Amino Methylene Phosphonic Acid Research Articles

Synthesis and Study of Modified Polyaspartic Acid Coupled Phosphonate and Sulfonate Moieties As Green Oilfield Scale Inhibitors

The petroleum industry has strived for several years to explore environmentally friendly scale inhibitors with no acute environmental impact. Well-known industrial biodegradable polyaspartic acid is widely used as a potent scale inhibitor (SI) against various inorganic scales in industrial circulating cooling water and topside petroleum applications. However, polyaspartic acid showed weak thermal stability at the petroleum reservoir temperatures. Here, we attempt to develop a new class of polyaspartic acid for squeeze treatment applications under harsh conditions. In this project, a series of modified polyaspartic acid, including pendant anionic functional moieties (phosphonate and sulfonate) were synthesized and investigated as new SIs to inhibit the calcium carbonate (calcite, CaCO3) and barium sulfate (barite, BaSO4) scales under oilfield conditions. These classes were synthesized via aminolysis of polysuccinimide with nucleophilic amine reagents under alkaline conditions. The products are polyaspartic acid-capped aminomethylene phosphonic acid (SI-2), polyaspartic acid-capped bisphosphonic acid (SI-3), polyaspartic acid-capped aminomethanesulfonic acid (SI-4), and polyaspartic acid-capped aminoethanesulfonic acid (SI-5), as well as in-house synthesized polyaspartic acid (SI-1). The scale inhibition activities of these compounds against carbonate and sulfate scales were determined using the dynamic scale loop test at 100 °C and 80 bar. Furthermore, the long-term thermal aging and calcium tolerance experiments were also investigated. It was found that polyaspartic-acid-capped aminomethylene phosphonic acid (SI-2) gave outstanding calcite scale inhibition performance and showed excellent thermal stability at 130 °C for 7 days compared to SI-1 and other modified SIs (SI-3-SI-5). This phosphonated polymer also exhibited superior calcium tolerance performance with Ca2+ ions up to 100 ppm, and moderate performance in the range of 1000–10 000 ppm calcium ions. This project highlights the success of designing and developing a new environmentally friendly calcite SI-based polyaspartic acid under harsh oilfield conditions.

Ion Exchange Treatment of Cobalt Acetate Solutions to Remove Iron(III) Impurity

The possibility of removing an iron(III) impurity from cobalt acetate solutions by sorption was examined. Among a number of tested ion exchange resins with various functional groups (Purolite С150 sulfonic cation exchange resin, Purolite А500 strongly basic anion exchange resin, complexing ion exchange resins Purolite S930 with iminodiacetate and Purolite S950 with aminomethylenephosphonic acid groups, Purolite S957 cation exchange resin containing phosphonic and sulfonic acid groups simultaneously), only the ion exchange resins containing phosphonic acid groups, namely, Purolite S950 amphoteric resin and Purolite S957 cation exchange resin, are capable of the iron(III) sorption, with the latter resin showing considerably higher performance. The iron(III) distribution coefficients in sorption on these resins reach a maximum at рН 3.8–5.1. When passed through a column packed with Purolite S957 cation exchange resin, cobalt acetate solutions containing 40.6 and 57.2 g L–1 Co and 21 and 24 mg L–1 Fe undergo deep iron removal to its residual concentration no higher than 1.0–1.5 mg L–1. The sorbed iron(III) is virtually completely eluted from the cation exchange resin with 9 column volumes of 1.5 М sulfuric acid containing 10 g L–1 ascorbic acid after the resin pretreatment with an ascorbic acid solution.

Magnetite nanoparticles with aminomethylenephosphonic groups: synthesis, characterization and uptake of europium(III) ions from aqueous media.

