METHOD OF ISOLATION OF ARN ACIDS FROM NAPHTHENATE DEPOSITS

Abstract

Naphthenate deposition is formed from tetraprotic naphthenic acids having aliphatic chains and high molecular weight, provided with four carboxylic terminations, sometimes called ARN acids. Obtaining these species from their matrix of origin requires the prior use of sample preparation methods aiming at an efficient extraction of naphthenic acids. Obtaining ARN acids from naphthenate deposits is advantageous in the potential for reusing waste and reducing environmental damage. The process also adds value to waste materials from the oil production and exploration process.

The present invention relates to the field of laboratory-scale sample preparation, which describes a methodology for the specific isolation of tetraprotic naphthenic acids, called ARN acids, from residual naphthenate deposits from petroleum production.

The method consists of cleaning the naphthenate deposit, converting the naphthenate salts to naphthenic acids and isolating the ARN acids from the other organic acids, using a silica-based sorbent material with aminopropyl functional groups, previously selected for an efficient elution of different functional groups and polarities.

The results of ESI(−)-FT-ICR MS showed that the methodology is promising because it provided an excellent separation by difference in polarity and as a function of different molecular weight ranges, thus reducing the complexity of the organic acid extract obtained from the naphthenate deposit. Furthermore, it allowed the separation of the different acidic species that were present in the sample. The results of ESI(−)-FT-ICR MS also indicated that one of the fractions concentrated into ARN acids, including discharged species and especially ARN acids in the form of monocharged ions. The ESI(−)-Orbitrap MS data corroborated those obtained by ES(−)-FT-ICR MS, making consistent the statement that the extract obtained from the naphthenate deposit contains a mixture of acids and that the fractionation developed provided the isolation of ARN acids from naphthenate deposits. Furthermore, the integrations of the .sup.1H NMR spectra of acidic fractions as a function of molecular weight highlighted the expressive presence of alkyl compounds and absence of aromatic hydrogens in the fraction of interest.

Claims

1-6. (canceled)

7. A method for isolating high molecular weight, tetraprotic naphthenic acids (ARN acids) from naphthenate salt deposits formed during petroleum production, comprising the steps of: (i) cleaning the naphthenate salt deposit to remove residual crude oil; (ii) converting a portion of the naphthenate salts to naphthenic acids; and (iii) isolating the ARN acids from the naphthenic acids.

8. The method according to claim 7, wherein the naphthenate deposit is cleaned with an organic solvent in step (i).

9. The method of claim 8, wherein the organic solvent is toluene, dichloromethane, methanol, or a combination thereof.

10. The method according to claim 7, wherein a portion of the naphthenate salts are converted to naphthenic acids by exposing the naphthenic salts to an aqueous acid in step (ii).

11. The method of claim 10, wherein the aqueous acid is acetic acid, hydrochloric acid, nitric acid, phosphoric acids, or a combination thereof.

12. The method according to claim 7, wherein step (iii) comprises using an ion exchange mechanism to isolate the ARN acids from the naphthenic acids by exposing the naphthenic acids to an aminopropyl group-functionalized, silica-based sorbent material; and eluting the ion exchange mechanism with eluents to collect the naphthenic acids in separate eluates according to differences in polarities and as a function of molecular weights, wherein at least one of the eluates comprises ARN acids.

13. The method of claim 12, wherein the eluent for eluting the eluate comprising ARN acids is 100:5 (v/v) methanol: formic acid.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The embodiment of the invention can be better explained and understood by reference to the attached drawings, in a schematic and non-limiting way to the inventive scope, and the following description:

[0024] FIG. 1A attached shows the naphthenate deposit cleaning system, which is comprised of: (1) heating blanket, (2) borosilicate glass, round-bottomed balloon with short neck, (3) organic solvent to remove residual oil, (4) borosilicate glass Soxhlet extractor, (5) borosilicate glass extraction and reflux tube (6) borosilicate glass Allin cake condenser.

[0025] FIG. 1B attached shows the solid phase extraction system consisting of (7) manifold system (it must be more specific), (8) solid phase extraction cartridge with silica-based sorbent material with aminopropyl functional groups and (9) air pump.

[0026] FIG. 1C attached shows the process of obtaining the extraction of organic acids by liquid/solid extraction.

[0027] FIG. 1D attached presents the sequence of elutions for the specific isolation of ARN acids from other naphthenic acids, present in the extract recovered from the acidification of the naphthenate deposit.

[0028] FIG. 1E shows the main acidic sub moieties (SF1-SF4) obtained in the sequence of elutions.

[0029] FIG. 2 attached shows the FT-IR spectra of the acid extract recovered from the acidification of the naphthenate deposit and its main sub moieties (SF1-SF4).

