NZ588915A - Use of cementitious slurry containing graphite and metakaolin in the production of synthesis gas by underground coal gasification - Google Patents

Abstract

A method of producing synthesis gas by the underground gasification of coal from a coal seam is disclosed, which comprises the steps of: (a) cementing casing string in a production well and an injection well which penetrates the coal seam by pumping into the wellbore a cementitious slurry and allowing the slurry to set to form a cement sheath in the wellbore; (b) igniting the coal in the coal seam;(c) introducing oxidant gas into the injection well; and(d) generating syngas as a combustion front in the coal seam and advancing the combustion front through the production well, wherein the temperature of the combustion front is greater than or equal to 800 Deg. C and further wherein the heat from the combustion front is distributed along the cement sheath in the wellbore, wherein the cementitious slurry comprises a cement mix comprising: (i) between from about 10 to about 70 weight percent of a cementitious material; (ii) between from about 5 to about 70 weight percent of graphite; and (iii) between from about 5 to about 70 weight percent of an aluminium silicate as metakaolin, wherein the density of the slurry is between from about 7.0ppg to about 23.00 ppg, the bottom hole static temperature of the production well at the time of slurry placement is less than or equal to 65 Deg. C.

Description

Patent Form No, 5 Our Ref: 68366NZP00 Patents Act 1953 COMPLETE SPECIFICATION APPLICATION OF A SPECIALIZED SLURRY USED FOR CEMENTING TUBULARS IN WELLS PRODUCING SYNTHESIS GAS BY UNDERGROUND COAL GASIFICATION I/We, Baker Hughes Incorporated, a body corporate organised under the laws of United States of America of 2929 Alien Parkway, Suite 2100, Houston, Texas, 77019, UNITED STATES OF AMERICA hereby declare the invention, for which I/we pray that a patent may be granted to me/us, and the method by which it is to be performed, to be particularly described in and by the following statement- Total Fee Paid: NZ$250.00 - by Direct Debit (as per covering fetter) 502764S21J QOC/S858 APPLICATION OF A SPECIALIZED SLURRY USED FOR CEMENTING TL'Bl'LARS IN WELLS PRODUCING SYNTHESIS GAS BY UNDERGROUND COAL GASIFICATION SPECIFICATION Field of the Invention id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1"

[0001] Application of a cementitious slurry containing graphite and an aluminum silicate in 'the production of synthesis gas by underground coal gjhiticution is disclosed.

Background of the Invention id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2"

[0002] Underground coal gasification (UCG) is a technique for extraction of energy contained within, a coal seam. This method is a viable alternative to conventional milling by reducing the surface footprint, emission, and energy costs. In addition, UCG is useful in harvesting of energy in coal scams unsuitable for conventional mining techniques. UCG, in its simplest fonii, involves drilling a production well and an injector well from 15 the surface into an existing coal seam. These are linked together horizontally by drilling, fracturing, or combustion links. Once the wcllbore has been drilled, casing is lowered • 'i welibore, A cemcntinous slurry is then introduced into the wellbore and is pumped down the inside ol" the pipe or casing and back up the outside of the pipe or casing through the annular space between the exterior of the casing and the borehole. 20 1 Ik •- diciii slurry is then allowed to set and harden to hold the casing in place. This effectively seals the subterranean zones in the formation, called "zonal isolation" and supports the casing. id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3"

[0003] Once drilling and. cementing of the wells are complete, the coal is ignited underground, air or oxygen-enriched air (and sometimes also water) is then introduced 25 through an injector well. The air reforms with the combustion, materials (coal) and forms a synthesis gas (syngas f containing carbon monoxide, hydrogen and methane (as a minor compniKiU). The combustion front consumes the coal seam. The syngas moves under pressure through the coal seam, to the production well, where it travels upliole to the downstream, facility. The stream of syngas coming through the producing well to the surface can be used to drive a turbine and generate electricity. Furthermore the syngas is used as a chemical feedstock or as a fuel for power generation, id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4"

[0004] UCG offers several inherent advantages over conventional mining, including avoidance of the environmental impact which occurs during strip mining of coal, avoidance of problems of spoil banks, slag piles and acid mine drainage, reduction in emissions, lower energy costs and avoidance of safety and health hazards related to the underground mining of coal. id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5"

