Attchment/Release of Phosphonate to/from a CaCO3 Surface in Supersaturated Brines

2014 ◽  
Author(s):  
Nan Zhang ◽  
Amy T. Kan ◽  
Mason B. Tomson
Keyword(s):  
Calcium Carbonate ◽  
Produced Water ◽  
Saturation Index ◽  
Extended Period ◽  
Calcium Carbonate Precipitation ◽  
Flowback Water ◽  
High Supersaturation ◽  
Co Precipitation ◽  
Kinetics Of ◽  
Theoretical Limitation

Abstract One of the most intractable concerns when engineers try to reuse the produced water as frac fluid in the Bakken and some other shale plays is the scale formation caused by the incompatibility of produced water with additives in the frac fluids and with the formation. In order to obtain a more efficient scale treatment for a successful hydraulic fracing that handles the extraordinary amount of water with high supersaturation level, the better understanding of inhibitor retention and release in the production system is urgent. To explore the mechanism of attachment/release of phosphonate to/from a mineral surface, calcite supersaturated feed solutions with different diethylenetriamine penta (DTPMP) concentrations were introduced into the steel tubing that was internally pre-coated with a thin layer of CaCO3. It is unveiled that DTPMP attachment was dominated by the precipitation of calcium phosphonate solid once the solution is supersaturated with Ca3H4DTPMP (pKsp=53.5), and the total amount of DTPMP attached on the calcite surface added up with the increasing supersaturation of Ca3H4DTPMP. The co-precipitation of CaCO3 and Ca3H4DTPMP has facilitated the attachment of the inhibitor with the increase of supersaturation of CaCO3. The retained phosphonate was released from the surface with a steady and low level inhibitor concentration over extended period of time. Combining with the kinetics of calcium carbonate precipitation in the presence of inhibitor, a 1500 gram of calcium phosphonate precipitation can protect the scaling for about 100 days (100 bbl/day) when the saturation index of calcium carbonate (SIcalcite) is as high as 1.3. The results provide a better understanding of calcium-phosphonate-carbonate interaction, and show the phosphonate inhibitor can continuously accumulate on the carbonate and slowly dissolve. We anticipate this study can shed a light on how much inhibitor can be delivered to the unconventional reservoir as well as the theoretical limitation of inhibitor return in the flowback water.

scholarly journals Calcium Carbonate Scale Formation, Prediction and Treatment (Case Study Gumry Oilfield-PDOC)

2013 ◽  
Vol 17 ◽  
pp. 47-58 ◽  
Author(s):  
A. Saifelnasr ◽  
M. Bakheit ◽  
K. Kamal ◽  
A. Lila
Keyword(s):  
Calcium Carbonate ◽  
Produced Water ◽  
Saturation Index ◽  
Water Injection ◽  
Stability Index ◽  
Scale Formation ◽  
Injection Process ◽  
Langelier Saturation Index ◽  
Calcium Carbonate Scale

In this study the predictions and probabilities of calcium carbonate scale formation and corrosion occurrence inside Gumry Field Process Facilities (GFPF) and produced water injection process units (PWTP) was carried out. This was done calculating the Langelier Saturation Index (LSI), Ryznar Stability Index (RSI), Puckorius Scaling Index (PSI). The samples results for LSI index and PSI index were compared and found that all samples under threaten of calcium carbonate scale. The samples results for RSI index and found that all samples under formation of heavy calcium carbonate scale. Special excel computer program was designed to calculate the (LSI, RSI, PSI). The scale was cleaned and removed by 10% diluted hydrochloric acid and commercial scale inhibitor.

A Quantitative Study of Sr2+ Impact on Barite Crystallization and Inhibition Kinetics

2021 ◽  
Author(s):  
Yue Zhao ◽  
Zhaoyi Joey Dai ◽  
Chong Dai ◽  
Xin Wang ◽  
Samridhdi Paudyal ◽  
...  
Keyword(s):  
Induction Time ◽  
Produced Water ◽  
Saturation Index ◽  
The Novel ◽  
Inhibition Kinetics ◽  
Molar Ratios ◽  
Laser Apparatus ◽  
Scale Control ◽  
First Time ◽  
Kinetics Of

