USRE31127E - Oil well cementing process - Google Patents
Oil well cementing process Download PDFInfo
- Publication number
- USRE31127E USRE31127E US06/298,037 US29803781A USRE31127E US RE31127 E USRE31127 E US RE31127E US 29803781 A US29803781 A US 29803781A US RE31127 E USRE31127 E US RE31127E
- Authority
- US
- United States
- Prior art keywords
- cement
- lignin
- retarder
- hydraulic cement
- sulfoalkylated
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title claims abstract description 9
- 239000003129 oil well Substances 0.000 title abstract description 5
- 239000004568 cement Substances 0.000 claims abstract description 91
- 229920005610 lignin Polymers 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 62
- 238000001879 gelation Methods 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims description 64
- 239000011396 hydraulic cement Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000005086 pumping Methods 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000518 rheometry Methods 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 24
- 229920001732 Lignosulfonate Polymers 0.000 description 16
- 239000008186 active pharmaceutical agent Substances 0.000 description 13
- 239000011575 calcium Substances 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 229920005551 calcium lignosulfonate Polymers 0.000 description 11
- 239000000499 gel Substances 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 10
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- -1 alkylidene radical Chemical class 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- 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 3
- 239000011398 Portland cement Substances 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Chemical class 0.000 description 3
- 239000002184 metal Chemical class 0.000 description 3
- 125000004344 phenylpropyl group Chemical group 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 125000004964 sulfoalkyl group Chemical group 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 102100023431 E3 ubiquitin-protein ligase TRIM21 Human genes 0.000 description 2
- 101000685877 Homo sapiens E3 ubiquitin-protein ligase TRIM21 Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 239000003340 retarding agent Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000010755 BS 2869 Class G Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910004844 Na2B4O7.10H2O Inorganic materials 0.000 description 1
- 229910020895 NaBO2.4H2 O Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 101000703964 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 40S ribosomal protein S1-B Proteins 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 235000015115 caffè latte Nutrition 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical group C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
Definitions
- This invention relates to cement compositions and more particularly to the use of hydraulic cement compositions for sealing or cementing subterranean zones or subterranean zones penetrated by a well such as cementing the annular space in an oil well between the surrounding formation and casing.
- the invention relates to an improved hydraulic cement composition for cementing zones at elevated temperatures in which the setting time of the cement composition is controlled or extended by the addition of a highly efficient non-gelling retarding agent which produces a hydraulic cement composition having a degree of predictability for the setting time.
- the subterranean zones are cemented or sealed by pumping an aqueous hydraulic cement slurry into the zone.
- the cement slurry In cementing the annular space of an oil well, the cement slurry is pumped down the inside of the casing and back up the outside of the casing through the annular space. Any cement slurry remaining in the casing is displaced and segregated using plugs and an aqueous displacement fluid.
- the high temperatures encountered in subterranean zones will cause premature setting of the hydraulic cement. This requires additives which extend or retard the setting time of the cement slurry so that there is adequate pumping time in which to place and displace the aqueous cement slurry in the desired zones.
- Gelation refers to an abnormal increase of viscosity of the aqueous cement slurry to a value without a significant increase in the compressive strength of the cement composition. This increase in aqueous cement slurry viscosity makes the slurry difficult or impossible to pump at a viscosity of 70 poise or above which is defined as the set point herein. The cement composition has not attained an adequate compressive strength.
- the hydraulic cement compositions of this invention solve or eliminate many of the problems pointed out above.
- the hydraulic cement compositions of this invention do not have the gelation problem; the retarder composition is more efficient than prior art retarder compositions, the retarder has less variation with different brands of cement; cement compositions have much better predictability or reproducibility of setting times with a given brand of cement; and hydraulic cement compositions have better rheology characteristics.
- the improved cement compositions of this invention have practically eliminated the problems of unpredictability and irreproducibility of results which are particularly severe in high pressure deep wells where the temperatures may exceed 300° F. and 15,000 PSI.
- the concentration of retarder composition of this invention required to produce the desired pumping time for or delay in setting of a cement slurry at a given circulating temperature is not as critical as with conventional lignosulfonate retarders.
- the thickening time at a given retarder concentration is less temperature dependent than with conventional retarders. This reduces the possibility of over retarded slurries at cooler temperatures encountered at the top of long liners or tie back strings.
- the retarder compositions of this invention provide the desired pumping times and allow earlier strength development. When cementing long strings this can reduce the WOC (waiting on cement to set) time by 8-12 hours.
- the retarder compositions of this invention are more predictable in performance than conventional lignosulfonate retarders especially with various brands of cement.
- compositions of this invention act not only as retarders but also as a dispersing agent which can reduce fluid loss from gel type or high clay cement slurries.
- a dispersing agent which can reduce fluid loss from gel type or high clay cement slurries.
- viscosity of the slurry decreases slightly and remains constant or does not increase significantly until the cement begins to set. This improvement in rheology or viscosity characteristics with improved predictability makes use of the compositions much easier than with conventional retarders.
- the retarder compositions of this invention are generally non-toxic, non-flammable, non-hazardous; compatible with cements, other additives and with most other well fluids and mix readily in aqueous systems with minimum agitation.
- the high efficiency, non-gelling cement retarder composition of this invention has a high degree of predictability for controlling rheology and setting time of hydraulic cement comprising a low molecular weight sulfoalkylated lignin which is substantially sulfoalkylated in the lignin molecule at positions on the benzene ring which are ortho to the phenolic hydroxyl group.
- the sulfoalkyl group the sulfonic acid group (--SO 3 H) is connected to the ortho position on the benzene ring by a methylene or substituted methylene groups. This methylene or substituted methylene group is referred to herein as an alkylidene radical having one to five carbon atoms.
- This alkylidene radical with sulfonic acid radical can be represented by the formula (--R--SO 3 H) wherein R is the methylene group or alkyl portion having one to five carbon atoms and preferably one to three carbon atoms.
- the unexpected properties of this retarder are thought to be due to the differences in average molecular weight or average molecular size and molecular structure.
- the evidence showing these differences is illustrated in the examples which show the unexpected properties.
- the sulfoalkylated lignin of this invention is a low molecular weight material having an average molecular weight or molecular size in the range of about 2,000-10,000 and preferably about 3,000-5,000. It is also thought to have a narrow molecular weight distribution.
- Prior art lignosulfonate compounds have a molecular weight or molecular size of about 10,000 and higher and the sulfonate substituent or radical attached directly on the carbon atom of the lignin molecule which is in the alpha position of the phenyl propyl side chain. This phenyl propyl or aliphatic chain is attached at a position on the benzene ring which is para to the phenolic hydroxyl group discussed herein.
- the phenolic hydroxyl group can be replaced by an alkoxy group as indicated by R 1 --Ph--OR 2 wherein R 1 is the phenyl propyl side chain, Ph is phenyl or the benzene ring and R 2 is hydrogen or alkyl.
- the sulfoalkylated retarder composition of this invention has substantially all of the sulfoalkyl group (i.e., --R--SO 3 H) in the position ortho to the phenolic hydroxyl group of the benzene ring of the lignin molecule.
- the sulfoalkylated lignin retarder of this invention does not have a significant degree of sulfonation at the alpha carbon atom as do the prior art lignosulfonates.
- the sulfoalkylated lignin retarder of this invention is an entirely different chemical composition as shown by the unexpected and significantly different properties shown herein.
- the sulfoalkylated lignin retarder of this invention can be considered to be a sulfoalkylated lignin of high purity, low molecular weight with a narrow molecular weight distribution. This is thought to be due to the significantly different procedure used for its preparation.
- the sulfoalkylated lignin retarder for compositions of this invention can be prepared by catalytic oxidation of the sulfite liquor from a wood pulping process. This oxidation removes polysaccharides and wood sugars and substantially desulfonates the lignin molecule which is recovered as a residue. This purified lignin is separated from the liquid. The high purity, low molecular weight lignin molecule is then substantially sulfoalkylated by the addition of sulfonating agent such as sodium sulfite in the presence of an aldehyde or ketone having one to five carbon atoms at about 150°-190° C. and 180-220 atmospheres.
