Hydroisomerization performance of platinum supported on ZSM-22/ZSM-23 intergrowth zeolite catalyst

Hydroisomerization catalysts Pt/ZSM-22,Pt/ZSM-23,and Pt/ZSM-22/ZSM-23 were prepared by supporting Pt on ZSM-22,ZSM-23,and intergrowth zeolite ZSM-22/ZSM-23,respectively.The typical physicochemical properties of these catalysts were characterized by X-Ray Diffraction(XRD),N2 absorption-desorption,Pyridine-Fourier Transform Infrared(Py-FTIR),Transmission Electron Microscopy(TEM),X-Ray Fluorescence(XRF),Scanning Electron Microscopy(SEM) and NH3-Temperature Programmed Desorption(NH3-TPD),and the performance of these catalysts in n-dodecane hydroisomerization was evaluated in a continuous down-flow fixed bed with a stainless steel tubular reactor.The characterization results indicated that the intergrowth zeolite ZSM-22/ZSM-23 possessed the dual structure of ZSM-22 and ZSM-23,and the catalyst Pt/ZSM-22/ZSM-23 had similar pores and weak acidity to Pt/ZSM-22 and Pt/ZSM-23 catalysts.Moreover,Pt/ZSM-22/ZSM-23 catalyst showed a high selectivity in hydroisomerization of long chain n-alkanes to mono-branched isomers.The evaluation results for n-dodecane hydroisomerization indicated that the activity of Pt/ZSM-22/ZSM-23 was the lowest,while the hydroisomerization selectivity was the highest among the three catalysts.The maximum yield of i-dodecane product was 68.3% over Pt/ZSM-22/ZSM-23 at 320 oC.     

Catalytic Cracking of <Emphasis Type="Italic">n</Emphasis>-Hexane and <Emphasis Type="Italic">n</Emphasis>-Heptane over ZSM-5 Zeolite: Influence of SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Ratio

The performance of two types of ZSM-5 zeolite catalysts (MFI-type zeolite, SiO₂/Al₂O₃ = 50 and 300) was studied in the catalytic cracking of n-hexane and n-heptane as a model compound of light naphtha for production of light olefins at 500, 550, and 600°C. The physicochemical properties of ZSM-5 catalysts were characterized by means of XRD, BET, SEM and NH₃-TPD. The influence of SiO₂/Al₂O₃ molar ratio was investigated on conversion and product selectivity. ZSM-5 zeolite yielded higher conversion in the cracking of n-hexane compared to n-heptane and maximum conversion was achieved over ZSM-5(50) at 600°C. ZSM-5(50) showed higher alkane selectivity rather than olefins. It was found that ZSM-5(300) was more desirable in terms of having significant selectivity to light olefins as well as producing high propylene to ethylene ratio. The maximum propylene to ethylene ratio of 2.7 and 2.48 was observed over ZSM-5(300) at 500°C for n-hexane and n-heptane cracking, respectively.     

Conversions of mixtures of propane and benzene on Pt,Re/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> + H-zeolite systems

The conversion of C₆H₆: C₃H₈C mixtures on mixed catalysts composed of the metal catalysts Pt,ReOx/Al₂O₃ and zeolites Y, M, and ZSM-5 in the H form was studied. The products of benzene dehydroalkylation by propane and propane dehydrogenation products are formed at 180–350°C. It has been shown that propane is activated on the metal catalysts and C₆H₆ interacts with the zeolites yielding the C₆H₇ ⁺ intermediate, which acts as an agent of proton transfer from a zeolite to a metal catalyst, and another intermediate C₉H₁₃⁺ (I). Cumene, alkylbenzenes, and propene are formed as a result of the conversion of I. A comparison of the results of the conversion of these mixtures on the composite catalysts with different zeolites shows that the formation of cumene and propene is thermally controlled and the formation of the other products is kinetically controlled. It has been concluded that the coupling of the redox properties of the metal catalysts with the acid-base properties of the zeolite catalysts facilitates the low-temperature transformations of the mixtures.     