[0005] in many areas, UCG wells are very shallow and the majority of the coal seams are located very near the surface. In such instances, the wells may be drilled such that they penetrate the coal seam by only a feu meters. As such, only a small portion of the cement sheath is exposed directly to the combustion front. id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6"

[0006] Since coal typically resides at shallow depths, it is often necessary to introduce into the wellbore a cementitious slurry that sets at relatively low bottomhole static temperatures. Typically, it is desired that the cementitious slurry set at low bottomhole static temperatures. In addition, it is important that the set cement has the ability to withstand the extreme temperatures of the advancing combustion front. Typically, the temperatures of the combustion front are in excess of 800° C. While Portland cement has been used in geothermal wells, m which production temperatures can reach greater than 380° C, such cements typically disintegrate around 450° C. id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7"

[0007] More recently, cements containing calcium aluminate phosphate (CaP) have been proposed for the cementing of the casing strings for UCG applications. Although Ihe CaP cement can typically withstand the temperatures generated by the combustion front and the high production temperatures, it is not ideally suited for everyday cementing operations: Common cementing additives used for Portland cement based systems are unsuitable with CaP cement making it difficult to adjust reliable slurry performances (such as thickening and setting times, fluid loss and free water controls, rheologies) for CaP cement systems. Also, contamination of CaP with Portland cement residues in a cememiiig unit causes unpredictable setting limes. Therefore CaP systems must be handled separate!}, which requires advanced planning. 1 he cxpeiisive logistics and manufacturing, as ell as the tact that CaP cements are not available everywhere, significantly increase their costs as compared with Portland cements. The cementing of Received at IPONZ on 24-Apr-2012 wells with CaP cements have caused setting failures at the low static temperatures associated with the shallow depth of coal beds, thereby causing failure or incomplete establishment of zonal isolation within the cemented wellbore of the subsurface formations. This causes the undesirable result of gas communication with the surface.

Then, costly remedial work is required and lost hours of non-productive time are the consequence. id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8"

[0008] Alternative cementitious materials have been sought which set at relatively low bottomhole static temperatures and which provide zonal isolation along the majority of the wellbore at average production temperatures. In addition, 10 cementitious materials capable of maintaining integrity of the cement sheath at the combustion front at high temperatures are also desired; Ideally the cementitious materials should be based on Portland cement for which reliable slurry performances for a given wellbore condition can be adjusted with typical chemical additives to achieve a good primary cement job. Besides economics, logistics, and operations are simplified 15 for a Portland cement based system in comparison to a CaP based system.

Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.

It is an object of the present invention to overcome or ameliorate at least one 20 of the disadvantages of the prior art, or to provide a useful alternative.

Summary of the Invention According to a first aspect the present invention provides a method of producing synthesis gas by the underground gasification of coal from a coal seam 25 comprising: (a) cementing casing string in a production well and an injection well which penetrates the coal seam by pumping into the wellbore a cementitious slurry and allowing the slurry to set to form a cement sheath in the wellbore; (b) igniting the coal in the coal seam; (c) introducing oxidant gas into the injection well; and (d) generating syngas as a combustion front in the coal seam and advancing the combustion front through the production well, wherein the temperature of the Received at IPONZ on 24-Apr-2012 combustion front is greater than or equal to 800° C and further wherein the heat from the combustion front is distributed along the cement sheath in the wellbore, wherein the cementitious slurry comprises a cement mix comprising: (i) between from about 10 to about 70 weight percent of a cementitious 5 material; (ii) between from about 5 to about 70 weight percent of graphite; and (iii) between from about 5 to about 70 weight percent of an aluminum silicate, wherein the density of the slurry is between from about 7.0ppg to about 23.00 ppg.

According to a second aspect the present invention provides a method of 10 producing synthesis gas by the underground gasification of coal from a coal seam comprising: (a) pumping into the wellbore of a production well and an injection well a cementitious slurry comprising between from about 10 to about 70 weight percent of a cementitious material, between from about 5 to about 70 weight percent of graphite and between from about 5 to about 70 weight percent of an aluminum silicate and allowing the slurry to set form a cement sheath in the wellbore, wherein the density of the slurry is between from about 7 to about 23 ppg; (b) igniting coal in the coal seam; (c) introducing air and water through the injection well and forming a 20 syngas; and (d) transporting the syngas through the coal seam as a combustion front to the production well.