- sulfonating agent such as sodium sulfite in the presence of an aldehyde or ketone having one to five carbon atoms at about 150°-190° C. and 180-220 atmospheres.
- the aldehyde or ketone furnishes the alkylidene group which attaches at a vacant ortho position on the benzene ring in the lignin molecule and connects the sulfonate group through a methylene radical to the benzene ring at a position ortho to the free phenolic hydroxyl group.
- Some benzene rings may have more than one sulfoalkyl group attached and some benzene rings may have no sulfoalkyl substituents.
- the sulfur content of the sulfoalkylated lignin is between about 3-10% and preferably 3-8%.
- This sulfonate group can be in the form of the acid, a salt or combinations thereof.
- the salt can be in the form of ammonium or metal salt involving an alkali metal; an alkaline earth metal; or metals such as iron, copper, zinc, vanadium, titanium, aluminum, manganese, chromium, cobalt or nickel; or combinations thereof.
- the salts which are readily soluble in aqueous systems, such as those of the alkali metals, sodium and potassium, are preferred although the salts of alkaline earth metals and other metals can be used under certain circumstances.
- the alkyl portion of the sulfonate substituent is derived from the aldehyde or ketone used in the sulfoalkylation step.
- Formaldehyde is a preferred alkyl source because it simply connects the sulfonate group to the ortho position by a one-carbon atom methylene group.
- Acetone would produce an alkylidene group having a methyl group on each side of the methylene group; methyl ethyl ketone would result in a methyl and an ethyl alkyl group attached to the methylene group; and propionaldehyde would result in an ethyl group attached to the methylene bridge.
- a preferred sulfoalkylated lignin of this invention has a molecular weight in the range of about 3,000-4,000, a one carbon atom alkylidene radical and sulfur content of about 3-8% by weight.
- Another preferred hydraulic cement composition of this invention can be considered to be a modified low molecular weight sulfoalkylated lignin.
- This modified retarder composition is a combination of the high purity substantially sulfoalkylated lignin described above and at least one water soluble hydroxy carboxylic acid. These hydroxy carboxylic acids have a synergistic effect of increasing the effectiveness and operable temperature range of the basic retarder composition.
- the preferred carboxylic acids are substantially alphatic carboxylic acids and preferably polyhydroxy carboxylic acids having at least one terminal carboxy group which can be in the form of the acid, a salt or mixtures thereof as described above for the sulfonate groups.
- Particularly preferred polyhydroxy carboxylic acids have a molecular weight in the range of about 125-250 and have a hydroxyl group attached to the carbon atom adjacent to the carboxy group as show by the formula ##STR1##
- These carboxylic acids include gluconic acid, tartaric acid and equivalents thereof. These equivalents include the various stereoisomers of the above acids particularly the asymmetric or optically active isomers.
- the preferred group of hydroxy carboxylic acids are substantially linear aliphatic acids having about 4-10 carbon atoms, and preferably 4-8 carbon atoms. The molecular size and number of hydroxy and carboxylic groups will affect the water solubility.
- the hydroxy carboxylic acid is preferably present with the sulfoalkylated lignin in a weight ratio of acid to lignin preferably in the range of about 1:0.1-5.0 and preferably in the range of about 1:0.2-3.0.
- the hydraulic cement compositions of this invention are typically used in the form of an aqueous slurry of hydraulic cement with a concentration of retarder mixed in the aqueous slurry to control or delay the cement setting time so that it exceeds the pumping time with an adequate safety margin. Sufficient water is added to the slurry to make the composition pumpable.
- the hydraulic cement is typically a Portland cement which is set by the water of the slurry in the absence of air which is excluded by placement of the cement in the zone to be sealed.
- the low molecular weight sulfoalkylated lignin retarder of this invention is preferably present in the aqueous hydraulic cement slurry in a concentration up to about 2%, and preferably up to 1%, by weight based on the dry cement. Higher retarder concentrations and other cement can be used when necessary in unusual circumstances.
- a deforming agent is typically added as are fluid loss additives, friction reducing additives, salts such as sodium chloride and potassium chloride, weighting additives and other conventional additives as described in the references cited above.
- Pozzolana cement, high alumina cement or high gel (high clay content) cement can be used for special applications.
- the low molecular weight sulfoalkylated retarder composition of this invention has high reproducibility and predictability when used with most high quality cements which are typically used in the petroleum industry.
- certain brands which are not manufactured to standard specifications such as those which are not sufficiently calcined or having varying degrees of free lime remaining in the cement, will produce substantial variations from the standard high quality brands. It is not clear whether the free lime causes the problems or is merely an indication when the problems exist. These variations can be readily determined by preliminary tests which make even these substandard cements readily predictable and may merely require slightly higher retarder concentrations to offset the chemical composition variations of the cement of excess lime content.
- the retarder composition is mixed with the hydraulic cement as an aqueous slurry with the retarder concentration up to about 2% on a dry cement weight basis.
- the hydraulic cement mixture is pumped without gelation into the zone to be sealed or cemented and the hydraulic cement mixture is maintained in the zone until an adequate compressive strength is attained.
- the retarder concentration preferably up to about 2% on a dry cement weight basis is calculated to control the setting time of the hydraulic cement slurry to exceed the pumping time within an adequate safety margin.
- the portion of the safety margin previously required for these variations can be substantially reduced.
- the safety margin now need primarily allow time only for unexpected equipment difficulties. This reduction in the safety margin time or time which the typical oil drilling rig is waiting for the cement to set can result in a substantial economic advantage due to the higher efficiency and predictability of the hydraulic cement compositions of this invention.
- the modified low molecular weight sulfoalkylated lignin of this invention or the combination of the sulfoalkylated lignin with the hydroxy carboxylic acids improve the efficiency and predictability of the compositions of this invention even more and therefore are preferably used.
- the basic sulfoalkylated lignin retarder composition of this invention can be used up to a temperature (i.e., BHCT) slighly in excess of about 210° F. and the modified retarder composition containing the hydroxy carboxylic acids can be used up to a temperature of about 400° F.
- a temperature i.e., BHCT
- the molecular weight of the sulfoallkylated portion of the composition of this invention is determined by diffusion techniques. These differences between the sulfoalkylated lignin compositions of this invention and the prior art lignosulfonates are shown by the examples.
- Samples of calcium (CaLS) and sodium lignosulfonates (NaLS) and a preferred sulfomethylated lignin (SML) composition of this invention were analyzed chemically by spectroscopy using X-ray, infrared, and ultraviolet radiation techniques.
- the samples were prepared and analyzed by standard procedures such as those described in ABSORPTION SPECTROSCOPY, by Robert P. Bauman, John Wiley & Sons, Inc., 1962, which is incorporated herein by reference to the extent necessary.
- X-ray diffraction merely showed that both the lignosulfonate and sulfoalkylated lignin were non-crystalline.
- the sulfur content of NaLS and SML was thought to include some inorganic sulfur (e.g. CaSO 4 ) entrained from cation exchange or sulfonation liquor.
- inorganic sulfur e.g. CaSO 4
- UV ultraviolet
- the infrared (IR) transmittance scan from 2.5-30 microns or 300-400 cm -1 showed peaks at the following wave lengths ( ⁇ ) in cm -1 :
- SML 3440; 2940; 2840; 1675; 1590; 1495; 1450; 1415; 1355; 1250*; 1200; 1140*; 1070; 1035; 930*; 850; 775; 735; 590 and 525.
- each sample was prepared by measuring an 800-gram portion of the designated dry cement into a cylindrical container of approximately 800 milliliters volume. Dry or powdered additives are designated as a percentage of the weight of the dry powdered cement unless indicated otherwise. Dry powdered additives are measured and blended with cement. A portion of tap water equal to the weight percentage of the dry cement is slurried with the dry cement and additives with vigorous mixing. The slurry is stirred for an additional 30 seconds at a high rate. Liquid additives are blended into the water. Samples were tested according to standard procedures as set forth in API Method RP-10B which is incorporated herein by reference.
