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Patent US4216829 - Gelled water epoxy sand consolidation system - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsParticular aqueous gels, epoxy resin compositions and optional additives such as diluents, retarders and accelerators are described which produce a practical composition and method for in situ sand consolidation and gravel packing by which a resin coated sand is positioned in a desired location and cured...http://www.google.com/patents/US4216829?utm_source=gb-gplus-sharePatent US4216829 - Gelled water epoxy sand consolidation systemAdvanced Patent SearchPublication numberUS4216829 APublication typeGrantApplication numberUS 05/966,185Publication dateAug 12, 1980Filing dateDec 4, 1978Priority dateOct 6, 1977Publication number05966185, 966185, US 4216829 A, US 4216829A, US-A-4216829, US4216829 A, US4216829AInventorsJoseph R. MurpheyOriginal AssigneeHalliburton CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (11), Non-Patent Citations (3), Referenced by (42), Classifications (25) External Links: USPTO, USPTO Assignment, EspacenetGelled water epoxy sand consolidation system
The portion in brackets is two anhydroglucose units, each having three reactive hydroxyl groups. N is an integer which would give the desired polymer molecule length and preferably an aqueous viscosity of about 105-130 viscosity units of consistency at 72� F. (approximately equal to centipoise [cp] on a V.G. Meter at 300 RPM with a 1% solution in fresh water.
The viscosity measurement and sample preparation must be carefully controlled. The viscosity measurement must be standardized because the viscosity reading is dependent upon rate of shear, temperature, amount of agitation prior to measurement and elapsed time between agitation and measurement. The sample must be completely dissolved and a moisture correction included. Samples are dried by heating in a correction oven at a constant temperature of about 105�0.5� C. for 3 hours. The samples are cooled in a desiccator and weighed at ambient temperature. The heating for about 45 minutes and cooling are repeated until repeated weights are within about 5 milligrams per each 5 grams of sample. The amount of moisture in the samples is used to calculate solution concentration of remaining portions of the cellulose polymer. The polymer solution and samples for moisture determination should be prepared at the same time to insure correspondense between the moisture correction and samples used for solution preparation. An estimated amount of polymer to prepare the desired concentration and amount of polymer solution should be weighed and stored in a moisture tight container. After the moisture correction factor is applied and the exact amount of water required is determined, the water and polymer should be carefully mixed with slow agitation. After the polymer appears to be completely dissolved, the solution should be vigorously agitated for 10-15 minutes. For viscosity measurement the solution should be at a constant temperature of 25�0.5� C. for at least 30 minutes but the viscosity must be measured within two hours of the vigorous agitation, or the solution should be vigorously re-agitated for ten minutes and held at a constant 25� C. for 30 minutes before measurement.
Thus it has been found that the use of particular breaking systems which employ an organic hydroperoxide, an amine surfactant and a cupric salt provide a breaking mechanism which is compatible with the particular resin compositions and coating agents required to coat the resin onto the sand particles in the presence of the aqueous gel. In other words, the preferred breaker system can oxidize the reducible sugar or polysaccharide gel polymers in the presence of the epoxy resin, the epoxy hardners, and other additives at ambient and low temperatures without appreciably oxidizing the amine hardners required to set the epoxy resin composition. In addition, the preferred amine type epoxy resin curing compositions can be delayed at temperatures of about 150-180� F. to provide adequate working and placement times for mixing and pumping the composition into the desired location. Thus by this invention there is provided in an epoxy resin composition for forming a porous permeable consolidated particulate mass, the composition characteristized as an aqueous gel with a neutral polysaccharide polymer producing a viscosity of at least about 30 centipoise containing a mixture of surfactants comprising at least one cationic surfactant with limited water solubility and at least one noncationic water miscible surfactant which mixture causes the epoxy resin composition to absorb onto and coat the surfaces of the particulate material in the presence of the aqueous polysaccharide polymer gel. The preferred eposy resin composition comprises a polymerizable epoxide, an optional organic diluent and an amine type curing agent. The epoxy resin composition also preferably contains an amine type cationic surfactant which promotes adsorption of the resin onto the surfaces and aids in curing the epoxy resin. The epoxy resin composition can optionally also contain a retarder and/or a silane type coupling agent. The aqueous gel containing the dispersed resin composition or dispersed resin coated sand would also preferably contain a gel breaker system such as a glucoside oxidizing enzyme, an organic C2 -C8 alkyl tertiary hydroperoxide, and optionally a water soluble salt capable of producing a cupric ion accelerator. The cupric salt can be any water soluble inorganic salt or low molecular weight organic hydrocarbon (e.g. C1 -C8) compound capable of supplying the cupric ion.