[0030] FIG. 3 shows the .sup.1H NMR spectra of naphthenic acid extract from calcium naphthenate deposit and its main sub moieties (SF1-SF4). The expansions show signs in the regions between 2.1 and 2.5 ppm, characteristic of hydrogens adjacent to carbonylcarboxylic acids. The inserted structure corresponds to an ARN acid already described by Lutnaes et al. (2006).

[0031] FIG. 4A shows the ESI(−)-FT-ICR MS spectra of acid extract recovered from the acidification of the naphthenate deposit.

[0032] FIG. 4B shows the main sub moieties (SF1-SF4) from FIG. 4A.

[0033] FIG. 5A shows the ESI(−) Orbitrap MS spectra of acid extract recovered from the acidification of the naphthenate deposit.

[0034] FIG. 5B shows the main sub moieties (SF1-SF4) from FIG. 5A.

[0035] FIG. 6A shows the DBE abundance distribution diagram versus the carbon number (NC) for the highlighted classes (O.sub.4[H] and O.sub.8[H]) of the extract of acids recovered from the acidification of the naphthenate deposit and its main sub moieties (SF1-SF4) identified by ESI(−)-FT-ICR MS.

[0036] FIG. 6B shows the DBE abundance distribution diagram versus the carbon number (NC) for the highlighted classes (O.sub.4[H] and O.sub.8[H]) of the extract of acids recovered from the acidification of the naphthenate deposit and its main sub moieties (SF1-SF4) identified by ESI(−) Orbitrap MS.

DETAILED DESCRIPTION

[0037] The present document shows a specific method for isolating ARN acids from other naphthenic acids that may be in naphthenate deposits from oil production.

[0038] The process comprises three steps: (i) cleaning the naphthenate deposit, submitting the deposit to an organic solvent to remove residual oil. In this step, the deposit is washed with an organic solvent, or a sequence of solvents repeated several times until the solvent color remains constant and clear. Here the suggested solvents are toluene, methylene chloride, methanol or any other light hydrocarbon capable of solubilizing the crude oil for its removal.

[0039] (ii) conversion of naphthenate salts to acids exposing the clean deposit to an aqueous acid and an organic solvent for the conversion of naphthenate salts to naphthenic acids. The solutions can be mixed directly into the deposit, such as sequentially where the acidic solution is first mixed into the deposit and then the acids are recovered by extraction with the organic solvent. It is important that the volumetric ratio between the two solutions is sufficient so that the free acid monomers remain dissolved in the organic phase (acid extract), leaving the counterions in the aqueous phase. Here the suggested acids are acetic acid, hydrochloric acid, nitric acid or phosphoric acid and possible organic solvents toluene, methylene chloride or any other light hydrocarbon capable of solubilizing and recovering the extracted acids.

[0040] (iii) the isolation of ARN acids occurs through an ion-exchange mechanism, which occurs exposing the acid extract to a silica-based sorbent material with aminopropyl functional groups. Importantly, the material works very well in retaining polar ions and separating structural isomers. Silica-based sorbents with aminopropyl functional groups are weaker ion exchangers than quaternary amine sorbents and are ideal for interacting with strongly acidic analytes or with multiple acidic groups. In addition, silica-based sorbent material with aminopropyl functional groups can be found commercially in one or more aspects and can be applied as the filling of a solid phase extraction column.

[0041] The sequence of elutions by polarity difference, FIG. 1D, wherein the first three initial steps refer to column preparation and sample introduction: (i) conditioning the column with 5-50 mL of methylene chloride; (ii) addition of the sample, which consists of acid extract (100-600 mg) dissolved in approximately (10-30 mL) methylene chloride; (iii) 5-20 minutes break for column activation.

[0042] The next four elutions refer to the cleaning step and the removal of neutral and moderately acidic species, which are not part of the scope: (iv) elution of 10-50 mL with methylene chloride; (v) elution with 10-50 ml methylene chloride and methanol solution (1:1 v/v); elution with 10-50 mL methanol; (vii) elution with 10-50 mL of methanol and water solution (70:30 v/v).

[0043] The separation of naphthenic acids according to the different molecular weight ranges occurs in the next four elutions, and consequently enables the isolation of ARN acids: (viii) elution with 10-50 mL methanol, water and formic acid solution (70:30:5 v/v); (ix) elution with 10-50 mL methanol, water and formic acid solution (80:20:5 v/v); (x) elution with 10-50 mL methanol, water and formic acid solution (90:10:5 v/v) and; (xi) elution with 10-50 mL methanol and formic acid solution (100:5 v/v).