Two adsorbents with covalently bound aminomethylenephosphonic acid functions (and referred to as MNPs/AMPA and MNPs/SiO2-AMPA) were synthesized from two types of amino-functionalized magnetic nanoparticles (MNPs) via Moedritzer-Irani reaction. The sorbents with anchored dopamine ligand (MNPs/dopa) or aminopropyl groups (MNPs/SiO2-NH2), and the MNPs/AMPA were characterized by X-ray diffraction, FTIR, transmission electron microscopy and vibrating sample magnetometry. Surface modification does not adversely impact the physical properties of the starting magnetite. Compared to the size of the unmodified Fe3O4 (magnetite) nanoparticles (7-12nm), the average size of functionalized nanoparticles is increased to 10-16nm. Similarly, the magnetic saturation decreased from 67.5emu g-1 to 42.0emug-1, and the surface area is increased up to 205 m2g-1 for MNPs/SiO2-AMPA. The kinetics of the adsorption of Eu(III) on the sorbent is ultra-fast, and equilibria are attained within 5-10min at room temperature. The adsorption kinetics can be described by a pseudo-second-order model. Adsorption and desorption conditions were tested with respect to the removal of Eu(III) ions from water solution. The adsorption capacities for Eu(III) at pH7.0 are 77mgg-1 and 69mgg-1 for MNPs/AMPA and MNPs/SiO2-AMPA nanoparticles, respectively. Eu(III) was quantified by ICP-MS. The limit of detection (LOD) for Eu(III) is 0.05ngL-1 (based on the 3σ criterion), with an enrichment factor of 150. The selectivity over ions such as Tb(III), Fe(III), Zn(II), Cu(II), and Ca(II) ions was studied. Under optimal condition the distribution coefficient for Eu(III) relative to these ions is near 105mLg-1. The sorbents can be easily retrieved from even large volumes of aqueous solutions by magnetic separations. The method was tested for spiked water samples (with recoveries from 96.6-102.5%) and for rock minerals. Graphical abstract A schematic showing the regeneration of magnetite nanoparticles (MNPs), core-shell (MNPs/SiO2), and the structures with covalently bonded aminomethylenephosphonic acid (AMPA) after preconcentration of Eu(III) from largewater sample volumes onto a small specimen.

Phosphonate-stabilized silver nanoparticles: one-step synthesis and monolayer assembly

The first case of phosphonic acid terminated, environmentally friendly silver nanoparticles (NPs) is described. The NPs are produced by a simple one-step synthesis using commercially available reagents, furnishing stable, rather monodisperse, size-controlled, aqueous-based Ag NPs, stabilized by aminomethylene phosphonic acid (AMP) molecules. In this synthesis the commercial reagent ethylenediamine tetra(methylene phosphonic acid) (EDTMP) serves as a reducing agent for Ag+ ions, while its oxidation product AMP is the stabilizer of the generated Ag NPs. The negatively charged, phosphonate-stabilized NPs were characterized by UV-vis spectroscopy, transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Variation of the EDTMP/AgNO3 molar ratio enables simple and efficient control of the average particle diameter in the range ∼5.5 to 15 nm. The AMP-stabilized Ag NPs are stable in water under an inert atmosphere for at least 2 months with no observed aggregation. Self-assembled layers of phosphonate-coated Ag NPs were prepared on substrates primed with positively charged molecular self-assembled monolayers (SAMs) or with polyelectrolyte (PE) layers. The NP films were studied by UV-vis spectroscopy, polarization modulation Fourier-transform infrared reflection-absorption spectroscopy (PM-IRRAS), and high-resolution scanning electron microscopy (HRSEM). While NP monolayers commonly undergo extensive aggregation upon drying, the present phosphonate-stabilized Ag NP monolayers display homogeneously dispersed, mostly isolated NPs over large areas after adsorption and drying. The NP distribution and degree of aggregation can be modulated by the substrate type (gold, glass), the colloid solution pH, the nature of the primer layer (charged molecules, PEs), and the surface charge density. Phosphonate-terminated Ag NPs provide unique physical and chemical properties, including a negatively charged surface in a wide pH range, long-term stability, size control, and the possibility of participating in electrostatic and coordination binding processes.

Synthesis of Amino Methylene Phosphonic Acid Resin-Supported Hydrated Cerium Oxide Hybrid Sorbent and its Application in Drinking Water

The hydrated cerium oxide (CeH) was synthesized and it was loaded on amino methylene phosphonic acid resin (APAR) to form the hybrid adsorbent CeH-APAR. The structure and thermal properties of CeH-APAR were tested by FTIR and TGA. And then, it was investigated that pH values and temperatures affected the adsorption property of CeH and CeH-APAR for fluoride ion. The results showed that CeH-APAR hybrid sorbent formed by Ce4+ and APAR with coordination bond is relatively stable below 270°C. Its adsorption property is similar to that of CeH, i.e. it is less affected by pH value, so it can be used in a wide pH range. Besides, under a stable pH, adsorption capacity of CeH-APAR also increases along with increasing temperature. As a result, it is a temperature-controlled sorbent and belongs to chemical adsorption.

