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Catalytic cracking of naphtha: Theeffect of Fe and Cr impregnated ZSM-5 on olefin selectivity

Catalytic cracking of naphtha: Theeffect of Fe and Cr impregnated ZSM-5 on olefin selectivity This study focuses on the modification of ZSM-5 in order to enhance the catalytic cracking of refinery naphtha to produce light olefins. ZSM-5 was metal modified using different loadings (0.5–5 wt%) of Fe and Cr via the impregnation method. The metal modified ZSM-5 samples are compared and the effect of metal loading on the physicochemical properties and catalytic performance is investigated. Fe and Cr modification had an effect on both the physicochemical properties of the catalysts as well as catalytic activity and selectivity. Metal loading caused a decrease in the specific surface area which decreased further with increased metal loading. Fe had a greater effect on the total acidity in particular strong acid sites when compared to Cr. The optimum Fe loading was established which promoted selectivity to olefins, in particular propylene. Fe also had a dominant effect on the P/E ratio of which a remarkable ratio of five was achieved as well as enhanced the stability of the catalyst. Cr was found to be a good promoter for selectivity to BTX products with a two-fold increase observed when compared to Fe-modified catalysts. Keywords ZSM-5 · Metal-modified · Catalytic cracking · Naphtha · Olefins Introduction Catalytic cracking of various types of hydrocarbons including naphtha range hydrocarbons has been investi- Production of light olefins such as ethylene and propylene gated over ZSM-5 zeolites to produce light olefins. The vital to many petrochemical processes has been achieved reaction occurs at much lower temperatures of 550–600 °C through steam cracking of hydrocarbons for almost half a compared to steam cracking and the yields of ethylene and century [1]. However, it is a high energy consuming process propylene are high enough to compete with steam cracking. that requires temperatures in excess of 800 °C. Together with Additionally, higher P/E ratios is excess of one are attainable other disadvantages such as high C O emissions, limited compared to 0.4–0.7 for steam cracking [3]. This is highly control over the propylene/ethylene (P/E) ratio and increas- advantageous as the demand or propylene continues to grow. ing propylene demand, has led researchers to identify more Zeolites, in particular ZSM-5 are active catalysts and/or efficient routes of light olefin production to overcome these supports for a range of reactions such as cracking, alkyla- disadvantages. Many catalytic processes focusing on “on tion, aromatization and isomerization of hydrocarbons, due purpose” light olefin production have been developed to to their activity, shape selectivity [4, 5], ion-exchanging supplement the demand such as propane dehydrogenation, properties, special three dimensional micropore struc- methanol to olefins, olefin metathesis and catalytic cracking ture and large specific surface area in ZSM-5 [ 6, 7]. They of naphtha [2]. play a significant part in the olefin industry and in current processes that are under development and modification in order to commercialize these technologies. For instance P/E ratios can be adjusted to meet global demands by control- * Masikana M. Mdleleni ling the acid type, strength and distribution of Bronsted/ masikana.mdleleni@petrosa.co.za Lewis acid sites of the ZSM-5 catalyst as well as the operat- ing conditions of temperature, pressure and WHSV. Other PetroSA Synthetic Fuels Innovation Center, South African Institute for Advanced Materials Chemistry, University modifications of the ZSM-5 catalyst include alterations of of the Western Cape, Robert Sobukwe Road, Bellville 7535, the acidic properties using transition metals [1]. Previous South Africa Vol.:(0123456789) 1 3 120 Applied Petrochemical Research (2018) 8:119–129 studies conducted by Lu et al. [8] have shown that Fe and isotherms at − 196 °C using the Micromeritics Tristar 3000 Cr promoted ZSM-5 have good selectivity to C and C analyzer. Prior to N physisorption samples were degassed at 2 3 2 olefins in the cracking of Isobutane at 625 °C. This may 150 °C for 4–5 h using helium. NH -TPD was used to deter- be due to metals such as Fe and Cr being able to enhance mine the amount and strength of acid sites in the ZSM-5 the dehydrogenative cracking of Isobutane. Isobutane when zeolites. TPD profiles were obtained using an Autochem dehydrogenated to isobutene can then be easily cracked to II Micromeritics chemisorption analyser. Typically 0.1 g lighter olefins. However, the effect of Fe and Cr metal load- of catalyst is loaded into the reactor. This is then activated 6+ 3+ ing and Cr /Cr ion ratio on altering the acidity as well as by heating rapidly to 500 °C and holding for 20 min under electronic promoter effects to enhance selectivity to olefins helium flow at 30 ml/min. The catalyst is then cooled to is not clearly understood. Therefore, Fe and Cr were seen as 120 °C under flowing helium. The gas was then switched a suitable choices as a metal promoters for the cracking of to 5% NH in balance helium and the NH was adsorbed 3 3 refinery naphtha. Moreover, due to the difference in reactiv - at 120 °C for 30 min at a flow rate of 15 ml/min. Helium ity of the various compounds present in naphtha, selectivity was once again allowed to flow over the catalyst to remove to valuable olefins may be affected. Further investigations any physisorbed NH . Under flowing helium NH desorp- 3 3 using complex refinery naphthas are required to understand tion occurred. The flow rate was kept constant at 25 ml/min the process under industrial conditions. while the temperature was ramped up to 700 °C at a rate of In this study we examined the use of Fe and Cr modi- 10 °C/min. The signal was detected using a thermal conduc- fied ZSM-5 as catalysts for the catalytic cracking of naptha tivity detector (TCD) and the outputs recorded on a com- obtained from the Chevron refinery to enhance light olefin puter. H -TPR was performed to determine the reducibility selectivity. Catalysts with loadings of 0.5–5 wt% of Fe and of the metal impregnated samples as well as to confirm the Cr have been prepared and its effects of the catalyst prop- metal oxide phase. Typically 0.1 g of catalyst is loaded into erties such as porosity and acidity have been studied. The the reactor. This is then purged with Argon while the cold catalytic performance has also been evaluated and its effect trap is being prepared. 10% H balance Argon was used in on activity and selectivity to olefins is investigated. the experiment. The 10% H /Ar was allowed to flow over the sample at 50 ml/min as the temperature was ramped to 900 °C at 10 °C/min. Scanning electron microscopy (SEM) Experimental micrographs were obtained using a high resolution–SEM EHT 5.00 kV. All samples were carbon coated before imag- Catalyst preparation ing. The HRSEM was also equipped with an EDS spectrom- eter with the AZTEC EDS system by Oxford Instruments for Catalysts with different Fe and Cr loadings were prepared elemental analysis of zeolites. using the impregnation method. Fe and Cr (0.5, 2 and 5 wt%) were loaded onto to Zeolyst ZSM-5 (SiO /Al O = 30) using Catalytic testing 2 2 3 Fe(NO ) ·9H O and Cr(NO ) ·9H O salts. The total mass of 3 3 2 3 3 2 impregnated zeolite was 5 g. The appropriate amount of the The catalytic performance was evaluated using a stainless steel nitrate salts were dissolved in excess distilled water (25 ml) fixed bed reactor. Typically 0.25 g of catalyst was loaded and and stirred until the salt completely dissolved. For example, supported using quartz beads. The reaction conditions were −1 approximately 0.192 g of Cr(NO ) ·9H O was added to the as follows T = 550  °C, P = atmospheric, WHSV = ~ 16  h . 