of 15 or greater but which may contain impurity levels of hydrocarbons having carbon numbers of less than 15. The term “Cx-Cy”, where x and y are numbers greater than zero, refers to a mixture of hydrocarbon compounds wherein the predominant component hydrocarbons, collectively about 90% or greater by weight, have carbon numbers between x and y inclusive. For example, the term C5-C9 hydrocarbons means a mixture of hydrocarbon compounds which is predominantly comprised of hydrocarbons having carbon numbers between 5 and 9 inclusive, but may also include impurity level quantities of hydrocarbons having other carbon numbers.
- As used herein the term “high lubricity” means having a wear scar of average diameter of about ≦0.46 mm at 60° C. tested in accordance with ASTM Standard D-6079-02 entitled “Standard Test Method for Evaluating Lubricity of Diesel Fuels by the High-Frequency Reciprocating Rig.” The terms “high stability” and “high oxidative stability” mean having a total solids ≦1.5 mg/100 ml tested in accordance with ASTM Standard D-22-74-Ola entitled “Standard Test Method for Oxidation Stability of Distillate Fuel Oil (Accelerated Method).” Note that these methods are being applied herein to the analysis and characterization of synthetic products although the standards refer expressly to petroleum derived products.
- Unless otherwise specified, all quantities, percentages and ratios herein are by weight.
- Embodiments of the drilling fluid of the invention contain a base fluid having from about 5 to about 90 wt % linear alpha- and internal olefins, from about 5 to about 20 wt % isoparaffins, from about 5 to about 90 wt % n-paraffins and from about 0 to about 10 wt % oxygenates. To fully realize the lower cost potential of the invention, the base fluid for the drilling fluid of such embodiments may be obtained from a Fischer-Tropsch synthesis using synthesis gas as a feed stock. Moreover, production of the drilling fluid from a base fluid produced by the Fischer-Tropsch synthesis and subsequent processing as described herein is desirable as it results in a product having the desirable olefin and paraffin contents. However, the base fluid composition may be otherwise produced while yet retaining the remaining advantages of the invention. Thus, some embodiments of the base and drilling fluids of the invention are not produced by Fischer-Tropsch synthesis.
- Three basic techniques may be employed for producing a synthesis gas, or syngas, which is used as the starting material of a Fischer-Tropsch reaction. These include oxidation, reforming and autothermal reforming. As an example, a Fischer-Tropsch conversion system for converting hydrocarbon gases to liquid or solid hydrocarbon products using autothermal reforming includes a synthesis gas unit, which includes a synthesis gas reactor in the form of an autothermal reforming reactor (ATR) containing a reforming catalyst, such as a nickel-containing catalyst. A stream of light hydrocarbons to be converted, which may include natural gas, is introduced into the reactor along with oxygen (O2). The oxygen may be provided from compressed air or other compressed oxygen-containing gas, or may be a pure oxygen stream. The ATR reaction may be adiabatic, with no heat being added or removed from the reactor other than from the feeds and the heat of reaction. The reaction is carried out under sub-stoichiometric conditions whereby the oxygen/steam/gas mixture is converted to syngas. Examples of Fischer-Tropsch systems are described in U.S. Pat. Nos. 4,973,453; 5,733,941; 5,861,441; 6,130,259, 6,169,120 and 6,172,124, the disclosures of which are herein incorporated by reference.
- The Fischer-Tropsch reaction for converting syngas, which is composed primarily of carbon monoxide (CO) and hydrogen gas (H2) may be characterized by the following general reaction:
- 2nH 2 +nCO →(—CH2—)n +nH 2 O (1)
- Non-reactive components, such as nitrogen, may also be included or mixed with the syngas. This may occur in those instances where air or some other non-pure oxygen source is used during the syngas formation.
