四氢萘催化脱氢反应动力学的研究

四氢萘在Ni Mo/Al_2O_3、Fe_2O_3、FeS_2上常压脱氢是典型的连串可逆反应,1,2-二氢萘及微量的1,4-二氢萘是反应的中间产物.脱氢反应速度随四氢萘分压提高和氢分压下降而提高.对二氢萘反应性能的考察表明它具有比四氢萘和萘高得多的反应活性,能迅速地催化转化为萘和四氢萘.氢加快二氢萘的加氢是它阻滞四氢萘脱氢的主要原因.各种催化剂对四氢萘脱氢、二氢萘转化和萘高压加氢都具有基本相同的活性顺序.根据可逆连串表面反应的历程及表面吸附的二氢萘为非常活泼的反应中间体的假设,作者推导了动力学模型,计算得到各反应物在Ni Mo/Al_2O_3、Fe_2O_3、Fe_2O_3/Al_2O_3上表面吸附常数和表面反应速率常数,并进行模拟计算.理论计算与实验能很好地吻合,证明了模型的合理性.模型及参数也进一步解释了一些实验事实.     

Kinetics of conversion of tetralin during hydrogenation of coal

Tetralin has been considered a reasonably good hydrogen donor for the hydrogenation of coal, but in the literature little attention has been given to the kinetics of its conversion. In this paper it is suggested that the conversion of tetralin, mainly to naphthalene, may be either a reversible or a non-reversible reaction depending on the catalyst employed. It is further concluded that stannous chloride, though considered one of the best coal hydrogenation catalysts, is inferior to cobalt oxide when the side reaction tetralin^→ decahydronaphthalenes and the rate of dehydrogenation of tetralin are considered.     

Coal liquefaction mechanism using a tritium tracer method

To determine the behavior of hydrogen in tetralin, the reaction of tetralin with tritiated gaseous hydrogen was studied in a flow reactor at 400–450°C, 2.5–9.8 MPa for various residence times. The amount of hydrogen exchange between tetralin and tritiated hydrogen was estimated from the balance of hydrogen and tritium. Although yields of methylindan and naphthalene, and the hydrogen-exchange ratio (HER) of tetralin increased monotonously with residence time, these values were scarcely influenced by the reaction pressure at every temperature. It was thought that the formation of tetralyl radicals in this system would be the rate-determining step for both the conversions of tetralin into methylindan and naphthalene, and the hydrogen exchange of tetralin. Conversions of tetralin into methylindan and naphthalene, and the hydrogen-exchange reaction using the autoclave were very close to those using the flow reactor.     

高温下工业NiW/Al2O3催化剂上萘的加氢饱和反应

在中压固定床中,高温条件下研究了工业NiW/Al2O3催化剂上硫化氢气氛中反应温度、反应压力和空速对萘加氢饱和反应过程的影响。实验结果表明,在液时空速为10—30 h-1,氢油体积比为800,高反应温度区320—380℃的实验条件下,萘加氢主要生成四氢萘和十氢萘,而进一步加氢裂化产物较少;提高反应温度,萘转化率和四氢萘的收率下降,加氢裂化产物略有升高,表明高温不利于芳环的加氢饱和;提高加氢反应压力,萘的转化率和四氢萘的芳环加氢程度提高;综合反应结果,提出了高温条件下萘加氢的简化可逆连串反应途径。     

Activity of Ni-Moly catalysts in tetralin or decalin dehydrogenation and in hydrogenation of coal-extract solution

The activity of several NiMoly catalysts in the processes of dehydrogenation of tetralin or decalin and hydrogenation of coal-extract solution has been determined. In both processes studied, the activities of the catalysts investigated have been found to follow rectilinear relations with quantity. It has also been shown that the activity of a NiMoly catalyst can be predicted in hydrogenation of coal-extract solution, from its activity in dehydrogenation of tetralin or decalin; the latter reaction is relatively simple to conduct in laboratory conditions. However, caution must be exercised when very narrow pores, making possible Knudsen diffusion of hydrogen at high pressure, exist in the catalyst.     

Thermal dissociation of tetralin between 300 and 450 °C

Most studies of the hydrogenation of coal in hydrogen-donor solvents involve the reaction of hydrogen with coal slurried in tetralin, with or without catalysts. Reaction schemes proposed usually ignore the possibility of the contribution of products of the thermal breakdown of tetralin itself. In the work presented below tetralin was heated for various periods at temperatures between 300 and 450 °C without hydrogen or coal, and the products were analysed by capillary chromatography. The main products formed were naphthalene and the tetralin isomer 1-methyl indan. Tetralin did not disproportionate to naphthalene and decalin, although this has been suggested in the literature as a mechanism for the formation of the naphthalene usually observed. Naphthalene was produced, at temperatures as low as 350 to 400 °C, by dehydrogenation of the saturated ring. This ring also rearranged to give 1-methyl indan, and at higher temperatures broke open to yield alkyl benzenes. This cracking of the saturated ring was found to enhance the naphthalene formation.     

