SPE 37474 Society of Petroleum Engineers Synthesizing of Dispersant for MTC Design and Its Effect on Slurry Rheology Hou virui and Liu Zhongchun/Daging Petroleum Inst. China, Abstract A new method of obtaining improved zonal isolation using drilling fluid solidification technology has been developed. A water-base drilling fluid is converted into a cementitious slurry by the special method, is called simply MTC(Mud To Cement) The MTC technology used for cementing operation can improve the quality of cementing and reduce the disadvantageous cffect resulting from flocculation in the mixture of drilling mud-cement and cracking of solidified cement as the filter cake and drilling fluid in washed out sections thereby contain a hydraulic material. The dispersant’s synthesizing and its effect on slurry rheology are the base of MTC technique application This paper provides ‘wo methods of which the dispersant is synthesized by using fractions of C5 which are the by-product of Daging ethene unit. The dispersant is cheaper, and it can be used for MTC design by experiment’s verification. The effects of amounts of dispersant and mud on the rheology of MTC slurcy are studied and discussed . The results show that. the thickening time of MTC slurry is extended clearly with mixing of dispersant, and the mobility of slurry is improved. We find ‘that there is a low mobility or high consistency region when MTC slurry is making up. The appropriate measures for improving quality of MTC are provided in this paper Moreover, the rheological model of MTC slurry is studied Through lots of calculation the H-B model is the most accurate for describing MTC slurry Last, the application of MTC technology in Changaing field is introduced. Introduction Conversion of drilling Muid(mud) into cement suitable for ‘well cementing operations has been an area of interest within the petroleum industry for over fifty years Improved zonal isolation in the annular space between casing and borehole has been and continues to be the primary reason for pursuing this technology For nearly a century, zonal isolation has been attempted largely by the placement of Portland cement formulations in the annular space. The widely practiced cementing process is plagued by variables which are often difficult to predict or control yet have a critical impact upon the quality of seal achieved Two of variables include effective removal of the drilling fluid occupying the annulus and the effects of mud or spacer fluid contamination on cement formulation properties in the liquid (sturry) and solid states. With prior art methods ‘and compositions, the displacement of the drilling fluid has been incomplate due to gelation and has often resulted in poor cement bonds or incomplete filling of the casing-to- ‘wellbore annulus with a homogencous cement “Mad solidification has been pursued as @ means to improve zonal isolation because of (1) better rheological compatibility between the cementing fluid and the mud which contributes to better mud displacement,(2) lower impact of mud contamination on the performance properties of the coverted ‘mud in the fluid and solid state.and (3) improved sealing in the annulus because of the potential solidification ofthe filter cake and any undisplaced mud? The conversion of drilling fluid or mud to a cementitious slurry is without some operational problems and undesirable compositional changes.For example, the addition of cementitious materials such as mixtures of lime and silicia and alumina or lime and magnesia.silica and alumina and iron oxide ,or cement materials such as calcium sulphate and Portland cements to aqueous drilling fuild can substantially increase the viscosity of the fuid mixture and result in severe Aocculation, Efforts to circulate such mixtures through a wellbore can result in a highly unsatisfactory circulation rate, plugging of the wellbore annulus breakdown of the carth formation in the vicinity of the wellbore and a failure of the cement slurry to properly mix. (On the base of development of Macromolecule synthesizing technology, the MTC technology has been developed really Til the first of 1990's the MT technology has been to have the value of industry application because of the2 Hou Jr Liu 2hengehun development of the high-quality dispersant. This paper introduces the dispersan’s synthesizing at first The