- The syngas is delivered to a synthesis unit, which includes a Fischer-Tropsch reactor (FTR) containing a Fischer-Tropsch catalyst. Numerous Fischer-Tropsch catalysts may be used in carrying out the reaction. These include cobalt, iron, ruthenium as well as other Group VIIIB transition metals or combinations of such metals, to prepare both saturated and unsaturated hydrocarbons. For purposes of this invention, a non-iron catalyst may be used. The F-T catalyst may include a support, such as a metal-oxide support, including silica, alumina, silica-alumina or titanium oxides. For the purposes of this reaction, a Co catalyst on transition alumina with a surface area of approximately 100-200 m2/g is used in the form of spheres of 50-150 μm in diameter. The Co concentration on the support may also be 15-30%. Certain catalyst promoters and stabilizers may be used. The stabilizers include Group IIA or Group IIIB metals, while the promoters may include elements from Group VIII or Group VIIB. The Fischer-Tropsch catalyst and reaction conditions may be selected to be optimal for desired reaction products, such as for hydrocarbons of certain chain lengths or number of carbon atoms. Any of the following reactor configurations may be employed for Fischer-Tropsch synthesis: fixed bed, slurry reactor, ebullating bed, fluidizing bed, or continuously stirred tank reactor (CSTR). For the purposes of this reaction, a slurry bed reactor is used. The FTR may be operated at a pressure of 100 to 500 psia and a temperature of 375° F. to 500° C. The reactor gas hourly space velocity (“GHSV”) may be from 1000 to 8000 hr−1. Syngas useful in producing a Fischer-Tropsch product useful in the invention may contain gaseous hydrocarbons, hydrogen, carbon monoxide and nitrogen with H2/CO ratios from about 1.8 to about 2.4. The hydrocarbon products derived from the Fischer-Tropsch reaction may range from methane (CH4) to high molecular weight paraffinic waxes containing more than 100 carbon atoms. An overhead product stream is recovered from the FTR and may be separated into tail gas and light Fischer-Tropsch liquid (“LFTL”) products in a cold separator. The LFTL stream may then be distilled to yield a hydrocarbon product of primarily C13-C22 olefins and paraffins.
- The C13-C22 distillation cut may be used directly as the base fluid. Low levels of C13−hydrocarbons may be present in the C13-C22 cut provided such levels do not cause the drilling fluid to exceed current regulatory limits. C13−hydrocarbons may be present in amounts between about 0.01 and 10 wt %. The presence of such small amounts of C13− hydrocarbons permits incorporation of a wider distribution of C13+hydrocarbons, particularly C16+hydrocarbons, for improved lubricity. The hydrocarbon number distribution is such as to result in a drilling fluid pour point below about 10° C.
- Embodiments of the base fluid contains from about 5 to about 90 wt % linear alpha- and internal olefins. The olefin content may provide the mixture with lower pour-point, better surface activity, better lubricity and better adherence to metal. When the base fluid is produced from the Fischer-Tropsch synthesis with the appropriate Fischer-Tropsch catalyst and operating conditions, the Fischer-Tropsch product will have approximately 5% alpha and internal olefin content. Depending upon the reaction conditions of the FTR and catalyst used in the Fischer-Tropsch reaction, it may be necessary to concentrate the olefin content to achieve the higher percentages of olefins in the base fluid. Concentration of olefins may be undertaken, for example, by one or more of the following known techniques: (1) molecular sieve separation of olefins and paraffins, such as UOP's OLEX® process, and (2) distillation of paraffins away from individual CX cuts.
- The base fluid may contain between about 5 to about 95 wt % paraffins. Of the total paraffin content from about 3 to about 20 wt % are isoparaffins. Substantially all of the isoparaffins are terminal monomethyl species. As used herein, the terminal species include 2- and 3-methyl branched. The presence of monomethyl isoparaffins improves low temperature properties, such as pour point, as well as lubricity and viscosity. Moreover, because the isoparaffins are predominantly terminally branched, the paraffin content of the base fluid is substantially wholly biodegradable. Using the Fischer-Tropsch synthesis described herein, about 5 wt % terminal methyl branched paraffins are produced in the LFTL.
