Chemistry and Technology of Fuels and Oils, Vol. 48, No. 4, September, 2012 (Russian Original No.

4, July-August, 2012)

RESEARCH

THERMODYNAMIC PARAMETERS OF CONVERSION REACTIONS OF SOME HEAVY OIL COMPONENTS UNDER THE ACTION OF STEAM AND HEAT

V. A. Lyubimenko, N. N. Petrukhina, B. P. Tumanyan, and I. M. Kolesnikov

The mechanism of the reactions of conversion of heavy oil components, viz., heteroatomic compounds and polycyclic aromatic hydrocarbons, under conditions of steam and thermal action on the oil reservoir is studied. Based on the calculation of the thermodynamic parameters of the reactions, conclusions are drawn regarding the feasibility of the reactions and the primary directions of conversion of heavy oil components at the steam and thermal action temperature. The possibility, in principle, of occurrence of hydrogenolysis, hydrogenation, and hydrocracking in the presence of such hydrogen donors as polycyclic naphthenic-aromatic hydrocarbons and formic acid in the reaction system is demonstrated. Key words: heavy oil, native asphalts, steam and thermal action, steam and gravity drainage, Gibbs energy, aquathermolysis, hydrolysis, hydrogen donor. Russia possesses substantial reserves of native asphalts - variously predicted to range from 30 to 75 billion tons [1], of which the recoverable reserves, even at very low recovery factors, exceed 1 billion tons [2]. More than 500 heavy crude oil deposits are concentrated in the Volga-Ural oil- and gas-bearing province [3]. The total recoverable reserves of heavy crude oils in this province comprise more than 660 million tons. Note that the major part (97%) of these oils is high-sulfur. These deposits cannot be recovered by traditional means, which makes search for economically efficient techniques of heavy oil and native asphalt recovery an urgent task. Steam-thermal action (STA) on the reservoir, such as cyclic, area, steam-gravity drainage, etc., is well studied and used widely [4]. Steam injected into the reservoir is not only an effective heat carrier and a displacing agent, but also leads to chemical conversion of the crude oil. This is confirmed by comparative studies of the physicochemical properties of native oil and the oil ____________________________________________________________________________________________________ I. M. Gubkin Russian State University of Oil and Gas. Translated from Khimiya i Tekhnologiya Topliv i Masel , No. 4, pp. 27 33, July August, 2012. 292 0009-3092/12/48040292 2012 Springer Science+Business Media, Inc.

recovered by STA [5]: these specimens differ in density, fractional and group composition, IR spectral characteristics, content of heteroatoms, etc. In modeling STA in a flow-type reactor [6], resin-asphaltene components, in particular, were shown to undergo transformation with increase in oil content in the transformed material. Modeling of hydrothermal transformations of asphaltenes of native asphalt in hydrogen and steam helped detect considerable increase in radical paramagnetism [7]. The content in the aqueous phase of products of reaction of hydrocarbons and oxygen-containing compounds as well as redistribution of group components of native asphalt upon hydrothermal transformation makes it possible to suggest that asphaltene degradation occurs at alkyl substituents containing carbon-heteroatom bonds [6-8]. This is corroborated by slightly lower values of the energy of the C-S and C-O bonds in sulfides and ethers than the energy of the C-C bond [9]. In [10, 11], modeling of STA indicated steep rise in volume of carbon dioxide and hydrogen sulfide liberated at temperatures above 200C. It is suggested that hydrogen sulfide is formed upon thermal decomposition of organosulfur compounds, reaction between sulfur and paraffins with formation of mercaptans and decomposition of the latter. Steam was shown to have a catalytic effect on carbon dioxide generation. Catalytic effect of water on transformation of organic compounds is reported also in [12]. With rise of temperature the solubility of organic compounds in water increases and, moreover, at 250C the negative logarithm of the ionic product of water is 11 (at 20C it is 14). So with rise of temperature water simultaneously becomes a stronger acid and a stronger base, catalyzing reactions of hydrolysis of some heteroatomic compounds. As shown in [13], in STA water may not only be a catalyzer but also a reagent. Analysis of thiophane and thiophene transformation products under conditions of thermolysis in steam [13] showed relatively high carbon monoxide and carbon dioxide content in the reaction gas, although the initial sulfur compounds do not seem to contain oxygen, i.e., water is the only source of oxygen in the system. Summing up the foregoing it can be suggested that STA may stimulate reactions of thermal cracking of hydrocarbons and heteroatomic components, high-temperature hydrolysis (aquathermolysis) of heteroatomic compounds [14], condensation, hydrogen migration, i.e., dehydrogenation of some compounds simultaneously with saturation and hydrogenolysis of others. It is of interest to determine the thermodynamic feasibility of occurrence of these reactions of transformation of some components of heavy crudes at temperatures typical for STA. For this purpose, the thermodynamic parameters ( f H T and S T ) of the reactants considered as model compounds of heavy crudes were calculated by the roentgenometric method PM6 using the MOPAC 2007 software package and the change in Gibbs energy of the reactions was calculated by the equation rG T = r H T - T r S T . Transformation of organosulfur compounds. Hydrolysis of carbon-heteroatom bonds is stimulated by partial negative charge on the heteroatom, i.e., by its ability to bind a proton (protonate), so hydrolysis intensifies in acidic medium. The following mechanism of high-temperature hydrolysis of cyclohexylphenyl sulfide can be suggested [15]:

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or in the shortened form

(1)

(2)

(3)

For cyclic sulfides, particularly for thiophane, the following transformation chain was suggested in [13]:

To check the feasibility of the chain of transformations, the thermodynamic parameters were calculated for the first stage: (4)

Since hydrogen sulfide formed upon STA is a weak acid, it is capable of protonating heteroatomic compounds of crude oil and initiating their hydrolysis, i.e., autocatalytic reactions may occur under the action of H 2S [13]. The initial reagents noted above may be a part of resin molecules and asphaltene structures. The following aquathermolysis reaction at the C S bond can be written for the model of the molecule of resinous matter:

(5)

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As can be seen, destruction of C-S bonds may cause detachment of individual fragments from the resin and asphaltene particles. Note that the chains containing heteroatoms bind aromatic plates into asphaltene packets [16]. Upon breakup of carbon-heteroatom bonds, alongside a change in the group and fractional composition, the structure of the asphaltene particles may undergo transformation, causing, in turn, a change in the rheological properties of the material. Apparently, at temperatures between 200 and 350C, reactions of thermal cracking of sulfur-containing compounds will occur with formation of hydrogen sulfide, hydrocarbons, condensation products, etc.:

C 6 H13 S C 6 H13 H 2S 2C 6 H12

(6)

In some works, [17, 18] in particular, use of hydrogen donors for accelerating transformation of heavy oil components by STA is proposed. The most common hydrogen donor is tetralin (tetrahydronaphthalene), which is amenable to dehydrogenation with liberation of active hydrogen:

(7)

Decomposition of formic acid may also be a source of hydrogen:

HCOOH H 2 CO 2
But, according to [19], in gas phase formic acid undergoes decomposition by the reaction:
HCOOH H 2 O CO

(8)

(9)

Gibbs energy, kJ/mole

Temperature, K
Fig. 1. Dependence of change in Gibbs energy of hydrogen formation reaction on temperature (the digits on the curves correspond to reaction numbers in the text).

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In liquid phase, on the other hand, formic acid forms with water complexes that decompose to hydrogen and carbon dioxide; this reaction is catalyzed by water, on the concentration of which depends the acid decomposition rate [19]. Reaction between steam and carbon dioxide - a product of decarboxylation of oxygencontaining organic compounds, may also be another source of hydrogen in the system:
CO H 2 O CO 2 H 2

(10)

In order ascertain the thermodynamic feasibility of reactions (7)-(10), which may be sources of hydrogen in the productive stratum, their rG T values were calculated (Fig. 1). As will be seen, tetralin hydrogenation is possible at temperatures above 337C, and both formic acid decomposition reactions and reaction (10) are possible at the STA temperature. The thiophane hydrogenolysis reaction in the presence of tetralin as the hydrogen donor can be written as

(11)

Upon dissociation of formic acid to the ions H + and HCOO - , the latter will react with the organosulfur compounds following the scheme [20]:

or in the shortened form

(12)

A similar reaction for thiophane is:

(13)

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The results of calculation of the Gibbs energy of reactions (1) (6) and (11) (13) at various temperatures are plotted in Fig. 2 a . The positive r G T values of cyclohexylphenyl sulfide hydrolysis reactions (1) and (2) attest to occurrence of these reactions with low yield of products; the equilibrium is shifted toward the initial reagents. Reaction (1) is somewhat more probable than reaction (2). At the same time, decomposition of cyclohexylphenyl sulfide to thiophenol and cyclopentane (3) is possible at temperatures above 227 C. Hydrolysis of the C S bond in the model resin compound (5) is thermodynamically feasible in the whole STA temperature range, so transformation of resins and asphaltenes with detachment of side fragments and formation of hydrocarbons and heteroatomic components with a lower molecular weight is possible. The calculated rG T values for the first stage of thiophane transformation (4) are positive, which indicates that this reaction is improbable under the STA conditions. From a comparison of reactions (1), (4), and (5) it is obvious that as the structure becomes more complex and the molecular weight of the organosulfur compounds increases, the probability of occurrence of hydrolysis reactions increases. Hydrolysis with ring scission, on the other hand, is highly improbable.