Para-xylene Maximization—Part VI: Shape-Selective Platinum-Promoted Methylation of Toluene

Abstract

The need for increased production of para-xylene, which is the primary material for producing the polyester fibers, activated this research. Although the alkylation reaction is acid catalyzed, we found that a Pt promoter activates this reaction by virtue of the presence of a vacant d-orbital in the Pt atom. In this work, a series of catalysts containing 0.1, 0.2, or 0.3% Pt in H-ZSM-5 zeolite was tested for alkylating toluene with methanol, aiming to produce the xylenes and maximizing para-xylene production in a temperature range of 300°C–500°C in the presence of hydrogen flow in a continuous-flow fixed-bed reactor. The catalysts were characterized by temperature programmed desorption (TPD) of ammonia for acid sites distribution analysis and platinum dispersion in the catalysts by hydrogen chemisorption. Moreover, the diffusion resistance extent in the current catalysts during the alkylation reaction has been evaluated via estimation of the Thiele modulus, Φ _L . The selectivity for para-xylene production was found to increase systematically with increasing the Pt content in the catalysts, whereas the unloaded zeolite did not follow this order. The Φ _L values calculated were accordingly found to increase also with increasing Pt content in the catalysts. Although para-xylene was the highest on the 0.3% Pt/H-ZSM-5 catalyst, the heavy undesired trimethylbenzenes were the lowest to be formed on this catalyst.     

The Catalytic Dehydration of Bio-ethanol to Ethylene on SAPO-34 Catalysts

SAPO-34 catalysts were synthesized by hydrothermal method, and characterized by X-ray diffraction (XRD), NH₃ temperature-programmed desorption (NH₃-TPD) and thermogravimetric-differential thermal analysis (TG-DTA). The synthesized catalysts were tested for dehydration of bio-ethanol to ethylene in comparison with commercial ZSM-5 and γ-Al₂O₃. The home-made SAPO-34 catalysts exhibited similar bio-ethanol conversion and ethylene selectivity at 60°C and 110°C lower compared to commercial ZSM-5 and γ-Al₂O₃ catalysts, respectively, indicating higher low-temperature activity. It was found that the crystallinity and surface acidity of synthesized SAPO-34 decreased after 4 h on stream, which is attributed to the carbonaceous deposits on catalyst confirmed by TG-DTA.     

Preparation of a highly efficient Pt/USY catalyst for hydrogenation and selective ring-opening reaction of tetralin

Ultrastable Y zeolite(USY)-supported Pt catalyst was prepared by gas-bubbling-assisted membrane reduction. The influence of reaction conditions and the metal and acid sites of catalysts on the catalytic performance of catalyst in hydrogenation and selective ring opening of tetralin, 1,2,3,4-tetrahydronaphthalene(THN), was studied. It was found that the optimal reaction conditions were at a temperature of 280 °C, hydrogen pressure of 4 MPa, liquid hourly space velocity of 2 h~(-1) and H_2/THN ratio of 750. Under these optimal conditions, a high conversion of almost 100% was achieved on the 0.3 Pt/USY catalyst. XRD patterns and TEM images revealed that Pt particles were highly dispersed on the USY, favorable to the hydrogenation reaction of tetralin. Ammonia temperature-programmed desorption and Py-IR results indicated that the introduction of Pt can reduce the acid sites of USY, particularly the strong acid sites of USY. Thus, the hydrocracking reaction can be suppressed.     

Oxidative Dehydrogenation of Methanol on Chromium Oxide/Montmorillonite K10 Catalysts

Abstract

Methanol conversion was carried out on a mesoporous material—chromia/montmorillonite K10 (MK10)—in a pulse microcatalytic system. Methanol was converted to formaldehyde and ethylene by two different mechanisms. Methanol dehydrogenation increases by increasing reaction temperature (300–400°C) and as chromia loading decrease. On the other hand, the dehydration of methanol occurs at a higher temperature (400–500°C) and as chromia loading increase, 3–18% Cr. Redox and exposed nonredox Cr³⁺ are responsible for formaldehyde formation. There is a relationship between increased C₂H₄ production and the increase of Cr⁶⁺ phase according to the acidity of chromia catalysts 34 and 76 μL tert-Butylamine/g catalyst for 3% Cr and 18% Cr, respectively. Formaldehyde formation is diffusionally controlled at high temperatures (400–500°C) and kinetically controlled at a lower reaction temperature (300–400°C), while methanol dehydration to ethylene is surface reaction controlled at 400–500°C.     