- Concentration of isoparaffins may be increased by one or more of the following techniques: (1) molecular sieve separation of linear and branched paraffins, such as UOP's OLEX® process, and (2) isomeric distillation of isoparaffin.
- Embodiments of the base fluid contain between about 0 and about 10 wt % oxygenates. The oxygenates are principally primary alcohols. Other oxygenates, including aldehydes, ketones, carboxylic acids and esters and di-esters of carboxylic acids are also present in small amounts. Oxygenate content in the C13-C22 cut of the Fischer-Tropsch reaction product ranges from between about 0.5 to about 5.0 wt %. Low levels of oxygenates in the drilling fluid from between about 0 and about 10 wt % provide improved lubricity. Moreover, oxygenates may assist in emulsification in invert drilling muds.
- Oxygenate control may be used on the C13-C22 cut of the Fischer-Tropsch product stream. In one embodiment of the invention, a base fluid is produced by vaporizing a product stream and passing the vaporized product over an activated alumina catalysts to dehydrate alcohols to corresponding olefins. The conversion of the alcohol content of the product stream occurs according to the following reaction:
- CH3—(CH2)x—CH2—CH2OH→CH3—(CH2)x—CH═CH2+H2O (2)
- For example, the LFTL, C13-C22 or other product stream may be vaporized at a temperature from about 400° F. to about 800° F. and then passed over one or more dehydration beds containing activated treated alumina or silica-alumina. In some embodiments, the dehydration beds are packed beds. Essentially all of the primary and internal alcohols present in the vaporized stream are dehydrated to their corresponding olefins, with conversion rates of at least 95%.
- Dehydration reaction temperature may range from between about 400° and 800° F. The vaporized feed for the dehydration unit may be superheated prior to being fed into the dehydration beds or alternatively, may be heated within packed beds. The LHSV of packed beds may range from about 0.10 hr−1 to about 2.0 hr−1. Reaction pressure may be maintained by the pressure of the accumulator and must be such to vaporize all of the dehydration feed. Typically, the pressure may range from between about 0 psia to about 100 psig.
- In an alternative embodiment, a moving bed of alumina or silica-alumina catalyst may be used. Fluidized beds, slurry beds or ebullating beds may be used with continuous batch or semi-batch catalyst removal and regeneration. The catalyst may be removed by one of these methods and regenerated by passing a mixture of nitrogen and oxygen or air at elevated temperatures over the catalyst.
- Depending upon the alumina used, some of the olefins present or produced in the dehydration beds may also be isomerized to internal olefins. Alumina catalysts useful for the dehydration of alcohols are known and include, for example, gamma-alumina, theta-alumina, pacified alumina, and activated alumina. High surface area aluminas are particularly useful in the invention and include those aluminas having a surface area of about 100 m2/gm or greater. Commercially available alumina useful in the integrated Fischer-Tropsch process include, for example, S-400, which has a surface area of about 335 m2/gm, and DD-470, which has a surface area of about 375 m2/gm. S-400 ad DD-470 are alumina catalysts made and sold by Alcoa. Alumina catalysts for use in the integrated Fischer-Tropsch process generally contain at least about 90 wt % Al2O3, oxides of silicon and iron present in amounts of less than about 0 wt %, and oxides of sodium present in an amount of less than about 1 wt %. The alumina catalysts are generally supplied as substantially spherical particles having diameter from about ⅛ to about ¼ inch.
- In another embodiment of the invention, molecular sieve or zeolitic molecular sieve forms of the alumina or silica-alumina catalysts may be used. For example, silico alumino phosphate (“SAPO”) molecular sieves may be used in the packed beds. SAPO molecular sieves contain a 3-dimensional microporous crystal structure having 8, 10, or 12 membered ring structures. The ring structures can have an average pore size ranging from between about 3.5 angstroms to about 15 angstroms. Other silica-containing zeolitic molecular sieve catalysts, such as ZSM-5, may be used in the dehydration bed.
- Following dehydration, the aqueous and organic phases may be separated. Such dehydration process may further be used to increase the olefin content of the product stream to be used to produce the base fluid.