The epoxy resin composition for use with this invention contains an epoxy resin with a hardening agent. The preferred class of epoxy resin is a polyepoxide type with an amine type hardner as described herein. The amine hardner can also serve as a surfactant or even a cationic surfactant which aids in coating epoxy onto the silica surfaces. However, this is generally not the case. Optional components include diluents, retarders or accelerators. The preferred diluents are hydrocarbons or substituted hydrocarbons in which the epoxy resin is soluble and which are at least partially soluble in water. A preferred class of diluents are the esters such as ethyl acetate, methyl formate, ethyl glycol acetate and other normally liquid low molecular weight esters and ethers including the ethers of ethylene glycol. Esters containing alkyl or aryl groups having about 2 to 18 carbon stoms per radical are preferred. For high temperature applications, the substituted esters having higher boiling points and slower rates of hydrolysis are preferred. The retarders used in the epoxy composition of this invention are acid or acid producing compositions, some of which can also serve as diluents. The retarders should also be at least partially soluble in water and soluble in the epoxy resin composition. The retarder should be selected to produce the desired rate of hydrolysis or acid production according to the temperature and working times desired. The low molecular weight organic acid retarders are preferably produced by hydrolysis of an organic compound having a hydrolysis constant of about K 4�10-5. The acid produced by hydrolysis should have at least two carbon atoms such as 2-5 carbon atoms and preferably 2-3 carbon atoms. The other half of the organic compound (i.e., ester or ether) should not interfere with the coating or setting of the resin and preferably acts as a diluent for the resin. The other half of the hydrolysis product can have up to 18 carbon atoms. The accelerators used with the composition of this invention are weak organic acids with additional water soluble components. These water soluble compounds can be low molecular weight inorganic or organic salts containing about 2 to 18 carbon atoms which are water soluble and readily dispersed in the gelled aqueous fluid and are also at least partially soluble in the epoxy resin composition. Examples of the diluents include ethyl acetate, ethylene glycol monoalkyl ether (C1 -C4), acetone and C2 -C4 ketones. Examples of the hardening agents include most conventional amines, polyamines, amides and polyamides known to those skilled in the art. Examples of the retarders include methyl and ethyl esters of low molecular weight alkyl acid (C2 -C3) and the esters of the above diluents. Examples of the accelerators include salicyclic, hydroxybenzoic, citric, fumaric, oxalic and maleic acids.
A particularly preferred composition of this invention uses an aqueous HEC gel and a polyepoxide resin composition which can be used over a temperature range of about 100� to 170� F. for a practical application temperature or slightly higher than about 220� F. The preferred aqueous gels as described herein are formulated to produce a working time or to break the aqueous gel within a period of about 11/2 to 2 hours. The preferred catalyst or epoxide hardner for use with the preferred epoxy and other additives is methylene-dianiline. Other hardeners can also be used as described herein. An accelerator such as salicylic acid is preferred with the methylenedianiline at temperatures of about 140� F. and lower. Amino functional silanes and surfactants are also preferred to promote resin adsorption and coating onto the sand in the presence of the HEC gel. For retarding the curing of the epoxy resin, acetic acid can be used at higher temperatures. Ethyl acetate and higher boiling esters such as ethyl glycol diacetate an also be used. Additional esters which can be used include the methyl esters of acrylic and fumaric acid and similar strength organic acids which have some water solubility and some solubility in the epoxy resin composition. Ethyl glycol diacetate can be used to prolong working time of the methylene dianiline catalyzed resin at temperatures of about 170� F. and above since the diacetate has a boiling point of over about 300� F. while the ethyl acetate ester has a boiling point of about 160� F. The preferred aqueous fluid for dispersing the sand and epoxy resin of this invention can contain from about 2% to 10% and preferably 5% to 10% of an alkali or alkaline earth salt such as the halides and an ammonium halide such as ammonium chloride. In addition, sea water can be used if care is taken to avoid calcium precipitation with some of the components of the system. Salts which can be present in the aqueous gel include sodium chloride, calcium chloride, potassium chloride, calcium bromide, ammonium chloride and buffering agents such as fumaric acid and ammonium carbonate. The aqueous gel is preferably buffered so that the pH is in the range of about 6 to 7 for greater predictability of the gel breaking time and epoxy resin hardening time.