According to a third aspect the present invention provides a method of producing synthesis gas by the underground gasification of coal from a coal seam 25 comprising: (a) pumping into the wellbore of a production well and an injection well a cementitious slurry comprising Portland cement, graphite and raetakaolin and allowing the slurry to set form a cement sheath in the wellbore, wherein the density of the slurry is between from about 14 to about 17.0 ppg; (b) igniting coal in the coal seam; (c) introducing air and water through the injection well and forming a syngas; Received at IPONZ on 24-Apr-2012 (d) transporting the syngas through the coal seam as a combustion front to the production well, wherein the bottom hole static temperature of the production well, at the time of slurry placement, is less than or equal to 65° C. and the temperature of the combustion 5 front is greater than or equal to 800° C.

According to a fourth aspect the present invention provides a synthesis gas when produced by the method according any one of to the first to third aspects.

Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an 10 inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to".

According to an embodiment of the invention there is provided a cement mix comprising: (a) between from about 10 to about 70 weight percent of a cementitious 15 material; (b) between from about 5 to about 70 weight percent of graphite; and (c) between from about 5 to about 70 weight percent of an aluminum silicate According to another embodiment of the present invention there is provided a cementitious slurry comprising the cement mix of the above embodiment. id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9"

[0009] A cement mix containing a cementitious material, graphite and an aluminum silicate is useful in the cementing of casing in a production and/or injection well in UCG. A cementitious slurry of the cement mix may be pumped through Received at IPONZ on 24-Apr-2012 -6a- standardized pumping equipment and easily sets as a cement sheath at low bottomhole static temperatures characteristic of shallow coal beds. Zonal isolation may be created between the burning coal reservoir in the ground and the surface. id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10"

[00010] In addition to the cementitious material, graphite and aluminum silicate, 5 the cement mix or cementitious slurry may further contain other additives for dissipating generated heat during UCG. id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11"

[00011] The cement mix and cementitious slurry containing the cement mix is compatible with common Portland cement additives and eliminates the need for purchasing special equipment and chemicals, such as that used for high alumina phosphate cement based systems. id="p-12" id="p-12" id="p-12" id="p-12" id="p-12" id="p-12" id="p-12"

[00012] The density of the cemcnliiH'US slurry is normalh betw era* from about: 14,0 to about 17.0 pounds per gallon (ppg). but can be increased with weighting agents up to 23.0 ppg or decreased with light \\ eight additives or foaming down to 7,0 ppg. id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13"

[00013] The set cement i* further capable of withstanding extreme dry heat 5 temperatures greater than or equal to 800° C. Such high icntpercitures are characteristic of the ad\ diicing combustion front of an ignited coal seam when syngas is produced. id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14"

[00014] The set cement serves as a thermal conductor conducting the heat from the combustion front away from the cement shoe and distributing the heat along the annuhis of the wellbore at higher rate until it gets finally lost to the surrounding formation as it makes its way to the surface. Further, the set cement provides zonal isolation of the formation. id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15"

[00015] The set cement serves as thermal conductor and lowers the temperature of the produced syngas during its way along the wellbore for easier handling and processing at the surface, Brief Description of the Drawings id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16"

[00016] In order to more iitlly understand the drawings referred to in the detailed description of the present invention, a brief description of each drawing is presented, in which: id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17"

[00017] FIG. I is a cross-section, of a production well for UCC showing the coal seam, cement sheath and easing during combustion and demonstrates the durability from high heat of a combustion front during UCC of the cement sheath made froin the high temperature cement mix described herein Detailed Description of the Preferred Embodiments [000IS] A cementitious slurry containing a high temperature cement mix is introduced into the wellbore and may be used to cement the casing strings of both the injection and production wells which have been drilled into an existing coal seam. After cementing of the easing, the coal is ignited underground. Air and water are then introduced through 30 the injector well. The air reforms with the combustion materials and forms the synthesis gas (syngas). The syngas contains carbon monoxide, hydrogen and methane (as a minor coinpoiiei.it). The syngas then moves under pressure through the coal seam, as a combustion front to the production well, where it travels uphole for use downstream. id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19"

[00019] The high temperature cement has particular usefulness in the treatment of coal seams at shallow depths. Such coal seams are characterized by low bottomhole static temperatures less than or equal to 150° C, in some cases less than or equal to 65° C and in other cases less than or equal to 38°, and in some cases less than, or equal to 30° C. In addition to being set at such low temperatures, the high, temperature cement described herein further is capable of withstanding the extreme temperatures (dry heat) of the advancing combustion trout, which can exceed 800° C and which is often greater than 1000° C. Further, the high temperature cement is capable of maintaining zonal isolation at least to the combustion front. id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20"