Comparative study of the hydrogenation of tetralin on supported Ni, Pt, and Pd catalysts

The hydrogenation of tetralin in the vapor phase has been investigated over Ni, Pt, and Pd catalysts to determine the evolution of the trans- and cis-decalin products as a function of conversion over the different catalysts. The concentration of each isomer in the product may be important in subsequent ring opening steps if cetane number improvement is desired. The cis-decalin isomer is preferred to open the naphthenic ring in a selective way instead of multiple cracking. However, thermodynamically, this isomer is the least favored; so, kinetic control is the only solution. By selecting the proper catalyst and operating conditions, one could keep the trans/cis-decalin ratio low. In this study, we have prepared a series of supported metal catalysts and tested them in a flow reactor at 3540 kPa and 548 K. Kinetic parameters for the hydrogenation of tetralin and the cis-to-trans-decalin isomerization over the various catalysts investigated were obtained by fitting the data with a generalized Langmuir–Hinshelwood model.

The kinetic analysis revealed that the relative rates of tetralin hydrogenation, as well as the cis-to-trans isomerization are greatly affected by adsorption site competition of decalin and tetralin, which in turn has different magnitudes over the different catalysts. At tetralin conversions above 30%, the Ni catalyst yields the lowest trans/cis-decalin ratio. In contrast, the trans/cis ratio on Pd catalyst remains constant at all conversion levels and is highest at low tetralin conversion. It is concluded that the trans/cis ratio is a combination of the intrinsic selectivity of each isomer and the isomerization reaction.     

Free radicals in coal and coal conversions. 8. Experimental determination of conversion in hydroliquefaction

The results of conversion determinations on the products from Powhatan No.5 coal liquefied in an autoclave and in a high-pressure, high-temperature e.s.r. cavity are reported. Oil, asphaltene and preasphaltene yields, and overall conversion have been determined for Powhatan No.5 coal samples liquefied in tetralin, SRC-11 heavy distillate, and naphthalene at temperatures from 400 to 480 ° C in both reactor systems. The concept of reaction severity is introduced and used to formalize the relation between the effect of temperature and reaction time on oil yield and conversion. Oil is the predominant product in liquefaction in tetralin or naphthalene, asphaltene is the major product of liquefaction in SRC-II heavy distillate. Retrogressive reaction (THF-insoluble product formation) becomes severe when SRC-II heavy distillate is the liquefaction solvent and residence time of >10 min are used at temperatures >450 °C. Preasphaltenes appear to be the only intermediate species in Powhatan No.5 liquefaction.     

Kinetics and mechanism of thermolysis of dibenzyl ether

The kinetics of thermolysis of dibenzyl ether in tetralin have been studied at 350–410°C in a hydrogen atmosphere at 8.5 MPa pressure. A kinetic model has been proposed that satisfactorily describes the process and takes into account both the known transformation of ethers into toluene and benzaldehyde and the direct destruction of ether to benzene and toluene with elimination of CO and secondary conversions of benzaldehyde. It has been shown that at lower temperatures the first reaction prevails whereas at higher temperatures both reactions become competitive. The kinetic parameters support an intramolecular rearrangement as a pathway of the first reaction and a radical mechanism as a pathway of the second.     

Hydrogenolysis and hydrocracking of the carbon-oxygen bond. 2. Thermal cleavage of the carbon-oxygen bond in guaiacol

Low-rank coals and their precursors contain, in addition to aromatic hydroxy groups, aromatic methoxy groups. In the present work a model compound, guaiacol, is used for the study of the behaviour of the carbon-oxygen bonds under thermolytic conditions. The thermolysis of guaiacol is studied in tetralin, naphthalene and without solvent under hydrogen or nitrogen pressure at 578–618 K. The compound is homolytically converted by first-order kinetics. The major product is pyrocatechol. Phenol, o-cresol, methyl catechols and methyl guaiacols are also formed. When tetralin is present it reacts in a molar ratio of 1:4 with guaiacol to form naphthalene. The source of hydrogen when tetralin is not present is guaiacol itself because molecular hydrogen does not participate in the reaction. The kinetics and reaction mechanism are discussed.     

Response of inertinites from some Australian coals to non-catalytic hydrogenation in tetralin

Inertinite concentrates from three Australian bituminous coals were hydrogenated at various temperatures ranging from 350 to 475 °C in the presence of tetralin without any added catalyst. Both conversion yields and microscopic observations of the benzene-extracted hydrogenation residues have revealed that the hydrogenation of the inertinite macerals becomes significant only > 400 °C, whereas the dissolution-hydrogenation of the accompanying vitrinite macerals occurs mainly between 350 and 400 °C. The major reaction pathway for the inertinite particles in the hydrogenation process appears to be one of initial mild carbonization followed by hydrogenation. A simplified reaction scheme is proposed which describes the reaction pathway involved in the hydrogenation of inertinite.     

