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    SPE PAPER

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    SPE PAPER

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    Download as pdf
    15 views11 pages

    Dovan 1997

    Uploaded by

    ErickNewa
    SPE PAPER

    Copyright:

    © All Rights Reserved
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    SPE 37246 Delaying Gelation of Aqueous Polymers at Elevated Temperatures Using Novel Organic Crosslinkers H.T. Dovan, SPE, and R.D. Hutchins, SPE, Unocal and B.B. Sandiford, SPE, Polymer Applications Cony 007, Sx Parleumt agen ne “hie paper wes peste fr pseition ot the 1007 SPE wmanal Syaeeem on tlt Eryn ooo, Tne, 102 etary ‘ia pager wae lected peertaton t a SPE Prat Comming ong rin ot Abstract ‘This paper presents novel organic crossinkers that extend the temperature limitations of currently available polymer gel systems. These organic crosslinkers have application in steam injection, geothermal and high temperature oil and gas wells. One crosslinker exhibits a gelation time of several days at 350°F. Long-term stability has been verified for at least one year at 300°F. Some novel organic crosslinkers for low and medium temperature applications are also presented, Introduction Polymer gels have been applied in oil and gas wells for many ‘years to control the flow of fluids within the reservoir. They are inexpensive, simple to apply, versatile in their application and readily available. One major limitation of some gel systems currently in use is that the gelation reactions cannot be delayed for more than several minutes at elevated temperatures. When retardants are used to alleviate this problem, the gel typically weakens and loses some of its gel strength or becomes completely unstable. High Temperature Uses for Gels Several of the organic crosslinkers presented in this paper have application in steam injection wells, geothermal wells and in oil and gas wells where high reservoir temperatures have historically limited the use of polymer gels. 361 Steam Injectors. Steam injection is beneficial to the production of oil in many reservoirs and in particular, to heavy oil reservoirs, by reducing oil viscosities and removing tarry and paraffin deposits. However, due to heterogeneity and to the fact that steam rises to the top of injected zones because of its low density, steam channels can develop leaving potentially productive intervals unswept Polymer gels and foaming agents have been used to reduce flow through these channels. The temperature in these steam channels can be as high as 500°F which increases the difficulty in forming an in-depth stable foam or gel. Geothermal Wells. Steam and hot water production from ‘geothermal wells are economical sources of energy for the generation of electricity. This production is often ‘accompanied by high concentrations of salts and undesirable gases. Condensate is generally resinjected into the geothermal reservoir and can sometimes detrimentally affect nearby producing well temperatures, ‘Temperatures in these wells could be as high as 60°F. At this time, we do not have a timedelayed gel for these extreme temperatures; however, successful treatments should be possible below 400°F. High Temperature Oil and Gas Wells. Low temperature reservoirs have been successfully treated with current polymer gel technology. However, there is a need to extend these gel treatments to higher temperature formations because of the increasing depths of commercially productive reservoirs. Temperatures of some oil and gas bearing reservoirs can exceed 400°F, Most reservoirs have problems with channeling during primary and enhanced production, but in higher temperature reservoirs, the problem is more difficult to solve by the use of polymer gel treatments. Polymer instability, rapid gelation and improper placement can result in treatment failures. Definition of Temperature Ranges ‘The following definitions are used in this paper to reflect applicable ranges for currently available technology: 2 HT BOVAN, R.D. HUTCHINS, 8 B, SANDIFORD SPE 37246 <150°%F = low 150-220°F = medium 220-300°F - high >300°F - ultra high While the title of this paper mentions elevated temperatures, ‘our primary goal was to develop and test a set of organic crosslinkers that would form stable polymer gels in all the temperature ranges listed above. ‘Another goal was to achieve sufficient delays in gelation time at high temperatures. At low temperatures, the goal was to accelerate the reaction since the organic crosslinkers we currently use have gelation times of months at ambient temperature. Conventional Gel Systems Many gel systems have been reported in the literature, For temperatures in the low to medium range, the majority of polymer gel treatments employ either organic crosslinks using aldehydes or metal crosslinks using chromium, zirconium or aluminum, Inorganic systems such as silicate gels are also used on a moderate scale as are monomer systems which polymerize in situ. Some of these systems can also be applied in the high temperature range. For applications in the ultra