- a sample portion is stirred in a container of about 500 milliliters at a temperature and pressure schedule determined by API method RP 10B.
- the container is heated from ambient temperature under pressure. It contains a direct reading consistometer which is calibrated with a potentiometer calibrating device to read directly in units of consistency (API-RP-10B).
- the set time of setting point is the time or point at 70 units of consistency or viscosity.
- API Method RP-10B provides the following casing schedule for bottom hole circulating temperature (BHCT) and bottom hole static temperature (BHST) at the indicated depths:
- Fluid loss is the number of milliliters or cubic centimeters of liquid forced through No. 50 Whatman filter paper or through 325 mesh screen according to API publication RP-10B (Section 8).
- Compressive strength tests were run on slurries containing calcium lignosulfonate or sulfomethylated lignin.
- the cement employed in these tests was Lone Star Class H.
- slurries containing retarder to give four hour pumping times on a 12,000' casing schedule were used.
- the slurries were pumped two hours at a 12,000' casing schedule and placed in autoclaves at four different temperatures to simulate the actual conditions encountered from the top to the bottom of a cement column in a well.
- the compressive strengths were then determined after 8, 12 and 24 hours according to API publication RP-10B (Section 6). After 8 hours, the slurries containing lignosulfonate had not set at the lower tempertures. However, the slurries containing sulfomethylated lignin were all set with significant strengths. The sulfomethylated lignin slurries consistently showed more rapid strength development throughout these tests.
- Sulfomethylated lignin functions in gel cement slurries as a dispersant and fluid loss additive.
- two separate retarders were required; one for non-gel slurries which was calcium lignosulfonate and another for gel slurries which was calcium sodium lignosulfonate.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Oil well cementing compositions and processes are produced using a high efficiency sulfoalkylated lignin retarder composition and modifications thereof to produce cement compositions without gelation problems, having high early strength and with precisely controllable setting time.
Description
This invention relates to cement compositions and more particularly to the use of hydraulic cement compositions for sealing or cementing subterranean zones or subterranean zones penetrated by a well such as cementing the annular space in an oil well between the surrounding formation and casing. In particular the invention relates to an improved hydraulic cement composition for cementing zones at elevated temperatures in which the setting time of the cement composition is controlled or extended by the addition of a highly efficient non-gelling retarding agent which produces a hydraulic cement composition having a degree of predictability for the setting time.
Typically, the subterranean zones are cemented or sealed by pumping an aqueous hydraulic cement slurry into the zone. In cementing the annular space of an oil well, the cement slurry is pumped down the inside of the casing and back up the outside of the casing through the annular space. Any cement slurry remaining in the casing is displaced and segregated using plugs and an aqueous displacement fluid. Frequently the high temperatures encountered in subterranean zones will cause premature setting of the hydraulic cement. This requires additives which extend or retard the setting time of the cement slurry so that there is adequate pumping time in which to place and displace the aqueous cement slurry in the desired zones. Previously known retarding agents are frequently unpredictable, typically produce erratic results with different brands of cement and frequently cause premature gelation of the cement slurry. Gelation refers to an abnormal increase of viscosity of the aqueous cement slurry to a value without a significant increase in the compressive strength of the cement composition. This increase in aqueous cement slurry viscosity makes the slurry difficult or impossible to pump at a viscosity of 70 poise or above which is defined as the set point herein. The cement composition has not attained an adequate compressive strength.
Prior art cement compositions and additives are described in the following list of 14 patents:
U.S. Pat. No. 2,549,507 to Morgan et al
U.S. Pat. No. 2,579,453 to Post et al
U.S. Pat. No. 2,674,321 to Cutforth
U.S. Pat. No. 2,676,170 to Patterson et al
U.S. Pat. No. 2,680,113 to Adler et al
U.S. Pat. No. 2,775,580 to Scarth
U.S. Pat. No. 2,872,278 to Putnam et al
U.S. Pat. No. 3,034,982 to Monroe
U.S. Pat. No. 3,053,673 to Walker
U.S. Pat. No. 3,135,727 to Monroe
U.S. Pat. No. 3,344,063 to Stratton
U.S. Pat. No. 3,748,159 to George
U.S. Pat. No. 3,766,229 to Turner
U.S. Pat. No. 3,821,985 to George.
Fundamentals of oil well cementing are described in the book PETROLEUM ENGINEERING DRILLING AND WELL COMPLETIONS, by Carl Gatlin, Prentice Hall, 1960. Background of and information on hydraulic cement compositions and additives can be found in the following books:
LIGNIN STRUCTURE AND REACTIONS, ADVANCES IN CHEMISTRY SERIES, 1959, American Chemical Society, 1966;
MECHANICAL BEHAVIOR OF HIGH POLYMERS, by Turner Alfrey, Interscience Publishers, 1948; and
HACKH'S CHEMICAL DICTIONARY, 4th Ed., McGraw-Hill, 1969.
The above references and information cited therein are incorporated herein by reference to the extent necessary.
The hydraulic cement compositions of this invention solve or eliminate many of the problems pointed out above. The hydraulic cement compositions of this invention do not have the gelation problem; the retarder composition is more efficient than prior art retarder compositions, the retarder has less variation with different brands of cement; cement compositions have much better predictability or reproducibility of setting times with a given brand of cement; and hydraulic cement compositions have better rheology characteristics. Thus the improved cement compositions of this invention have practically eliminated the problems of unpredictability and irreproducibility of results which are particularly severe in high pressure deep wells where the temperatures may exceed 300° F. and 15,000 PSI.
The concentration of retarder composition of this invention required to produce the desired pumping time for or delay in setting of a cement slurry at a given circulating temperature is not as critical as with conventional lignosulfonate retarders. The thickening time at a given retarder concentration is less temperature dependent than with conventional retarders. This reduces the possibility of over retarded slurries at cooler temperatures encountered at the top of long liners or tie back strings. The retarder compositions of this invention provide the desired pumping times and allow earlier strength development. When cementing long strings this can reduce the WOC (waiting on cement to set) time by 8-12 hours. Thus, the retarder compositions of this invention are more predictable in performance than conventional lignosulfonate retarders especially with various brands of cement. The compositions of this invention act not only as retarders but also as a dispersing agent which can reduce fluid loss from gel type or high clay cement slurries. When the retarder composition of this invention is blended in a cement slurry, viscosity of the slurry decreases slightly and remains constant or does not increase significantly until the cement begins to set. This improvement in rheology or viscosity characteristics with improved predictability makes use of the compositions much easier than with conventional retarders. In addition, the retarder compositions of this invention are generally non-toxic, non-flammable, non-hazardous; compatible with cements, other additives and with most other well fluids and mix readily in aqueous systems with minimum agitation.
The high efficiency, non-gelling cement retarder composition of this invention has a high degree of predictability for controlling rheology and setting time of hydraulic cement comprising a low molecular weight sulfoalkylated lignin which is substantially sulfoalkylated in the lignin molecule at positions on the benzene ring which are ortho to the phenolic hydroxyl group. In the sulfoalkyl group the sulfonic acid group (--SO3 H) is connected to the ortho position on the benzene ring by a methylene or substituted methylene groups. This methylene or substituted methylene group is referred to herein as an alkylidene radical having one to five carbon atoms. This alkylidene radical with sulfonic acid radical can be represented by the formula (--R--SO3 H) wherein R is the methylene group or alkyl portion having one to five carbon atoms and preferably one to three carbon atoms.