[00020] The cement mix described herein, when formulated into a hydraulically-active, cementitious slimy and set in the wellbore forms a. cement sheath. FIG. 1 compares the beneficial behavior of the set high temperature cement described herein with a conventional set Portland cement containing silica after ignition of the well The right side of FIG. 1 illustrates a cement sheath composed of the set cement mix described herein. As illustrated, heat from the combustion front of the produced syngas is conducted away from the cement shoe and is distributed along the cement sheath in the wellbore. As the syngas proceeds to the surface, the heal from the combustion front is lost into the surrounding formation at a high rate. The temperature of the produced syngas decreases as the product travels upwards within the wellbore. The left side of FIG. 1 compares a cement sheath composed of the conventional Portland cement system where concentrated hot spots cause severe deterioration. Since the sheath composed of the cement mix described herein can withstand significant changes in temperature (such as thole affiliated with contacting of the wellbore with direct, flames, combustion and saigas production in the UCG process), the set cement provides a sufficient barrier at the combustion front at temperatures equal to or in excess of 800° C. As such, the successful isolation at the combustion front provides an effective banier so that catastrophic failure of the sheath does not cause a chain reaction and. propagate up the cemented annutus. id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21"

[00021] The high temperature cement system described herein tolerates the elevated dry temperatures at the combustion front and maintains compressive strength in normal API compressive strength (CS) tests. id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22"

[00022] Further, use of the ccmcnt mix defined herein results in a reduction in the 5 temperature low of the produced gu,> stream. For instance, when compared to a treatment of a well cemented with CaP cement, the same well treated with the cement mix defined herein delivered syngas to the surface which was about 45° C to about 60° C cooler. Such syngas is easier to process than the syngas obtained from a well cemented with CaP cement. id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23"

[00023] In addition to exhibiting high thermal heat conductivity (even with cementitious slurries having reduced water content) and a cement sheath exhibiting superior mechanical properties, including compressive strength, the high temperature cement mix is almost less than half the cost of CaP cement. Further, in. light of its superior mechanical properties, internal stresses in. the set cement are reduced. 15 [00024] The cement mix contains a cementitious material, graphite and an aluminum silicate. id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25"

[00025] A variety of cementiiious materials may be used in the cement mix including those comprised of calcium, aluminum, silicon, oxygen and/or sullui which set and harden by reaction with water. Hydraulically active cementitious materials, suitable for 20 use in the cementitious slurry, include materials with hydraulic properties, such as hydraulic cement, slag and blends of hydraulic cement and slag (slagment), which are well known in the ait. As used herein, the term "hydraulic cciiium" refers to any inorganic cement that hardens or sets due to hydration. As used herein, the term "hydraulically-active" refers to properties of a cementitious material that allow the 25 material to set in a manner like Imlraulic cement, either with or without additional activation. Hydraulic cements, for instance, include Portland cements, high alumina cements, phosphate cements, pozzolan cements, fly ash cements, silica fume and the like. Any of the oil well type cements of the class "A-H" and. "J" as listed in the API Spec I OA, (22nd ed.. January 199.5 or altemamely ISO 10426-1), are suitable. Especially 30 preferred is Portland cement, preferably an API Class A, C, G or H cement. Alternatively, the Portland cement may be a Type I, II, III or V A5TM construction. cement. The cementitious material may further include a mixture of two or more components selected from Portland cement, fly ash, slag, silica fame, gypsum, limestone and bentonite, id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26"

[00026] Typically, between, from about 10 to about 70, preferably between from about 5 20 to about 65, most preferably from about 35 to about 65, weight percent of the cement mix is Portland cement or the referenced mixture, id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27"

[00027] The aluminum silicate is typically comprised of SiOi/AiiOj/FeiOB, Must typically the aluminum silicate is kaolin, calcined kaolin or kaolinite (metakaolin) or mixtures thereof. Such aluminum silicate may also be referred to as China Clay. Other suitable forms of aluminum silicate include, but are not limited to, halloysite. dictate, and nacnk*. .and mixtures thereof as well as mixtures of these with materials with kaolin and/or metakaolin. The amount of aluminum silicate in the cement mix is typically between, from about 5 to about 70 weight percent, preferably from about 8 to about 45 weight percent. id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28"