Break times were determined with a standard 80-pound per 1000 gallon HEC gel (prepared using synthetic sea water containing 2% by weight of NH4 Cl heated to the indicated temperatures. These times, for most downhole applications, can be expected to be somewhat longer since the gels are pumped at fast rates. Warm up of the gels from surface to formation temperatures is therefore delayed until after placement in the formation. However, even in 220� F. formations it has been calculated that the temperature of the gel will not reach 170� F. at the time it reaches the formation. The formations in many cases, may have been cooled by loss of large volumes of fluid thereto prior to placing the resin-sand-gel slurry. Placement of slurry and its composition must be engineered to take variables such as this into account. Gel breaker action is retarded in epoxy resin-sand gel slurry as compared to its use in neat gel.
______________________________________Resin Formulations:Resin                          Parts byFormulation   Chemical On Material                          Weight______________________________________A (Basic or   Epon 828 Resin   112.5  Standard)   Ethyl Acetate    37.5         Methylene dianiline                          31.0         Silane A-1120    1.5         Surfactant II    1.0B             Resin Formulation "A"                          10.0         and Glacial Acetic         AcidC             Resin Formulation "A"                          1.5         and Salicylic AcidD             Resin Formulation "A"                          3.0         and Salicylic AcidE             Resin Formulation "A"                          100.0         and Ethylene Glycol         diacetate for temp-         eratures above about         160�F.F-5           Epon 828         135.0         Ethyl Acetate    15.0         Silane A-1120    1.5         Surfactant II    1.0         Shell Hardener F-5                          60.0______________________________________
For these tests, reins formulation "C" was used. In addition a combination of the best concentration of enzyme for 120� F. and the best concentration of CuCl2 and TBH at 140� F. was used. The formulation was checked over the range and appeared to give fairly consistent rapid breaks. The gel tested was generally "D".
Initial work with the Shell F-2 and F-5 hardeners gave good strengths at 100� F. to 120� F. However, the catatlyst seem too hot, as the mixes were stiffening in 11/2 to 2 hours. After addition of acetic acid to retard the resin cure, which was successful, the breaker system became quite erratic, the acetic acid apparently taking the enzyme breaker to the lower limit of its pH range. Tests run with CuCl2 and TBH at 120� F. broke well at this time.
Cellulose gels are used in several different applications in the oil industry; for example, as carrying fluids in sand packing and in fracturing. In these two instances, it is desirable to break the gel latently after it has served its purpose in transporting the solids into place. This is done presently by one of several methods. The pH of the gel may be lowered either by direct addition of acid or by addition of an acid forming material, so that the acid is formed later under downhole conditions of heat and time. This method is usually used only at temperatures around 200� F. and above, due to the volume of acid required at lower temperature. Another method is to add an enzymatic breaker to the gel. This method works well with some cellulose gel at temperatures up to about 140� F., and preferably only only up to 120� F., as the enzymes are denatured at higher temperatures and lose their effectiveness. A third method is to add an oxidizing material. This method is particularly favored in the range from 120� F. to 200� F. and some of the oxidizing agents which have been used are sodium and ammonium salts of persulfate and various organic peroxides and hydroperoxides including t-butyl hydroperoxide (TBH).