dispersant used for the design of MTC is styrene sulfonic acid-maleic anhydride copolymer (SSMA)On the base of cexperiments.the effects of amounts of dispersant and mud on the rheology of MTC slurry are studied and discussed . This work will bring mud solidification into widespread use. Synthesizing Methods of SSMA ‘The general MTC is that drilling fluid (mud) and cement are mixed by a dispersant.Apperently,the dispersant is the key which mix mud with cement? . There are many kinds of dispersant for MTC design’ ’ But lots of dispersant is ‘expensive The dispersant is made by using fractions of Cs, (bp. is between 328~475K, the content of styrene and methyl styrene is 36.7%) which are by-product of Daging ethene unit in this paper The fractions of C> and acid-maleic anhydride are polymerized at first. Then,the product is sulphidized and saponified, The last product is the dispersant for MTC design. Synthesizing Mechanism.In fractions of Cs,Styrene and its derivative are active composition. When the polymerization reaction takes place between the fractions of C3 and. acide maleic anhydride there is a alternation tendency between them ,because styrene is the monomer which has a group to repel electron and the acid-maleic anhydride is the monomer ‘which has a group to atract electron“. So far. there are two explanations®? The first is that there are movement of electrons between the monomers, then the complex compound is formed Moreover, the synthesizing reaction is initiated and increased by the complex compound. The reaction is, H HC=CH on CHR=CR’ tot Ky ft ‘C CHR | +0-¢ COT} oO gat Ph 1 ‘Xe | 4 Seer ° o-c7| | H Ph ‘The other explanation is that the addition reaction takes place between the monomers The reaction is CH=CH R CHCH | | 1 ~CHR—CR'+ CO CO © ~CHR-C CC. Ve owe Ph ° Ph’ O 0 or 680 spe a7474 *CH—CH- ~CH—"CH CHR | | CHR=CR'+CO CO CO CO CR 1 V4 Vi | PhO ooh (where R or R’ is H or CH.) SynthesizingMethods.Through lots of experiment , two synthesizing methods is found for the dispersant. (Q) Free radical polymerization reaction Fractions of Cs + MA——3SMA ——> SMA (2) Catalytic polymerization reation MA+C9+S Na+S+Al ‘The catalyzers used for the reaction are Na naph); and AIG- Bu)s is called simply Nd and Al. The fractions of C3 and acid-maleic anhydride and catalyzers dissolve in benzene at first The copolymerization reaction takes place inthe system. The saponated production is coverted into brown power (SSMA) by drying up and powering. Its purty is more higher than 80 percent. Product Verification,When the reference is styrone, the ‘molecular weight of SMA is measured by Water-208 type gel chromatograph at thirty degrees centigrade M, is 1800~2000,The infrared spectrum of SMA is measured by Nicolet-Dx type infrared spectrometer. The special absorption of styrone is showed at wave number 70cm" and é0cm".The special absorption of acid-maleic anhydride appears at 1780cm'. The absorption peak vanishes at 1792cm" Laboratory Investigations Experimental materials and important apparatus dispersant-SSMA :synthesized Portland cement ‘class G ‘mud: (1) Changging Mud, 9 =1.05e/em? (Bentonite, PHPA, PACI41, PACI42, PACI43, CMC, NaCOs, NaOH) @) Daging Mud, p=1.64g/em?; (KTN, KOH, KPM, Tannin extract) ) Bentonite Mud,p =1.42g/em? conventional chemical agent (A.R.) Wali stirrer (Che highest rate is 12000 r/min) pressure thicken apparatus ‘manual stirrer‘SPE 37474 SYTHESZING OF HE DISPERSANT FOR MTC DESIGN AND ITS EFFECT ON SLURRY RHEOLOGY 3 Fan-35 viscosimeter, determining mobility apparatus etc Experimental method ‘The mixture of watercement and dispersant mixed with a certain mixture ratio in Walin stirer is stred for one minute ‘The mobilty.viscosity and thikening time of cement slurry fare determined. Mixing the cement slurry with the drilling fluid can be accomplished by batch mixing? The samples are ‘manually stired fortwo minutes.then the base properties are determined Considering actual cementing operation, the rate which mix cement slurry with drilling fluid is 100 slow to achieve the rate of Walin stirer.he manual stirrer is selected in experiment. Experimental Results and Discussion Effect of SSMA on the slurry viscosity. Fig.1 shows the ‘viscosity variation of slurry with various proportions of SSMA. It demonstrates clearly that the viscosity of slurry is reduced with increasing of the amount of SSMA. Because