Reaction of Athabasca asphaltene with tetralin

Interaction of Athabasca asphaltene with a hydrogen-donating solvent such as tetralin at temperatures between 195 and 390 °C has been investigated. The reaction resulted in lowering the molecular weight of the treated asphaltene. At 390 °C, 50% of the original asphaltene was converted into pentane-solubles and the sulphur and oxygen contents were each depleted by about 40%. The results, which were interpreted in terms of thermal cleavage of sulphide bonds, are complementary to those obtained in the radical-ion electron-transfer reduction of the asphaltene with potassium in tetrahydrofuran. The negligible amount of coke formation at 390 °C proves the excellent stabilizing properties of tetralin in thermal reactions.     

Free radicals in coal and coal conversions. 6. Effects of liquefaction process variables on the in-situ observation of free radicals

To determine the effects and relative importance of process variables in coal liquefaction, a uniquely designed and fabricated high-pressure/high-temperature electron spin resonance (e.s.r.) apparatus is used to monitor the in-situ formation and behaviour of free radicals, which are generally assumed to be the key factor. It is concluded that the temperature is the most significant single process variable that affects free radical formation; for Powhatan No. 5 coal there is a 9-fold increase in going from 400 to 460 °C. At 460 °C the other process variables tested can affect significantly the free radicals significantly, but at 400 °C these variables have essentially no effect on free radicals formation. The next most significant effect is due to the combination of solvent nature and residence time. Tetralin and the SRC-II heavy distillate quench the free radicals from Powhatan No. 5 to the same extent with one significant difference. In tetralin the maximum concentration is observed shortly after the slurry achieves its highest temperature, whereas in the SRC-II heavy distillate experiments the concentration is still increasing, at 460 °C, even after 1 h of reaction. The heating time, pressures and types of gas used affect the free radical concentration to a much smaller extent. The conversions obtained in the in-situ e.s.r. experiments using SRC-II heavy distillate as the solvent are somewhat lower than those obtained with tetralin as the solvent. The corresponding oil yields with tetralin are considerably higher than with SRC-II heavy distillate.     

四氢萘加氢裂化集总模型的建立与考察

选用国产３８２５加氢裂化催化剂，利用ＷＦ８０００Ａ型连续流动固定床微型反应器，以四氢萘为模型化合物，研究了重质馏分加氢型裂化集总动力学，根据原料，生成物的性质和沸点差异，建立了四氢萘加氢裂化七集总反应网络。     

Pyrolysis of hydrocarbon mixtures characteristic of coal: Application to dibenzyl mixture

Thermal cracking of dibenzyl dissolved in two solvents, tetralin and decalin, has been studied in a flow reactor, in the presence of steam, under atmospheric pressure and at temperatures between 600 and 750 °C. The nature of the products obtained depends upon the structure of the hydrogen-donor agent, but is independent of the structure of dibenzyl. Valuable products such as ethylene and a benzene, toluene and xylene (BTX) mixture, obtained by a β-scission reaction with a monomolecular mechanism, are predominant when decalin is used as solvent. The dehydrogenation of tetralin to naphthalene precedes cracking reactions of the bimolecular type, which lead to significant production of hydroaromatics such as indene. Cracking of dibenzyl, followed by hydrogen transfer from the solvent to the radicals formed, leads to toluene irrespective of the chemical nature of the hydrogen donor.     

Hydrogenolysis and hydrocracking of the carbonoxygen bond. 3. Thermolysis in tetralin of substituted anisoles

Mild pyrolysis and hydrogenolysis products of coal contain substantial amounts of pyrocatechol and resorcinol and their homologues whereas hydroquinone and its homologues are absent or present in only low amounts. In the present work the model compounds anisole and methyl-, methoxy- or hydroxy-substituted anisoles were studied to elucidate substituent effects on the carbon—oxygen bond cleavage in the presence of tetralin. The experiments were carried out at 618 K and 6 MPa (H₂). The major reaction is demethylation to the corresponding phenols. A steric effect can be seen in the ortho compounds and an electronic effect when the substituent is a strongly electron-releasing group. In compounds with oxygen substituents para to each other little or no hydroquinone can be isolated whereas the ortho and meta compounds, respectively, give pyrocatechol and resorcinol. It is suggested that the low yield or absence of hydroquinone in this work and in coal pyrolysis is due to the high reactivity of the intermediate p-hydroxyphenoxy radical, which gives rise to adducts and other compounds of high molar mass. The ortho radical is sterically hindered and the meta radical has a lower reactivity and are hence abstracting hydrogen from the hydrogen donor or coal.     