The unexpected properties of this retarder are thought to be due to the differences in average molecular weight or average molecular size and molecular structure. The evidence showing these differences is illustrated in the examples which show the unexpected properties. The sulfoalkylated lignin of this invention is a low molecular weight material having an average molecular weight or molecular size in the range of about 2,000-10,000 and preferably about 3,000-5,000. It is also thought to have a narrow molecular weight distribution. Prior art lignosulfonate compounds have a molecular weight or molecular size of about 10,000 and higher and the sulfonate substituent or radical attached directly on the carbon atom of the lignin molecule which is in the alpha position of the phenyl propyl side chain. This phenyl propyl or aliphatic chain is attached at a position on the benzene ring which is para to the phenolic hydroxyl group discussed herein. For lignosulfonate the phenolic hydroxyl group can be replaced by an alkoxy group as indicated by R1 --Ph--OR2 wherein R1 is the phenyl propyl side chain, Ph is phenyl or the benzene ring and R2 is hydrogen or alkyl. The sulfoalkylated retarder composition of this invention has substantially all of the sulfoalkyl group (i.e., --R--SO3 H) in the position ortho to the phenolic hydroxyl group of the benzene ring of the lignin molecule.
The sulfoalkylated lignin retarder of this invention does not have a significant degree of sulfonation at the alpha carbon atom as do the prior art lignosulfonates. Thus, the sulfoalkylated lignin retarder of this invention is an entirely different chemical composition as shown by the unexpected and significantly different properties shown herein. The sulfoalkylated lignin retarder of this invention can be considered to be a sulfoalkylated lignin of high purity, low molecular weight with a narrow molecular weight distribution. This is thought to be due to the significantly different procedure used for its preparation.
The sulfoalkylated lignin retarder for compositions of this invention can be prepared by catalytic oxidation of the sulfite liquor from a wood pulping process. This oxidation removes polysaccharides and wood sugars and substantially desulfonates the lignin molecule which is recovered as a residue. This purified lignin is separated from the liquid. The high purity, low molecular weight lignin molecule is then substantially sulfoalkylated by the addition of sulfonating agent such as sodium sulfite in the presence of an aldehyde or ketone having one to five carbon atoms at about 150°-190° C. and 180-220 atmospheres. In this process, the aldehyde or ketone furnishes the alkylidene group which attaches at a vacant ortho position on the benzene ring in the lignin molecule and connects the sulfonate group through a methylene radical to the benzene ring at a position ortho to the free phenolic hydroxyl group. Some benzene rings may have more than one sulfoalkyl group attached and some benzene rings may have no sulfoalkyl substituents. The sulfur content of the sulfoalkylated lignin is between about 3-10% and preferably 3-8%.
This sulfonate group can be in the form of the acid, a salt or combinations thereof. The salt can be in the form of ammonium or metal salt involving an alkali metal; an alkaline earth metal; or metals such as iron, copper, zinc, vanadium, titanium, aluminum, manganese, chromium, cobalt or nickel; or combinations thereof. The salts which are readily soluble in aqueous systems, such as those of the alkali metals, sodium and potassium, are preferred although the salts of alkaline earth metals and other metals can be used under certain circumstances.
The alkyl portion of the sulfonate substituent is derived from the aldehyde or ketone used in the sulfoalkylation step. Formaldehyde is a preferred alkyl source because it simply connects the sulfonate group to the ortho position by a one-carbon atom methylene group. Acetone would produce an alkylidene group having a methyl group on each side of the methylene group; methyl ethyl ketone would result in a methyl and an ethyl alkyl group attached to the methylene group; and propionaldehyde would result in an ethyl group attached to the methylene bridge. Theoretically, any aldehyde or ketone could be used for forming the alkylidene radical but the stereo chemistry and solubility must be considered in selecting the size and configuration of the aldehyde or ketone use for this component. A preferred sulfoalkylated lignin of this invention has a molecular weight in the range of about 3,000-4,000, a one carbon atom alkylidene radical and sulfur content of about 3-8% by weight.
Another preferred hydraulic cement composition of this invention can be considered to be a modified low molecular weight sulfoalkylated lignin. This modified retarder composition is a combination of the high purity substantially sulfoalkylated lignin described above and at least one water soluble hydroxy carboxylic acid. These hydroxy carboxylic acids have a synergistic effect of increasing the effectiveness and operable temperature range of the basic retarder composition. The preferred carboxylic acids are substantially alphatic carboxylic acids and preferably polyhydroxy carboxylic acids having at least one terminal carboxy group which can be in the form of the acid, a salt or mixtures thereof as described above for the sulfonate groups.
Particularly preferred polyhydroxy carboxylic acids have a molecular weight in the range of about 125-250 and have a hydroxyl group attached to the carbon atom adjacent to the carboxy group as show by the formula ##STR1## These carboxylic acids include gluconic acid, tartaric acid and equivalents thereof. These equivalents include the various stereoisomers of the above acids particularly the asymmetric or optically active isomers. Thus, the preferred group of hydroxy carboxylic acids are substantially linear aliphatic acids having about 4-10 carbon atoms, and preferably 4-8 carbon atoms. The molecular size and number of hydroxy and carboxylic groups will affect the water solubility. The hydroxy carboxylic acid is preferably present with the sulfoalkylated lignin in a weight ratio of acid to lignin preferably in the range of about 1:0.1-5.0 and preferably in the range of about 1:0.2-3.0.
The hydraulic cement compositions of this invention are typically used in the form of an aqueous slurry of hydraulic cement with a concentration of retarder mixed in the aqueous slurry to control or delay the cement setting time so that it exceeds the pumping time with an adequate safety margin. Sufficient water is added to the slurry to make the composition pumpable. As used herein the hydraulic cement is typically a Portland cement which is set by the water of the slurry in the absence of air which is excluded by placement of the cement in the zone to be sealed. The low molecular weight sulfoalkylated lignin retarder of this invention is preferably present in the aqueous hydraulic cement slurry in a concentration up to about 2%, and preferably up to 1%, by weight based on the dry cement. Higher retarder concentrations and other cement can be used when necessary in unusual circumstances. A deforming agent is typically added as are fluid loss additives, friction reducing additives, salts such as sodium chloride and potassium chloride, weighting additives and other conventional additives as described in the references cited above. Pozzolana cement, high alumina cement or high gel (high clay content) cement can be used for special applications. The low molecular weight sulfoalkylated retarder composition of this invention has high reproducibility and predictability when used with most high quality cements which are typically used in the petroleum industry. However, certain brands which are not manufactured to standard specifications, such as those which are not sufficiently calcined or having varying degrees of free lime remaining in the cement, will produce substantial variations from the standard high quality brands. It is not clear whether the free lime causes the problems or is merely an indication when the problems exist. These variations can be readily determined by preliminary tests which make even these substandard cements readily predictable and may merely require slightly higher retarder concentrations to offset the chemical composition variations of the cement of excess lime content.
In a preferred process for using the non-gelling hydraulic cement composition of this invention having a degree of predictability of setting time and containing the high efficiency retarder, the retarder composition is mixed with the hydraulic cement as an aqueous slurry with the retarder concentration up to about 2% on a dry cement weight basis. The hydraulic cement mixture is pumped without gelation into the zone to be sealed or cemented and the hydraulic cement mixture is maintained in the zone until an adequate compressive strength is attained. In this process the retarder concentration preferably up to about 2% on a dry cement weight basis is calculated to control the setting time of the hydraulic cement slurry to exceed the pumping time within an adequate safety margin. Due to the higher efficiency of the retarder and greater predictability of the hydraulic cementing compositions of this invention, the portion of the safety margin previously required for these variations can be substantially reduced. The safety margin now need primarily allow time only for unexpected equipment difficulties. This reduction in the safety margin time or time which the typical oil drilling rig is waiting for the cement to set can result in a substantial economic advantage due to the higher efficiency and predictability of the hydraulic cement compositions of this invention. The modified low molecular weight sulfoalkylated lignin of this invention or the combination of the sulfoalkylated lignin with the hydroxy carboxylic acids improve the efficiency and predictability of the compositions of this invention even more and therefore are preferably used. The basic sulfoalkylated lignin retarder composition of this invention can be used up to a temperature (i.e., BHCT) slighly in excess of about 210° F. and the modified retarder composition containing the hydroxy carboxylic acids can be used up to a temperature of about 400° F.