______________________________________  ConcentrationBreaker  Breaker     Additive Tested,Added  �10-3 g              in cc's       Time to Break______________________________________SP     1,000       none          20 minutesAP     1,000       none          20 minutesTBH    1,000       none          4 hoursTBH      100       none          20 hoursSP     1,000       Surfactant XII                            Did not breakSP     1,000       CaBr2, 5 g                            Did not breakSP     1,000       Shell F-5, 5 g                            Partial break                            in 3 hoursSP     1,000       Shell F-5, 5 g                            2 hoursSP     1,000       MDA, 5 g      Did not breakTBH      100       Shell F-5, 5 g                            Partial break                            in 20 hoursTBH      100       MDA, 5 g      No break in 44                            hoursTBH      100       CaBr2, 5 g                            Did not break______________________________________
______________________________________Breaker and Concentration           Additive TestedUsed, �10-3 g           (1 cc per 100 cc gel)                         Break Time______________________________________TBH     1,000           CaBr2  Did not breakTBH     1,000           None        4 hoursTBH     1,000           NoneSurfactant   II 400                      2 hoursTBH     1,000Surfactant   II 400          None        1 hourCuCl2     1.7______________________________________
A problem arises in the use of epoxy resins in oil field applications. In some cases, the working time for formulations is not great enough. That is, that while the formulation is suitable and laboratory tests give consolidations of suitable strengths and permeabilities, the mechanical problems associated with pumping and placing the resinous material while it is still in a low viscosity liquid state require longer amounts of time than the resin will remain workable at such elevated temperatures. For example, a few resin consolidation jobs are run in the industry at 1/4 barrel per minute (bpm) using 4" tubing, a standard tubing. This means that 200 minutes would be required to pump the resin to 4500 feet at such rates. The tubing size and the pumping rates can be varied from this extreme case; however, it can be seen that the problem of treating 10,000 feet deep formations where the bottom hole temperature approached 220� F. can easily mean longer than practical working times.
______________________________________Resin Gel Time TestsResin Formulation Temp.   Gel Time(pbw)             �F.                     Minutes______________________________________Epon 828    112.5         --    --MDA         31            --    --Silane A-1120       1.5            80   &gt;600                     100   &gt;360                     140   120                     150   90                     160   &lt;45                     180   &lt;20______________________________________
TABLE3______________________________________Interactions of Surfactants With HEC Gel Breakers            Temp.Surfactant   Breaker  �F.                     Observations______________________________________I       SP, AP   160      No break, using recommended                     quantity.II      SP, AP   160      No break using recommended                     quantities.IV      SP, AP   160      No break using recommended                     quantities.II      Enzyme   120      Broke in 24 hours using                     recommended amount.IV      Enzyme   120      Broke in 24 hours using                     recommended quantities.VI      Enzyme   120      Broke in 24 hours using                     recommended quantities.XI      Enzyme   120      No break in 24 hours using                     recommended quantities.II      TBH      160      Broke in 20 minutes.XI      TBH      160      Broke in 20 minutes.IV      TBH      160      Similar conditions to two                     cases above. However the -   gel did not______________________________________                     break.
TABLE 4______________________________________TBH Breaker Effectiveness On HEC GelsaFollowing Addition of CuCl2 and Surfactant                    Test     ViscosityTest                     Time     InNo.  Additives Besides TBH                    In Hrs.  Centipoise______________________________________Tests at 140� F.1    CuCl2 present; no Surfactant II                    Start    1381                        1        1241                        11/2     941                        2        781                        3        561                        4        202    CuCl2 and Surfactant II                    Start    1382                        1/2      952                        1        352                        2        31at 130� F.3    CuCl2 present; no Surfactant II                    Start    1443                        1        1133                        3        99At this point 0.5% Surfactant II was added to #33                        31/2     363                        4        143                        41/2     14______________________________________ a Gel: 20 grams KCl, 9.6 grams HEC, 1 liter tap water TBH: .001 M all tests CuCl2 : 1.25 -10-3 g/l, all tests.
Table 5______________________________________Breaks of 80 Lbs./1000 Gal. of HECWith FeCl3, TBH and Surfactant At 120� F.Conc.    Conc.of TBH   of FeClMolar    Molar    Conc.    Time    ViscosityTest �  �  Surfactant                           at 120� F.                                   300 RPMNo.  0.0001   0.0001   cc's/100 cc                           Hrs.    Fann______________________________________1    --       --       --       Start   125--       --       --       12      109--       --       --       36      972    --       --       0.5      Start   125--       --       0.5      12      67--       --       0.5      36      473    --       1.25     --       Start   125--       1.25     --       12      103--       1.25     --       36      724    --       1.25     0.5      Start   125--       1.25     0.5      12      95--       1.25     0.5      36      555    --       5.00     --       Start   125--       5.00     --       12      55--       5.00     --       36      246    2.44     1.25     --       Start   1252.44     1.25     --       12      312.44     1.25     --       36      137    2.44     2.50     --       Start   1252.44     2.50     --       12      292.44     2.50     --       36      14______________________________________ These tests demonstrate that any combination of the surfactant and the metal chloride will not break the gel. They have had to be acting with th TBH.