Adsorption behavior and mechanism of amino methylene phosphonic acid resin for Ag(I)

The sorption properties of amino methylene phosphonic resin(APAR) for Ag(I) were studied. The amino methylene phosphonic acid resin(APAR) has a good adsorption ability for Ag(I) at pH=6.0 in the HAc-NaAc medium. The statically saturated adsorption capacity is 272 mg/g resin, Ag(I) adsorbed on APAR can be eluted by 5% (NH 2) 2CS-0.5 mol/L hydrochloric acid quantitatively. The adsorption rate constants determined under various temperatures are k 15°C=3.89 × 10 −5S −1, k 25°C=5.93 × 10 −5S −1, k 35°C=7.59 × 10 −5S −1, k 45°C=9.45 × 10 −5S −1, respectively. The apparent activation energy of adsorption, E a is 22.8 kJ/mol, the enthalpy change (Δ H) of sorption is 17.4 kJ/mol. The adsorption mechanism shows that the functional group of APAR coordinates with Ag(I) to form coordination bond, the coordination molar ratio of the functional group of APAR to Ag(I) is 1:1.

An atomic force microscopy and molecular simulations study of the inhibition of barite growth by phosphonates

The effect of five phosphonic acids (hydroxyethylene diphosphonic acid, HEDP; nitro trimethyl phosphonic acid, NTMP; methylene diphosphonic acid, MDP; amino methylene phosphonic acid, AMP; and sodium phosphonobutane tricarboxylic acid, PBTC) on the growth of the barite(0 0 1) face has been investigated using atomic force microscopy (AFM). Experimental data have been obtained by in situ measurements of the velocities of barite monomolecular steps growing from solutions with different concentrations of each phosphonic acid. Adsorption isotherms, constructed by plotting individual monomolecular step rates versus inhibitor concentrations, indicate a Langmuir adsorption mechanism in the range of concentrations from 0.5 to 10 μmol/l. Both affinity constants calculated from adsorption isotherms and measurements of growth rates of barite monomolecular steps as a function of inhibitor concentration allowed us to give the following ranking of inhibitor effectiveness: PBTC > NTMP > MDP > HEDP ≫ AMP. Molecular simulations of the interaction of the phosphonic acids with barite(0 0 1) surfaces indicate that only kink sites along monomolecular steps can be considered as possible inhibition sites. This is in agreement with the AFM observations and measurements.

Sorption behavior and mechanism of indium(III) onto amino methylene phosphonic acid resin

The sorption behavior of amino methylene phosphonic acid resin (APAR) for In(III) was investigated. Experimental results show that In(III) adsorbed on APAR can be eluted with 2mol·L−1 HCl. The apparent rate constant is k298=1.50×10−5s−1. The sorption behavior of APAR for In(III) obeys the Freundlich isotherm. The thermodynamic parameters of sorption, enthalpy change ΔH, free energy change ΔG and entropy change ΔS of sorption (APAR) for In(III) are 24.1kJ·mol−1, −35.1kJ·mol−1 and 200J·mol−1·K−1, respectively. The coordination molar ratio of the functional group of APAR to In(III) is 2∶1. The sorption mechanism of APAR for In(III) was examined by IR spectrometry.