the addition of certain proportions of SSMA reduces the flocculation or gelling of the mud converted to cement mixture, further effort has led to a reduced viscosity To net cement sturry, the surface of cement grains charge ‘minus electricity because of converting CS and C2S into hydrated calcium silicate by hydration reaction -Si-OH + OF >-SiO"+ 0 ‘The Ca’* ion in liquid phase and the charge on the surface of cement grains interact on each other . A Ca" ion can attract two-SiO on a particleor two different -SiO on different particle to form bridged complex ,so the flocculation is produced As the adsorption of dispersant on surface of solid phase.the repulsion of static electricity prevents the flocculation producing. Moreover.the chelate effect by the action of SSMA reduces the bridging groups ( Ca® ) ion to restrain the flocculation. Because water molecules in the system ate increased relatively in consequence of presenting of SSMA , the viscosity is descreased. The more SSMA concentrations is increased ,the lower viscosity of slurry is decreased, Clay is the main composition in mud.and is the ‘main factor to impact the rheology of slurry The hydrated clay with lots of high valence ion in mud which have been ‘mixed to the cement slurry shows minus electricity therefore the flocculation is more severe The Mocculation can be restricted by increasing the amount of SSMA in the slurry Fig) Effect of SSMA and mud on the slurry mobility.The samples which contained different amounts of polymer mud by batch mixing to 300 ml cement slurry were prepared to determine the mobilities of slurrys with various mixture ratios (Fig.2)Results provided in Fig? illustrates the 681 mobility of slurry improvement with increased amounts of SSMA Moreover ,there is a minimum mobility of the sample ‘The minimum is gradually vanished with increasing of SSMA amounts. There is not the minimum mobility of the sample which contain 0.8 percent or much more than 0.8 percent SSMA Because the flocculation is restricted, the beiter mobility is improved by increasing the amount of SSMA, To the slurry with low SSMA content ,because the bridging group ’s increasing is more fastly than of water content with adding mud, the flocculation is more important than water's, dilution, so the mobility is decreased till the minimum With increasing of mud added in the system, the water's dilution which has been a main factor makes the mobility of slurry further decrease. The minimum mobility depends on the density of mud. The conclusion is verified by experiment using Daging polymer mud (Density,1.64g/em’) and Bentonite mud (Density, 142g/em’). The results are showed in Fig.2 (Cunes £f,¢.°). At the same condition, the density of ‘mud is more higher,the minimum mobility appeares. more late For making MTC slurry to have the property of preventing ‘mud damages, the compositions which have the lower ‘mobility should not be selected,and the lower mobility region should be got over,when MTC slurry used to cementing is, made, Effect of SSMA on thickening time.There are many factors affecting MTC thickening time, for example temperature and the amount of mud and dispersant.ctc Results show that, the thickening time is extended clearly with mixing of dispersant Moreover .the early consistency of MTC slurry comerted from polymer mud is high The problem can be solved by mixing of NasCO; (Fig.3).Because of the adsorption of dispersant on surface of solid phase,the repulsion of static electricity prevents the particles to assemble Moreover,the chelate effect by the action of SSMA. reduces the bridging groups (Ca* ions) to restrain the flocculation. Thereby, results show that the thickening time is, extended The thickening time is in direct proportion to the amounts of SSMA.The high early consistency is due to the flocculation of which the HAMP is flocculated by Ca in the first 30 minates , or OH whose concentration increased in liquid phase with increasing of temperture is reacted with ca Ca" +20H'= Ca(OH), (colloid) ‘The colloid has a strong flocculation which results in the hhigh early consistency of MTC slurty.A experiment is performed to demonstrate the inference. The experiment is to determine the mobility of the sample with 0.4 percent NaxCOs .The result shows that the problem of high early consistency has been successfully restricted It is due to that