The molecular weight of the sulfoallkylated portion of the composition of this invention is determined by diffusion techniques. These differences between the sulfoalkylated lignin compositions of this invention and the prior art lignosulfonates are shown by the examples.
The following examples serve to illustrate various embodiments of the invention and enable one skilled in the art to practice the invention. Parts, percentages, proportions and concentrations are by weight unless indicated otherwise.
Samples of calcium (CaLS) and sodium lignosulfonates (NaLS) and a preferred sulfomethylated lignin (SML) composition of this invention were analyzed chemically by spectroscopy using X-ray, infrared, and ultraviolet radiation techniques. The samples were prepared and analyzed by standard procedures such as those described in ABSORPTION SPECTROSCOPY, by Robert P. Bauman, John Wiley & Sons, Inc., 1962, which is incorporated herein by reference to the extent necessary. X-ray diffraction merely showed that both the lignosulfonate and sulfoalkylated lignin were non-crystalline.
Chemical analysis indicated the following constituents by weight:
______________________________________ % C % H.sub.2 % Ca % S ______________________________________ CaLS 39.1 4.3 7.6 3.9 NaLS 42.2 4.6 0.3 7.4 SML 45.0 3.8 0.2 6.2 ______________________________________
The sulfur content of NaLS and SML was thought to include some inorganic sulfur (e.g. CaSO4) entrained from cation exchange or sulfonation liquor.
For ultraviolet (UV) technique which scanned 190-360 millimicrons (mμ) for both NaLS and SML showed a major peak at about 202-205 millimicrons with shoulder or decreasing peaks at about 230 and 310-320 millimicrons. The samples were in water at a 0.02 gram per liter concentration and were run in a one cm path length cell.
The infrared (IR) transmittance scan from 2.5-30 microns or 300-400 cm-1 showed peaks at the following wave lengths (λ) in cm-1 :
NaLS*3440; 2940; 2840*; 1590; 1495; 1450; 1415; 1250*; 1200; 1140*; 1035; 930*; 640 and 590.
SML: 3440; 2940; 2840; 1675; 1590; 1495; 1450; 1415; 1355; 1250*; 1200; 1140*; 1070; 1035; 930*; 850; 775; 735; 590 and 525.
The starred values (*) are shoulder peaks or peaks which are not very distinct. Samples for the IR scan were mulled in NUJOL mineral oil and run between salt plates.
For the following examples each sample was prepared by measuring an 800-gram portion of the designated dry cement into a cylindrical container of approximately 800 milliliters volume. Dry or powdered additives are designated as a percentage of the weight of the dry powdered cement unless indicated otherwise. Dry powdered additives are measured and blended with cement. A portion of tap water equal to the weight percentage of the dry cement is slurried with the dry cement and additives with vigorous mixing. The slurry is stirred for an additional 30 seconds at a high rate. Liquid additives are blended into the water. Samples were tested according to standard procedures as set forth in API Method RP-10B which is incorporated herein by reference.
For thickening time tests a sample portion is stirred in a container of about 500 milliliters at a temperature and pressure schedule determined by API method RP 10B. The container is heated from ambient temperature under pressure. It contains a direct reading consistometer which is calibrated with a potentiometer calibrating device to read directly in units of consistency (API-RP-10B). The set time of setting point is the time or point at 70 units of consistency or viscosity.
API Method RP-10B provides the following casing schedule for bottom hole circulating temperature (BHCT) and bottom hole static temperature (BHST) at the indicated depths:
______________________________________ Depth (ft.) BHCT (°F.) BHST (°F.) ______________________________________ 8,000 (2440 m)* 125 (51.67° C.)* 200 (93.33° C.)* 10,000 (3050 m) 144 (62.22° C.) 230 (110.00° C.) 12,000 (3660 m) 172 (77.78° C.) 260 (126.67° C.) 14,000 (4270 m) 206 (96.67° C.) 290 (143.33° C.) 15,000 (4575 m) 226 (107.78° C.) 305 (151.66° C.) 16,000 (4880 m) 248 (120.00° C.) 320 (160.00° C.) 18,000 (5490 m) 300 (148.89° C.) 350 (176.67° C.) 20,000 (6100 m) 340 (171.11° C.) 380 (193.33° C.) 22,000 (6710 m) 380 (193.33° C.) 410 (210.00° C.) ______________________________________ *Metric Equivalents
Fluid loss is the number of milliliters or cubic centimeters of liquid forced through No. 50 Whatman filter paper or through 325 mesh screen according to API publication RP-10B (Section 8).
TABLE I ______________________________________ Predictable Behavior Thickening Times Hours:Minutes SML* API Casing Simulation Tests % Retarder 8,000' 10,000' 12,000' 14,000' ______________________________________ Lone Star Class H Cement 38% H.sub.2 O 0.20 2:35 2:04 1:33 -- 0.25 4:20 2:37 -- -- 0.30 5:50 3:11 2:31 1:58 0.35 -- 5:20 -- -- 0.40 -- -- 4:12 3:01 0.50 -- -- 7:18 3:47 0.60 -- -- -- 4:09 0.70 -- -- -- 5:12 Lone Star Class H Cement 46% H.sub.2 O 0.16 2:43 -- -- -- 0.20 -- 2:25 2:15 1:55 0.24 3:51 -- -- -- 0.30 6:40 3:28 3:01 2:32 0.34 -- -- 3:58 -- 0.35 -- 6:13 -- -- 0.38 -- -- 4:17 -- 0.40 -- 11.22 -- 3:32 0.44 -- -- 5:37 -- 0.60 -- -- -- 6:10 ______________________________________ *Sulfomethylated lignin retarder.
Increasing the retarder concentration results in corresponding increase in thickening time until a saturation point is reached. Beyond this point, slight increases in the retarder concentration result in greatly increased thickening times.
TABLE II ______________________________________ Set Times Obtained with Commercially Available Calcium Lignosulfonate and the Sodium Salt of Sulfomethylated Lignin.sup.a Percent Set Times - Percent Sodium Hours:Minutes Retarder Chloride API Casing (by wt. (by wt. Simulation Tests 206° F.Cement) water) 14,000' ______________________________________ Sulfomethylated Lignin 0.3 0 1:58 0.4 0 3:01 0.5 0 3:47 0.6 0 4:09 0.7 0 5:12 Calcium Lignosulfonate 0.3 0 3:25 0.4 0 4:05 0.5 0 1:34.sup.b 0.6 0 1:35.sup.b Sulfomethylated Lignin 0.3 18.0 1:44 0.4 18.0 2:27 0.5 18.0 2:45 0.6 18.0 3:42 0.7 18.0 4:33 0.8 18.0 5:12 Calcium Lignosulfonate 0.2 18.0 1:32.sup.b 0.3 18.0 1:40.sup.b 0.4 18.0 1:48.sup.b 0.5 18.0 2:05.sup.b 0.6 18.0 2:40.sup.b ______________________________________ .sup.a All slurries consisted of 800 grams Lone Star Class H Cement with 304 grams (38%) water, and indicated amounts of additive and sodium chloride. .sup.b Slurry gelation was observed, i.e., viscosity reached 70 units of consistency but slurry had not developed significant compressive strength at that time. Others reached a viscosity of 70 units and set with compressive strength at approximately the same time.
AT higher temperatures slurries containing the conventional retarder tend to form unpumpable heavy gels prior to development of significant compressive strength, however, use of the sulfomethylated compound yielded slurries which were well dispersed until final hard set of the cement was obtained. This is illustrated in Table II which lists the set time and percent added retarder for both fresh and salt water slurries containing either the commercially available calcium salt of lignosulfonate or the sodium salt of the new sulfomethylated compound. As noted in the table, many of the slurries containing the calcium salt tended to form heavy gels (i.e., slurry is unpumpable and thus, considered set when the viscosity reaches 70 units of consistency even though it may have gelled with no compressive strength at that time); this results in an erratic dependence of set time on retarder cocentration. For example, in the fresh water slurries, increases in retarder concentration in excess of approximately 0.4% (Table II) result in decreased rather than the expected increased set times; this effect is not found for the new compound which shows a reasonable set time increase as the retarder concentration is increased in both fresh and salt water slurries.