A new photopolymerization system for vinyl monomers

AbstractA mixture of Ce+3 salt and an aminomethylene phosphonic acid, such as amino tri(methylene phosphonic acid) (ATMP), diethylene triamine penta(methylene phosphonic acid), N,N‐di(methylene phosphonic acid) ethanol amine, N,N‐di(methylene phosphonic acid)‐N‐methylamine, N‐oxo‐N,N,N‐tri(methylene phosphonic acid), or 1‐hydroxy‐ethylidene‐1,1‐diphosphonic acid, was used for the photopolymerization of acrylonitrile, vinyl acetate, acrylic acid, and styrene in water. Molecular weights of the polymers decreased with increasing concentration of both Ce+3 salt and ATMP. The effect of oxygen, light, pH, and the addition order on polymerization were also studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2494–2499, 2002

Low molecular weight polyacrylic acid with pendant aminomethylene phosphonic acid groups

Low molecular weight poly(acrylic acid-co-vinyl aminomethylene phosphonic acid)s were prepared by consecutively applying the Hofmann degradation and the Mannich reaction to polyacrylamide and poly(acrylamide-co-acrylic acid)s. 1H-NMR, 31P-NMR, and microanalysis were used for structural analyses. These polymers were tested as anti-scalent and they showed better anti-scalent effect than commercial poly(acrylic acid)s. The scale inhibition properties of copolymers increased with increasing amount of aminomethylene phosphonic acid groups. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 870–874, 2000

Aminomethylene phosphonic acid–ceric ion redox systems for aqueous polymerization of vinyl monomers

Aminomethylene phosphonic acids, such as amino tri(methylene phosphonic acid) (ATMP), 1-hydroxy-ethylidene-1,1-diphosphonic acid (HEDP), diethylene triamine penta(methylene phosphonic acid) (DTPMPA), N, N-di(methylene phosphonic acid) ethanol amine (DMPEA), N, N-di(methylene phosphonic acid)- N-methylamine (DMPAMA), N-oxo- N, N, N-tri(methylene phosphonic acid) (OTMPA), and ceric ammonium nitrate redox systems are used for the polymerizations of acrylonitrile, vinyl acetate, acrylic acid and acrylamide. The effects of concentration of ceric ion and aminomethylene phosphonic acid on the yield and molecular weight show that oxidative termination reaction becomes important at higher ceric concentration and considerable chain-transfer reaction occurs at higher ATMP concentration. The redox reaction in the complex of ceric ion and ATMP forms a primary radical on an ATMP molecule, which in turn initiates polymerization to give polymer containing amino tri(methylene phosphonic acid) chain end.

Complexes of Aminoalkylphosphonic Acids and Phosphonodipeptides with Pt(II) and Pd(II)

Abstract Complexing properties of aminomethylenephosphonic acid and dipeptides glycyl-aminomethylenephosphonic acid and both diastereoisomers of (S)-methionyl-1-aminoethylphosphonic acid with Pt(II) and Pd(II) were investigated pH-metrically at 25 °C and at ionic strength of 0.1 mol dm−3 (KNO3). The stability constants calculated indicate formation of the complexes with a metal: ligand molar ratio of 1 : 1 and 1 : 2. The differences found for diastereoisomers are much higher than for systems with common dipeptides. Distribution of all species found by potentiometry were confirmed by 31P and 1H NMR titrations.

Thermal Decomposition of EDTA, NTA, and Nitrilotrimethylenephosphonic Acid in Aqueous Solution

The decomposition of ethylenediaminetetraacetic acid (EDTA) in water solution at 200 and 260 °C, nitrilotriacetic acid (NTA) at 260 and 293 °C, and of nitrilotrimethylenephosphonic acid (NTPO) at 260 °C was studied by n.m.r. as a function of time at pH 9.5 and decomposition rates and products were determined. The primary (fast) decomposition reaction of EDTA involves the hydrolytic cleavage of the ethylenic C—N bond to produce the relatively stable pair: N-(2-hydroxyethyl)iminodiacetic acid and iminodiacetic acid. NTA does not cleave below 260 °C but decomposes at about 290 °C and above through a stepwise decarboxylation reaction. NTPO cleaves hydrolytically at 260 °C at two C—N bonds to produce aminomethylenephosphonic acid and 2 mol of hydroxymethylenephosphonic acid. The further breakdown of the primary products of EDTA at higher temperatures occurs by the loss of carbon dioxide producing the corresponding methylamines, concomitantly with the hydrolytic cleavage of the remaining CH2CH2—N bond giving ethylene glycol. The pseudo first order rate constant kobs for NTA decarboxylation at 293 °C and pH 9.3 is 0.19 ± 0.01 h−1. The value of kobs for EDTA hydrolysis at 200 °C is 1.4 ± 0.2 h−1.