Abstract Scale inhibitors have been widely used for barite scale control. Our group has developed several barite crystallization and inhibition models to predict the crystallization and inhibition kinetics of pure barite with different inhibitors and calculate the minimum inhibitor concentration (MIC) required. However, instead of pure barite scale formation, the incorporation of Sr2+ can be frequently found in the oilfield, because of the coexistence of Ba2+ and Sr2+ in the produced water, which can influence the kinetics of crystallization and inhibition significantly. As a result, the MIC predicted could be off significantly. Therefore, in this study, the effect of Sr2+ on barite crystallization and inhibition kinetics is quantitatively investigated to evaluate the accuracy of MIC values under various conditions. The induction time of barite with different concentrations of Sr2+ was measured by laser apparatus without or with different concentrations of scale inhibitor diethylenetriamine penta(methylene phosphonic acid) (DTPMP) at the conditions: barite saturation index (SI) from 1.5 to 1.8; temperature (T) from 40 to 70 ℃; and [Sr2+]/[Ba2+] molar ratios from 0 to 15, all with celestite SI < 0. The results show that the induction time of the barite increases with [Sr2+]/[Ba2+] ratio at a fixed barite SI, T and DTPMP dosage. That means the MIC will be overestimated if it is calculated by previous semiempirical pure barite crystallization and inhibition models, without considering the presence of Sr2+. Based on the experimental results, the novel quantitative barite crystallization and inhibition models that include the influence of Sr2+ were developed for the first time as follows: Barite crystallization model with the influence of Sr2+: l o g 10 t 0 B a S O 4 ,   S r = ( 1.523 − 10.88 S I − 895.67 T ( K ) + 5477 S I × T ( K ) + 0.829 × [ C a 2 + ] ) + ( 0.823 S I + 85.44 T ( K ) − 0.667 ) × ( [ Sr 2 + ] [ B a 2 + ] ) Barite inhibition model including the influence of Sr2+ l o g 10 ( t i n h B a s o 4 , S r t 0 B a S O 4 , S r ) = b B a S O 4 , S r × C i n h l o g 10 b B a S O 4 , S r = ( − 2.187 − 1.411 × S I + 1329.29 T ( K ) + 0.153 × p H ) + ( 0.0983 × S I − 74.66 T ( K ) + 0.099 ) × ( [ Sr 2 + ] [ B a 2 + ] ) These novel models are in good agreement with the experimental data. They are used to predict the induction time and MIC more accurately at these common Ba2+ and Sr2+ coexisting scenarios. The observations and new models proposed in this study will significantly improve the barite scale management when Ba2+ and Sr2+ coexist in the oilfield.

scholarly journals Assessment of calculation methods for calcium carbonate saturation in drinking water for DIN 38404-10 compliance

2013 ◽  
Vol 6 (2) ◽  
pp. 115-124 ◽  
Author(s):  
P. J. de Moel ◽  
A. W. C. van der Helm ◽  
M. van Rijn ◽  
J. C. van Dijk ◽  
W. G. J. van der Meer
Keyword(s):  
Drinking Water ◽  
Calcium Carbonate ◽  
Saturation Index ◽  
Computer Programs ◽  
Maximum Temperature ◽  
Chemical Databases ◽  
Calcium Carbonate Precipitation ◽  
Chemical Modeling ◽  
Practical Applications ◽  
Chemical Database

Abstract. The new German standard on the calculation of calcite saturation in drinking water, DIN 38404-10, 2012 (DIN), marks a change in drinking water standardization from using simplified equations applicable for nomographs and simple calculators to using extensive chemical modeling requiring computer programs. The standard outlines the chemical modeling and presents a dataset with 10 water samples for validating used computer programs. The DIN standard, as well as the Standard Methods 2330 (SM) and NEN 6533 (NEN) for calculation of calcium carbonate saturation in drinking water were translated into chemical databases for use in PHREEQC (USGS, 2013). This novel approach gave the possibility to compare the calculations as defined in the standards with calculations using widely used chemical databases provided with PHREEQC. From this research it is concluded that the computer program PHREEQC with the developed chemical database din38404-10_2012.dat complies with the DIN standard for calculating Saturation Index (SI) and Calcite Dissolution Capacity (Calcitlösekapazität) or Calcium Carbonate Precipitation Potential (CCPP). This compliance is achieved by assuming equal values for molarity as used in DIN (obsolete) and molality as used in PHREEQC. From comparison with widely used chemical databases it is concluded that the use of molarity limits the use of DIN to a maximum temperature of 45 °C. For current practical applications in water treatment and drinking water applications, the PHREEQC database stimela.dat was developed within the Stimela platform of Delft University of Technology. This database is an extension of the chemical database phreeqc.dat and thus in compliance with SM. The database stimela.dat is also applicable for hot and boiling water, which is important in drinking water supply with regard to scaling of calcium carbonate in in-house drinking water practices. SM and NEN proved to be not accurate enough to comply with DIN, because of their simplifications. The differences in calculation results for DIN, SM and NEN illustrate the need for international unification of the standard for calcium carbonate saturation in drinking water.