Predictable Behavior One Cement to Another
TABLE III ______________________________________ Predictable Behavior One Cement to Another Effect of Cement Brand on Set Time.sup.a Percent Additive Set Time - (by wt. Hours:Minutes of API Casing Type of Cement 206° F.ditive cement) 14,000' ______________________________________ Lone Star Class H Sulfomethylated (Maryneal).sup.b Lignin 0.5 3:37 Lone Star Class H Calcium (Maryneal).sup.b Lignosulfate 0.5 1:34.sup.h Lone Star Class H Sulfomethylated (New Orleans).sup.c Lignin 0.5 2:45 Lone Star Class H Calcium (New Orleans).sup.c Lignosulfate 0.5 0:40.sup.h Trinity Class H.sup.d Sulfomethylated Lignin 0.5 2:46 Trinity Class H.sup.d Calcium Lignosulfate 0.5 3:02.sup.h Southwestern Sulfomethylated Class H.sup.e Lignin 0.5 3:19 Southwestern Calcium Class H.sup.e Lignosulfate 0.5 4:05 Oklahoma Class H.sup.f Sulfomethylated Lignin 0.5 3:00 Oklahoma Class H.sup.f Calcium Lignosulfate 0.5 3:45.sup.h Dyckerhoff Class B.sup.g Sulfomethylated Lignin 0.5 2:44 Dyckerhoff Class B.sup.g Calcium Lignosulfate 0.5 2:45 ______________________________________ .sup.a Slurries consisted of 800 grams indicated cement, 304 grams (38%) water (by wt. of cement), and additive with the exception of the slurries containing Dyckerhoff Class B which contained 368 grams (46%) water. .sup.b Cement manufactured by Lone Star Industries, Inc., Maryneal, Texas .sup.c Cement manufactured by Lone Star Industries, Inc., New Orleans, Louisiana. .sup.d Cement manufactured by Trinity, Portland Cement Division, Dallas, Ft. Worth, Houston, Texas. .sup.e Cement manufactured by Southwestern Portland Cement Company, El Paso, Texas. .sup.f Cement manufactured by OKC Corporation, Pryor, Oklahoma. .sup.g Cement manufactured by Dyckerhoff Zementwerke AG, WiesbadenBiebrich, Germany. .sup.h These slurries gelled prior to hard set.
At constant concentration of the new retarder, reasonably consistent set times are obtained for slurries containing cements produced by different manufacturers (Table III). This contrasts with the similar results for calcium lignosulfonate which vary drastically from one cement to another.
TABLE IV ______________________________________ Slurry Gelation Effect Viscosity versus Pumping Time of the Slurries Containing Calcium Lignosulfonate or the Sodium Salt of Sulfomethylated Lignin Pumping Times Hours:Minutes Viscosity Type Percent 14,000' API In Units of of Cement Additive.sup.d Additive Casing - 206° F. Consistency.sup.e ______________________________________ Lone Star SML 0.5 0:00 9 Class H 0:30 6 (Maryneal) 0:45 6 1:00 6 1:15 6 1:30 6 2:00 12 2:15 21 3:00 26 3:15 29 3:30 31 3:47.sup.b 70 NaLS 0.5 0:00 1 0:30 4 0:45 13 1:00 37 1:15 41 1:30 45 1:34.sup.c 70 ______________________________________ .sup.a Slurries consisted of cement, 38% water and additive. .sup.b Slurry reached a viscosity of 70 units and set with compressive strength at approximately the same time. .sup.c Slurry reached a viscosity of 70 units but had no compressive strength until approximately two hours later. .sup.d SML is sulfomethylated lignin and NaLS is sodium lignosulfonate. .sup.e Consistency measured directly in units of consistency according to API publication RP10B.
TABLE V ______________________________________ Lower Temperatures Set Times Obtained with Calcium Lignosulfonate and the Sodium Salt of Sulfomethylated Lignin Percent Retarder Set Times - Hours:Minutes (by wt. API Casing Simulation Tests Retarder Cement) 10,000' 12,000' ______________________________________ Sulfomethylated Lignin.sup.a 0.3 -- 2:30 0.4 -- 3:57 0.5 -- 8:00 Calcium Lignosulfonate.sup.a 0.3 -- 3:10 0.4 -- 2:21 0.6 -- 1:40 Sulfomethylated Lignin.sup.b 0.08 2:58 -- 0.12 3:29 -- 0.16 4:00 -- 0.20 4:50 -- 0.24 6:33 -- Calcium Lignosulfonate.sup.b 0.40 1:44.sup.c -- 0.80 3:20.sup.c -- ______________________________________ .sup.a Slurries consisted of Dyckerhoff Class G, 44% water and indicated additive. .sup.b Slurry consisted of Longhorn Class H Cement with 44% water, 35% coarse silica flour (60-140 mesh), 0.75% CFR2 friction reducer and 18% sodium chloride salt. CFR2 is betanaphthalene sulfonic acid condensed wit formaldehyde and mixed with 10% polyvinyl pyrrolidone. CFR2 is described in U.S. Pat. No. 3,359,225 which is incorporated herein by reference. .sup.c Slurries showed severe gelation effects.
TABLE VI ______________________________________ Compressive Strength Class H Cement with 38% Water Retarder Concentration Giving 4.0 Hr. Pumping Time on 12,000 ft. Schedule Slurries Pumped 2 hrs. on 12,000 ft. Schedule and placed in Autoclaves at Indicated Temperature Compressive Strength Compressive Strength Using Conventional Using SML Lignosulfonate Retarder Cement Retarder (PSI) Temperature (PSI) 8 hrs. 12 hrs. 24 hrs. °F. 8 hrs. 12 hrs 24 hrs ______________________________________ NS* 290 2260 170 650 1690 2790 NS 2080 2660 200 1010 2020 3980 NS 2270 2840 230 1670 2800 4260 1360 3480 3310 260 2040 3660 5420 ______________________________________ *Not Set
Compressive strength tests were run on slurries containing calcium lignosulfonate or sulfomethylated lignin. The cement employed in these tests was Lone Star Class H. In these tests, slurries containing retarder to give four hour pumping times on a 12,000' casing schedule were used. The slurries were pumped two hours at a 12,000' casing schedule and placed in autoclaves at four different temperatures to simulate the actual conditions encountered from the top to the bottom of a cement column in a well. The compressive strengths were then determined after 8, 12 and 24 hours according to API publication RP-10B (Section 6). After 8 hours, the slurries containing lignosulfonate had not set at the lower tempertures. However, the slurries containing sulfomethylated lignin were all set with significant strengths. The sulfomethylated lignin slurries consistently showed more rapid strength development throughout these tests.
TABLE VII __________________________________________________________________________ Compatibility With Fluid Loss Additives Compatibility of New Sulfomethylated Lignin and Common Fluid Loss Additives.sup.a Consistometer Percent Fluid Loss Additive Sodium Readings Retarder 1.sup.b 2.sup.c Chloride Fluid at 100° F. (Poise) By Wt. % By Wt. % By Wt. % By Wt. Loss Initial Final Retarder Cement Cement Cement Water (cc) __________________________________________________________________________ Sulfomethylated 9 8 Lignin 0.5 0.6 0- -- 44 Calcium 9 10 Lignosulfonate 0.5 0.6 0- 0- 141 Sulfomethylated 10 10 Lignin 0.5 0.6 0- 18.0 98 Calcium 10 10 Lignosulfonate 0.5 0.6 0- 18.0 188 Sulfomethylated 12 12 Lignin 0.5 0- 0.6 0- 38 Calcium 10 10 Lignosulfonate 0.5 0- 0.6 0- 137 Sulfomethylated 12 12 Lignin 0.5 0- 0.6 18.0 82 Calcium 11 11 Lignosulfonate 0.5 0- 0.6 18.0 154 __________________________________________________________________________ .sup. a All slurries contained Lone Star Class H Cement, 28% water, and indicated amounts of retarder, Halliburton fluid loss additive, and sodiu chloride. After mixing, the slurries were stirred on the Halliburton Consistometer for 20 minutes at 100° F. and fluid loss determination conducted at 100 PSI pressure on a 325 mesh screen at the same temperature. .sup.b 56% HEC (hydroxyethyl cellulose) with 44% CFR2. .sup.c 60% HEC, 20% defoamer with 20% CFR2.