- Other methods of oxygenate control include, for example, reaction of the alcohol content of the C13-C22 cut of a Fischer-Tropsch product stream with maleic or succinic anhydride or with a carboxylic acid, such as formic acid, acetic acid, or other acids. The carboxylic acid esters may be retained in the stream as they are excellent lubricants which are also highly biodegradable. Both the lubricity and the biodegradability of the base fluid may be improved by converting at least a portion of the alcoholic oxygenate content to carboxylic acid esters.
- The drilling fluid may optionally include one or more surfactants (e.g., emulsifiers, wetting agents), viscosifiers, weighting agents, fluid loss control agents, and proppants. Because the drilling fluid should be non-toxic, these optional ingredients, like the base fluid, are preferably also non-toxic. Acceptable emulsifiers include, but are not limited to, fatty acids, and fatty acid derivatives including amido-amines, polyamides, polyamines, esters, imidaxiolines, and alcohols. Typical 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. Exemplary weighting agents include, but are not limited to, barite, iron oxide, gelana, siderite, calcium oxide, and calcium carbonate. Acceptable proppants include sand, gravel, and nut shells. Exemplary viscosifiers include, but are not limited to, organophilic clays, non-organophilic clays, oil soluble polymers, polyamide resins, and polycarboxylic acids and soaps. Where additives are used in the drilling fluid, the base fluid constitutes from about 25 to about 85 volume percent of the total drilling fluid. Illustrative fluid loss control agents include, but are not limited to, asphaltics (e.g., asphaltenes and sulfonated asphaltenes), modified lignites, and polymers, such as polystyrene, polybutadiene, polyethylene, polypropylene, polybutylene, polyisoprene, natural rubber, and butyl rubber.
- The following examples illustrate, but are not intended to limit, the invention.
- A pilot installation consisting of two distillation columns was used to produce C6-10 naphtha, C10-13 light kerosene, and C13-20+ drilling fluid feedstock streams. The columns were fed approximately 3400 g/hr of light Fischer Tropsch liquid (LFTL). The LFTL feed had approximately the composition shown in Table 1:
TABLE 1 Carbon # % by wt. 4 <0.1 5 0.01 6 0.3 7 1.0 8 2.9 9 5.9 10 8.1 11 9.2 12 9.5 13 9.2 14 8.4 15 7.9 16 7.1 17 6.2 18 5.4 19 4.6 20 3.7 21 3.0 22 2.3 23 1.7 24 1.2 25+ 2.6 Total 100.00 - The LFTL feed was introduced into a first packed distillation column and C13 and lighter materials were distilled overhead. The first distillation column was operated at the following conditions: 10 psig, 480° F. feed preheat temperature, 407° F. overhead temperature, 528° F. bottoms temperature. The first distillation column had approximately 98 inches of Sulzer Mellapack 750Y packing. The bottoms of the first distillation column constituted a C13-20+hydrocarbon fraction, the composition of which is shown in Table 2. The overhead stream of the first distillation column was fed into a second packed distillation column operated at 12 psig, 370° F. overhead temperature and 437° F. bottoms temperature. The second distillation column had about 28 inches of Sulzer EX packing. The bottoms of the second column
TABLE 2 Total n-paraffins, isoparaffins, olefins and alcohols C11−: Mass % 0.97 C12: Mass % 1.77 C13: Mass % 11.43 C14: Mass % 13.68 C15: Mass % 12.35 C16: Mass % 10.96 C17: Mass % 9.06 C18: Mass % 7.84 C19: Mass % 6.79 C20: Mass % 7.04 C21: Mass % 5.66 C22: Mass % 4.63 C23+: Mass % 7.83 100.00 - The C13-20 and stream from Example 1 was fed via a syringe pump and mixed with 20 cc/min of nitrogen. The gas/liquid mixture was introduced upflow into a vessel packed with stainless steel mesh saddles, where the liquid was vaporized and superheated to reaction temperature of 675° F. The vaporized feed was fed upflow into a reactor packed with ⅛ Alcoa S-400 alumina catalyst and suspended in a heated sandbath. The sandbath was maintained at the reaction temperature and ebulated by air. Reactor LHSV was maintained at about 0.26 hr−1. The outlet pressure was maintained at about 5 psig. The reaction product composition is shown in Table 3.
