Deepening of Crude Oil Processing Using Ozonation and High-Energy Impacts

V. V. Lunin,* V. K. Frantsuzov,** and N. M. Likhterova** *Faculty of Chemistry, Moscow State University, Moscow, 119899 Russia **Lomonosov State Academy of Fine Chemical Technology, pr. Vernadskogo 86, Moscow, 117571 Russia Abstract
The concept of advanced technology for processing heavy petroleum feedstock is disclosed, which consists in the chemical pretreatment of the feedstock by reacting with ozone followed by decomposition of ozonolysis products under exposure to ionizing radiation of various types. Experimental data to support the basics of the concept are presented.

Introduction
The enhancement of the current classical petroleum refining processes deals with the development of novel high-performance catalytic systems and more perfect manufacturing equipment, which insignificantly increases the yield and quality of a commercial product. The existing views on the progress in petroleum processing do not take into account a growing tendency towards deterioration of produced oils and do not consider environmental problems due to thermal pollution. According to world expert evaluation, the quality of produced oils by mid-XXI century will approach that of highviscosity crude oils and natural bitumens. This will necessitate the design and implementation of manufacturing processes similar to the Flexicoking process. The experience of commercial operation of natural-bitumen processing units has been gained only in Canada [1--5]. Technical and economic assessments of basic processes for the manufacturing of synthetic oil from Athabaska bitumens show that about 30% of energy containing in a produced bitumen is consumed for its isolation from the rock and upgrading [3]. The carbonization process of natural bitumen in a fluidized bed of coke followed by its gasification is unfavorable because of environmental impact: heat emissions into the atmosphere are about 40% of energy input to the process, and sulfur dioxide emissions reach 3.2 kg/m3 of bitumen processed [1,2]. The complexity of processing of heavy hydrocarbon feedstock close in properties to high-viscosity crude oils and natural bitumens is due to the specific features of its composition and structure. To date, a great amount of experimental information has been gathered and basic theoretical concepts on the inner colloid structure of petroleum-like systems have been developed. According to the current ideas, petroleums and petroleum-like systems (heavy petroleum bottoms) are thermodynamically labile, paramagnetic, associated solutions characterized by high concentrations of resinous--asphaltenic substances and hetero (sulfur, nitrogen, and oxygen) compounds. The resinous-asphaltenic substances form the disperse phase of a petroleum-like system in which the dispersing medium is composed of high-molecular-weight hydrocarbons, predominantly of a hybrid structure, and sulfur compounds . The dispersed phase of petroleum-like systems is characterized by the presence of a large number of fused arene moieties in resins and asphaltenes (2.1--4.7 aromatic nuclei per molecule) and organometallic compounds . The aforementioned components of heavy petroleum feedstock facilitate the intense coking and poisoning of catalysts. For this reason, heavy petroleum feedstock is preliminarily freed of resinous-asphaltenic substances and organometallic compounds by deasphalting, demetalation, and hydrotreating. These heavy-feedstock processing and pretreatment methods are power-consuming and do not meet environmental safety requirements. A radically new approach to solving the problems of processing of heavy hydrocarbon stock can be the conversion of resinous--asphaltenic matter, organometallic substances, and organic sulfur and nitrogen compounds into compounds of other classes by controlled chemical reactions with simultaneous breaking up the components of heavy petroleum feedstock with the greatest molecular mass into smaller units. The selective addition of ozone to sulfur and nitrogen atoms and across metal--carbon and proton-unsaturated bonds of polyaromatic structures followed by transition from thermal chemistry to selective high-energy chemistry seems to be the most promising in this respect. The input of energy required for occurrence of physical and chemical processes to a system by