high range, these gel systems show poor stability, limited utility because of rapid gelation, or "uncontrollable gelation. High Temperature Gel Systems ‘A number of gel systems have been proposed specifically for use in high and ultra high temperature oil and gas reservoirs ‘These systems include polymer-based gels, phenol- formaldchyde formulations, lignosulfonates, styrene butadiene polymers crosslinked by organic peroxides, ‘organic resins, and polyacrylamide-based gel systems crosslinked with hexamethylenetetramine. Each of these systems have various characteristics which either limit or promote their use in a particular application. Parameters which influence the selection of one system over another include temperature stability, brine salinity, DH, gel or hardening time, placement technique. radial penetration and cost. Of course, many of these parameters are ‘determined of affected by the nature of the problem present. Polymer-Based Gels. Polyviny! alcohols will crosslink with glutaraldehyde’. In our tests, however, these gels typically show excessive syneresis ‘and gel’ shrinkage at high temperatures. Copolymer-based gels employing organic crosslinkers have been discussed by Moradi-Araghi?. The copolymers are {termed harsh environment polymers because of their stability 362 in hot brines containing divalent ions where conventional polyacrylamides are expected to precipitate, Although a mumber of organic crosslinkers are revealed, the preferred agents appear to include phenol or resorcinol combined with formaldehyde. Hydroquinone and hexamethylenetetramine, described in more detail in this paper, can also be used for crosslinking these harsh environment polymers, Phenol-Formaldehyde. Phenol-formaldehyde formulations will gel without the need for an added polymer when relatively high concentrations are used. Resorcinol and other phenoltype chemicals can be substituted for the pheno!’ ‘The use of phenoplasts has also been reported’ Hexamethylenetetramine has been used in place of the formaldehyde for higher temperature applications. LLignosulfonate. Lignosulfonate gels were developed for both Jow and high temperature applications using a paper mill byproduct’, At temperatures of 300°F and higher, lignosulfonates will gel without added crosslinking agents ‘The lignosulfonate gel properties are quite sensitive to the properties of the original wood and the process used in the paper mill. These variations in product properties result in lunpredictable gel times and inconsistent gel formation. One particularly attractive feature of the lignosulfonate gels is their stability at temperatures of 500° and higher, which allows their use in some steam and geothermal applications Styrene-Butadiene. Styrene-butadiene block copolymers have been reported for use in steam injection wells". Various peroxides are used for initiating the gelation and formulations are teported to be stable 10 SO0°F. Some attempts to strengthen the resulting gel have also been reported using silica flour, Resins, High temperature resins have been tested on wells in steamfloods’. These resins are typically applied with the use of a dump bailer and can effectively seal within a gravel pack. Formulations must be prepared to allow sufficient time for placement before the resin hardens, These resins cannot be chemically removed once they solidify Hexamethylenetetramine. The present authors have previously revealed a gel system stable at temperatures as high as 350°F which is based on hydroquinone and hexamethylenetetramine organic ‘The gels have shown laboratory stability for more than one year when mixed in either seawater or freshwater and have been successfully field tested at 250°F. Including stabilizing agents allows inexpensive, conventional polyacrylamides to bbe used. At temperatures of 300°F or more, the best stability is seen with cationic polymers. One problem at temperatures above 300°F is that short gelation time may limit the use of this gel system to small ‘SPE 37246 DELAYING GELATION OF AQUEOUS POLYMERS AT ELEVATED TEMPERATURES USING NOVEL ORGANIC CROSSLINKERS 3 volume treatments unless measures are taken to reduce the reservoir temperature. Also, thermal stability becomes more dependent upon the purity of the crosslinkers and polymers employed. Description of Novel Organic Crossiinkers ‘The stability and time-setting characteristics of crosslinked gels depend on the polymer, crosslinker and selection of other additives which could include secondary crosslinkers, secondary polymers, oxygen scavengers and acids or bases ‘The formulation to be used for a specific treatment should be determined based upon laboratory gel screening tests performed at reservoir temperature. The gels should be ‘mixed in a water with a similar salt content as the anticipated mix water to be used on site. The objective of the gel treatment and the location of the well will also influence the gel formulation. Data for a large number of organic crosslinkers are presented in this paper with hexamethylenetetramine (HMT), terephthalaldehyde (TPA) and a mixture of dibasic esters, (DBE) of primary interest