TABLE 6______________________________________Breaker Concentrations for Gelled WaterAt Various Temperatures                         Concen-Temper- Breaker or  Breaker   tration Breakature   Breaker     Gms/1000  cc/1000 TimeRange   Blend       Gms H2 O                         Gms H2 O                                 Hrs:Min.______________________________________100-120� F.Range   Enzyme      0.067(a) 100                               2:00(b) 110                               1:30(c) 120                               0:50120-150� F.   Enzyme      0.033Range   CuCl2 . 2H2 O*               0.055   TBH                   3.30(a) 120                               1:15(b) 130                               0:45(c) 140                               1:10(d) 150                               1:00150-160� F.   CuCl2 . 2H2 O*               0.055Range   TBH                   1.67(a) 160                               1:30160-170� F.   CuCl2 . 2H2 O*               0.028Range   TBH                   1.67(a)                                   1:40(b)                                   1:00170� F.-   CuCl2 . 2H2 O*               0.028Up      TBH                   0.84(a) 170                               1:00______________________________________ *For the lab tests, CuCl2 . 2H2 O was added to the gel as a 0.1 molar solution (17 g/liter). The weight is calculated from that as CuCl2 . 2H2 O. Gel included 0.5% Surfactant II in all tests.
TABLE 7______________________________________Various Epoxy Resin Systems Evaluated           Com-           pressiveDescription of Resin           Strengthand Hardener System           in PSI   Observations______________________________________Shell Epon 828, Versamid-140, Surfactant I @ 120� F.             571    This was a successfulwith enzyme breaker      formulation.           NoWith SP breaker at 160� F.           Strength The gel failed to break.           NoWith TBH breaker at 160� F.           strength The gel failed to break.Shell Epon 828, Shell F-5,           Soft     The gel appeared toSurfactant I0@ 120� F.                    break, apparently catal-with enzyme              lyst is a higher temp-                    erature catalyst.Shell Epon 828, Shell F-2,           1,121    This is about the upperSurfactant II @ 120� F. with                    temperature limit forenzyme                   the enzyme.Shell Epon 828, Shell F-2,           1,568Surfactant II @ 160� F. withTBH breakerShell Epon 828, diluted 10%           1,130    20-40 mesh sand usedEtOAc, Shell F-2 catalyst                    for temperature this test,(30 pbw) Surfactant II,  40-60 mesh sand would160� F. TBH breaker                    presumably been higher,                    but was unavailable.Shell Epon 820, Shell F-2             794    This resin includes acatalyst, Surfactant II, mono-functional diluent160� F. TBH breaker                    which lowers the final                    molecular weight of the                    product.Shell Epon 815, Shell F-2           1,321    This resin includes a di-catalyst, Surfactant II; glycidyl aliphatic diluent160� F. with TBH breaker                    which raises its re-                    activity but is thought                    to lower the heat stabil-                    ity of the final product.Epon 828, 40% diluted with             955EtOAc, MDA catalyst,160� F. with TBH breaker           NoEpon 828 diluted with Cyclo-           strength Emulsion formed, thesol 60, Versamid 140 di- resin apparently did notluted with Cyclosol 60;  completely coat sand.160� F., TBH breakerEpon 828, TBH, Surfactant           2,500    Gel broke and resinII at 150� F.; (30 pbhr) F-2;                    stiffened within 450.005 M TBH              minutes.           NoEpon 828, TBH, Surfactant           Strength No break, only went toII at 150� F.; (30 pbhr)                    1 hr 15 min. beforeF-2; 0.005 M TBH         resin tacky.Epon 828; DMP-30 (2 pbhr):                    Gel did not break. So-TBH .001 M; FeCl3 .002M;                    lids did not become tac-at 150� F.        ky and did not harden.Epon 828; DMP-30 10 phwr;             500    11/2 hrs. pot life atTBH 0.001 M; FeCl3 0.002                    150� F. Gel appeared toM; at 150� F.     break at about same                    time. Did not set much                    in 24 hours.______________________________________ Gel: 20 g KCl; 9.6 g HEC; in 1 liter tap water. Surfactant: 0.5% Surfactant II in gel. Breakers: 0.2 cc/200 cc of gel of TBH. Temperature: 160� F. Sand: 100 g/100 cc of gel, 40-60 mesh Ottawa. Resin: 10 cc/100 g of sand. Cyclosol: an aromatic solvent.