3 3 2 aqueous solution to obtain a 0.5 wt% metal loading. ZSM-5 The feed flow rate was kept at 0.1 ml/min while nitrogen was was then added to the solution slowly and stirred at 80 °C passed through at 74.8 ml/min to obtain a N /Feed ratio of 4:1. until all the water had evaporated. It was then left to air dry Products were analysed by on a Bruker 450-GC. Gas products and was then further dried in an oven at 110 °C overnight. were analysed on a BR—Alumina–Na SO column while liq- 2 4 The catalysts were then calcined at 500 °C for 6 h to convert uid products were analysed on a RTX-100-DHA 100 m sta- the metals to the oxide form. The metal modified ZSM-5 tionary phase column. The method used to determine product samples were characterised using XRD, N physisorption, distribution was the ASTM D6729 method. Hydrocarbons NH-TPD, H TPR, HRSEM and EDS. in the C –C range were analysed and identified as paraf- 3 2 1 14 fins, olefins, aromatics and others using PONA analysis. A Characterisation significant amount of products which could not be identified was grouped as others and was not included in the selectivity XRD powder patterns were recorded using a Bruker AXS to BTEX products. Naphtha conversion was calculated based D8 Advance (Cu-Kα radiation λKα1 = 1.5406 Å) 40 kV in on the product distribution results obtained from the detailed the 2θ range 5°–90°. Surface area measurements and poros- hydrocarbon analysis (DHA). Naphtha hydrocarbons present ity analysis were determined by N adsorption/desorption in the liquid product were assumed to be unconverted feed 1 3 Applied Petrochemical Research (2018) 8:119–129 121 and therefore conversion was calculated as feed hydrocarbons Results and discussion minus product hydrocarbons. This was done for each indi- vidual component for example: [C = (feed)–C = (prod)]. All The Fe and Cr loaded ZSM-5 catalysts are characterised 5 5 positive deltas were summed up as they were assumed to be using XRD, BET, and NH -TPD to determine the structure, converted hydrocarbons while all negative deltas which repre- porosity and acidity, respectively. The XRD diffractograms sent additional compounds appearing after reaction were con- of Fe loaded 0.5–5 wt% and Cr loaded 0.5–5 wt% samples sidered as zero. The selectivities to C –C olefins and BTEX are shown in Fig. 1a, b, respectively. 2 5 products were calculated only on feed that had been converted. The peaks observed in the patterns in the range 7°–9° The equations are shown below: and 22°–25° 2θ in both Fig. 1a, b correspond to that of a crystalline ZSM-5 zeolite. From Fig. 1a it is noticed that Naphtha conversion = Feed C − Product C , the ZSM-5 zeolite containing different loadings of Fe in the nA nA range 0.5–5 wt% show a slight decrease in intensity of the where n is the hydrocarbon number and A is the hydrocarbon peaks when compared to the unmodified ZSM-5. The rela- type, e.g., paraffin. tive crystallinity is calculated and shown in Table 1. Inter- estingly, the Fe loaded samples show a decrease in crystal- Mass component x %Product selectivity = ∑ × 100 linity (90–65%) as the metal loading increases from 0.5 to 5 wt% indicating that the impregnation with Fe may cause Fig. 1 a XRD diffractograms of ZSM-5 with different Fe metal loadings (0.5–5 wt%). b XRD diffractograms of ZSM-5 with different Cr metal load- ings (0.5–5 wt%) and diamond marking peak corresponding to Cr O phase 2 3 1 3 122 Applied Petrochemical Research (2018) 8:119–129 Table 1 BET and NH -TPD results of Fe and Cr modified ZSM-5 catalysts a 2 a d SampleRel. cryst (%)SSA (m /g) Micropore s/a External s/a Pore vol. Acid sites 2 b 2 3 c (m /g) (m /g) (cm /g) Peak 1 Peak 2 Acidity T (° C) Acidity T (° C) max max (µmol/g) (µmol/g) ZSM-5 100 350 223 127 0.21 443 193 190 395 0.5% Fe 90 341 207 134 0.22 407 183 75 375 2% Fe 87 332 210 122 0.21 336 180 55 387 5% Fe 65 317 203 114 0.20 359 187 59 391 0.5% Cr 100 331 208 123 0.21 443 200 130 395 2% Cr 100 320 209 111 0.22 395 195 123 378 5% Cr 90 308 195 113 0.20 363 194 79 382 Relative crystallinity determined from the five most intense XRD peaks in the 7°–9° and 22°–25° 2θ range Areas determined using t plot Determined using BJH method Acidity determined by NH -TPD measurements some change to the structure of the ZSM-5. Similar effects micropores of the zeolite which leads to pore blocking. The were observed by de Oliveira et al. [9] on iron impregnated surface areas for Cr-modified ZSM-5 compared to Fe are ZSM-5 in the 2.5–5 wt% range. Furthermore, no peaks cor- slightly lower for all comparable loadings. This may be due responding to that of iron oxide could be detected. This to a difference in metal particle size and dispersion. may be due to the metal loading being too low or the iron The un-modified ZSM-5 also has the highest amount of crystallites too small for X-ray diffraction indicating a high acidity. The total acidity decreases with an increase in metal dispersion [10]. loading from 0.5 to 5 wt% for both Fe and Cr modified sam- In Fig.  1b it is also noticed that the modification of ples. As shown in Fig. 2a, b, two peaks are observed in the ZSM-5 zeolite with Cr (0.5–5 wt%) by impregnation method NH -TPD profiles at approximately 190 and 390° C cor - did not affect the crystallinity of ZSM-5 as observed with responding to weak and strong acid sites, respectively. As the Fe modified catalysts. Chromium oxide can exist in two noticed in the TPD profiles, the area of the second peak cor - phases, i.e., CrO and Cr O corresponding to Cr(VI) and responding to stronger acid sites which may include Bron- 3 2 3 Cr(III), respectively. It is possible that both phases may be sted sites originating from framework aluminium within present in the sample; however, peaks corresponding to the the micropores decreases with increasing metal loading. It CrO phase are overlapped by ZSM-5 peaks. As the load- is possible that by metal particles blocking the micropo- ing increases from 0.5 to 5% it is noticed that there is slight res of the zeolite access to stronger acid sites are restricted. increase in intensity of the peak at 33.6° 2θ. This peak cor- Although the effect of Fe and Cr loading on the ZSM-5 sur - responds to chromium oxide(Cr O ) confirming the presence face area was quite similar, interestingly Fe has a greater 2 3 of chromium on the 5 wt% Cr loaded sample [11]. effect on the acidity in particular the amount of strong acid The physicochemical properties, acidity and porosity sites. As noticed in Table 1, Fe loading causes a much larger of Fe and Cr impregnated ZSM-5 were performed using decrease in the amount of strong acid sites than Cr for all NH -TPD and N physisorption, respectively. The results analogous weight loadings. This may be due to a difference 3 2 are shown in Table 1 below. in metal particle size and dispersion as well as metal/acid The un-modified ZSM-5 has both the largest micropore site interaction. Lai et al. [10] have shown using UV–Vis 3+ and external surface areas summing up to the highest SSA spectroscopy that Fe can exist as isolated Fe species, Fe O x y of 350 m /g. After metal loading the SSA is seen to decrease oligomeric clusters and F e O nanoparticles which can eas- x y and decreases further with increasing Fe and Cr loading ily access the pore network of ZSM-5. Krishna and Makkee from 0.5 to 5 wt%. A smaller decrease in the external sur- [12] have also reported Fe species associated with frame- face area compared to micropore surface area is observed work alumina using NO DRIFTS. From the XRD Fe could with increased metal loading from 0.5 to 5 wt% for both Fe not be detected whereas Cr at higher loading was present and Cr modified samples. For both metals, samples with indicating that Cr may have a larger particle size and less the highest loadings have the lowest micropore surface dispersion and therefore less interaction with strong Bron- areas. This suggests that Fe and Cr metals are located in the sted acid sites than Fe. 1 3 Applied Petrochemical Research (2018) 8:119–129 123 0.015 0.04 a 0.5% Fe ZSM-5 2% Fe 0.5% Fe-ZSM-5 5% Fe 2% Fe-ZSM-5 0.5% Cr 5% Fe-ZSM-5 0.03 2% Cr 5% Cr 0.010 0.02 0.005 0.01 0.000 0.00 0100 200 300 400500 600 100200 300400 500 600 Temperature (Deg. C) Temperature (C) b 0.04 Fig. 3 H -TPR profiles of Fe an Cr modified ZSM-5 with weight 0.5% Cr-HZSM-5 2 loadings (0.5, 2 and 5 wt%) 2% Cr-HZSM-5 5% Cr-HZSM-5 H-ZSM-5 0.03 CrO to Cr O . It is known that loadings of 5 wt% and less 6 2 3 6+ generally exist in the Cr form [14–16] and as loadings 0.02 increase chromium may exist as α-Cr O . Michorczyk et al. 2 3 [15] have shown that Cr content above 3.4 wt% results in the appearance of an additional low temperature reduction peak 0.01 at approximately 280 °C, which coincides with the reduc- 6+ 3+ 2+ tion of crystalline α-Cr O rom a Cr to a Cr [17] or Cr 2 3 [11] species. Thus, it is possible that the Cr modified sam- 0.00 ples contain both CrO and Cr O phases as the broad peaks 100200 300400 500600 3 2 3 observed in the TPR profiles extend over the temperature