at high and ultra high temperatures. Hydroquinone (HQ) or dihydroxynaphthalene (DHN) are usually added as secondary crosslinkers. The primary crosslinkers can be effective by themselves at high temperatures but the gels are often unstable. The secondary crosslinkers have little or no gelation properties by themselves, but they effectively stabilize the gels containing the primary crosstinkers at high temperatures. At low and ‘medium temperatures, the secondary crosslinkers can form gels with some polymers. In seawater, we also normally add sodium bicarbonate as a stabilizing agent. We also investigated the use of sulfides, sucrose and various organic acid crosslinkers for gel applications at the Jow to medium temperature ranges. Hexamethylenetetramine is also a viable crosslinker at low temperatures when combined with an acid. The main motivation for the low temperature studies was to develop gel systems for environmental applications such as containment of hazardous, chemical spills. While conventional get systems containing heavy metals, such as chromium, work quite well at these ow temperatures, resistance to the use of chromium still exists The crosslinking data discussed in this paper are preliminary but are being presented to introduce several novel crosslinkers (0 the industry. Additional testing of these crosslinkers needs to be performed prior to their use However, their commercial availability has been verified Terephthalaldehyde. Terephihalaldchyde can be used as @ ‘crosslinker at medium temperatures but itis most effective at hhigh and ultra high temperatures up 10 350°F. With proper polymer and secondary crosslinker selection, long-term gel stability can easily be obtained. Gel time delays from one 363 day to several weeks are possible at 30°F. ‘Aldehydes in general have toxicity problems but \erephihalaldchyde has poor reactivity at low temperatures, ‘This chemical property allows safe handling of the material at ambient temperatures since it is not reactive until it ‘encounters the elevated temperature of the reservoir. Dibasic Esters, The esters in this mixture include dimethyl succinate, dimethyl glutarate and dimethyl adipate. They are reactive at temperatures of 300F and 350°F with polyacrylamides and form strong. stable gels. In our laboratory tests, delays in gelation time from hours to days were achieved at elevated temperatures. Sodium Sulfide. This compound is the only inorganic crosslinker presented in this paper. Sodium sulfide will crosslink some polyacrylamide polymers but stability can be a problem at high temperatures. Sodium sulfide is usually used with a secondary crosslinker in order to achieve greater gel stability. Some acid is required to activate the ‘crosslinking reaction. ‘Sucrose. Sucrose can be creatively used as a crosslinker. In this process, itis necessary to oxidize the hydroxyl groups to aldehydes (o initiate the gelation reaction. We used periodic acid as the oxidizer, but other strong oxidizers such as hydrogen peroxide should also work. This formulation should be environmentally safe for treating sensitive areas, Acid Crosslinkers, Three acid crosslinkers _gallic, terephthalic and glutaric) have been identified as good ‘crosslinkers for forming song, stable gels. Gallic acid is used as a secondary crosslinker to be applied in combination with other crosslinkers. For example, it can be used in ‘combination with hexamethylenetetramine or sodium sulfide. ‘Terephthalic and glutaric acids can be precursors to their respective aldehydes and function as primary crosslinkers. As precursors, they should react slower than the corresponding aldehydes (terephthalaldehyde and glutaraldehyde) and provide extended gelation times. Very stable gels are formed which are relatively safe to handle, As mentioned previously, (erephthalaldehyde can be used safely at ambient temperatures because of its low reactivity at low temperatures, However, glutaraldehyde is relatively toxic at all temperatures and we recommend its replacement with glutaric acd. Hexamethylenetetramine. It was initially believed that hexamethylenetetramine could aot be used al low temperatures because the long gelation times were deemed to bbe impractical for field use. We have since discovered that by reducing the initial pH of the polymer crosslinking solution, gelation could be initiated in one day or less at temperatures as low as 55°F. This acid formulation does not 4 HT. DOVAN, R.D HUTCHINS, 8.8, SANDIFORD SPE 37246 require bicarbonate and substitutes acid for the hydroquinone. The resulting gel is less expensive and less toxic. Gel times can be controlled at temperatures from 55°F to about 150°F. This gel system has excellent potential for treating environmental problems in the shallow subsurface and low temperature wells. Another application is the reduction of ‘gas breakthrough during CO, flooding. Gelation will be restricted to zones where the reservoir pH has been lowered by the CO, Dihydroxynaphthalene. Both dihydroxynaphthalene and hydroquinone function as secondary crosslinkers, These

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