electron, ion, or photon impact results in substantially different proceeding of the processes as compared with the conventional thermal chemistry. Of ozone reactions with different substances, those with sulfur compounds are of the greatest interest. The pioneering studies on desulfurization of light petroleum fractions with the use of ozone date to 1930s. In these works, it was shown that up to 80% of sulfur compounds could be removed from the gasoline fractions of petroleum by ozonation and steam distillation. Of the works reported during the last decade on the interaction of ozone with petroleum and natural bitumens, the series of studies performed at the Institute of Petroleum Chemistry, Siberian Division, Russian Academy of Sciences, are worth mentioning. It was found that petroleum ozonation products were highly effective de-emulsifying agents. This finding allowed an original technology for breaking persistent water--oil emulsions to be developed, which was adjusted to the conditions of pretreatment of crude oil at the site of its production. The release of a thermal load on the environment is possible if electron beam radiation or photonic flux are used to activate reactions that follow the radical mechanism. In this case, the temperature in the reaction zone can be lowered by 373473 K . Unlike the heat treatment which activates all bonds in a molecule, excitation via electron impact or absorption of appropriate narrow-band radiation is selective in character. Thus, there is a practical possibility that the performance of the classical petroleum refining processes and the quality of the products obtained can be dramatically changed by the pretreatment of the feedstock with ozone and ionizing radiations.

EXPERIMENTAL Radiolysis and Ozonolysis of Crude Oils

The realization of the basics of the concept started with the investigation into radiolysis of crude oil. Earlier, we discussed in detail experimental procedures relevant to such research works and described the properties of the subjects of study. As follows from the results of experiments on irradiation of a blend of commercial oils destined for distillation at the Moscow refinery, with a beam of 1.8-MeV, the viscosity, density, and initial boiling point of petroleum increase (Table 1). These changes are due to the occurrence of two competing processes in the petroleum-like system: the degradation of dispersing-medium components (in particular, the cracking of higher alkanes and dealkylation reactions of alkane chains in hybrid hydrocarbons) and condensation due to radical combination. Since crude oils always contain dissolved air and water, oxidative processes are likely to occur under radiolysis conditions. This assumption is confirmed by IR spectroscopy data for some fractions of the virgin and the electron-beam treated petroleum. It was found that the intensity of the absorption band at 1700 cm--1 due to the carbonyl group increases in the IBP453K fraction of irradiated petroleum. The IR spectra of the 453523K and 523623K fractions of irradiated petroleum are less informative. In the second step of the study, the influence of the composition of crude oil on its ozonation and the effect of ozone treatment on the efficiency of electron beam-induced chemical transformation of petroleum components were examined. The results of ozonation of different crude oils show that the amount of smoothly absorbed ozone (up to effervescence and ozone breakthrough) depends on the resin and asphaltene content and sulfur content. It was noted that the ozonation regime became unstable after reaching a certain level of ozone uptake specific for each oil; the instability seems to be due to the rearrangement of complex structural units of the dispersed phase. The rearrangement of dispersed-phase complexes from one stable state to another occurs in an abrupt manner, which is preceded by their degradation. The explosive character of rearrangement is due to the buildup of long-lived radicals in the dispersing medium and their reaction with oxidizing agents. Similar phenomena were detected in the oxidation of vacuum and atmospheric residues with ambient oxygen. The pretreatment of crude oils with ozone followed by their thermolysis (3600s, 453K) and distillation showed that crudes with a high paraffin content (Dagestan oil) and low sulfur, resin, and asphaltene contents underwent oxidation through the radical mechanism when reacted with ozone. As a result of oxidation reactions of saturated moieties and subsequent thermolysis, reaction water accumulates in the dispersing medium. The electron beam-induced degradation of ozonides has a clear advantage over thermolysis. The process takes place at room temperature, and the yield of light fractions from crude oil increases by 10% (Table 2). The results obtained agree well with published data: the radiation-chemical yield of

conversion products from a hydrocarbon feedstock depends on the dose rate rather than dose as such (Table 2). The IR spectra of isolated fractions showed an increased intensity of the 1700-cm--1 band due to carbonyl absorption. A change in the intensity of the band at 520 cm--1 attributed to aromatic disulfides and thiosulfonates was also detected. The alkalization and water flushing of fuel fractions lead to a decrease in the total sulfur content from 70 to 20%. A dramatic increase in the dynamic viscosity of the residue at temperatures above 623K and in the shear strength after ozonolysis and radiolysis indicates a decrease in the size of fused arene moieties of molecules and in the average chain length of alkyl substituents. The decrease in the size of fused arene fragments is due to partial decomposition of organometallic compounds. Ozone attacks a porphyrin complex, destroying the ligand bound to the metal. The feasibility of demetalation of asphaltenes with oxidizing agents (sodium hypochlorite) was studied by Filimonova et al. To summarize, it is shown to be practicable to process petroleum feedstock by combined ozone and electron-beam treatment, which increases the yield of distillate fractions and decreases the amount of sulfur and organometallic compounds, i.e., contact poisons for catalysts in secondary processes. A distinctive feature of this pretreatment procedure is low temperature (323343K) and pressure (atmospheric) levels.