scholarly journals AVALIAÇÃO DA QUALIDADE E TRATAMENTO DAS ÁGUAS SUBTERRÂNEAS PARA IRRIGAÇÃO EM JAÍBA E JANAÚBA – PRECIPITAÇÃO QUÍMICA E CORROSÃO

Irriga ◽  
2009 ◽  
Vol 14 (3) ◽  
pp. 336-347
Author(s):  
Moises Santiago Ribeiro ◽  
Fabio Henrique de Souza Faria ◽  
Luiz Antonio Lima ◽  
Silvanio Rodrigues dos Santos ◽  
Marina Rosa de Jesus
Keyword(s):  
Water Quality ◽  
Calcium Carbonate ◽  
Hydrochloric Acid ◽  
Saturation Index ◽  
Stability Index ◽  
Chemical Precipitation ◽  
Underground Water ◽  
Minas Gerais ◽  
Calcium Carbonate Precipitation ◽  
Micro Irrigation

AVALIAÇÃO DA QUALIDADE E TRATAMENTO DAS ÁGUAS SUBTERRÂNEAS PARA IRRIGAÇÃO EM JAÍBA E JANAÚBA – PRECIPITAÇÃO QUÍMICA E CORROSÃO   Moisés Santiago Ribeiro1; Fábio Henrique de Souza Faria2; Luiz Antônio Lima1;Silvânio Rodrigues dos Santos2; Marina Rosa de Jesus31Departamento de Engenharia, Universidade Federal de Lavras, Lavras, MG, [email protected] de Ciências Agrárias, Universidade Estadual de Montes Claros, Janaúba, MG3Graduanda em Geografia, Instituto Superior de Educação de Janaúba, Empresa de Pesquisa Agropecuária de Minas Gerais, Janaúba, MG  1 RESUMO A qualidade inferior das águas subterrâneas e a adoção de sistemas localizados de irrigação agravam os problemas de obstruções dos equipamentos. A avaliação da qualidade das águas com relação a precipitações e corrosão é fundamental para seu uso e manejo. Objetivou-se neste trabalho avaliar a qualidade das águas subterrâneas dos municípios de Janaúba e Jaíba com relação a estes problemas, utilizando o banco de dados de análises de águas do Centro Tecnológico Norte de Minas (CTNM), da Empresa de Pesquisa Agropecuária de Minas Gerais (EPAMIG), referente ao período de 1993 a2006. Foram analisadas as características físico-químicas das águas: pH, CE, Ca2+, Mg2+, Na+, HCO3-  e CO32- e calculados o índice de saturação do carbonato de cálcio (IS), índice de estabilidade (IE) e cálcio corrigido (Caº). Foram estimados o volume de ácido fosfórico (H3PO4) e clorídrico (HCl) para neutralização da alcalinidade da água em quimigação sistemática, a fim de evitar precipitação de CaCO3. Elevados teores de HCO3-, severamente restritivos, foram verificados em mais de 63% dos poços amostrados. Isto, associado à alta relação Ca2+/Mg2+, indica o precipitante sob a forma de CaCO3. Pelos valores médios de IS pouco acima de 0,3, e de 6,0 para IE, evidencia-se o caráter precipitante em mais de 85% das águas analisadas, porém próximo da neutralidade. Incrustações podem ser evitadas pela aplicação de HCl e H3PO4 em quimigação sistemática nas quantidades médias de 1,0 e 0,3 L m-3, respectivamente, para os municípios de Janaúba e Jaíba. UNITERMOS: carbonato de cálcio, pH, poço tubular, irrigação, entupimentos  RIBEIRO, M. S.; FARIA, F. H. de S.; LIMA, L. A. L.;SANTOS, S. R. dos; JESUS, M. R. de. EVALUATION OF UNDERGROUND WATER QUALITY FOR IRRIGATION IN JAÍBA AND JANAÚBA, MG, BRAZIL – CHEMICAL PRECIPITATION AND CORROSION  2 ABSTRACT The lower quality of groundwater and the adoption of micro irrigation systems make chemical obstructions of  systems possible. Water quality evaluation regarding precipitation and corrosion is crucial for its use and management. The objective of this work was to evaluate groundwater quality in the towns of Janaúba and Jaíba using water analysis database from CTNM/EPAMIG from 1993 to 2006. The following physical and chemical characteristics were analyzed: pH, EC, Ca2+, Mg2+, Na+, HCO3- and CO32 calcium carbonate saturation index (SR), stability index (SI) and corrected calcium (Caº). The volume of phosphoric and hydrochloric acid necessary for neutralization of water alkalinity through systematic chemigation was estimated to avoid calcium carbonate precipitation. High levels of severely restrictive bicarbonate were found in more than 63% of the sampled wells. This, added to high Ca2+/Mg2+ relation, indicates the precipitate in the form of calcium carbonate. SR values a little over 0.3and 6.0 for SI show the precipitating potential in more than 85% of the analyzed water samples, but close to neutrality. Incrustations can be avoided through application of phosphoric and hydrochloric acid through continuous injection in amounts varying from 1.0 to 0.3  L.m-3, respectively, for the towns of Janaúba and Jaíba. KEYWORDS: calcium carbonate, pH, well, irrigation, clogging