Gibbs energy, kJ/mole

Temperature, K
Fig. 2. Dependence of change in Gibbs energy of reactions of transformation of heavy oil components by STA on temperature: a - organosulfur compounds; b - organooxygen and organonitrogen compounds; c - PCAH (the digits on the curves correspond to reaction numbers in the text). 297

Calculations show that thermal degradation of dihexyl sulfide (6) is possible at temperatures not below 227 C. It is interesting to note that reactions (12) and (13) of sulfur compound hydrolysis in the presence of formic acid may occur in the whole investigated temperature range, whereas thiophane hydrogenolysis reaction in the presence of tetralin (11) may occur at temperatures above 120 C, i.e., it is also possible under STA. Note that in this work tetralin is considered as one of the polycyclic naphthenic aromatic crude oil hydrocarbons that exhibit hydrogen donor properties. Thus, under STA hydrogen will be transferred from these hydrocarbons to other components, heteroatomic in particular, and the latter will undergo hydrogenolysis. Transformation of oxygen- and nitrogen-containing organic compounds. The structure of resins and asphaltenes contain R O R2 groups whose hydrolysis will probably occur with formation of phenols [20]:

(14)

For the model of the molecule of resinous matter, referred to above, we may write two hydrolysis reactions occurring with breakup of only the C O bond of aliphatic ether and breakup of C O bonds of both aliphatic and cyclic ether:

(15), (16)

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Akin to reactions (1) and (3), reactions of phenylcyclohexylamine hydrolysis and degradation may occur as follows [15]:

(17), (18)

In the presence of formic acid, aniline and cyclohexane may form:

(19)

The results of calculation of the change in Gibbs energy of reactions (14) (19) at various temperatures are plotted in Fig. 2 b . As can be seen, the referred reactions of hydrolysis of oxygen-containing compounds are possible in the whole STA temperature range. Thus, hydrolysis of C O bonds will occur with greater transformation than hydrolysis of C S bonds. Hydrolysis of phenylcyclohexylamine by reaction (17) is possible only at 230 C and above, and its decomposition by reaction (18), at a temperature above 130 C. Transformation of nitrogen-containing compounds in the presence of formic acid, like oxygen-containing compounds, is thermodynamically possible in the whole investigated temperature range. Transformation of polycyclic aromatic hydrocarbons (PCAH). Calculation of thermodynamic characteristics of PCAH transformation reactions under STA conditions is of interest from the standpoint of determination of the most probable paths of their transformation: condensation, hydrogenation, hydrogen rearrangement, and breakup of C C bonds joining the rings. The latter reaction helps get an idea of the possibility of detachment of aromatic fragments from resins and asphaltenes as a result of breakup of the C C bond rather than the carbon heteroatom bond as was shown earlier. Let us examine the trinaphthyl transformation reactions. Condensation:

(20)

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Hydrolysis in the presence of hydrogen donors:

(21), (22)

For phenanthrene, we may suggest hydrogenolysis reaction in the presence of hydrogen donors in the system:

(23), (24)

The results of calculation of Gibbs energy of reactions (20)-(24) at various temperatures are plotted in Fig. 2 c . It is quite predictable that from the point of thermodynamics condensation reaction (20) may occur in the whole investigated temperature range. Reactions of PCAH hydrogenolysis in the presence of formic acid as the hydrogen donor many also occur in the whole STA temperature range. This cannot be said, however, about polycyclic naphthenic aromatic hydrogen donors. Thus, reaction (21) of hydrogen transfer from tetralin to trinaphthyl is possible at a temperature higher than 227C, but reaction (24) of hydrogen transfer from tetralin to phenanthrene is not possible at all. Based on the results of the performed calculations it can be concluded that the following chemical transformations are most likely when heavy crude oils and native asphalts are recovered by steam-thermal technique: hydrolysis of ether, sulfide, and amine bridges with detachment of lower-molecular fragments such as paraffinic, aromatic, heteroatomic, etc.; thermal cracking of heteroatomic components and PCAH, including with formation of gases, lower-molecular components, and condensation products;

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