Temperature (deg. C) ranges in which both phases are reduced. Furthermore, the Cr O phase was detected by XRD for the 5% Cr sample fur- Fig. 2 a NH -TPD profiles of unmodified and Fe loaded ZSM-5 cata- 2 3 lysts. b NH -TPD profiles of unmodified and Cr loaded ZSM-5 cata- ther supporting this notion. It may be worthwhile to conduct 6+ 3+ lysts an XPS analysis to confirm the Cr /Cr ratio as the two species have a different effect on the catalytic performance. H -TPR was used to confirm the reducibility character - SEM, EDS and XRF analysis were used to confirm the istics and metal species present in the samples. The profiles ZSM-5 Si/Al ratio and metal loading. The results are shown of Fe and Cr- modified ZSM-5 are shown in Fig.  3 and the in Table 3. peak concentrations are shown in Table 2. From Table 3 it is noticed that the average Si/Al molar From the profiles in Fig.  3 it can be observed that there and atomic ratios as determined by XRF and EDS are about are two reduction maxima for the Fe modified ZSM-5 at 30 and 17, respectively, for all samples and are close to the approximately 350 °C and 450–500 °C. This corresponds given Si/Al ratio of the commercial Zeolyst ZSM-5. Thus, 3+ 2+ to the reduction of Fe O to Fe O (Fe → Fe ) and Fe O 2 3 3 4 3 4 2+ 0 to Fe metal (Fe →Fe ), respectively [13]. It is also noticed Table 2 Hydrogen consumption that the area under the reduction peaks increase as the iron Sample H consumption for the Fe and Cr loaded ZSM-5 (µmol/g) loading increases as more hydrogen is being consumed in samples the reduction reaction. The H uptake is shown in Table 2 Peak 1 Peak 2 and increases from 12 µmol/g for the 0.5% Fe to 337 µmol/g 0.5% Fe 1 11 for 5% Fe. The reduction temperature also increases from 2% Fe 44 45 approximately 450 to 500 °C. 5% Fe 104 233 The Cr doped ZSM-5 samples exhibit a single reduction 0.5% Cr 135 peak. A broad peak from 200 to 450 °C with a maximum 2% Cr 152 at approximately 300 °C can be attributed to the reduction 5% Cr 169 6+ 3+ of Cr → Cr species corresponding to the reduction of 1 3 TCD Signal (a.u) TCD Signal (arb.units) TCD Signal (a.u.) 124 Applied Petrochemical Research (2018) 8:119–129 Table 3 XRF and EDS analysis a b Sample Si/Al ratio-XRF Si/Al ratio-EDS Metal loading (%) of Fe and Cr modified ZSM-5 XRF EDS Fe Cr Fe Cr ZSM-5 31.6 15 – – – – 0.5% Fe 33 17.2 0.8 – 2% Fe 31.5 17.0 2.6 2.0 5% Fe 31.1 17.1 6.4 3.9 0.5% Cr 30.8 16.6 0.3 1.3 2% Cr 30.4 15.9 0.9 3.1 5% Cr 30.4 18.2 2.1 11.0 Molar ratio from XRF analysis Atomic ratio from EDS analysis metal loading by impregnation method has not resulted in The results of the catalyst activity and selectivity are dealumination of the zeolite. The metal loadings as deter- shown below. The effect of metal loading on the activity mined by XRF show that ZSM-5 impregnated with Fe are of the catalysts is shown in Fig. 5 and is compared to the in close agreement with the theoretical loadings and all parent ZSM-5. sample was successfully loaded onto the zeolite. However, Figure 5 shows the conversions as a function of time on the ZSM-5 loaded with Cr seems to be slightly below the stream for the various metal modified catalysts. It is noticed theoretical loadings of 0.5, 2 and 5 wt% for all analogous that the initial conversions are in the range of 44–56%. The loadings. The metal loading for the 0.5% Fe sample could parent ZSM-5 catalyst has the highest initial conversion of not be detected by EDS analysis. This may be due to the 56%. The initial conversions are lower for metal modified loading being below the detection limit of 1 wt%. However, catalysts compared to the parent ZSM-5. As the Fe loading for the 2% Fe and 5% Fe samples the metal detected by increases from 0.5 to 5% the initial conversion decreases EDS increases as the loading increases and is in agreement from ~ 55 to 47%. This may be due to Fe particles block- with the batch loading. Interestingly, the Cr metal loading ing stronger Bronsted sites responsible for cracking reac- percentages determined by EDS are slightly higher with the tions. The Cr modified ZSM-5 catalysts have initial con - 5% Cr sample having a loading of ~ 11%. Although lower versions much lower than the Fe modified catalysts. The loadings were detected by XRF the higher loadings observed 2% Cr–ZSM-5 has the lowest conversion of 44%. No clear with EDS analysis may be due to lower dispersion and clus- trend is observable as to the effect of chromium loading on tering of Chromium particles on the zeolite compared to the conversion of naphtha as the 5% Cr has a slightly higher that of Iron. X-ray mapping of the samples with the highest initial conversion than the 2% Cr and is similar to 0.5% Cr loadings, i.e., 5% Fe and Cr was conducted and is shown in catalyst. As the reaction proceeds, all catalysts show some Fig. 4. The results show that both Fe and Cr are well dis- deactivation. Interestingly, The Fe promoted catalysts show persed although chromium appears to have a greater amount a lesser decrease in activity between the initial and final con- of metal present on the surface and small clusters are visible. versions. The parent ZSM-5 shows the largest decrease of approximately 12%. As the Fe loading increases the reduc- Catalytic performance tion in activity is less significant with the 5% Fe–ZSM-5 only decreasing by 5%. Thus, it can be said that modification ZSM-5 was modified with Fe and Cr via the incipient wet- with Fe enhances the stability of the catalyst. The Cr cata- ness impregnation method. ZSM-5 was loaded with 0.5, 2 lysts also show some slight deactivation. The 0.5 and 5% Cr and 5 wt% Fe. The catalysts were calcined at 500 °C for catalysts show similar stability. However, the 2% Cr catalyst 6 h to convert Fe and Cr to the oxide form. The catalysts which had the lowest initial conversion seems to be the most were then used in the cracking of Naphtha at the following stable of the Cr modified catalysts. −1 reaction conditions, i.e., T = 550  °C, WHSV = 16 h, N : The effect of Fe and Cr on the selectivity to lower olefins, Naphtha feed ratio of 4:1 at atmospheric pressure. Naphtha i.e., C –C olefins for the third and last hours of the reaction 2 5 obtained from Chevron was analysed prior to being used as is shown in Table 5. a feed to determine the hydrocarbon composition. This was All the Fe modified catalysts show a similar selectivity to done by GC analysis and the Detailed Hydrocarbon Analysis total olefins in the third hour of the reaction of ~ 48% with (DHA) software. The composition is shown in Table 4. a slight decrease observed for the 5% Fe catalyst. The same 1 3 Applied Petrochemical Research (2018) 8:119–129 125 Fig. 4 X-ray mapping of 5% Fe and 5% Cr ZSM-5 samples trend is observed for the selectivity to propylene of which hour decreases the selectivity also decreases. However, the 5% Fe has the lowest (16.2%). The 2% Fe catalyst has in the last hour of the reaction in which the conversion is the highest selectivity to propylene of 21.6%. The trend lower than in the third hour for all catalysts the selectivity indicates that the selectivity to total olefins and propylene to total olefins increases. This is due to the increase in C is related to the conversion. As the conversion in the third olefins. The selectivity to propylene tends to decrease except 1 3 126 Applied Petrochemical Research (2018) 8:119–129 Table 4 Hydrocarbon Paraffins Paraffins Paraffins Olefins Olefins Olefins Aromatics Others Total composition of naphtha Cyclo Iso Normal Cyclo Iso Normal obtained from Chevron Naphtha feed C 0 0 0.03 0 0 0.06 0 0 0.09 C 0.47 0.77 0 0 4.5 1.27 0 0.56 7.57 C 0.39 1.73 0.85 0.67 15.15 0 0 0.66 19.45 C 0.1 2.05 0 0.77 7.93 0 2.42 4.166 17.436 C 0.86 1.42 0.52 0.05 7.91 1 3.31 0.585 15.655 C 2.17 1.3 0 0 4.29 0.05 5.91 0.275 13.995 C 1.36 2.6 0.29 0 1.35 0.25 5.01 0 10.86 C 0.07 3.54 0.35 0 0.2 0 3.65 0.075 7.885 C 0 2.75 0.23 0 0 0 2.58 0.686 6.246 C 0 0 0.12 0 0 0 0.32 0.373 0.813 Total 5.42 16.16 2.39 1.49 41.33 2.63 23.2 7.38 100 for the 2% Fe–ZSM-5 catalyst in which a slight increase is observed. The trend that selectivity is related to conversion is maintained as the 2% Fe–ZSM-5 catalyst has the high- est conversion in the last hour approximately 50% and the highest selectivity to total olefins of 60% is obtained. The results indicate that a conversion of 50% and above needs to be maintained for high propylene selectivity and the optimum metal loading seems to be 2%. The