Ozone Initiation of the Hydrotreating Process for Diesel Fractions.

According to the product specifications of Russia and West European countries for environmentally clean diesel fuel, strictly controlled in it are the sulfur content (0.035--0.05 wt %) and the concentration of polycyclic aromatic hydrocarbons (6--11 wt %)]. It is commonplace that, under hydrotreating conditions, thiophene sulfur compounds are most difficult to remove and aromatic hydrocarbons almost do not undergo transformations for thermodynamic reasons. For effective simultaneous removal of thiophene sulfur and polycyclic aromatic hydrocarbons, it is necessary to increase pressure in the hydrogen treatment up to 8.0 MPa and to decrease the feed space velocity. This lowers the production capacity of hydrotreating units and increases power consumption and capital costs, thus increasing the prime cost of commercial fuel. One of the possible ways of enhancing the diesel fuel hydrotreating process is the preliminary ozonolysis of the starting material. Used in the study as a starting material was the straight-run diesel cut obtained on an atmosphericand-vacuum pipe still at the Ryazan refinery and used as a raw material for the diesel fuel hydrotreating process (Table 3). This cut was ozonized at room temperature according to the procedure with a specific ozone uptake rate of 6 g/kg. Experiments on the hydrotreating of the original and ozonized diesel fractions were run on a pilot hydrogenation unit with a catalyst charge of 0.1m3 under conditions simulating those of the industrial hydrotreater at the Ryazan refinery. The process 6 2 was conducted over the industrial catalyst GP-497T at a hydrogen pressure of 410 N/m , a --1 temperature of 623K, a feed space velocity of 10800s , and a hydrogenous gas to feed ratio of 300 (STP)m3/m3. The catalyst was preliminarily sulfurized by treating with a straight-run kerosene cut with a total sulfur content of 0.27 wt % for two days. The desired products were analyzed according to the technical specifications TU 38.1001-1348-90. The results obtained (Table 3) convincingly proved the efficiency of feedstock pretreatment with ozone. For example, the total sulfur content of the fuel after hydrotreating of the ozonized diesel cut is three times lower than that for the hydrotreating of the straight-run cut. A similar result was obtained for polycyclic aromatic hydrocarbons. Their amount in the fuel after ozonolysis and hydrotreating was 1.47 versus 2.17 wt % for the fuel obtained from the straight-run fraction.

Ozone Initiation of the Visbreaking of Atmospheric-Still Bottoms

Visbreaking, Flexicoking, and production of oxygenated asphalts are usually classified with the most significant thermal processes enhancing the severity of petroleum refining. In the scientific-technical literature on the visbreaking technology, it is reported that this method can be used to process both vacuum- and atmospheric-still bottoms. However, systematic data on the visbreaking of atmospheric residue are virtually lacking. In this connection, the basic task of the present study was to examine the effect of ozone treatment on the degree of conversion of atmospheric residue under the visbreaking conditions. To do that, we assembled a laboratory-scale visbreaking unit. As a feedstock, we used the straight-run black oil isolated from a blend of West Siberia commercial oils. The starting black oil contained 2.3 wt % total sulfur, 24.5 wt % resins, 4 wt % asphaltenes, 6.2 wt % solid alkanes with the melting point 330K and had the pour point 287K. The visbreaking process was initiated at low specific uptake rates