TABLE VIII __________________________________________________________________________ Dispersant and Fluid Loss Properties in Gel Cement Slurries Class H Cement 12% Gel 11.46 gal. water/sack Fluid Loss cc/30 Min. 100 PSI % Addition Fann Data No. 50 1000 PSI (By wt. Shear Stress lb/ft.sup.2 at 80° F. Whatman 325 Mesh Retarder Cement) 600 RPM 300 RPM 200 RPM 100 RPM Paper Screen __________________________________________________________________________ Sulfomethylated Lignin 0- 1.22 1.16 1.12 1.05 190 372 0.34 0.47 0.34 0.31 0.26 132 265 0.52 0.42 0.27 0.21 0.17 104 188 Calcium Sodium.sup.a Lignosulfonate 0.34 0.58 0.47 0.43 0.37 149 258 0.52 0.69 0.56 0.51 0.46 113 217 __________________________________________________________________________ .sup.a A mixed calciumsodium lignosulfonate is used in gel cement slurrie instead of simple calcium lignosulfonate due to the tendency of the latte to gel slurries of this type.
Sulfomethylated lignin functions in gel cement slurries as a dispersant and fluid loss additive. Previously, two separate retarders were required; one for non-gel slurries which was calcium lignosulfonate and another for gel slurries which was calcium sodium lignosulfonate.
TABLE IX ______________________________________ Extension with Tartaric Acid Set Times Obtained with a Mixture of the Sodium Salt of Sulfomethylated Lignin and Tartaric Acid in a 2:1 Weight Ratio* Set Times % Retarder Hours:Minutes (By Wt. API Casing Simulation Tests Cement) 16,000' 18,000' 20,000' 22,000' ______________________________________ 0.4 1:55 -- -- -- 0.5 4:20 -- -- -- 0.6 5:57 1:40 -- -- 0.8 -- 2:31 -- -- 0.9 -- 3:43 -- -- 1.0 -- 4:34 -- -- 1.1 -- 5:13 -- 2:00 1.2 -- -- 3:43 -- 1.3 -- -- -- 2:28 1.6 -- -- 5:10 -- 1.8 -- -- 6:32 3:12 2.0 -- -- -- 3:25 2.6 -- -- -- 4:10 ______________________________________ *All slurries consisted of Lone Star Class H Cement, 35% SSA1, 54% water, and indicated amounts of retarder. SSA1 is fine silica flour which is added to cement slurries at high temperature to prevent strength retrogression. Over 97% of the silica particles pass through a 200mesh (U.S. Std. Sieve Series) screen.
TABLE X ______________________________________ Extension of Set Times of Slurries Containing Sulfomethylated Lignin by the Addition of Borax Percent Percent Sulfomethylated Borax Set Time - Hours:Minutes Lignin (By Wt. (By Wt. API Casing Schedule Cement) Cement) 15,000' 16,000' ______________________________________ 0.7 0.6 3:00 -- 0.8 0.6 4:22 -- 0.9 0.6 5:12 -- 0.4 0.7 -- 1:54 0.6 0.7 -- 3:54 0.8 0.7 -- 5:20 0.95 0.7 -- 7:10 ______________________________________
Set times obtained with sulfomethylated lignin can be extended by the addition of boric acid or water soluble salt of boric acid (e.g., salts of ammonia, alkali or alkaline earth metals). This extension makes possible the use of the sulfomethylated lignin retarder at higher temperatures. Examples of extenders of this type are:
1. Boric acid,
2. Na2 B4 O7.10H2 O (Borax),
3. Na2 B5 O8.5H2 O,
4. KB5 O8.4H2 O,
5. Li1 B5 O8.5H2 O,
6. NaBO2.4H2 O,
similar compounds and mixtures thereof.
Claims (3)
1. A process for sealing at an elevated temperature a zone penetrated by a wellbore using a high efficiency non-gelling hydraulic cement retarder composition having a high degree of predictability for controlling rheology and setting time comprising mixing an aqueous slurry of hydraulic cement with up to about 2% on a dry cement weight basis of a retarder consisting essentially of a low molecular weight sulfoalkylated lignin; wherein the concentration of retarder is calculated to control the setting time of said hydraulic cement to exceed the pumping time; wherein the sulfoalkylated lignin has a molecular weight in the range of about 2,000-10,000 and which is substantially sulfoalkylated on the benzene ring of the lignin molecule in the position ortho to the free phenolic hydroxy group and the sulfonate group is attached to the ortho position by an alkylidene radical having one to three carbon atoms; pumping said hydraulic cement mixture into said zone and maintaining said hydraulic cement mixture in said zone until a high compressive strength is attained..].
2. A process for sealing at an elevated temperature a zone penetrated by a wellbore using a high efficiency non-gelling hydraulic cement composition having a high degree of predictability for controlling rheology and setting time comprising mixing an aqueous slurry of hydraulic cement with up to about 2% on a dry cement weight basis of a retarder consisting essentially of at least one water soluble hydroxy carboxylic acid and a low molecular weight sulfoalkylated lignin; wherein the concentration of retarder is calculated to control the setting time of said hydraulic cement to exceed the pumping time; wherein the weight ratio of acid to lignin is in the range of about 1:0.1-5.0; wherein said carboxylic acid is a substantially linear aliphatic acid having at least one terminal carboxyl group in the form of acid, salt of mixtures thereof; wherein said sulfoalkylated lignin has a molcular weight in the range of about 2,000-10,000 and which is substantially sulfoalkylated on the benzene ring in the lignin molecule in the position ortho to the free phenolic hydroxy group and the sulfonate group is attached to the ortho position by an alkylidene radical having one to three carbon atoms; pumping said hydraulic cement mixture into said zone without gelation and maintaining said hydraulic cement mixture in said zone until a high compressive strength is attained.