Fe promoted ZSM-5 catalysts also show a lesser decrease in selectivity to pro- 0.5% Fe 2% Fe pylene with time compared to the parent ZSM-5 with the 5% Fe highest metal loading of 5% Fe–ZSM-5 catalyst having the 0.5% Cr 2% Cr smallest decrease. This is related to the enhanced stability of 5% Cr 5% Fe–ZSM-5 catalyst. Therefore, the results indicate that 150 200 250 300350 400450 modification with Fe enhances both selectivity to olefins and Time (min) the stability of the catalyst. The selectivities to C and C for the Cr modified cata- 2 3 lysts decrease slightly from the third to the last hour and fol- Fig. 5 Naphtha conversions as a function of time over the parent and metal modified ZSM-5 catalysts low the trend that at higher conversions higher selectivities Table 5 Selectivity to olefins in the gas product for parent, Fe and Cr modified ZSM-5 Olefin selectivity ZSM-5 0.5% Fe 2% Fe 5% Fe Third hour Last hour Third hour Last hour Third hour Last hour Third hour Last hour C 9.0 2.0 6.3 3.6 8.3 5.4 4 2.6 C 20.8 12.6 19.0 14.9 21.6 23.6 16.2 13.5 C 7.6 11.7 8.7 8.4 8.7 10.9 8.7 11.2 C 10.7 26.2 14.6 24.2 8.7 21.4 16.4 23.6 Total 48.1 52.5 48.6 51.1 47.3 61.3 45.3 50.9 Olefin selectivity 0.5% Cr 2% Cr 5% Cr Third hour Last hour Third hour Last hour Third hour Last hour C 3.0 1.9 3.1 1.7 3.4 1.5 C 9.7 8.1 9.0 5.7 11.4 7.0 C 11.1 11.3 9.9 7.2 9.9 10.3 C 12.7 16.2 19.0 16.6 13.3 25.0 Total 36.5 37.5 41.0 31.2 38.0 43.8 1 3 Conversion (%) Applied Petrochemical Research (2018) 8:119–129 127 are observed. Interestingly, no change in selectivity to eth- From the results of selectivity to gas olefins the 2% Fe had ylene or propylene is observed for an increase in chromium the greatest selectivity therefore it is expected that it would loading. The ethylene and propylene selectivity in the third have a lower selectivity to olefins. However, this may sug- and last hours of the reaction of 3 and 1.7% and approxi- gest that Cr catalysts actually promote aromatics production mately 10 and 7%, respectively, is maintained. Selectivity of which the 2% Cr–ZSM-5 is the best catalyst. to C olefins remains constant for all catalysts while a slight A plot of the selectivity to BTEX products is shown in increase to C olefins is noticed. However, when compared Fig. 7. to Fe modified catalysts the Cr catalysts have a much lower From Fig. 7 it is noticed that BTEX selectivity is higher selectivity to lower olefins (C –C ) in both the third and last initially for all Fe catalysts (~ 20–24%) and decreases with 2 5 hours of the reaction. A difference of 30% is observed when time on stream as the conversion decreases to between 13 2% Fe is compared to 2% Cr in the last hour. This indicates and 15%. No clear trend is observed with respect to BTEX that Fe is a better promoter to enhance selectivity to light selectivity However, it is evident that the Cr–ZSM-5 cata- olefins than Cr. It is possible that the difference in acid- lysts are more selective to aromatic products than Fe–ZSM-5 ity is responsible for the difference in selectivity. As the Cr and reaches a maximum for the 2% Cr-catalyst. The 2% Cr ZSM-5 has slightly higher total acidities when compared to catalyst has the highest selectivity of ~ 29% of which the Fe, readsorption of light olefins on acid sites may occur lead- composition is mainly toluene and xylenes and small amount ing to secondary aromatisation reactions thus also indicating zeolites with a lower acid site density would give selectivity 3rd Hour to light olefins while suppressing aromatics formation [18]. Last Hour The selectivity to liquid products for the metal modified catalysts is shown in Fig. 6. The hydrocarbon composition of the liquids range from C to C and consist of aromat- 5 14 ics, paraffins, naphthenes and olefins as observed from GC analysis using a DHA column of which aromatics make up the bulk of the product. From the graph it is noticed that the selectivity to liquids remains constant for the parent ZSM-5 in the initial and final hour of the reaction. Interestingly, the Fe and Cr modified ZSM-5 show stark differences in selectivity. The Cr–ZSM-5 catalysts show higher selectivi- ties compared to Fe–ZSM-5 catalysts in the initial hours of the reaction. As the reaction proceeds, the Cr catalysts Parent 0.5% Fe 2% Fe 5% Fe 0.5% Cr 2% Cr 5% Cr increase in selectivity, whereas the Fe catalysts decrease. Catalysts Remarkably the 2% Cr catalyst has the highest increase in selectivity to liquid products (~ 65%) compared to the 2% Fig. 7 Bar graph showing selectivity to BTEX products for all metal Fe which shows the largest decrease in selectivity (~ 35%). modified catalyst Fig. 6 Total liquid product selectivity of metal modified catalysts ZSM-5 0.5% Fe 2% Fe 5% Fe 0.5% Cr 2% Cr 5% Cr 150 200 250 300350 400450 Time (min) 1 3 Total Liqui Selectivity (%) BTEX selectivity (%) 128 Applied Petrochemical Research (2018) 8:119–129 5.5 3rd Hour Conclusion Last Hour 5.0 4.5 Metal modification with Fe and Cr had an effect on both 4.0 the physicochemical properties of the catalysts as well as the catalytic performance. Metal loading did not affect 3.5 the crystallinity of the ZSM-5 but caused a decrease in 3.0 the specific surface area which decreased further with 2.5 increased metal loading. Fe had a greater effect on the total 2.0 acidity in particular strong acid sites when compared to Cr. 1.5 Fe acted as a promoter of both selectivity to olefins, in par - 1.0 ticular propylene as well as enhanced the stability of the 0.5 catalyst. The best results were achieved with a Fe loading 0.0 of 2% which gave the greatest selectivity to propylene of Parent 0.5% Fe 2% Fe 5% Fe 0.5% Cr 2% Cr 5% Cr 23.6% and total olefin selectivity of 60%. Furthermore Fe Catalysts modification improved the P/E ratio from two to a maxi- mum of five. Cr modification was found cause a decrease Fig. 8 P/E ratios for all metal-modified catalysts in selectivity to lower olefins and an increase in selectivity to BTX products. The highest selectivity to BTX of ~ 65% of benzene is produced. Lu et al. [8] have shown that Cr was obtained with the 2% Cr–ZSM-5 catalyst. in small amounts between 0.004 and 0.038 mmol/g alters Acknowledgements The authors would like to thank the Petroleum, acidity and plays an important role in promoting cracking Oil and Gas Corporation of South Africa (PetroSA) for their financial of isobutane and dehydrogenation of isobutane to isobutene support and technical discussions, the electron microscope unit, Phys- which is then easily cracked to lighter olefins and is similar ics Department, University of the Western Cape for the SEM images to iron in promotional effects. However, the differences in and Ithemba labs for the XRD work. product distribution observed in this study between Fe and Open Access This article is distributed under the terms of the Crea- Cr modified samples indicate different promotional mecha- tive Commons Attribution 4.0 International License (http://creat iveco nisms in the cracking of refinery naphtha. In particular Cr mmons.or g/licenses/b y/4.0/), which permits unrestricted use, distribu- ions are shown to favour aromatization and alkylation reac- tion, and reproduction in any medium, provided you give appropriate tions. The chromium loadings in our study fall in the range credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. of 0.059–0.409 mmol/g which is higher than the range estab- lished by Lu et al. [8] for promotion of dehydrogenative cracking which may suggest that higher loadings of chro- mium above 0.038 mmol/g may promote aromatization reac- References tions. The exact cause, i.e., role of acidity and metal support interaction is not clearly understood and further analysis of 1. Rahimi N, Karimzadeh R (2011) Catalytic cracking of hydro- the amount of Lewis and Bronsted acid sites as well as XPS carbons over modified ZSM-5 zeolites to produce light olefins: and DRIFTS analysis may be required to elucidate the role a review. Appl Catal A Gen 398:1–17. https://doi.or g/10.1016/j. of the Fe and Cr ions. apcat a.2011.03.009 2. Mitchell S, Boltz M, Liu J, Pérez-Ramírez J (2017) Engineering The propylene to ethylene P/E ratios were calculated for of ZSM-5 zeolite crystals for enhanced lifetime in the produc- all catalysts and are shown in Fig. 8. tion of light olefins via 2-methyl-2-butene cracking. Catal Sci It is clearly observed that Fe enhances the P/E ratio as Technol 7:64–74. https ://doi.org/10.1039/C6CY0 1009A all Fe-modified catalysts have a better ratio than the parent 3. Sattler JJHB, Ruiz-Martinez J, Santillan-Jimenez E, Weck- huysen BM (2014) Catalytic dehydrogenation of light alkanes ZSM-5. 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Catalytic cracking of naphtha: Theeffect of Fe and Cr impregnated ZSM-5 on olefin selectivity