[00028] The amount of graphite in the cement mix is typically between from about 5 to about 70 weight percent, preferably from about 8 to about 45 weiglitpercent. id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29"

[00029] I lie cement mix described provides a slurry with lower water content. For instance, a shirty having a desired density of 15 ppg requires a lower concentration of water to attain the dctitcd density than a substantially similar slurry composed of a conventional cement mix. id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30"

[00030] The cementitious shiny, formulated from the cement mix, typically has a density in. the range of from about 7 to about 23 pounds per gallon (ppg), more typically from about 1.1. to about 17, most typically from about 15,6 to about 16.6 ppg. In some instances, it is desirable to add a density weighting agent or a density reducing agent. For instance, when the density of the cementitious slurry is required, to be above 17 ppg. it is necessary to add a density weighting agent. Suitable density weighting agents include ilmenite, manganese oxide, iron oxide, iron II oxide, ferrous-ferric oxide, ter.rosil.icon, speeularite, ferrophosphorus. galena, iron, arsenite, barium sulfate, and the like. Such density weigliting agents increase the density of the cementitious slurry at reduced water 30 content (over a substantially similar cementitious slurry containing a cement mix of the prior art). Further, when the density of the slurry is required to be below 14 ppg, it is - It - necosary to add a density ieducing agent 01* a (burning agent. Suitable density reducing agents include such lightweight additives include naturally occurring ceramic spheres called cenospheres or manufactured glass spheres. Such density reducing agents decrease the density of the slurry at reduced water content (over a substantially similar 5 cementitious slurry containing a cement mix of the prior art). 'When present, the amount of density weighting agents or density reducing agents in the slurry is between from about 5 to about 150 "0 BWOC. [00031J The slimy may contain fresh water, sail water, formation brine or synthetic brine or a mixture thereof. Generally, the water is present in the slmry in an amount 10 sufficient to form a slurry pumpable through standardized pumping equipment. As permeability of the set cement increases with increased water content, it is desirable to pump a cementitious slurry having the lowest water content possible in order to minimize permeability of the set cement. Generally, the amount of mixing water in the slurry may range from about 30 to 150 weight percent based upon the dry weight of cement and 15 preferably is in the range of about 35 to 90 weight percent. id="p-32" id="p-32" id="p-32" id="p-32" id="p-32" id="p-32" id="p-32"

[00032] The cement mix, and cementiiious slurries of the invention may further include other additives commonly utilized in cement compositions and which are well known to those skilled in the art. For example, weighting agents, lightweight additives, lluid loss control additives, set retarders, plasiicizer, set accelerators or activators, dispersing agents, extenders, foam preventers, etc. in such conventional amounts, for instance, of from about 0.1 % to about 12% by weigh! of cement (BWOC) may be included, preferably from, about 0.1 to about 2 % BWOC. id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33"

[00033] Suitable additives for controlling fluid loss include polyvinyl alcohol, optionally with boric acid, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, synthetic anionic polymers and synthetic cationic polymers. Such fluid loss control additives, when present,, are typically a component of the cement mix. though it could be introduced into the cementitious slurry. id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34"

[00034] Suitable dispersants include polyaerylates, naphthalene sulfonic acid and the like. id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35"

[00035] Activators include solutions of Group IA and IIA hydroxides, such as sodium hydroxide, magnesium hydroxide and calcium hydroxide; sulfates, such as sodium sulfate; aluminates, such as sodium aluminate and potassium aluniinate; carbonates, such as sodium carbonate; silicates; triethanolamine (TEA) and calcium chloride. Preferred activators are sodium silicates. Typical concentrations of activator range from about 0.05 gps to 3.5 gps dependent on application. id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36"

[00036] A plasticizing agent may further be used in the cement mix (or added directly to the slurry) to assist in control of the fluidity of the slurry. Specific examples of plasticizing agents include melamine sulfonic acid polymer condensation product, sodium polyacrylate, naphthalene sulfonic acid, sodium salt of naphthalene sulfonate formaldehyde condensate, sodium sulfonated melamine formaldehyde (SMF) and 10 sulfbnated-styrene maleic anhydride polymer. id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37"