[0044] The four eluates obtained, in steps viii, ix, x and xi, correspond to the acidic sub moieties, successfully separated as a function of molecular weight, which comprised the extract of acids recovered from the calcium naphthenate deposit. Of these, it is in the fourth sub moiety (xi) that ARN acids are safely concentrated.

[0045] To obtain a concentrated sample, the eluate can be further evaporated for solvent removal and acid recovery.

EXAMPLES

Example 1—Investigation of Acidic Species Present in a Calcium Naphthenate Deposit

[0046] The novel methodology for the isolation of ARN acids by separating naphthenic acids from calcium naphthenate deposits allowed the following results to be achieved.

[0047] The cleaning of the deposit was carried out with the aid of a Soxhlet coupled to a condenser (FIG. 1A), under repeated washes with toluene and dichloromethane, resulted in a mass of approximately 4.1 g of clean, dry deposit (˜20% m/m recovery). And from that clean deposit mass, 1.9 g of organic acid extract were obtained, which corresponds to a yield close to 47.7% m/m.

[0048] The organic acid extract was subjected to solid phase extraction, using a manifold and a commercial ion exchange column Mega Bond Elut-NH2 (2 g×12 mL, Agilent Technologies, USA) supplied by Agilent), as shown in FIG. 1B, producing four main acidic sub moieties (SF1-SF4) obtained from the elution sequence, FIG. 1E.

[0049] The FT-IR spectra (FIG. 2) revealed important and common signs to the sub moieties, which were attributed to the major presence of carboxylic acids, revealed by intense bands close to 1,705 cm.sup.−1 referring to elongations of linkages C═O and bands in 2,915, 2,850 and 1,450 cm.sup.−1 attributed to C—H elongations of C—H groups CH.sub.2 and CH.sub.3. However, at wavelengths less than 1,500 cm.sup.−1 attributed to the fingerprint region, fundamental transitions occur with numerous different elongations.

[0050] The FTIR spectra of the SF1, SF2 and SF3 moieties reveal a set of bands (940, 730 and 690 cm.sup.−1) typical of aromatics, which were not observed for the organic acid extract and for the SF4 sub moiety.

[0051] The SF4 still differs from the others by the strong and wide band at 3,420 cm.sup.−1, which indicates a high concentration of acids, and at 1,040 cm.sup.−1 which are associated with C—O vibrations of carboxyl groups.

[0052] .sup.1H NMR spectra (FIG. 3) reveal some differences between the spectrum of origin (acid extract or organic extract) and fractionated samples. It is noted that the region of total aliphatic hydrogens (H.sub.5), chemical shift (8) between 0 and 4 ppm, present the greatest number of signals, with emphasis on the region between 0.7 and 1.4 ppm attributed to overlapping of methyl and methylene groups. Signals corresponding to carboxylic acid protons should appear in the range of 10.0 to 14.0 ppm, but hydrogen bonds cause the signal to broaden, making it difficult to visualize and integrate. Such sign was only observed in the organic extract. However, hydrogens adjacent to carboxyl of carboxylic acids can be identified by signs between 2.1 to 2.5 ppm.

[0053] The structural detailing of the aliphatic hydrogens presents in the naphthenic acid extract of its main sub moieties indicated that, in all samples, the aliphatic predominance (with values greater than 88.4% mol for SF1 and greater than 91% mol for the other samples). The results highlight a structural diversity between the samples due to the variation of different hydrogen species, where the major presence of H.sub.p, in all samples, indicates the existence of branches confirming the complexity of the structures.

[0054] The predominance of H.sub.6 and H.sub.y in the naphthenic acid extract from calcium naphthenate deposit and the SF2 and SF3 sub moieties suggest that the compounds have long chains and greater number of substitutions.

[0055] On the other hand, it is possible to observe a higher proportion of H.sub.β and H.sub.α in sub moieties SF1 and SF4. However, they differ by the absence of aromatic hydrogens in the SF4 sub moiety, while the SF1 sub moiety has aromatic hydrogen content (11.7% mol) which is higher than the values of the other samples.

[0056] These results corroborate the FTIR results, as they indicate that the SF4 sub moiety is different from the others, due to the absence of aromatics and reduced number of substitutions (revealed by the H.sub.α content, 23.2% mol).

[0057] The ESI(−)-FT-ICR MS spectra are shown in FIG. 4A. The results reveal that classes O.sub.4[H] and O.sub.8[H] are predominant in the extract recovered from the acidification of the naphthenate deposit, concentrating in three regions that appeared in the spectrum: (i) with a Gaussian profile of m/z 200-600, attributed to a mixture of compounds with a predominance of class O.sub.4[H], which can be attributed to dimer species formed by the self-association of naphthenic acids, which have the same DBE as their constituent monomers (class O.sub.2); (ii) with m/z in the range 610-640, attributed to double-charged ions of type [MH].sup.−2, ARN.sup.−2, resulting from the deprotonation of two groups of the four carboxylic groups of the tetraprotic acid that originated it (ARN) and further; (iii) with m/z 950-1,300, attributed to monocharged ions of the type [M-H].sup.−1 (ARN.sup.−1), formed by the deprotonation of only one carboxylic group of the acid of origin.