Comparative Evaluation of Catalysts Containing 0.35% Pt Supported on H-BEA Zeolite Dealuminated via EDTA,HCl Leaching,or Hydrothermally With Steam

Abstract

H-BEA was steamed at 500°C for 2 hr and then loaded with Pt to produce 0.35% Pt/St-H-BEA catalyst. Also, H-BEA was dealuminated with ethylenediamine tetraacetic acid (EDTA) and then loaded with Pt to produce 0.35% Pt/EDTA-H-BEA catalyst. Finally, H-BEA was dealuminated via HCl leaching followed by Pt loading to produce 0.35%Pt/HCl-H-BEA catalyst. These catalysts were reduced under H₂ flow at 500°C to give Pt metal. All catalysts were tested at 250°C–450°C for n-hexane hydroconversion. Maximum hydroisomerization of n-hexane was attained (75.1%) on 0.35% Pt/EDTA-H-BEA and 0.35% Pt/HCl-H-BEA catalysts but at 275°C on the former catalyst and at 300°C on the latter. At this temperature, n-hexane hydrocracking is only 1.2%. The hexane isomers selectivity on both catalysts was >99%. For the 0.35% Pt/St H-BEA catalyst, isohexanes yield and selectivity were lower than the above-mentioned catalysts. The catalyst of choice is 0.35% Pt/EDTA-H-BEA for its economic application at 275°C.     

n-Pentane Hydroconversion Using Pt-loaded Zeolite Catalysts

Abstract

Pt/H-ZSM-5 and Pt/H-MOR catalysts with different Pt contents were prepared via impregnation using H₂PtCl₆ · 6H₂O or via exchange using Pt(NH₃)₄Cl₂, calcination in air at 530°C and reduction in H₂ at 500°C. The prepared catalysts were tested for n-pentane hydroisomerization and hydrocracking via bifunctionality at 250–500°C using a micro-catalytic pulse reactor. It is found that the dispersion of Pt-exchanged zeolites is higher than the corresponding Pt-impregnated zeolites at all Pt contents. It is also found that the dispersion of Pt/H-ZSM-5 catalysts either exchanged or impregnated are higher than the corresponding Pt/H-MOR catalysts. Temperature-programmed desorption (TPD) data showed that the impregnated catalysts possess a higher acid sites number than the exchanged catalysts; and that the Pt/H-ZSM-5 catalysts have a higher number of acid sites than do the Pt/H-MOR catalysts, whereas the latter catalysts possess higher strength of acid sites at all Pt contents. The hydroisomerization activities using Pt exchanged catalysts, supported either on H-ZSM-5 or H-MOR, are higher than the impregnated catalysts at almost all Pt contents. It is also concluded that the H-ZSM-5-supported catalysts, either exchanged or impregnated, are more active than the H-MOR supported ones. Hydrocracking is higher using all loaded H-MOR catalysts.     