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Springer Journals
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Copyright © 2018 by The Author(s)
Subject
Chemistry; Catalysis; Industrial Chemistry/Chemical Engineering; Nanochemistry; Energy Technology; Nanotechnology and Microengineering
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2190-5525
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2190-5533
DOI
10.1007/s13203-018-0200-2
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Abstract

This study focuses on the modification of ZSM-5 in order to enhance the catalytic cracking of refinery naphtha to produce light olefins. ZSM-5 was metal modified using different loadings (0.5–5 wt%) of Fe and Cr via the impregnation method. The metal modified ZSM-5 samples are compared and the effect of metal loading on the physicochemical properties and catalytic performance is investigated. Fe and Cr modification had an effect on both the physicochemical properties of the catalysts as well as catalytic activity and selectivity. Metal loading caused a decrease in the specific surface area which decreased further with increased metal loading. Fe had a greater effect on the total acidity in particular strong acid sites when compared to Cr. The optimum Fe loading was established which promoted selectivity to olefins, in particular propylene. Fe also had a dominant effect on the P/E ratio of which a remarkable ratio of five was achieved as well as enhanced the stability of the catalyst. Cr was found to be a good promoter for selectivity to BTX products with a two-fold increase observed when compared to Fe-modified catalysts. Keywords ZSM-5 · Metal-modified · Catalytic cracking · Naphtha · Olefins Introduction Catalytic cracking of various types of hydrocarbons including naphtha range hydrocarbons has been investi- Production of light olefins such as ethylene and propylene gated over ZSM-5 zeolites to produce light olefins. The vital to many petrochemical processes has been achieved reaction occurs at much lower temperatures of 550–600 °C through steam cracking of hydrocarbons for almost half a compared to steam cracking and the yields of ethylene and century [1]. However, it is a high energy consuming process propylene are high enough to compete with steam cracking. that requires temperatures in excess of 800 °C. Together with Additionally, higher P/E ratios is excess of one are attainable other disadvantages such as high C O emissions, limited compared to 0.4–0.7 for steam cracking [3]. This is highly control over the propylene/ethylene (P/E) ratio and increas- advantageous as the demand or propylene continues to grow. ing propylene demand, has led researchers to identify more Zeolites, in particular ZSM-5 are active catalysts and/or efficient routes of light olefin production to overcome these supports for a range of reactions such as cracking, alkyla- disadvantages. Many catalytic processes focusing on “on tion, aromatization and isomerization of hydrocarbons, due purpose” light olefin production have been developed to to their activity, shape selectivity [4, 5], ion-exchanging supplement the demand such as propane dehydrogenation, properties, special three dimensional micropore struc- methanol to olefins, olefin metathesis and catalytic cracking ture and large specific surface area in ZSM-5 [ 6, 7]. They of naphtha [2]. play a significant part in the olefin industry and in current processes that are under development and modification in order to commercialize these technologies. For instance P/E ratios can be adjusted to meet global demands by control- * Masikana M. Mdleleni ling the acid type, strength and distribution of Bronsted/ masikana.mdleleni@petrosa.co.za Lewis acid sites of the ZSM-5 catalyst as well as the operat- ing conditions of temperature, pressure and WHSV. Other PetroSA Synthetic Fuels Innovation Center, South African Institute for Advanced Materials Chemistry, University modifications of the ZSM-5 catalyst include alterations of of the Western Cape, Robert Sobukwe Road, Bellville 7535, the acidic properties using transition metals [1]. Previous South Africa Vol.:(0123456789) 1 3 120 Applied Petrochemical Research (2018) 8:119–129 studies conducted by Lu et al. [8] have shown that Fe and isotherms at − 196 °C using the Micromeritics Tristar 3000 Cr promoted ZSM-5 have good selectivity to C and C analyzer. Prior to N physisorption samples were degassed at 2 3 2 olefins in the cracking of Isobutane at 625 °C. This may 150 °C for 4–5 h using helium. NH -TPD was used to deter- be due to metals such as Fe and Cr being able to enhance mine the amount and strength of acid sites in the ZSM-5 the dehydrogenative cracking of Isobutane. Isobutane when zeolites. TPD profiles were obtained using an Autochem dehydrogenated to isobutene can then be easily cracked to II Micromeritics chemisorption analyser. Typically 0.1 g lighter olefins. However, the effect of Fe and Cr metal load- of catalyst is loaded into the reactor. This is then activated 6+ 3+ ing and Cr /Cr ion ratio on altering the acidity as well as by heating rapidly to 500 °C and holding for 20 min under electronic promoter effects to enhance selectivity to olefins helium flow at 30 ml/min. The catalyst is then cooled to is not clearly understood. Therefore, Fe and Cr were seen as 120 °C under flowing helium. The gas was then switched a suitable choices as a metal promoters for the cracking of to 5% NH in balance helium and the NH was adsorbed 3 3 refinery naphtha. Moreover, due to the difference in reactiv - at 120 °C for 30 min at a flow rate of 15 ml/min. Helium ity of the various compounds present in naphtha, selectivity was once again allowed to flow over the catalyst to remove to valuable olefins may be affected. Further investigations any physisorbed NH . Under flowing helium NH desorp- 3 3 using complex refinery naphthas are required to understand tion occurred. The flow rate was kept constant at 25 ml/min the process under industrial conditions. while the temperature was ramped up to 700 °C at a rate of In this study we examined the use of Fe and Cr modi- 10 °C/min. The signal was detected using a thermal conduc- fied ZSM-5 as catalysts for the catalytic cracking of naptha tivity detector (TCD) and the outputs recorded on a com- obtained from the Chevron refinery to enhance light olefin puter. H -TPR was performed to determine the reducibility selectivity. Catalysts with loadings of 0.5–5 wt% of Fe and of the metal impregnated samples as well as to confirm the Cr have been prepared and its effects of the catalyst prop- metal oxide phase. Typically 0.1 g of catalyst is loaded into erties such as porosity and acidity have been studied. The the reactor. This is then purged with Argon while the cold catalytic performance has also been evaluated and its effect trap is being prepared. 10% H balance Argon was used in on activity and selectivity to olefins is investigated. the experiment. The 10% H /Ar was allowed to flow over the sample at 50 ml/min as the temperature was ramped to 900 °C at 10 °C/min. Scanning electron microscopy (SEM) Experimental micrographs were obtained using a high resolution–SEM EHT 5.00 kV. All samples were carbon coated before imag- Catalyst preparation ing. The HRSEM was also equipped with an EDS spectrom- eter with the AZTEC EDS system by Oxford Instruments for Catalysts with different Fe and Cr loadings were prepared elemental analysis of zeolites. using the impregnation method. Fe and Cr (0.5, 2 and 5 wt%) were loaded onto to Zeolyst ZSM-5 (SiO /Al O = 30) using Catalytic testing 2 2 3 Fe(NO ) ·9H O and Cr(NO ) ·9H O salts. The total mass of 3 3 2 3 3 2 impregnated zeolite was 5 g. The appropriate amount of the The catalytic performance was evaluated using a stainless steel nitrate salts were dissolved in excess distilled water (25 ml) fixed bed reactor. Typically 0.25 g of catalyst was loaded and and stirred until the salt completely dissolved. For example, supported using quartz beads. The reaction conditions were −1 approximately 0.192 g of Cr(NO ) ·9H O was added to the as follows T = 550  °C, P = atmospheric, WHSV = ~ 16  h . 