[0058] FIG. 4B shows the ESI(−)-FT-ICR mass spectra of the sub moieties obtained from the submission of the acid extract, recovered from the acidification of the naphthenate deposit, to the ion exchange resin. It is possible to observe that the first spectra corresponding to the first two sub moieties (SF1 and SF2) presented typical gaussians of naphthenic acids that were separated as a function of their molecular mass. While the SF3 sub moiety presents a gaussian profile referring to a mixture of acids. On the other hand, sub moiety 4 showed a spectrum with predominance of acidic species of higher molecular weight, typical of ARN acids.

[0059] The high resolution and mass precision given by ESI(−)-FT-ICR MS provided the detailed identification and differentiation of the species present in the sample. Thus, in the SF4 sub moiety, single charge ions were identified [C.sub.81H.sub.142O.sub.8—H].sup.−1, [C.sub.81H.sub.144O.sub.8—H].sup.−1 and [C.sub.71H.sub.124O.sub.8—H].sup.−1 under the respective m/z 1,242.062480, 1,244.07806 and 1,103.92154, as the most abundant. While the most abundant double charged ions identified were [C.sub.81H.sub.141O.sub.8-2H].sup.2−, [C.sub.81H.sub.143O.sub.8-2H].sup.2− and [C.sub.80H.sub.141O.sub.8-2H].sup.0 with m/z 620.52781, 621.53558 and 614.52782, respectively. It was also possible to observe the series of natural tetra-acid, C.sub.8, described by Lutnaes et al. (2006).

[0060] Detailed acid speciation revealed hydrocarbon skeletons between C.sub.65 and C.sub.76 with DBE of 8 and 9 of double charged species. Among the ions of lower molecular weight, it was further identified the double charged ions in SF4 sub moiety [C.sub.70H.sub.122O.sub.8-2H].sup.2− and [C.sub.71H.sub.124O.sub.8-2H].sup.2− (m/z 544.44980 and 551.45745) and the monocharged ions [C.sub.70H.sub.122O.sub.8—H].sup.−, [C.sub.71H.sub.124O.sub.8—H].sup.− and [C.sub.72H.sub.126O.sub.8—H].sup.− (m/z 1,089.90584, 1,103.92154 and 1,117.93715) to which correspond the homologous series C.sub.70H.sub.121O.sub.8, C.sub.71H.sub.123O.sub.8 and C.sub.72H.sub.125O.sub.8, which was also identified by Juyal et al. (2015) in deposits of calcium naphthenates from oil fields in the South America.

[0061] The ESI(−) Orbitrap MS spectra are shown in FIG. 5A and FIG. 5B. Note that the spectral profiles are similar to those obtained by ES(−)-FT-ICR MS, making consistent the statement that the naphthenic acid extract sample from the calcium naphthenate deposit contains a mixture of acids which were separated according to their molecular weight allowing the isolation of ARN acids from naphthenate deposits.

[0062] Molecular structures can be related to the number of non-saturations present represented by DBE (number of rings and double bonds), calculated from equation (1) (MCLAFFERTY and TURECEK, 1993):

[00001]$\begin{array}{cc}\mathrm{DBE}=C-\frac{H}{2}+\frac{N}{2}+1& \left(1\right)\end{array}$

where C, H and N represent, respectively, the number of carbons of hydrogen and nitrogen present in the molecular formula of a compound.

[0063] Thus, there is a significant similarity of the graphs generated between ESI(−)-FT-ICR MS (FIG. 6A) and ESI(−) Orbitrap MS (FIG. 6B).

[0064] Note that the first two moieties (SF1 and SF2) have mostly class O.sub.4 compounds, the third sub moiety (SF3) concentrates compounds of double charged species, which were even present in three moieties (SF2, SF3 and SF4), such as the ion [C.sub.81H.sub.140O.sub.8-2H].sup.−2 of m/z 620.52758, resulting from the deprotonation of two groups of the four carboxylic groups of the ARN acid that originated it, C.sub.81H.sub.140O.sub.8. While the fourth sub moiety (SF4), in addition to presenting these recharged species, is highlighted by presenting predominantly long carbon chains (above C.sub.70) and especially for class O.sub.8 (class of ARN acids) with domain for chains with 80 carbons and DBE close to 12.