TABLE 8______________________________________ Compressive Strengths of 40-60 Mesh Ottawa SandConsolidated With Various Epon 828 FormulationsAfter 24 Hour Cure at 160�  F. in HEC Gel*                     CompressiveHardener and Resin          Surfactant Strength in PSI______________________________________Shell F-2 (20 pbhwr);**          I          482no diluentCiba 9130 (20 pbhwr);          II          509% EtOAcShell F-2 (20 pbhwr);          II         113010% EtOAcShell Catalyst-U;          II         Soft gel; gel did10% EtOAc                 not break.Anchor LO;     II          7010% EtOAc                 Gel did not break.Anchor LOS-LO; II          7010% EtOAc                 Gel did not break.Shell Catalyst Z;          II         71410% EtOAcShell Catalyst Z;          III        62310% EtOAcMDA;           II         66010% EtOAc1MDA;           II         55510% EtOAc2Shell F-2;     II         1571no diluentShell F-2;     XII        200no diluentShell F-2;     I          473no diluentShell Catalyst Z;          III        62310% EtOAcShell Catalyst Z;          II         71410% EtOAcShell F-2;     II         113010% EtOAcShell F-2;     VII        No strength. The gel10% EtOAc                 did not break and an                     emulsion appeared.______________________________________ *80 lbs/1000 gal. concentration HEC gel of 2% KCl water, tbutyl hydroperoxide with the breaker (0.1% by wt.).  **pbhwr  parts by hundred weight resin. 1 For this test, the resin was added to the 2% KCl water before gelation. 2 For this test, the resin was added to the gelled 2% KCl before the sand.
TABLE 9______________________________________Retarder Formulations EvaluatedFor F-5 Hardener                 Test      ConsistometerTest   Retarder       Temp.     Pump TimeNo.    Formulation    � F.                           Hrs:Min.______________________________________1      Acetic acid    150       2:00  30% by wt. of F-52      Acetic acid    150       0:55  6% by wt. of F-53      Acetic acid    150       1:10  6% by wt. ethyl  acetate  30% by wt. F-54      MDA hardener   150       2:00  an equal wt. of  ethyl acetate  Epon 815 resin5      Similar to #4  150       1:35  above, no EtOAc6      Epon 815       180       Terminated In  MDA                      1:00  No retarder  TBH breaker7      Epon 815       180       Terminated In  MDA                      1:30  15% EtOAc                as EtOAc boiled  Added to slurry          off.______________________________________
TABLE 10______________________________________Consolidation Compressive Strengths And Gel BreakTimes of Tests Run At 100�  F. Using Methylene Di-aniline Hardener With Enzyme Breaker   Consolidation              Concentration   Compressive              Of Enzyme Inbreak Time   Strength   Gms/300 cc ofHrs:Min.   In PSI     Gel         pH of Gel______________________________________1:00    2770       6.01        3.5Over 4 hrs.   Not Run    0.01        6.22:00    Not Run    0.02        6.2                          (phosphate buffer)1:40    Not Run    0.03        6.2                          (phosphate buffer)1:00    3480       0.04        6.20:30    2900       0.08        6.2Tests Run At 110�  F.Over 2 hrs.   Not Runa              1.0         9.0                          (estimate)1:20    Not Runa              2.0         9.01:20    1610a 3.0         9.01:00    1875a 4.0         9.0                          (estimate) Over 1 hr.   2750       1.0         7.01:30    3930       2.0         7.01:20    Not Run    3.0         7.02:00    Not Run    0.2         6.21:00    1430       0.4         6.20:30    Not Run    0.6         6.2______________________________________ a Resin Formulation F5 (page 30).