[00037] The set retarcler, when employed, should be chosen in order to allow sufficient thickening time of the slurry upon setting for proper placement in the annulus of the wellbore. Suitable set retarders include glucoheptonates, such as sodium glucoheptonate, calcium glucoheptonate arid magnesium glucoheptonate; lignin sulfonates, such as sodium lignosulfonate and calcium sodium lignosulfonate: gluconic acids gluconates, such as sodium gluconate, calcium gluconate and calcium sodium gluconate; phosphorates, such a> the sodium salt ot'EDTAphosphonic acid; sugars, such as sucrose; hydroxycarbo\\ lie acids, such as citric acid; and the like, as well as their blends. id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38"

[00038] The cement mix may further contain a strength retrogression additive for 20 limiting deterioration of the cement, loss of strength of the cement and increase permeability of the cement. Such additives include silica flour and crystalline silica such as coarse and fine grain crystalline and prevent the conversion of tegular calcium-silicate-hydrate phases into alpha dicalcium silicate. The amount of strength retrogression additive typically added is that amount which is necessary in order to obtain a CaO:SiC>2 25 ratio of 1. Typical!}, die amount of".strength retrogression additive in the cement mix is between from about 10% to about SO0,, BWOC, preferably from about 20 to about 50% BWOC. id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39"

[00039] The following examples are illustrative of some of the embodiments of the present invention. Other embodiments within the scope of the claims herein will be apparent to one skilled in the art from consideration of the description set forth herein. It is intended that the specification, together with the examples, be considered exemplary only, with the scope and spirit of the invention being indicated by the claims which follow. id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40"

[00040] All percentages set forth in the Examples are given in terms of weight units by weight of cement (BWOC) except as may otherwise be indicated.

EXAMPLES id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41"

[00041] Example 1. A cementitious slurry was prepared by mixing neat Class G Portland cement with 81.7% fresh water at room temperature. To the slurry was added 35% silica flour, 15% graphite, 12.5% metakaolin, 0,3 gallons per sack cement (gps) fluid loss additive, commercially available from BJ Services Company LLC as. FL-66L + 0.7% CD-31 (a cement dispersant available from BJ Services Company LLC). The resultant slurry, 15.6 ppg, was kept with occasional agitation. Standard API viscosity and a fluid loss test were conducted on the cement slurry. The "Thickening Time" represents the amount of time that the slurry remained in a liquid, state and to reach 100 Be. 15 Thickening Time to 100 Be = 2:40 hfannm API Free Water = 0% API Fluid Loss = 64 cc/30 min The rheology readings, shown in Table 1, were taken on Fann 35 viscometer, at 38° C: Table I Rheometer RPM's Initial Fann readings after Farm readings after 20 mixing minutes conditioning at 38 oC 600 300+ 300+ 300 270 261 200 100 135 100 105 102 60 67 66 3S 37 6 12 12 3 0 9 [0<>o42i Example 2. I he cementitious slurry recited in Example 1 was prepared arid placed into nine cylindrical curing vessels of 1 in. diameter x 3 in. long and cured at 39° C for 120 hours in a standard API water bath. This simulates pumping the cement slurry . 14- in thi' well and setting under the normal curing temperature until the coal seam is ignited. Once cured, the 1 x 3 in. cylinders were cut into 2-in. sections and squared off. Cylinders S-l, S-2 and 8-3 were crashed immediately after 48 hours. Cylinders 8-4 through. S-9 were then placed into a 2 in. diameter x 6 in. long cylinders along with enough water to 5 cover the cylinders and 20 g silica flour. The cylinders were then placed into a muffle furnace and cured at 350° C. Cylinders S-4, S-5 and S-6 were removed from the furnace after 72 hours of exposure and allowed to cool slowly over 48 hours while submersed in water inside the testing vessel. After the 48 hour cooling period, the cylinders were removed and measured. None of the tests showed change in circumference or length. The 10 same procedure was used for Cylinders S-7, S-8 and S-9 after they were exposed, for 30 days. Compressive strength was obtained through API KP-10B destructive crash test. The results are set forth in Table 11: Table II Sample Number s-1 S-2 -3 S-4 S-5 S-6 -7 S-8 S-9 Mass (») after V) C 63.y 3 63.8 n > 61.88 63.95 63.65 64,22 64.9 6 65.03 64.8(1 Mass (e! alter 350 C N \ NA MA 61.91 61.61 62.15 62..6 0 62.73 62.46 | C S IpM) w c 1925 1025 1635 NA NA NA NA NA _ M_j CS (psi) 350" c NA N A NA 42 4243 4140 4525 4429 3-55 1 As shown, in the destructive compressive strength data of Table II, no strength retrogression was noted. The changes in strength between the 72 hours and 30 days tests are within the standard deviation. id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43"