3 3 2 aqueous solution to obtain a 0.5 wt% metal loading. ZSM-5 The feed flow rate was kept at 0.1 ml/min while nitrogen was was then added to the solution slowly and stirred at 80 °C passed through at 74.8 ml/min to obtain a N /Feed ratio of 4:1. until all the water had evaporated. It was then left to air dry Products were analysed by on a Bruker 450-GC. Gas products and was then further dried in an oven at 110 °C overnight. were analysed on a BR—Alumina–Na SO column while liq- 2 4 The catalysts were then calcined at 500 °C for 6 h to convert uid products were analysed on a RTX-100-DHA 100 m sta- the metals to the oxide form. The metal modified ZSM-5 tionary phase column. The method used to determine product samples were characterised using XRD, N physisorption, distribution was the ASTM D6729 method. Hydrocarbons NH-TPD, H TPR, HRSEM and EDS. in the C –C range were analysed and identified as paraf- 3 2 1 14 fins, olefins, aromatics and others using PONA analysis. A Characterisation significant amount of products which could not be identified was grouped as others and was not included in the selectivity XRD powder patterns were recorded using a Bruker AXS to BTEX products. Naphtha conversion was calculated based D8 Advance (Cu-Kα radiation λKα1 = 1.5406 Å) 40 kV in on the product distribution results obtained from the detailed the 2θ range 5°–90°. Surface area measurements and poros- hydrocarbon analysis (DHA). Naphtha hydrocarbons present ity analysis were determined by N adsorption/desorption in the liquid product were assumed to be unconverted feed 1 3 Applied Petrochemical Research (2018) 8:119–129 121 and therefore conversion was calculated as feed hydrocarbons Results and discussion minus product hydrocarbons. This was done for each indi- vidual component for example: [C = (feed)–C = (prod)]. All The Fe and Cr loaded ZSM-5 catalysts are characterised 5 5 positive deltas were summed up as they were assumed to be using XRD, BET, and NH -TPD to determine the structure, converted hydrocarbons while all negative deltas which repre- porosity and acidity, respectively. The XRD diffractograms sent additional compounds appearing after reaction were con- of Fe loaded 0.5–5 wt% and Cr loaded 0.5–5 wt% samples sidered as zero. The selectivities to C –C olefins and BTEX are shown in Fig. 1a, b, respectively. 2 5 products were calculated only on feed that had been converted. The peaks observed in the patterns in the range 7°–9° The equations are shown below: and 22°–25° 2θ in both Fig. 1a, b correspond to that of a crystalline ZSM-5 zeolite. From Fig. 1a it is noticed that Naphtha conversion = Feed C − Product C , the ZSM-5 zeolite containing different loadings of Fe in the nA nA range 0.5–5 wt% show a slight decrease in intensity of the where n is the hydrocarbon number and A is the hydrocarbon peaks when compared to the unmodified ZSM-5. The rela- type, e.g., paraffin. tive crystallinity is calculated and shown in Table 1. Inter- estingly, the Fe loaded samples show a decrease in crystal- Mass component x %Product selectivity = ∑ × 100 linity (90–65%) as the metal loading increases from 0.5 to 5 wt% indicating that the impregnation with Fe may cause Fig. 1 a XRD diffractograms of ZSM-5 with different Fe metal loadings (0.5–5 wt%). b XRD diffractograms of ZSM-5 with different Cr metal load- ings (0.5–5 wt%) and diamond marking peak corresponding to Cr O phase 2 3 1 3 122 Applied Petrochemical Research (2018) 8:119–129 Table 1 BET and NH -TPD results of Fe and Cr modified ZSM-5 catalysts a 2 a d SampleRel. cryst (%)SSA (m /g) Micropore s/a External s/a Pore vol. Acid sites 2 b 2 3 c (m /g) (m /g) (cm /g) Peak 1 Peak 2 Acidity T (° C) Acidity T (° C) max max (µmol/g) (µmol/g) ZSM-5 100 350 223 127 0.21 443 193 190 395 0.5% Fe 90 341 207 134 0.22 407 183 75 375 2% Fe 87 332 210 122 0.21 336 180 55 387 5% Fe 65 317 203 114 0.20 359 187 59 391 0.5% Cr 100 331 208 123 0.21 443 200 130 395 2% Cr 100 320 209 111 0.22 395 195 123 378 5% Cr 90 308 195 113 0.20 363 194 79 382 Relative crystallinity determined from the five most intense XRD peaks in the 7°–9° and 22°–25° 2θ range Areas determined using t plot Determined using BJH method Acidity determined by NH -TPD measurements some change to the structure of the ZSM-5. Similar effects micropores of the zeolite which leads to pore blocking. The were observed by de Oliveira et al. [9] on iron impregnated surface areas for Cr-modified ZSM-5 compared to Fe are ZSM-5 in the 2.5–5 wt% range. Furthermore, no peaks cor- slightly lower for all comparable loadings. This may be due responding to that of iron oxide could be detected. This to a difference in metal particle size and dispersion. may be due to the metal loading being too low or the iron The un-modified ZSM-5 also has the highest amount of crystallites too small for X-ray diffraction indicating a high acidity. The total acidity decreases with an increase in metal dispersion [10]. loading from 0.5 to 5 wt% for both Fe and Cr modified sam- In Fig.  1b it is also noticed that the modification of ples. As shown in Fig. 2a, b, two peaks are observed in the ZSM-5 zeolite with Cr (0.5–5 wt%) by impregnation method NH -TPD profiles at approximately 190 and 390° C cor - did not affect the crystallinity of ZSM-5 as observed with responding to weak and strong acid sites, respectively. As the Fe modified catalysts. Chromium oxide can exist in two noticed in the TPD profiles, the area of the second peak cor - phases, i.e., CrO and Cr O corresponding to Cr(VI) and responding to stronger acid sites which may include Bron- 3 2 3 Cr(III), respectively. It is possible that both phases may be sted sites originating from framework aluminium within present in the sample; however, peaks corresponding to the the micropores decreases with increasing metal loading. It CrO phase are overlapped by ZSM-5 peaks. As the load- is possible that by metal particles blocking the micropo- ing increases from 0.5 to 5% it is noticed that there is slight res of the zeolite access to stronger acid sites are restricted. increase in intensity of the peak at 33.6° 2θ. This peak cor- Although the effect of Fe and Cr loading on the ZSM-5 sur - responds to chromium oxide(Cr O ) confirming the presence face area was quite similar, interestingly Fe has a greater 2 3 of chromium on the 5 wt% Cr loaded sample [11]. effect on the acidity in particular the amount of strong acid The physicochemical properties, acidity and porosity sites. As noticed in Table 1, Fe loading causes a much larger of Fe and Cr impregnated ZSM-5 were performed using decrease in the amount of strong acid sites than Cr for all NH -TPD and N physisorption, respectively. The results analogous weight loadings. This may be due to a difference 3 2 are shown in Table 1 below. in metal particle size and dispersion as well as metal/acid The un-modified ZSM-5 has both the largest micropore site interaction. Lai et al. [10] have shown using UV–Vis 3+ and external surface areas summing up to the highest SSA spectroscopy that Fe can exist as isolated Fe species, Fe O x y of 350 m /g. After metal loading the SSA is seen to decrease oligomeric clusters and F e O nanoparticles which can eas- x y and decreases further with increasing Fe and Cr loading ily access the pore network of ZSM-5. Krishna and Makkee from 0.5 to 5 wt%. A smaller decrease in the external sur- [12] have also reported Fe species associated with frame- face area compared to micropore surface area is observed work alumina using NO DRIFTS. From the XRD Fe could with increased metal loading from 0.5 to 5 wt% for both Fe not be detected whereas Cr at higher loading was present and Cr modified samples. For both metals, samples with indicating that Cr may have a larger particle size and less the highest loadings have the lowest micropore surface dispersion and therefore less interaction with strong Bron- areas. This suggests that Fe and Cr metals are located in the sted acid sites than Fe. 1 3 Applied Petrochemical Research (2018) 8:119–129 123 0.015 0.04 a 0.5% Fe ZSM-5 2% Fe 0.5% Fe-ZSM-5 5% Fe 2% Fe-ZSM-5 0.5% Cr 5% Fe-ZSM-5 0.03 2% Cr 5% Cr 0.010 0.02 0.005 0.01 0.000 0.00 0100 200 300 400500 600 100200 300400 500 600 Temperature (Deg. C) Temperature (C) b 0.04 Fig. 3 H -TPR profiles of Fe an Cr modified ZSM-5 with weight 0.5% Cr-HZSM-5 2 loadings (0.5, 2 and 5 wt%) 2% Cr-HZSM-5 5% Cr-HZSM-5 H-ZSM-5 0.03 CrO to Cr O . It is known