Catalytic Dewaxing for Lube Oil Production

Abstract

The selective cracking of long-chain normal paraffin's of medium neutral raffinate, derived from a lube oil-phenol extraction unit, by the catalytic dewaxing technique over H-ZSM-5 and NiMo-H-mordenite catalysts was studied. The runs were conducted to produce lube oils with acceptable cold flow properties. The influences of zeolite types, metals loading, and operating reactor temperatures (290°C–475°C) can have a great effect on cracking high pour point n-paraffins into lower ones, and hence a reduction in pour points. An increase in temperature (between 290°C and 375°C) increased wax conversion (percent dewaxing) on H-ZSM-5 compared with NiMo-H-mordenite catalysts due to its higher cracking activity. As a result, large amounts of C₁-C₄ gases and C₅-170°C naphtha were produced. The low pour point lube oils produced from catalytic dewaxing over H-ZSM-5 compared with NiMo-H-mordenite catalyst indicates that the former was more selective for removing wax components than the later. On the other hand, high concentrations of aromatics were obtained on both catalysts, since the waxy paraffins are converted to lower boiling products. The reduction in dewaxed pour points (Δpp) was observed to be in the range of 38°C–42°C over H-ZSM-5, compared to 37°C–40°C over NiMo-H-mordenite at the same reaction temperature ranges (290°C–375°C), but NiMo-H-mordenite has advantages at higher temperature ranges (above 375°C) in pour point reduction (Δpp range: 41°C–42.5°C). The addition of bimetallic components to the mordenite-catalyst enhances its activity, and the rate of normal paraffin cracking was increased due to the hydrogenolysis activity of the active metals. This means that the bimetallic H-mordenite catalyst has the advantage over H-ZSM-5 in its refining activities (hydrodesulfurization [HDS] and hydrodenitrogenation [HDN]) under the tested operating conditions. These results may be attributed to shape-selective discriminating behavior due to differences in zeolite pore openings (i.e., 6.5 × 7.0 Å for mordenite and 5.3 × 5.6 Å for ZSM-5). In other words, a combination of isomerization and selective cracking reactions of high n-paraffins may occur during the dewaxing process using NiMo-H-mordenite catalyst. The influences of process parameters (temperature, pressure, and liquid hourly space velocity [LHSV]) on the relations between wax conversion to maintain maximum low pour points and maximum dewaxed oil yields or minimum yields of the least desired gases were optimized to produce dewaxed lube oils of acceptable characteristics.     

Hydrotreating of Maya Crude Oil: II. Generalized Relationship between Hydrogenolysis and HDAs

Abstract

Studies of hydrodeasphaltenization (HDAs) and hydrodemetallization (HDM) of Maya heavy crude oil at temperature of 380°C and pressure of 5.4 MPa have been carried out in a high pressure microreactor. Different pore diameter alumina CoMo-supported catalysts were prepared and their catalytic effect is estimated. The fresh and spent catalysts were characterized by textural properties; and the average pore diameter of a fresh catalyst was found to be proportional to the HDM and HDA conversions. The hydrogen elemental analysis of reactant and products indicated that asphaltene conversion is a combination of cracking and hydrogenation (HYD), since HDM correlated well with HDAs, which is due to the complex nature of both molecules (asphaltene and metals).     

Conversion of n-heptane over different catalysts: Effect of catalyst-to-oil ratio and temperature

Catalytic cracking of n–heptane was investigated over various catalysts including ZSM-5, MCM-41, USY and mordenite. The influence of reaction temperature and catalyst-to-oil ratio was investigated in the case of ZSM-5 as more favorable catalyst in terms of conversion and light olefins yield. The highest n-heptane conversion of 97.3 wt.% was achieved over USY zeolite. Both conversion and olefin selectivity were increased by temperature over ZSM-5 zeolite. Increasing catalyst-to-oil ratio enhanced conversion with no significant changes in olefins selectivity. The highest olefin production was achieved over ZSM-5 zeolite in catalyst-to-oil ratios of 1.5 and 3.0 (g/g) at 550°C.     

COMPARATIVE REACTION STUDY OF METHYLCYCLOHEXANE AND 3-METHYLHEXANE IN H2 AND N2 ON Pt/Al2O3 CATALYST

ABSTRACT

The reaction of methylcyclohexane and 3-methylhexane were studied in a pulse microcatalytic reactor using H₂ and N₂ carriers on Pt/Al₂O₃ catalyst at temperatures from 350 to 500°C, contact times (W/F) of 1.25 × 10^?3–3.75 × 10^?3 g min/ml and a total pressure of 4.0 kg/cm². In N₂, there was complete conversion of methylcyclohexane to methane, benzene and toluene while similar products were produced for 3-methylhexane, albeit with diminished conversion level. In H₂, methane was produced from 3-methylhexane conversion while aromatization without demethylation was obtained in addition to some cracking for methylcyclohexane at the low temperature range (350–400°C); a higher temperature range (460–500°C) resulted in complete fragmentation for methylcyclohexane. In H₂–N₂ mixtures, the presence of N₂ of not less than 50% in the carrier gas stream yielded an aromatic catalyst at conditions where only cracking activity was previously evident. The differences in product distribution and/or product types for the two reactants in H₂ and N₂ suggest a different reaction mechanism for both reactants.     