[00043] Example 3. A cementitious slurry was prepared by mixing neat Class G Portland cement with 67% fresh water al room temperature. To the shiny was added 55% silica flour, 15% graphite, 12.5% metakaolin, 0.3 gps fluid loss additive, commercially available from BJ Services Company LLC as FL-66L + 1.4% CD-3.1 (a cement dispersant available from BJ Services Company t 1 CI. The resultant shiny. 16.6 25 ppg, was kept with occasional agitation. The slurry of this* kxaniple and the slurry of Example 1 were then placed into cylindrical curing vessels of I in. diameter * 2 in. long and cured at 39° C for 120 hours in a standard API water bath. The c\ lindei's were then removed from the water bath and placed directly in a muffle fiiraaee at 1000° C, These conditions are believed to simulate the ignition, of the coal bed in the ground and extreme conditions at the combustion front. The cured cylinders remained intact with no 5 detectable cracking after exposure to 1000° C (dry heat) for 72 hours. id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44"

[00044] Examples 4-8. Cementitious slurries were prepared by mixing neat Class G Portland cement with fresh water at room temperature. To the slurry was added 35% silica flour, 15% graphite, 12,5% metakaolin, surfactants as foam preventer (PF) 10 minimizing entraining of air during mixing styrene-butadiene latex suspension as fluid loss additive (FLA), hydrated lime as accelerator, a multi liquid additive (MLA) for fluid loss control and slurry stability, and CD-31 as cement dispersant (CD). The resultant slurry was kept with occasional agitation. The formulations of the slurries are set forth in Table HI: Table III Ex. No.

Graphite Metakaolin, % IBWOO Silica Flour. 0 0 (BWOC) FP. gps FLA, Gps CD.

LipS MLA. gps Accelerator, gps Density. ppg 4 27.5 ~ t).t)54 1,0 .6 27.5 — 0.054 - - - .6 6 40 0.054 — „ -- .8 7 0.054 0.1 0.1 .8 8 40 0.054 1.4 0.1 14.0 Cubes of each of the samples were then subjected to dry heat (450° C) for 48 hours. During exposure to dry heat, ph\sL-,tlh absorbed water in the cement pores and 20 chemically bonded water in the cement hydrate phases tried to evaporate: internal pressure was exerted within the cubes. Cement systems crack if unable to withstand such stresses. The cube of Example 8 is a low-density (14.0 ppg) design with the highest water content. Thus, it experienced the highest internal stresses, resulting in the most severe cracks. Internal pressure has also detrimental!) affected the standard cement designs at 15.8 ppg (cubes of Examples 6 and 7} usually applied for temperatures above 110° C In the contrary, the cubes of Examples 4 and 5 are 15.6 ppg, but contained the high temperature blend (graphite and. metakaolin), combining a lower water content with the 5 ability to buffer internal stresses due to suitable mechanical properties. As a result, cubes of Examples 4 and 5 exhibited no cracking or malformation.

Example 9. A cementitious slurry was prepared by mixing neat Class G Portland cement with fresh water at room temperature. To the slmry were added 15% graphite, 12.5% 10 metakaolin, and 0.054 gps of a surfactant as foam preventer. The resultant slurry, 16.0, was kept with occasional agitation and then used to cement a liner to the wellbore in a UCG field. The coal seam was ignited and syngas was generated to fuel a power plant. A reduction in the temperature flow of the produced gas stream was noted. In particular, it was noted that the syngas was delivered to the surface 45 - 60° C cooler than from 15 substantially similar wells which had been cemented with CaP cement. Use of the high temperature cement blend yielded excellent thermal heat conductivity at reduced water content and provided a durable cement sheath at extreme temperatures at about less than hul 1" the cost of the substantially similar well cemented with the CaP cement. [0i)045] From the foregoing, it will be observed that numerous variations and modifications may be effected without departing from the true spirit and scope of the novel concepts of the invention.