that loadings of 5 wt% and less 6 2 3 6+ generally exist in the Cr form [14–16] and as loadings 0.02 increase chromium may exist as α-Cr O . Michorczyk et al. 2 3 [15] have shown that Cr content above 3.4 wt% results in the appearance of an additional low temperature reduction peak 0.01 at approximately 280 °C, which coincides with the reduc- 6+ 3+ 2+ tion of crystalline α-Cr O rom a Cr to a Cr [17] or Cr 2 3 [11] species. Thus, it is possible that the Cr modified sam- 0.00 ples contain both CrO and Cr O phases as the broad peaks 100200 300400 500600 3 2 3 observed in the TPR profiles extend over the temperature Temperature (deg. C) ranges in which both phases are reduced. Furthermore, the Cr O phase was detected by XRD for the 5% Cr sample fur- Fig. 2 a NH -TPD profiles of unmodified and Fe loaded ZSM-5 cata- 2 3 lysts. b NH -TPD profiles of unmodified and Cr loaded ZSM-5 cata- ther supporting this notion. It may be worthwhile to conduct 6+ 3+ lysts an XPS analysis to confirm the Cr /Cr ratio as the two species have a different effect on the catalytic performance. H -TPR was used to confirm the reducibility character - SEM, EDS and XRF analysis were used to confirm the istics and metal species present in the samples. The profiles ZSM-5 Si/Al ratio and metal loading. The results are shown of Fe and Cr- modified ZSM-5 are shown in Fig.  3 and the in Table 3. peak concentrations are shown in Table 2. From Table 3 it is noticed that the average Si/Al molar From the profiles in Fig.  3 it can be observed that there and atomic ratios as determined by XRF and EDS are about are two reduction maxima for the Fe modified ZSM-5 at 30 and 17, respectively, for all samples and are close to the approximately 350 °C and 450–500 °C. This corresponds given Si/Al ratio of the commercial Zeolyst ZSM-5. Thus, 3+ 2+ to the reduction of Fe O to Fe O (Fe → Fe ) and Fe O 2 3 3 4 3 4 2+ 0 to Fe metal (Fe →Fe ), respectively [13]. It is also noticed Table 2 Hydrogen consumption that the area under the reduction peaks increase as the iron Sample H consumption for the Fe and Cr loaded ZSM-5 (µmol/g) loading increases as more hydrogen is being consumed in samples the reduction reaction. The H uptake is shown in Table 2 Peak 1 Peak 2 and increases from 12 µmol/g for the 0.5% Fe to 337 µmol/g 0.5% Fe 1 11 for 5% Fe. The reduction temperature also increases from 2% Fe 44 45 approximately 450 to 500 °C. 5% Fe 104 233 The Cr doped ZSM-5 samples exhibit a single reduction 0.5% Cr 135 peak. A broad peak from 200 to 450 °C with a maximum 2% Cr 152 at approximately 300 °C can be attributed to the reduction 5% Cr 169 6+ 3+ of Cr → Cr species corresponding to the reduction of 1 3 TCD Signal (a.u) TCD Signal (arb.units) TCD Signal (a.u.) 124 Applied Petrochemical Research (2018) 8:119–129 Table 3 XRF and EDS analysis a b Sample Si/Al ratio-XRF Si/Al ratio-EDS Metal loading (%) of Fe and Cr modified ZSM-5 XRF EDS Fe Cr Fe Cr ZSM-5 31.6 15 – – – – 0.5% Fe 33 17.2 0.8 – 2% Fe 31.5 17.0 2.6 2.0 5% Fe 31.1 17.1 6.4 3.9 0.5% Cr 30.8 16.6 0.3 1.3 2% Cr 30.4 15.9 0.9 3.1 5% Cr 30.4 18.2 2.1 11.0 Molar ratio from XRF analysis Atomic ratio from EDS analysis metal loading by impregnation method has not resulted in The results of the catalyst activity and selectivity are dealumination of the zeolite. The metal loadings as deter- shown below. The effect of metal loading on the activity mined by XRF show that ZSM-5 impregnated with Fe are of the catalysts is shown in Fig. 5 and is compared to the in close agreement with the theoretical loadings and all parent ZSM-5. sample was successfully loaded onto the zeolite. However, Figure 5 shows the conversions as a function of time on the ZSM-5 loaded with Cr seems to be slightly below the stream for the various metal modified catalysts. It is noticed theoretical loadings of 0.5, 2 and 5 wt% for all analogous that the initial conversions are in the range of 44–56%. The loadings. The metal loading for the 0.5% Fe sample could parent ZSM-5 catalyst has the highest initial conversion of not be detected by EDS analysis. This may be due to the 56%. The initial conversions are lower for metal modified loading being below the detection limit of 1 wt%. However, catalysts compared to the parent ZSM-5. As the Fe loading for the 2% Fe and 5% Fe samples the metal detected by increases from 0.5 to 5% the initial conversion decreases EDS increases as the loading increases and is in agreement from ~ 55 to 47%. This may be due to Fe particles block- with the batch loading. Interestingly, the Cr metal loading ing stronger Bronsted sites responsible for cracking reac- percentages determined by EDS are slightly higher with the tions. The Cr modified ZSM-5 catalysts have initial con - 5% Cr sample having a loading of ~ 11%. Although lower versions much lower than the Fe modified catalysts. The loadings were detected by XRF the higher loadings observed 2% Cr–ZSM-5 has the lowest conversion of 44%. No clear with EDS analysis may be due to lower dispersion and clus- trend is observable as to the effect of chromium loading on tering of Chromium particles on the zeolite compared to the conversion of naphtha as the 5% Cr has a slightly higher that of Iron. X-ray mapping of the samples with the highest initial conversion than the 2% Cr and is similar to 0.5% Cr loadings, i.e., 5% Fe and Cr was conducted and is shown in catalyst. As the reaction proceeds, all catalysts show some Fig. 4. The results show that both Fe and Cr are well dis- deactivation. Interestingly, The Fe promoted catalysts show persed although chromium appears to have a greater amount a lesser decrease in activity between the initial and final con- of metal present on the surface and small clusters are visible. versions. The parent ZSM-5 shows the largest decrease of approximately 12%. As the Fe loading increases the reduc- Catalytic performance tion in activity is less significant with the 5% Fe–ZSM-5 only decreasing by 5%. Thus, it can be said that modification ZSM-5 was modified with Fe and Cr via the incipient wet- with Fe enhances the stability of the catalyst. The Cr cata- ness impregnation method. ZSM-5 was loaded with 0.5, 2 lysts also show some slight deactivation. The 0.5 and 5% Cr and 5 wt% Fe. The catalysts were calcined at 500 °C for catalysts show similar stability. However, the 2% Cr catalyst 6 h to convert Fe and Cr to the oxide form. The catalysts which had the lowest initial conversion seems to be the most were then used in the cracking of Naphtha at the following stable of the Cr modified catalysts. −1 reaction conditions, i.e., T = 550  °C, WHSV = 16 h, N : The effect of Fe and Cr on the selectivity to lower olefins, Naphtha feed ratio of 4:1 at atmospheric pressure. Naphtha i.e., C –C olefins for the third and last hours of the reaction 2 5 obtained from Chevron was analysed prior to being used as is shown in Table 5. a feed to determine the hydrocarbon composition. This was All the Fe modified catalysts show a similar selectivity to done by GC analysis and the Detailed Hydrocarbon Analysis total olefins in the third hour of the reaction of ~ 48% with (DHA) software. The composition is shown in Table 4. a slight decrease observed for the 5% Fe catalyst. The same 1 3 Applied Petrochemical Research (2018) 8:119–129 125 Fig. 4 X-ray mapping of 5% Fe and 5% Cr ZSM-5 samples trend is observed for the selectivity to propylene of which hour decreases the selectivity also decreases. However, the 5% Fe has the lowest (16.2%). The 2% Fe catalyst has in the last hour of the reaction in which the conversion is the highest selectivity to propylene of 21.6%. The trend lower than in the third hour for all catalysts the selectivity indicates that the selectivity to total olefins and propylene to total olefins increases. This is due to the increase in C is related to the conversion. As the conversion in the third olefins. The selectivity to propylene tends to decrease except 1 3 126 Applied Petrochemical Research (2018) 8:119–129 Table 4 Hydrocarbon Paraffins Paraffins Paraffins Olefins Olefins Olefins Aromatics Others Total composition of naphtha Cyclo Iso Normal Cyclo Iso Normal obtained from Chevron Naphtha feed C 0 0 0.03 0 0 0.06 0 0 0.09 C 0.47 0.77 0 0 4.5 1.27 0 0.56 7.57 C 0.39 1.73 0.85 0.67 15.15 0 0 0.66 19.45 C 0.1 2.05 0 0.77 7.93 0 2.42 4.166 17.436 C 0.86 1.42 0.52 0.05 7.91 1 3.31 0.585 15.655 C 2.17 1.3 0 0 4.29 0.05 5.91 0.275 13.995 C 1.36 2.6 0.29 0 1.35 0.25 5.01 0 10.86 