3. In a process for cementing a zone at an elevated temperature by pumping an aqueous hydraulic cement slurry into said zone, the improvement of controlling the setting time of said cement and preventing gelation of said cement by mixing with said hydraulic cement a high efficiency non-gelling retarder consisting essentially of a mixture of at least one water soluble hydroxy carboxylic acid and a low molecular weight sulfoalkylated lignin; wherein the concentration of retarder is calculated to control the setting time of said hydraulic cement to exceed the pumping time; wherein the weight ratio of said acid to lignin is in the range of about 1:0.1-5.0; wherein the carboxylic acid is a substantially linear aliphatic acid having at least one termial carboxyl group in the form of acid, salt or mixtures thereof; wherein said sulfoalkylated lignin has a molecular weight in the range of about 2,000-10,000 and which is substantially sulfoalkylated on the benzene ring in the lignin molecule in the position ortho to the free phenolic hydroxy group and the sulfonate group is attached to the ortho position by an alkylidene radical having one to three carbon atoms.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/298,037 USRE31127E (en) | 1976-02-02 | 1981-08-31 | Oil well cementing process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/654,497 US4047567A (en) | 1976-02-02 | 1976-02-02 | Oil well cementing process |
US06/298,037 USRE31127E (en) | 1976-02-02 | 1981-08-31 | Oil well cementing process |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/654,497 Reissue US4047567A (en) | 1976-02-02 | 1976-02-02 | Oil well cementing process |
Publications (1)
Publication Number | Publication Date |
---|---|
USRE31127E true USRE31127E (en) | 1983-01-18 |
Family
ID=26970436
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/298,037 Expired - Lifetime USRE31127E (en) | 1976-02-02 | 1981-08-31 | Oil well cementing process |
Country Status (1)
Country | Link |
---|---|
US (1) | USRE31127E (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4676317A (en) | 1986-05-13 | 1987-06-30 | Halliburton Company | Method of reducing fluid loss in cement compositions which may contain substantial salt concentrations |
US4703801A (en) | 1986-05-13 | 1987-11-03 | Halliburton Company | Method of reducing fluid loss in cement compositions which may contain substantial salt concentrations |
US4926944A (en) | 1989-01-17 | 1990-05-22 | Westvaco Corporation | Lignin-based cement fluid loss control additive |
US4990191A (en) * | 1989-02-21 | 1991-02-05 | Westvaco Corporation | Aminated sulfonated or sulfomethylated lignins as cement fluid loss control additives |
WO1991017968A1 (en) * | 1990-05-18 | 1991-11-28 | Specrete-Ip Incorporated | A silica fume hydrating and plasticizing admixture for concrete |
US20080156491A1 (en) * | 2005-09-09 | 2008-07-03 | Roddy Craig W | Extended Settable Compositions Comprising Cement Kiln Dust and Associated Methods |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2674321A (en) * | 1949-12-19 | 1954-04-06 | Phillips Petroleum Co | Low water-loss cement slurry |
US2676170A (en) * | 1950-07-15 | 1954-04-20 | Du Pont | Water-soluble derivatives of unsulfonated lignin |
US2680113A (en) * | 1949-12-22 | 1954-06-01 | Svenska Cellulosaforeningens C | Method of producing water-soluble products from black liquor lignin |
US2775580A (en) * | 1953-05-25 | 1956-12-25 | Phillips Petroleum Co | Sulfobenzyl lignins |
US3053673A (en) * | 1960-03-18 | 1962-09-11 | Halliburton Co | Oil well cement compositions |
US3296159A (en) * | 1962-10-19 | 1967-01-03 | Diamond Alkali Co | Waste sulfite liquor aliphatic aldehyde reaction products |
US3634387A (en) * | 1969-06-02 | 1972-01-11 | Westvaco Corp | Sulfomethylated lignin-ferrochrome complex and process for producing same |
US3662830A (en) * | 1970-06-01 | 1972-05-16 | Dow Chemical Co | Aqueous hydraulic cement composition having improved retardation to set and use thereof in high temperature environments |
US3723145A (en) * | 1971-04-05 | 1973-03-27 | Lone Star Cement Corp | Well cementing compositions and method |
US3772045A (en) * | 1971-04-05 | 1973-11-13 | Lone Star Cement Corp | Additive cement compositions and method |
US3821985A (en) * | 1972-04-20 | 1974-07-02 | Halliburton Co | Well cementing method using high temperature cementing compositions |
-
1981
- 1981-08-31 US US06/298,037 patent/USRE31127E/en not_active Expired - Lifetime
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2674321A (en) * | 1949-12-19 | 1954-04-06 | Phillips Petroleum Co | Low water-loss cement slurry |
US2680113A (en) * | 1949-12-22 | 1954-06-01 | Svenska Cellulosaforeningens C | Method of producing water-soluble products from black liquor lignin |
US2676170A (en) * | 1950-07-15 | 1954-04-20 | Du Pont | Water-soluble derivatives of unsulfonated lignin |
US2775580A (en) * | 1953-05-25 | 1956-12-25 | Phillips Petroleum Co | Sulfobenzyl lignins |
US3053673A (en) * | 1960-03-18 | 1962-09-11 | Halliburton Co | Oil well cement compositions |
US3296159A (en) * | 1962-10-19 | 1967-01-03 | Diamond Alkali Co | Waste sulfite liquor aliphatic aldehyde reaction products |
US3634387A (en) * | 1969-06-02 | 1972-01-11 | Westvaco Corp | Sulfomethylated lignin-ferrochrome complex and process for producing same |
US3662830A (en) * | 1970-06-01 | 1972-05-16 | Dow Chemical Co | Aqueous hydraulic cement composition having improved retardation to set and use thereof in high temperature environments |
US3723145A (en) * | 1971-04-05 | 1973-03-27 | Lone Star Cement Corp | Well cementing compositions and method |
US3772045A (en) * | 1971-04-05 | 1973-11-13 | Lone Star Cement Corp | Additive cement compositions and method |
US3821985A (en) * | 1972-04-20 | 1974-07-02 | Halliburton Co | Well cementing method using high temperature cementing compositions |
Non-Patent Citations (2)
Title |
---|
Goheen et al., "Lignite", Kirk-Othmer Encyclopedia of Chemical Technology, 2d. Ed., vol. 12, Interscience Publishers, Div. of John Wiley & Sons, Inc., New York, N.Y., 1967, pp. 361-381. * |
Schubert, "Light Stability of Polymers-Lignin", Encyclopedia of Polymer Science and Technology, vol. 8, Interscience Publishers, a Div. of John Wiley & Sons, Inc., New York, N.Y., 1968, pp. 233-272. * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4676317A (en) | 1986-05-13 | 1987-06-30 | Halliburton Company | Method of reducing fluid loss in cement compositions which may contain substantial salt concentrations |
US4703801A (en) | 1986-05-13 | 1987-11-03 | Halliburton Company | Method of reducing fluid loss in cement compositions which may contain substantial salt concentrations |
US4926944A (en) | 1989-01-17 | 1990-05-22 | Westvaco Corporation | Lignin-based cement fluid loss control additive |
US4990191A (en) * | 1989-02-21 | 1991-02-05 | Westvaco Corporation | Aminated sulfonated or sulfomethylated lignins as cement fluid loss control additives |
WO1991017968A1 (en) * | 1990-05-18 | 1991-11-28 | Specrete-Ip Incorporated | A silica fume hydrating and plasticizing admixture for concrete |
US20080156491A1 (en) * | 2005-09-09 | 2008-07-03 | Roddy Craig W | Extended Settable Compositions Comprising Cement Kiln Dust and Associated Methods |
US7478675B2 (en) | 2005-09-09 | 2009-01-20 | Halliburton Energy Services, Inc. | Extended settable compositions comprising cement kiln dust and associated methods |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
USRE31190E (en) | Oil well cementing process | |
US4047567A (en) | Oil well cementing process | |
US4450009A (en) | Method of preparing a light weight cement composition from sea water | |
EP1319798B1 (en) | Sealing subterranean zones | |
US5049288A (en) | Set retarded cement compositions and methods for well cementing | |
US4083407A (en) | Spacer composition and method of use | |
US4941536A (en) | Set retarded cement compositions and methods for well cementing | |
US4557763A (en) | Dispersant and fluid loss additives for oil field cements | |
US5358049A (en) | Conversion of emulsion mud to cement | |
US3499491A (en) | Method and composition for cementing oil well casing | |
CA2281178C (en) | Cement compositions and biodegradable dispersants therefor | |
US5370185A (en) | Mud solidification with slurry of portland cement in oil | |
US4806164A (en) | Method of reducing fluid loss in cement compositions | |
US7338923B2 (en) | Settable drilling fluids comprising cement kiln dust | |
CA2317004C (en) | Dispersant and fluid loss control additives for well cements, well cement compositions and methods | |
US4258790A (en) | Well cementing method using low fluid-loss cement slurry | |
US5135577A (en) | Composition and method for inhibiting thermal thinning of cement | |
US3053673A (en) | Oil well cement compositions | |
CA1091438A (en) | Method of controlling fluid loss from thixotropic cement | |
US4461644A (en) | Light weight composition and a method of sealing a subterranean formation | |
US4149900A (en) | Oil well cementing composition | |
US3558335A (en) | Well cementing compositions | |
US4791989A (en) | Low fluid loss salt saturated cement slurries, additives and methods | |
USRE31127E (en) | Oil well cementing process | |
CA2648747C (en) | Settable drilling fluids comprising cement kiln dust and methods of using them |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: HALLIBURTON COMPANY, DUNCAN, OK. A CORP. OF DE. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:CHILDS, JERRY D.;LOVE, ROOSEVELT;REEL/FRAME:003947/0557 Effective date: 19820126 |