of ozone. According to the procedure we described, ozone was introduced into the feed in an amount of 210-3 kg/kg. In this set of experiments, we studied the influence of temperature over the range 698773K on the transformations of components of the starting and the ozonized black oil. The degree of thermal conversion of feedstock in the visbreaking process is usually determined in terms of the total yield of gas and gasoline fraction. In industrial-scale processes, this value varies over the range 4.8--10 wt %. In this case, it is assumed that the higher the yield of gaseous products, the worse the performance characteristics of the process. Elevation of the process temperature from 698 to 500K favored the intense formation of light products. The conversion monotonically increased (Fig. 1) with increasing temperature. However, the temperature dependence of conversion is not linear. It was found that a dramatic increase in the yield of light fractions with insignificant gas formation took place in the range 723748K (Figs. 2a--2d). The severity of conditions for the visbreaking process affects the composition of the gas produced (Fig. 3). Temperature elevation up to 773K favored the buildup of C1--C3 hydrocarbons in the gaseous products, which seems to be due to the secondary degradation of previously formed low-molecularweight products. In this set of experiments, the initiating effect of small amounts of ozone on the visbreaking process as a whole was established (Fig. 2). A relative increment in distillate fractions detected in the experiments with ozonized black oil is 6.44 wt %. The maximum yield of gasoline fraction was observed at a temperature of 748K, the gas yield under these conditions being no more than 1%. A higher degree of conversion of ozonized black oil as compared with the untreated black oil is due to the appearance in the system, along with hydrocarbon radicals, of peroxyl radicals formed via degradation of the products of ozonolysis of black oil components. The peroxyl radicals actively influence the propagation of radical chain reactions. The degradation of ozonation products by the action of temperature increases the total concentration of reactive, short-lived radicals capable of sustaining the propagation reactions of cracking. Due to the presence of thermolyzed products of ozonolysis of black oil components, the rates of secondary reactions of polycondensation of diene structures also increase. In addition, the presence of hydrogen sulfide and carbon dioxide in the gaseous products was detected on the qualitative level in the course of experiments. Thus, the effectiveness of ozonation pretreatment of heavy petroleum feedstock for the enhancement of traditional thermal destructive processes and a possibility of lowering the process temperature down to 698723K were shown.

Ozone/UV Enhancement of the Process of Manufacturing Liquid Road Asphalts

In this section, we present the results of laboratory studies that show a feasibility of designing a new process for the manufacture of oxygenated road asphalts and a feedstock for the lube oil production or catalytic cracking. Traditionally, asphalt--mineral compositions are used in road building. Such compositions are comprised of BND brand oxygenated asphalt mixed with fuel fractions or bottoms from straight-run distillation of crude oil. The real durability of paving is determined by the action of various oxidants, water, solar radiation, seasonal behavior of temperature, mechanical impact, etc. When condensed systems are exposed to the UV portion of the solar electromagnetic radiation spectrum, electron transfer takes place as an elementary event. Absorbed photon energy is frequently comparable in value with the strength of C--C bonds. Upon thermal oxidation and exposure to UV radiation, these bonds break to yield volatile lower hydrocarbons whose vaporization leads to the loss of elasticity and cracking of a paving. Therefore, we believe that the use of ozone and UV radiation treatment in the step of asphalt manufacture will allow the most reactive compounds to be removed from it. The implementation of ozonation technology in industry is hampered by a considerable power consumption for ozone generation (20 kW per kg of ozone); therefore, the problem of the specific ozone uptake rate per unit quantity of desired product determines the practicability of the process. The effect of small uptake rates of ozone (1610-3kg/kg) on the transformations of components of residuum in its ozonolysis, thermolysis, and UV photolysis was studied at temperatures of 323333K. The results of these studies have been described. Let us briefly outline the most significant of them: (1) it was found that liquid oxygenated asphalt obtained at a specific ozone uptake rate of 4.310-3 kg/kg possessed the best rheological properties; (2) it was shown that, along with road asphalt, an additional amount of distillate fractions was formed during ozonolysis, thermolysis, or UV photolysis; (3) the photochemical decomposition of ozonolysis products for 3600 s improved the rheological properties of asphalt;

(4) chemical transformation of the atmospheric residue and distillate fractions isolated from it were studied; using the IR and mass spectrometric techniques, it was shown that the combined ozone and hard UV radiation treatment led to favorable accumulation of naphthenic structures; and (5) a fundamentally new process flow chart was proposed for the manufacture of liquid road asphalt using the ozonation and photochemical treatment of black oil.

Nontraditional Processes for the Preparation and Regeneration of Heterogeneous Catalysts

The most significant advance in our approaches to the processing of heavy hydrocarbon feedstock has been achieved using the radiation-thermal treatment of catalytic systems in their preparation and regeneration. This problem has been discussed in most detail using the regeneration of a coked Claus process catalyst. An industrial batch of this catalyst was subjected to regeneration according to the technology proposed. After regeneration, the catalyst appeared to have even a higher activity than before the treatment, and it continues to operate till now (for 5 years) without noticeable loss in activity. The coked Claus catalyst was regenerated for the removal of sulfur and carbon compounds by radiation-thermal treatment in an air and steam atmosphere at relatively low temperatures of 573 623K and a treatment time of 660s. The residual carbon content did not exceed 0.01 wt %, which is practically unattainable with the existing thermal regeneration procedures.