TABLE 4 Sample Reference Number FEED B PRODUCT D TOTAL N-PARAFFIN mass % 82.46 82.87 ALPHA OLEFIN mass % 2.26 3.48 INTERNAL OLEFIN mass % 2.75 3.68 BRANCHED PARAFFIN mass % 10.10 9.97 ALCOHOL mass % 2.45 0.00 100.00 100.00 - An LFTL feed, substantially having the composition shown in Table 1, was hydrotreated at reactor conditions of 800 psig and 550° to 590° F. The resulting hydrotreated stream was distilled under conditions as described in Example 1 forming a hydrotreated analog of the C10-13 light kerosene product. This hydrotreated light kerosene material was analyzed on a Hewlett Packard Series II gas chromatograph with 60 m RTX 1 column with 0.32 mm diameter and 3 micron film thickness. The isomer content of this product is shown in Table 4.
TABLE 5 Component Wt. % nC9- 0.02 2- and 3-monomethyl C10 0.20 4- and higher - monomethyl C10 0.03 nC10 22.22 2- and 3-monomethyl C11 1.19 4- and higher - monomethyl C11 0.42 nC11 27.93 2- and 3-monomethyl C12 1.09 4- and higher - monomethyl C12 0.50 nC12 24.96 2- and 3-monomethyl C13 0.92 4- and higher - monomethyl C13 0.48 nC13 18.99 2- and 3-monomethyl C14 0.11 4- and higher - monomethyl C14 0.13 nC14 0.41 Total normal hydrocarbon 94.54 Total 2- and 3-monomethyl 3.51 substituted hydrocarbons Total 4- and higher - 1.55 monomethyl substituted hydrocarbons Total monomethyl hydrocarbons 99.61 Others 0.39 - While the foregoing describes preferred embodiments of the invention, it is apparent that a number of changes and variations are within the scope and spirit of the invention.
Claims (39)
1. A base fluid comprising:
at least about 5 wt % olefins;
at least about 5 wt % n-paraffins; and
between about 2 and 50 wt % branched paraffins wherein substantially all of the branch groups are monomethyl and wherein the ratio of terminal monomethyl branching to internal monomethyl branching is at least about 1:1.5.
2. The base fluid of claim 1 wherein the ratio of terminal monomethyl branching to internal monomethyl branching is at least about 1:1.
3. The base fluid of claim 1 wherein the n-paraffins are present in an amount of at least about 20 wt % and wherein the ratio of terminal monomethyl branching to internal monomethyl branching is at least about 1.5:1.
4. The base fluid of claim 1 wherein the n-paraffins are present in an amount of at least about 40 wt % and wherein the ratio of terminal monomethyl branching to internal monomethyl is at least about 2:1.
5. The base fluid of claim 1 wherein the base fluid is a product of a Fischer-Tropsch reaction.
6. The base fluid of claim 5 wherein the Fischer-Tropsch reaction incorporates feed syngas having 10-60% N2.
7. A drilling fluid comprising:
the base fluid of claim 1 .
8. The drilling fluid of claim 7 further comprising:
at least one additive selected from the group of surfactants, viscosifiers, weighting agents, fluid loss control agents and proppants.
9. A drilling fluid comprising:
from about 2 to about 90 wt % olefins;
from about 2 to about 50 wt % isoparaffins; wherein the isoparaffins are substantially terminal monomethyl branched.
from about 5 to about 90 wt % n-paraffins; and
from about 0 to about 10 wt % oxygenates.