Received at IPONZ on 24-Apr-2012 17

Claims (18)

1. A method of producing synthesis gas by the underground gasification of coal from a coal seam comprising: 5 (a) cementing casing string in a production well and an injection well which penetrates the coal seam by pumping into the wellbore a cementitious slurry and allowing the slurry to set to form a cement sheath in the wellbore; (b) igniting the coal in the coal seam; (c) introducing oxidant gas into the injection well; and 10 (d) generating syngas as a combustion front in the coal seam and advancing the combustion front through the production well, wherein the temperature of the combustion front is greater than or equal to 800° C and further wherein the heat from the combustion front is distributed along the cement sheath in the wellbore, wherein the cementitious slurry comprises a cement mix comprising: 15 (i) between from about 10 to about 70 weight percent of a cementitious material; (ii) between from about 5 to about 70 weight percent of graphite; and (iii) between from about 5 to about 70 weight percent of an aluminum silicate, wherein the density of the slurry is between from about 7.0ppg to about 23.00 ppg. 20

2. The method according to claim 1, wherein the temperature of the syngas production stream is at least 40° C less than the temperature of a syngas production stream produced in a production well having a casing cemented with a cementitious slurry other than that of step (a). 25

3. The method according to claim 1 or claim 2, wherein the aluminum silicate is metakaolin.

4. The method according to any one of claims 1 to 3, wherein the cementitious 30 material is a Portland cement.

5. The method according to any one of claims 1 to 4, wherein the hydraulically-active cementitious slurry further comprises a strength retrogression additive. Received at IPONZ on 24-Apr-2012 18

6. The method according to claim 5, wherein the strength retrogression additive is silica. 5

7. The method according to any one of claims 1 to 6, wherein the bottom hole static temperature of the production well at time of cement placement is less than or equal to 65° C.

8. The method according to any one of claims 1 to 7, wherein the temperature of the 10 combustion front is in greater than or equal to 1000° C.

9. The method according to claim 8, wherein the temperature of the combustion front is greater than or equal to 1000° C. 15

10. The method according to any one of claims 1 to 9, wherein the set cement maintains its compressive strength and does not form hot spots within the cement sheath.

11. The method according to any one of claims 1 to 10, wherein the cementitious slurry further comprises a density reducing agent or a density weighting agent. 20

12. A method of producing synthesis gas by the underground gasification of coal from a coal seam comprising: (a) pumping into the wellbore of a production well and an injection well a cementitious slurry comprising between from about 10 to about 70 weight percent of a 25 cementitious material, between from about 5 to about 70 weight percent of graphite and between from about 5 to about 70 weight percent of an aluminum silicate and allowing the slurry to set form a cement sheath in the wellbore, wherein the density of the slurry is between from about 7 to about 23 ppg; (b) igniting coal in the coal seam; 30 (c) introducing air and water through the injection well and forming a syngas; and Received at IPONZ on 24-Apr-2012 19 (d) transporting the syngas through the coal seam as a combustion front to the production well.

13. The method according to claim 12, wherein the temperature of the combustion 5 front is greater than or equal to 800° C.

14. The method according to claim 13, wherein the temperature of the combustion front is greater than or equal to 1000° C. 10 15. The method according to any one of claims 12 to 14, wherein at least one of the following conditions prevail: (a) the aluminum silicate is metakaolin; (b) the bottom hole static temperature of the production well at the time of slurry placement is less than or equal to 65° C;

15. (c) the density of the cementitious slurry is between from 7.5 to 14 and contains from about 5 to about 150 % BWOC of a density reducing agent; or (d) the density of the cementitious slurry is between from 16.5 to 23 ppg and contains from about 5 to about 150% BWOC of a density weighting agent. 20

16. A method of producing synthesis gas by the underground gasification of coal from a coal seam comprising: (a) pumping into the wellbore of a production well and an injection well a cementitious slurry comprising Portland cement, graphite and metakaolin and allowing the slurry to set form a cement sheath in the wellbore, wherein the density of the slurry is 25 between from about 14 to about 17.0 ppg; (b) igniting coal in the coal seam; (c) introducing air and water through the injection well and forming a syngas; (d) transporting the syngas through the coal seam as a combustion front to 30 the production well, Received at IPONZ on 24-Apr-2012 20 wherein the bottom hole static temperature of the production well, at the time of slurry placement, is less than or equal to 65° C. and the temperature of the combustion front is greater than or equal to 800° C. 5

17. A synthesis gas when produced by the method according to any one of claims 1 to 16.

18. A method of providing synthesis gas by the underground gasification of coal from a coal seam according to claim 1, 12 or 16 or synthesis gas provided by the method 10 of underground gasification of coal from a coal seam according to claim 17 substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying drawings and/or examples.