Table II______________________________________Consolidation Strengths And Gel Break Times.sup. b Of Tests Run At130�  F. And Using Methylene Dianiline Hardener And TBH WithCuCl2 Breakers   Consol-   idation   Com-Gel     pressive                      Esti-Break Time   Strength,            Conc. TBH   Conc. CuCl                                 matedHrs.:Min.   PSIc            cc/300 cc Gel                        cc/300 cc Gel                                 pH______________________________________3+      1430c            1           1        52:00    1000c            2           2        51:20    2050     3           3        50:30    2850     4           4        51:00    1100     2 (+Enzyme)a                        0.5      5.90:40    1050     2 (+Enzyme)a                        1        5.9Tests Run at 150�  F.0:20     980     1           1        30:30    1120     0.5         0.5      30:30     980     0.25        0.25     32:00    1340     2.1         1.5      5.1Over 3 hrs.   1780     1.5         0.9      5.12:00    1070     2.1         1.5      6.5______________________________________ a Concentration of Enzyme: 0.02 cc of 1% aqueous solution of Enzyme in water per 300 cc of gel. b Gel Formulation D: CuCl2 used as a 0.1 Molar solution.  c 24 hour cure, 40-60 mesh sands. Resin Formulation B, first two entries, Resin Formulation A for other tests.
TABLE 12______________________________________Compressive Strength Development Versus TimeFor Consolidations At Various Temperatures         Compressive Strength         of ConsolidationTemp. of   Resin       After 8   After 16                                 After 24Cure, �F.   Formulation Hrs., PSI Hrs., PSI                                 Hrs., PSI______________________________________100     A           Soft      1560    2500120     C           1790      2230    2550120     C           3170      4240    4910140     C           5350      4110    6030140     A           2732      2230    2860150      Eb     465       980    2010160      Aa     3090a                         2900    3270160     E            555       825    1110200      Ec    1835      1875    2320______________________________________ a This mixture gave a working time of slightly less than one hour an fortyfive minutes. b This formulation is recommended for use only above 160�  F. c This formulation can be used for BHST up to 210�  F., assuming well preparation and placement techniques maintain the slurry temperature at 160�  F. or below until it is placed.
The consolidations above were prepared at 140� F. using Resin Formulation C. Consolidation time was 48 hours at 140� F. Strengths were tested after 24 hours.
TABLE 14______________________________________Compressive Strengths And PermeabilitiesOf Uncompacted Epoxyb Coated SandsCured 24 Hours At 140�  F.Ottawa Sand Compressive Strength                      PermeabilitySize Meshd       In PSIa   In Darciesa______________________________________40-60       3941           Over 180c20-40       2380           Over 180c10-20       2890           Over 180c______________________________________ a Compressive strengths and permeabilities are the averages of three tests. b The gel was a 2% NH4 Cl2 in a sea salt water solution, gelled with 80 lbs./1000 gal. HEC. The gel breakers were the 140� F. formulation calling for enzyme, CuCl2 and TBH. The resin mix was the standard mix with no accelerator or retarder. c Limitations of equipment prevented measurements above 180 Darcies. d 15 pounds of sand per gallon of gel.
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RaghavaMethods of consolidating formationsUS20040154796 *Feb 6, 2003Aug 12, 2004Nguyen Phillip D.Methods of preventing gravel loss in through-tubing vent-screen well completionsUS20040213905 *Apr 26, 2002Oct 28, 2004Christopher BreenTreatment fluids and methods for consolidating substrates without simultaneous substantial loss of permeabilityUS20040261990 *Jul 18, 2002Dec 30, 2004Bosma Martin Gerard ReneWellbore system with annular seal memberWO2002088520A1 *Apr 26, 2002Nov 7, 2002Breen ChristopherTreatment fluids and methods for consolidating substrates without simultaneous substantial loss of permeabilityWO2004070166A1 *Dec 16, 2003Aug 19, 2004Halliburton Energy Serv IncMethods of preventing gravel loss in through-tubing vent-screen well completions* Cited by examinerClassifications U.S. Classification166/276, 507/211, 507/219, 428/407, 523/402, 166/295, 427/221, 523/216, 507/926, 427/386International ClassificationC04B20/10, C09K8/80, C09K8/575, C08L63/00, C04B26/14Cooperative ClassificationC04B20/1037, C09K8/5751, C04B26/14, Y10T428/2998, C08L63/00, Y10S507/926European ClassificationC08L63/00, C04B26/14, C04B20/10B4F, C09K8/575BRotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services