Highly efficient and organic nitrogen‐containing cation‐promoted aerobic oxidation of alkylaromatics in the presence of N‐hydroxyphthalimide

BACKGROUD: Direct oxidation of alkylaromatics to the corresponding aromatic ketone is an important process in the manufacture of perfumes, pharmaceuticals, flavors, dyes and agrochemicals. For example, tetralin is oxidized to produce 1‐tetralinone, which is a key intermediate in the commercial production of 1‐naphthol, 2‐hydroxy‐1‐tetralone, aureolic acid antibiotics and other pharmaceuticals. RESULTS: In this investigation, it was found that alkylaromatics could be efficiently and selectively oxidized to the corresponding aromatic ketones when methyl violet was employed as a promotor in the presence of N‐hydroxyphthalimide (NHPI); tetralin was oxidized with 89% conversion and 76% selectivity to 1‐tetralinone under 0.3 MPa of O₂ at 75 °C for 2.5 h. The effects of temperature, oxygen pressure, reaction time and additive inclusion were studied in detail. A possible reaction mechanism for tetralin oxidation has been proposed. CONCLUSION: It was demonstrated that methyl violet could efficiently promote the aerobic oxidation of alkylaromatics in the presence of NHPI under mild conditions. Further investigations indicated that the nitrogen cation had a crucial promotion effect in the oxidation process. Copyright © 2009 Society of Chemical Industry     

Behaviour of huminite macerals from Victorian brown coal in tetralin in autoclaves at temperatures of 300–380 °C

The behaviour of various huminite macerals and submacerals in a hydrogen-donor solvent, tetralin, at high temperature under hydrogen pressure was investigated. Small granular samples of three Victorian brown coals of different lithotype were treated with tetralin in two types of autoclave, at temperatures of 300–380 °C and under pressures of 5 or 10 MPa. The residual materials were investigated microscopically. This tetralin treatment caused huminite macerals and submacerals derived from highly gelified cellular material to become plastic even at temperatures as low as 340 °C, whereas it had no such effect on those derived from ungelified material. This relation between the degree of gelification and the tendency to become plastic during tetralin treatment in an autoclave is very similar to that found for vitrinite macerals and submacerals from bituminous coals.     

Upgrading of tall oil to fuels and chemicals over HZSM-5 catalyst using various diluents

The upgrading of crude tall oil (CTO) to fuels and chemicals was studied at atmospheric pressure and in the temperature range 370 to 440°C in a fixed bed microreactor containing HZSM-5. The oil was co-fed with diluents such as tetralin, methanol and steam. High oil conversions of the order of 80–90 wt. % were obtained using tetralin and methanol as diluents but with steam the conversion only ranged between 36 to 70 wt. %. The maximum concentration of gasoline range aromatic hydrocarbons in the liquid product was 52 and 57 wt. % with tetralin and steam but only 39 wt. % with methanol. The amount of gas product in most of the runs was 1–4 wt.%. A reaction scheme is postulated based on the results.     

Alkanes and solvent dimers in successive extract fractions released from coal during liquefaction in a flowing-solvent reactor

Types of alkanes present in liquefaction product fractions released from coal during successive time—temperature intervals were examined by g.c.—m.s. Experiments were carried out in a flowing-solvent reactor where solubilized products are continuously removed from the reaction zone; tetralin, quinoline and hexadecane were used as the solvent. At 450°C (with 400 s holding) total conversions in tetralin, quinoline and hexadecane were 82.5, 74.7 and 24 wt% (daf), respectively. In tetralin, alkanes were released from coal more readily and at lower temperatures than in quinoline or hexadecane; m.s. signal intensities fell rapidly with increasing reaction temperature. In quinoline, lower intensities of alkane peaks were observed than in tetralin, although the trend with temperature was similar. In hexadecane however, the trend of intensity with temperature was reversed compared with liquefaction in tetralin or in quinoline; the range of alkanes detected was also smaller than in tetralin or in quinoline. The presence of alkenes in the hexadecane extracts suggested a pyrolytic mechanism for the thermal breakdown. Isoprenoid alkanes, pristane and phytane, were detected in the tetralin and quinoline extracts but not those prepared in hexadecane. Materials present in product mixtures and thought to originate with each solvent were briefly investigated: dimers were the most prominent species in tetralin extracts, with only low-intensity dimers being found in quinoline extracts and no apparent formation of higher homologues from hexadecane. These results were compared with the pattern of alkane release from coal during liquefaction in tetralin in a conventional minibomb reactor and in the pentane-soluble fraction of the total (unfractionated) extract from the F-S reactor.