C 0.07 3.54 0.35 0 0.2 0 3.65 0.075 7.885 C 0 2.75 0.23 0 0 0 2.58 0.686 6.246 C 0 0 0.12 0 0 0 0.32 0.373 0.813 Total 5.42 16.16 2.39 1.49 41.33 2.63 23.2 7.38 100 for the 2% Fe–ZSM-5 catalyst in which a slight increase is observed. The trend that selectivity is related to conversion is maintained as the 2% Fe–ZSM-5 catalyst has the high- est conversion in the last hour approximately 50% and the highest selectivity to total olefins of 60% is obtained. The results indicate that a conversion of 50% and above needs to be maintained for high propylene selectivity and the optimum metal loading seems to be 2%. The Fe promoted ZSM-5 catalysts also show a lesser decrease in selectivity to pro- 0.5% Fe 2% Fe pylene with time compared to the parent ZSM-5 with the 5% Fe highest metal loading of 5% Fe–ZSM-5 catalyst having the 0.5% Cr 2% Cr smallest decrease. This is related to the enhanced stability of 5% Cr 5% Fe–ZSM-5 catalyst. Therefore, the results indicate that 150 200 250 300350 400450 modification with Fe enhances both selectivity to olefins and Time (min) the stability of the catalyst. The selectivities to C and C for the Cr modified cata- 2 3 lysts decrease slightly from the third to the last hour and fol- Fig. 5 Naphtha conversions as a function of time over the parent and metal modified ZSM-5 catalysts low the trend that at higher conversions higher selectivities Table 5 Selectivity to olefins in the gas product for parent, Fe and Cr modified ZSM-5 Olefin selectivity ZSM-5 0.5% Fe 2% Fe 5% Fe Third hour Last hour Third hour Last hour Third hour Last hour Third hour Last hour C 9.0 2.0 6.3 3.6 8.3 5.4 4 2.6 C 20.8 12.6 19.0 14.9 21.6 23.6 16.2 13.5 C 7.6 11.7 8.7 8.4 8.7 10.9 8.7 11.2 C 10.7 26.2 14.6 24.2 8.7 21.4 16.4 23.6 Total 48.1 52.5 48.6 51.1 47.3 61.3 45.3 50.9 Olefin selectivity 0.5% Cr 2% Cr 5% Cr Third hour Last hour Third hour Last hour Third hour Last hour C 3.0 1.9 3.1 1.7 3.4 1.5 C 9.7 8.1 9.0 5.7 11.4 7.0 C 11.1 11.3 9.9 7.2 9.9 10.3 C 12.7 16.2 19.0 16.6 13.3 25.0 Total 36.5 37.5 41.0 31.2 38.0 43.8 1 3 Conversion (%) Applied Petrochemical Research (2018) 8:119–129 127 are observed. Interestingly, no change in selectivity to eth- From the results of selectivity to gas olefins the 2% Fe had ylene or propylene is observed for an increase in chromium the greatest selectivity therefore it is expected that it would loading. The ethylene and propylene selectivity in the third have a lower selectivity to olefins. However, this may sug- and last hours of the reaction of 3 and 1.7% and approxi- gest that Cr catalysts actually promote aromatics production mately 10 and 7%, respectively, is maintained. Selectivity of which the 2% Cr–ZSM-5 is the best catalyst. to C olefins remains constant for all catalysts while a slight A plot of the selectivity to BTEX products is shown in increase to C olefins is noticed. However, when compared Fig. 7. to Fe modified catalysts the Cr catalysts have a much lower From Fig. 7 it is noticed that BTEX selectivity is higher selectivity to lower olefins (C –C ) in both the third and last initially for all Fe catalysts (~ 20–24%) and decreases with 2 5 hours of the reaction. A difference of 30% is observed when time on stream as the conversion decreases to between 13 2% Fe is compared to 2% Cr in the last hour. This indicates and 15%. No clear trend is observed with respect to BTEX that Fe is a better promoter to enhance selectivity to light selectivity However, it is evident that the Cr–ZSM-5 cata- olefins than Cr. It is possible that the difference in acid- lysts are more selective to aromatic products than Fe–ZSM-5 ity is responsible for the difference in selectivity. As the Cr and reaches a maximum for the 2% Cr-catalyst. The 2% Cr ZSM-5 has slightly higher total acidities when compared to catalyst has the highest selectivity of ~ 29% of which the Fe, readsorption of light olefins on acid sites may occur lead- composition is mainly toluene and xylenes and small amount ing to secondary aromatisation reactions thus also indicating zeolites with a lower acid site density would give selectivity 3rd Hour to light olefins while suppressing aromatics formation [18]. Last Hour The selectivity to liquid products for the metal modified catalysts is shown in Fig. 6. The hydrocarbon composition of the liquids range from C to C and consist of aromat- 5 14 ics, paraffins, naphthenes and olefins as observed from GC analysis using a DHA column of which aromatics make up the bulk of the product. From the graph it is noticed that the selectivity to liquids remains constant for the parent ZSM-5 in the initial and final hour of the reaction. Interestingly, the Fe and Cr modified ZSM-5 show stark differences in selectivity. The Cr–ZSM-5 catalysts show higher selectivi- ties compared to Fe–ZSM-5 catalysts in the initial hours of the reaction. As the reaction proceeds, the Cr catalysts Parent 0.5% Fe 2% Fe 5% Fe 0.5% Cr 2% Cr 5% Cr increase in selectivity, whereas the Fe catalysts decrease. Catalysts Remarkably the 2% Cr catalyst has the highest increase in selectivity to liquid products (~ 65%) compared to the 2% Fig. 7 Bar graph showing selectivity to BTEX products for all metal Fe which shows the largest decrease in selectivity (~ 35%). modified catalyst Fig. 6 Total liquid product selectivity of metal modified catalysts ZSM-5 0.5% Fe 2% Fe 5% Fe 0.5% Cr 2% Cr 5% Cr 150 200 250 300350 400450 Time (min) 1 3 Total Liqui Selectivity (%) BTEX selectivity (%) 128 Applied Petrochemical Research (2018) 8:119–129 5.5 3rd Hour Conclusion Last Hour 5.0 4.5 Metal modification with Fe and Cr had an effect on both 4.0 the physicochemical properties of the catalysts as well as the catalytic performance. Metal loading did not affect 3.5 the crystallinity of the ZSM-5 but caused a decrease in 3.0 the specific surface area which decreased further with 2.5 increased metal loading. Fe had a greater effect on the total 2.0 acidity in particular strong acid sites when compared to Cr. 1.5 Fe acted as a promoter of both selectivity to olefins, in par - 1.0 ticular propylene as well as enhanced the stability of the 0.5 catalyst. The best results were achieved with a Fe loading 0.0 of 2% which gave the greatest selectivity to propylene of Parent 0.5% Fe 2% Fe 5% Fe 0.5% Cr 2% Cr 5% Cr 23.6% and total olefin selectivity of 60%. Furthermore Fe Catalysts modification improved the P/E ratio from two to a maxi- mum of five. Cr modification was found cause a decrease Fig. 8 P/E ratios for all metal-modified catalysts in selectivity to lower olefins and an increase in selectivity to BTX products. The highest selectivity to BTX of ~ 65% of benzene is produced. Lu et al. [8] have shown that Cr was obtained with the 2% Cr–ZSM-5 catalyst. in small amounts between 0.004 and 0.038 mmol/g alters Acknowledgements The authors would like to thank the Petroleum, acidity and plays an important role in promoting cracking Oil and Gas Corporation of South Africa (PetroSA) for their financial of isobutane and dehydrogenation of isobutane to isobutene support and technical discussions, the electron microscope unit, Phys- which is then easily cracked to lighter olefins and is similar ics Department, University of the Western Cape for the SEM images to iron in promotional effects. However, the differences in and Ithemba labs for the XRD work. product distribution observed in this study between Fe and Open Access This article is distributed under the terms of the Crea- Cr modified samples indicate different promotional mecha- tive Commons Attribution 4.0 International License (http://creat iveco nisms in the cracking of refinery naphtha. In particular Cr mmons.or g/licenses/b y/4.0/), which permits unrestricted use, distribu- ions are shown to favour aromatization and alkylation reac- tion, and reproduction in any medium, provided you give appropriate tions. The chromium loadings in our study fall in the range credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. of 0.059–0.409 mmol/g which is higher than the range estab- lished by Lu et al. [8] for promotion of dehydrogenative cracking which may suggest that higher loadings of chro- mium above 0.038 mmol/g may promote aromatization reac- References tions. The exact cause, i.e., role of acidity and metal support interaction is not clearly understood and further analysis of 1. 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Published: May 4, 2018

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