10. The drilling fluid of claim 9 wherein the olefins are present in an amount of from about 7 to about 10 wt %.
11. The drilling fluid of claim 9 wherein the isoparaffins are present in an amount of from about 3 to about 15 wt %.
12. The drilling fluid of claim 9 wherein the n-paraffins are present in an amount of from about 65 to about 90 wt %.
13. The drilling fluid of claim 9 wherein the oxygenates are present in an amount of from about 0 to about 5 wt %.
14. The drilling fluid of claim 9 wherein the base fluid is a product of Fischer-Tropsch reaction on a synthesis gas.
15. The drilling fluid of claim 14 wherein the Fischer-Tropsch reaction incorporates feed syngas having 10-60% N2.
16. The drilling fluid of clam 14 wherein the synthesis gas is produced by autothermal reformation.
17. The drilling fluid of claim 16 wherein the autothermal reformation occurs in the presence of air.
18. The drilling fluid of claim 16 wherein the autothermal reformation occurs in the presence of 10-60% N2.
19. The drilling fluid of claim 9 further comprising:
at least one additive selected from the group of surfactants, viscosifiers, weighting agents, fluid loss control agents and proppants.
20. The drilling fluid of claim 9 wherein the olefins are:
from about 7 to about 10 wt %;
the isoparaffins are from about 2 to about 15 wt %; wherein the isoparaffins are substantially terminal monomethyl branched.
The n-paraffins are from about 65 to about 90 wt %; and
the oxygenates are from about 0 to about 5 wt %.
21. The drilling fluid of claim 20 wherein the drilling fluid is a product of a Fischer-Tropsch reaction.
22. The drilling fluid of claim 20 further comprising:
at least one additive selected from the group of surfactants, viscosifiers, weighting agents, fluid loss control agents and proppants.
23. The drilling fluid of claim 20 wherein the base fluid comprises from about 25 to about 85 volume % of the drilling fluid.
24. The drilling fluid of claim 23 wherein the base fluid comprises from about 25 to about 85 volume % of the drilling fluid.
25. The drilling fluid of claim 22 wherein the Fischer-Tropsch reaction incorporates feed syngas having 10-60% N2.
26. The drilling fluid of claim 23 wherein the feed syngas is produced by autothermal reformation in the presence of air.
27. A process for producing a drilling fluid comprising the steps of:
(a) producing a light Fischer-Tropsch liquid;
(b) distilling the light Fischer-Tropsch liquid to obtain a C13-C20+ product having C13-C20+ hydrocarbons and oxygenates.
(c) dehydrating all or a part of the alcohols in the C13-C20+ product by passing the C13-C20+ product over an activated alumina catalyst to produce a dehydrated product;
(d) recovering the dehydrated product; and
(e) separating the aqueous and organic phases of the dehydrated product.
28. The process of claim 27 further comprising the step of:
(f) adding one or more additive selected from the group of surfactants, viscosifiers, weighting agents, fluid loss control agents and proppants to the organic phase of the dehydrated product.
29. The process of claim 27 further comprising the step of (b1) vaporizing the C13-C20+ product before step (c) and after step (b).
30. The process of claim 29 wherein the dehydrated product from step (c) is in the gaseous state and step (d) further includes condensing the dehydrated product.
31. The process of claim 30 wherein the heat from condensing the dehydrated product is recycled to at least partially vaporize the C13-C20+ product in step (b1).
32. The process of claim 27 wherein the light Fischer-Tropsch liquid is produced from a feed syngas having 10-60% N2.
33. The process of claim 27 wherein the feed syngas is produced by autothermal reformation in the presence of air.
34. The process of claim 27 wherein a C14-C18 product is obtained in step (b) and dehydrated in step (c).
35. A method of drilling a borehole in a subterranean formation comprising the steps of:
(a) rotating a drill bit at the bottom of the borehole;
(b) introducing a drilling fluid into the borehole wherein the drilling fluid comprises a base fluid comprising:
from about 5 to about 90 wt % olefins;
from about 2 to about 50 wt % isoparaffins; wherein the isoparaffins are substantially terminal monomethyl branched;
from about 5 to about 90 wt % n-paraffins; and
from about 0 to about 10 wt % oxygenates.