FCC Gasoline Hydroisomerization Over Pt/HZSM-5 Catalysts

Abstract

Pt/HZSM-5 bifunctional catalyst of fluid catalytic cracking (FCC) gasoline hydroisomerization was prepared. The influence of calcinations and reduction conditions, the metal-incorporation technique, and metal loading on the hydroisomerization of FCC gasoline over the Pt/HZSM-5 bifunctional catalyst was studied. The process opinion catalyst of FCC gasoline hydroisomerization was obtained under the condition of temperature 290–300°C; pressure 1.5–2.5 Mpa; liquid hour space velocity (LHSV) 2.0–3.0 hr^?1; V(H₂)/V(Oil) = 2.0–3.0. The results showed that calcination conditions have a significant influence on ion-exchanged catalysts, as they control the final metal distribution. The reduction conditions and the method used for platinum incorporation were found to be important factors that affected both the activity and selectivity of the catalysts. Pt/HZSM-5 bifunctional catalyst possessed good activity for hydrogenation and isomerization. The olefin hydrocarbons of FCC gasoline were hydrogenated and the stability of FCC gasoline was improved under condition of unchanged octane number.     

The Addition of ZSM-5 to a Fluid Catalytic Cracking Catalyst for Increasing Olefins in Fluid Catalytic Cracking Light Gas

Abstract

The second largest source of propylene supplied for petrochemical application is from fluid catalytic cracking (FCC) units. The primary function of the FCC unit has typically been to produce gasoline. However, refiners have been taking advantage of opportunity to produce and recover more propylene from their FCC unit by increasing reaction severity via riser temperature, adding shape selective catalyst, and installing a propylene recovery unit (PRU). At a conventional FCC process propylene exists in the off gas of FCC and it is about 6 wt% of off gas by changing the FCC process parameter quantity of propylene in off gas can be more than 20 wt% by using ZSM-5 additives and increasing temperature The effects of operating parameters, such as reaction temperature, and ZSM-5 as FCC catalyst additive, on the distribution of the product and the yield of propylene were investigated on a bench-scale fluidized bed reactor. It is the aim of this work to perform an overall analysis of the yields and selectivity of hydrocarbons obtained in the vacuum gas-oil conversion over FCC and ZSM-5 catalysts. The effectiveness of ZSM-5 additive in the FCC process was investigated by doing experimental work in a bench-scale setup. The experiment data of off gas analysis showed that vacuum gas oil cracking at high reaction temperatures of 450–550°C increases the yield of propylene. Similar behavior is observed with the addition of 10–25 wt% ZSM-5 additive. The combination of the two effects (high temperature and ZSM-5 addition) makes the FCC unit an excellent source of light olefins for downstream petrochemical units. Higher FCC reactor temperatures (600–650°C) would not have positive effects for increasing propylene yield.     

REFORMING OF N-OCTANE ON A Pt/Al2O 3 CATALYST. 1. PRODUCT DISTRIBUTION AND KINETIC ANALYSIS.

ABSTRACT

The conversion of n-octane on Pt/Al₂O₃ catalyst to hydrocracked products, isooctane, ethylbenzene, o-,p-,m-xylene and toluene was investigated in hydrogen in a Berty CSTR at three different partial pressures of n-octane, 101·325 KPa total pressure, temperatures between 400°C-460°C and W/F values up to 0·33gmincm^-3. The hydrocracked products were the most predominant. Of the other products, isooctane was present in the highest yield. A sequence of elementary steps based on the suggested reaction network of Ako and Susu (1986) was found to predict the experimental conversion-W/F data with the conversion of adsorbed isooctane to adsorbed o-xylene as the rate determining step. The activation energies for the forward and backward reactions of this step were determined to be 21·2 and 14·3 Kcal/gmol, respectively.     