CONCLUSION
In summary, the use of ozone, powerful electron accelerators, and open plasma sources of hard UV radiation opens up universal possibilities for the development of novel manufacturing processes and enhancement of the traditional processes of petroleum refining, synthesis, and regeneration of a wide variety of supported metal oxide catalysts, partially reducing or completely eliminating heat emissions into the atmosphere.

ACKNOWLEDGMENTS
We are greatly indebted to V.N. Torkhovskii, A.N. Bagacheva, O.N. Kalanicheva, G.G. Solov'ev, V.V. Kukulin, V.B. Saenko, and V.I. Shtein for the assistance in performing experiments and for the valuable discussion. This work was supported by the Russian Ministry of Education Federal Program "Research in Foreground Lines of Science and Technology in Higher Education Institutions," Subprogram Fuel and Energy, project no. 206.03.01.056.

REFERENCES
1. Hilsenteger J//Oil and Gas J., 1985,v.83,33, p. 132-135. 2. Simpson P.L.//Energy Progress, 1984, 1, p.56-63. 3. Chemical Engineering, 1982, v 89,7, p.20E-20H. 4. Columba J. Adaption of Canadian Refineries to use synthetic Crudes. The 11-th World Petroleum Congress, RD [1-9] London, 1983. 5. Brunn J.W.//Oil and Gas J., 1984, v.82, 13, p.90.

Table 1. Influence of irradiation time on the physicochemical properties of petroleum Petroleum Virgin 890 11 ---

Property Density at 293K kg/m3 Viscosity at 323K, mm2/s; Temperature elevation upon irradiation, K Initial boiling point, K Yield of fraction (wt %) IBP453K 453-523K 523-623K Total Refractive index, n20D of fraction IBP453K 453-523K 523-623K

After irradiation for (s) 600 1200 2400 896 898 916 12.1 274 13.9 275.5 14.8 292

326

338

339

343

22.5 2.8 15.9 41.2

22.89 3.6 13.9 40.39

19.87 5.12 15.45 40.44

22.14 2.12 16.12 40.38

1.4341 1.4622 1.4786

1.4323 1.4539 1.4755

1.4333 1.4559 1.4751

1.4361 1.4581 1.4753

Table 2. Influence of irradiation time on the yield of light fractions from ozonized petroleum (wt %) Ozonized petroleum* after Virgin electron-beam irradiation for petroleum (s) 600 1200 2400 22.5 22.75 23.18 22.05 2.8 2.97 3.00 3.52 15.9 24.44 23.76 26.24 41.2 51.16 49.94 51.81

Fraction

IBP--523-623K 453-523K 523-623K Total *The specific ozone consumption rate was 20.510-3kg/kg oil.

Table 3. Physicochemical characteristics of the feedstock and desired products of hydrotreating of ozonized and straight-run diesel cut*

Feedstock Property

Total sulfur content, wt %; 0.902 Flash temperature, K 347 Fractional composition, K IBP 448 447 446 10% 476 476 474 50% 533 531 532 90% 608 597 606 FBP 633 624 630 3 Soluble gums, mg/100 cm ; 7 9 3 3 Acidity, mg KOH/100 cm 1.91 0.15 0.15 Aromatic hydrocarbons, wt % -monocylic 16.23 17.66 16.88 - bicyclic 4.33 1.43 2.11 - tricyclic 0.12 0.04 0.06 *The quality characteristics of the raw material and fuel were studied in the product laboratory of the Ryazan refinery

HYDROTREATING ozonized straightcut run cut 0.032 0.099 329 322

Fig. 1. Conversion of ozonized black oil as a function of visbreaking temperature.

Fig. 2. Yield of distillate fractions from the (1) untreated and (2) ozonized black oil as a function of visbreaking temperature: (a) fraction IBP693 K, (b) fraction IBP453 K, (c) fraction 513693 K, and (d) gas yield.

Fig. 3. Composition of gaseous products as a function of visbreaking temperature (1) up to C3; (2) up to C4, (3) untreated, and (4) ozonized.