36. The process of claim 35 wherein the drilling fluid comprises:
from about 7 to about 10 wt % olefins;
from about 2 to about 15 wt % isoparaffins; wherein the isoparaffins are substantially terminal monomethyl branched;
from about 65 to about 90 wt % n-paraffins; and
from about 0 to about 5 wt % oxygenates.
37. The process of claim 35 wherein the base fluid is derived from a Fischer-Tropsch reaction.
38. The process of claim 37 wherein the Fischer-Tropsch reaction incorporates feed syngas having 10-60% N2.
39. The process of claim 37 wherein the feed syngas is produced by autothermal reformation in the presence of air.
Priority Applications (1)
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US10/785,317 US20040198618A1 (en) | 2003-02-24 | 2004-02-24 | High stability, high lubricity, low toxicity, high biodegradability drilling fluid |
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US44955703P | 2003-02-24 | 2003-02-24 | |
US10/785,317 US20040198618A1 (en) | 2003-02-24 | 2004-02-24 | High stability, high lubricity, low toxicity, high biodegradability drilling fluid |
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US20040198618A1 true US20040198618A1 (en) | 2004-10-07 |
Family
ID=32070018
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US10/785,317 Abandoned US20040198618A1 (en) | 2003-02-24 | 2004-02-24 | High stability, high lubricity, low toxicity, high biodegradability drilling fluid |
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US (1) | US20040198618A1 (en) |
BR (1) | BRPI0400580A (en) |
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US20070178339A1 (en) * | 2006-02-02 | 2007-08-02 | Syntroleum Corporation | Paraffinic hydrocarbon for fuel cell application |
US20070213229A1 (en) * | 2002-04-30 | 2007-09-13 | Petroleum Oil and Gas Corporation of South Africa (Pty) Ltd. | Process for reducing the toxicity of hydrocarbons |
WO2008130505A1 (en) * | 2007-04-20 | 2008-10-30 | Sasol North America Inc. | Compositions for use in well servicing fluids |
US20100113847A1 (en) * | 2005-01-31 | 2010-05-06 | Kowalik Ralph M | Olefin Oligomerization And Biodegradable Compositions Therefrom |
US20150126627A1 (en) * | 2012-07-16 | 2015-05-07 | Res Usa, Llc | Integration of syngas generation technology with fischer-tropsch production via catalytic gas conversion |
US9295966B1 (en) | 2011-07-19 | 2016-03-29 | Jacob G. Appelbaum | System and method for cleaning hydrocarbon contaminated water and converting lower molecular weight gaseous hydrocarbon mixtures into higher molecular weight highly-branched hydrocarbons using electron beam combined with electron beam-sustained non-thermal plasma discharge |
WO2019025358A1 (en) * | 2017-08-01 | 2019-02-07 | Shell Internationale Research Maatschappij B.V. | Drilling fluid |
US11319474B2 (en) | 2017-02-03 | 2022-05-03 | Saudi Arabian Oil Company | Oil-based fluid compositions for hydrocarbon recovery applications |
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RU2565592C2 (en) * | 2010-05-03 | 2015-10-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Spent lubricant composition |
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US11319474B2 (en) | 2017-02-03 | 2022-05-03 | Saudi Arabian Oil Company | Oil-based fluid compositions for hydrocarbon recovery applications |
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CN110869476A (en) * | 2017-08-01 | 2020-03-06 | 国际壳牌研究有限公司 | drilling fluid |
AU2018311027B2 (en) * | 2017-08-01 | 2021-01-14 | Shell Internationale Research Maatschappij B.V. | Drilling fluid |
US11332653B2 (en) | 2017-08-01 | 2022-05-17 | Shell Oil Company | Drilling fluid |
Also Published As
Publication number | Publication date |
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BRPI0400580A (en) | 2005-01-04 |
GB0404099D0 (en) | 2004-03-31 |
HK1074056A1 (en) | 2005-10-28 |
GB2400109A (en) | 2004-10-06 |
GB2400109B (en) | 2007-03-07 |
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