EFFECT OF IRON CATALYST ON THE COMPOSITION OF OIL FROM COAL LIQUEFACTION

ABSTRACT

The effect of two iron catalysts, red mud and CGS S-G, as well as C0-Mo/AI₂O3 and Ni-Mo/Al₂03 commercial catalysts on the composition of oil derived from the liquefaction of Japanese subbituminous coal have been investigated comparatively by conventional autoclave experiments at 440 and 450^°C under initial hydrogen pressure of 85kg/cm² G with tetralin to coal weight ratio of 3. From the results obtained at 450^°C, total conversion and the yield of gas revealed almost same level with four catalysts, but the oil product from molybdenum catalysts showed higher yield than that from iron catalysts. CGS S-G catalyst also showed higher yield of oil product than red mud catalyst. Reaction behavior of two iron catalysts were also tested by solvent recycle mode experiments.     

REFORMING OF N-OCTANE ON A Pt/Al2O3 CATALYST. II. KINETIC ANALYSIS OF HYDROGEN DEPENDENCE.

ABSTRACT

The conversion of n-octane on Pt/Al₂O₃ catalyst was found to pass through pronounced maxima with the variation of the partial pressure of hydrogen at temperatures between 420°C-460°C, P_N = 7·63 × 10^-3 atm and W/F = 0·11lg min cm_-3. The products of reaction were hydrocracked products, octane, ethylbenzene, o-.p-,m,-xylene and toluene. The order of appearance of the optimum PH for the various reactions were: Isooctane>Dehydrocyclized products>Hydrocracked products.

A sequence of elementary steps earlier postulated was found to predict the maximum in the n-octane P_H profiles for the three temperatures investigated. The rate determining steps for the two rate equations that were found suitable were conversion of adsorbed isooctane to adsorbed o-xylene and ethylbenzene.     

Dibenzothiophene Hydrodesulfurization Activity of MoS2 Supported in Sol–Gel ZrO2–TiO2 Mixed Oxides

Abstract

In this work, we report the effect of support composition on the properties of MoS₂ impregnated in sol–gel ZrO₂–TiO₂ mixed oxides as dibenzothiophene hydrodesulfurization catalyst. The supports calcined at 500°C were characterized by N₂ physisorption and X-ray diffraction (electronic radial distribution function). The oxidic impregnated materials (2.8 Mo atoms/nm²) were sulfided at 400°C under a H₂S/H₂ stream. The sample impregnated on the equimolar support showed the highest activity per mass of catalysts whereas the one with TiO₂ carrier was superior in a per mass of Mo basis. Marked differences in products selectivity were observed by TiO₂ addition in the supports. The hydrodesulfurization route to partially hydrogenated compounds was favored over the mixed oxides-supported catalysts meanwhile the direct desulfurization (to biphenyl) was promoted on the ZrO₂-supported solid. It is suggested that among other properties the dispersion and morphology of the MoS₂ phase could influence that behavior.     

Hydrocracking of Polyolefin Thermal Cracking Waxes Over Ni-loaded Molecular Sieve Catalysts

The hydrocracking of thermal cracking waxes obtained from pyrolysis of polyolefin at 360°C for 120 min has been studied using Ni-loaded molecular sieves catalysts. According to XRD, TPR, and BET data, the presence of nickel oxide did not seem to damage the crystalline framework of the catalytic supports. Hydrocracking experiments were carried out in a stirred autoclave reactor at 300°C for 120 min under 2.0 MPa of hydrogen. The results suggested the existence of a balance between the acid and metal function over bifunctional catalysts, which affects hydrogenation and hydroisomerization of thermal cracking waxes. Hydrocracking reactions took place extensively over mixture of Ni/HBeta and ZSM-5, leading toward higher fractions of gases (30.2%) and diesel (23.5%). The higher fractions of gasoline (33.5%) and lube base oil (19.0%) were obtained over mixture of Ni/HSAPO-11 and ZSM-5. In contrast, hydrocracking reaction occurred in a lower extent over mixture of Ni/NMCM-41 and ZSM-5, which produces lube base oil with lower pour point (–10°C), gasoline and diesel with lower bromine numbers (1.1 and 0.8 g Br₂/100 g sample). The viscosity index of lube base oil was in the range of 131–171 over all three mixed catalysts.