scholarly journals Effect of Divalent Cations (Cu, Zn, Pb, Cd, and Sr) on Microbially Induced Calcium Carbonate Precipitation and Mineralogical Properties

2021 ◽  
Vol 12 ◽  
Author(s):  
Yumi Kim ◽  
Sunki Kwon ◽  
Yul Roh
Keyword(s):  
Calcium Carbonate ◽  
Removal Efficiency ◽  
Metal Removal ◽  
Divalent Cations ◽  
Growth Media ◽  
Carbonate Precipitation ◽  
Calcium Carbonate Precipitation ◽  
Calcium Carbonates ◽  
Mineralogical Properties ◽  
Co Precipitation

Microbially induced calcium carbonate precipitation (MICP) is a bio-geochemical process involving calcium carbonate precipitation and possible co-precipitation of other metals. The study investigated the extent to which a urease-positive bacterium, Sporosarcina pasteurii, can tolerate a range of metals (e.g., Cu, Zn, Pb, Cd, and Sr), and analyzed the role of calcium carbonate bioprecipitation in eliminating these divalent toxicants from aqueous solutions. The experiments using S. pasteurii were performed aerobically in growth media including urea, CaCl2 (30 mM) and different metals such Cu, Zn, Pb, and Cd (0.01 ∼ 1 mM), and Sr (1 ∼ 30 mM). Microbial growth and urea degradation led to an increase in pH and OD600, facilitating the precipitation of calcium carbonate. The metal types and concentrations contributed to the mineralogy of various calcium carbonates precipitated and differences in metal removal rates. Pb and Sr showed more than 99% removal efficiency, whereas Cu, Zn, and Cd showed a low removal efficiency of 30∼60% at a low concentration of 0.05 mM or less. Thus the removal efficiency of metal ions during MICP varied with the types and concentrations of divalent cations. The MICP in the presence of divalent metals also affected the mineralogical properties such as carbonate mineralogy, shape, and crystallinity.

scholarly journals Co-Deposition Mechanisms of Calcium Sulfate and Calcium Carbonate Scale in Produced Water

Crystals ◽  
2021 ◽  
Vol 11 (12) ◽  
pp. 1494
Author(s):  
Yan Yan ◽  
Tao Yu ◽  
Huan Zhang ◽  
Jiayu Song ◽  
Chengtun Qu ◽  
...  
Keyword(s):  
Calcium Carbonate ◽  
Calcium Sulfate ◽  
Produced Water ◽  
Salt Crystallization ◽  
Mixed System ◽  
Pure Material ◽  
Material Deposition ◽  
Calcium Sulfate Scale ◽  
Co Precipitation ◽  
Calcium Carbonate Scale

Co-precipitation of mineral-based salts during scaling remains poorly understood and thermodynamically undefined within the water industry. This study focuses on investigating calcium carbonate and calcium sulfate mixed precipitation in scaling. Scaling is often observed in the produced water supply as a result of treatment processes. Co-precipitation results were compared with experimental results of a single salt crystallization. Several parameters were carefully monitored, including the electrical conductivity, pH value, crystal morphology and crystal form. The existence of the calcium carbonate scale in the mixed system encourages the loose calcium sulfate scale to become more tightly packed. The mixed scale was firmly adhered to the beaker, and the adhesion of the co-deposition product was located between the pure calcium sulfate scale and the pure calcium carbonate scale. The crystalline form of calcium sulfate was gypsum in both pure material deposition and mixed deposition, while the calcium carbonate scale was stable in calcite form in the pure material deposition. In the co-deposition, apart from calcite form, some calcium carbonate scale crystals had metastable vaterite form. This indicated that the presence of SO42− ions reduced the energy barrier of the calcium carbonate scale and hindered its transformation from a vaterite form to a calcite one, and the increase in HCO3− content inhibited the formation of calcium sulfate scale.

Scaling in domestic heating equipment: getting to know a complex phenomenon

2004 ◽  
Vol 49 (2) ◽  
pp. 129-136 ◽  
Author(s):  
H. Brink ◽  
P.G.G. Slaats ◽  
M.W.M. van Eekeren
Keyword(s):  
Drinking Water ◽  
Calcium Carbonate ◽  
Saturation Index ◽  
Carbonate Precipitation ◽  
Heating Equipment ◽  
Calcium Carbonate Precipitation ◽  
Domestic Heating ◽  
Scaling Properties ◽  
Langelier Saturation Index ◽  
Water Companies

Excessive scaling is one of the main nuisances in relation to the use of drinking water. Ever more water companies try to minimise scaling. Although scaling is an old problem, prediction of scaling has been proven to be very tricky. Traditionally, the (Langelier) Saturation Index is used to evaluate scaling properties of drinking water. From experience it is well known that this parameter is not suitable for proper prediction. New parameters have been developed and standardised for scaling prediction, namely the Calcium Carbonate Precipitation Potential, calculated at a temperature of 90°C (CCPP90); the Saturation Index, also calculated at a temperature of 90°C (SI90); the Nucleation Index (NI) and the Measured Calcium Carbonate Precipitation (MCCP). These parameters are currently successfully used in The Netherlands. The development of new parameters to predict scaling in domestic heating equipment has resulted in a better understanding of processes involved. Even now unexpected and at first sight contradictory results are obtained frequently. With the use of the developed measuring techniques, solutions may be found to combat excessive scaling.

Biotechnological Mineral Composites via Vaterite Precursors

2012 ◽  
Vol 1465 ◽  
Author(s):  
E. Weber ◽  
C. Guth ◽  
M. Eder ◽  
P. Bauer ◽  
E. Arzt ◽  
...  
Keyword(s):  
Calcium Carbonate ◽  
Organic Molecules ◽  
Organic Matrix ◽  
Stable Form ◽  
Ambient Conditions ◽  
Calcium Carbonate Precipitation ◽  
Mineral Phases ◽  
Mineralization Processes ◽  
Co Precipitation

ABSTRACTVaterite is one of the thermodynamically less stable polymorphs of calcium carbonate. Under ambient conditions it transforms into calcite, the most stable form of calcium carbonate. Organisms are able to stabilize minerals such as vaterite by means of organic molecules. The exact mechanisms how biomineralization proteins interact with metastable mineral phases are, however, less well understood. Many in vitro studies were performed using calcite as a model system. A deeper understanding of the interaction of organic molecules with metastable mineral phases would make them useful as a tool to control mineralization processes in vitro. In this study, we report on the co-precipitation of a natively soluble histidine-tagged GFP (green fluorecent protein) with a metastable vaterite phase and the subsequent insolubility of the fluorescent organic matrix in a 30μl calcium carbonate precipitation assay. The intrinsic fluorescence of GFP is conserved during the interaction with the mineral phase, indicating proper folding even in the insoluble state. This experiment can be extended to obtain deeper insights into some mechanistic models of biomineralization proteins by tracking native and modified GFP proteins microscopically during various stages of mineral precipitation and dissolution.

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