Luận văn thạc sĩ Kỹ thuật hóa dầu: Investigating catalysts based on ZSM-5 modified by phosphorus for propylene production from atmospheric residue

HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY LE TRUNG NGHIA INVESTIGATING CATALYST BASED ON ZSM-5 MODIFIED BY PHOSPHORUS FOR PROPYLENE PRODUCTION FROM ATMOSPHERIC RESIDUE MASTER THESIS

INTRODUCTION AND LITERATURE REVIEW

Propylene production technology review

There is a gradual rise of the light olefin consumption intensifying its production from current processes Moreover, annual Ethylene and Propylene production roughly 1.5×10 8 ton, 8×10 7 ton in the order given [1,2] , along with Propylene demand is increasing 5.7 - 6 % during 2016-2025 [3,4] Light olefins in general and Propylene in specific are important basic raw materials for the petrochemical industry, and the demand for light olefins such as ethylene and propylene consumption are increasing every year [5,6]

Besides, the high fatigue strength of components making by Polypropylene material is valuable property for household or industrial goods production [7,8]

The trend of some research in the recent year converts FCC feedstock to get higher Olefin yield to make polymer and various other petrochemicals [9,10] Because Petrochemical can get more benefits for non-fuel refinery products, while high- quality gasoline production is costly, and the electrical engine is also a new tendency of automobile production Using catalytic additives and adjusting operating conditions Propylene has broad application in a global market (Polypropylene, Acrylonitrile, Acrylic Acid, Propylene oxide, Cumene, and others) [11]

In fact, Propylene is producing in the catalytic processes only, and there are 3 technologies including Steam crackers or Pyrolysis which produce Propylene as an additional product, whereas Ethylene is the main product [12] , Fluid Catalytic Cracking, and Propane Dehydrogenation Giving details by latest statistic processes, Steam crackers provide about 60% of propylene, FCC units provide 30-35% and others such as Propane dehydrogenation, for instance, provide the remainder [12,13] Nevertheless, steam cracking needs high energy requirements and carbon dioxide emission, it boosted the Propylene production in Fluid Catalytic Cracking as

LE TRUNG NGHIA’S MASTER THESIS 2 alternatives [1] Making more propylene by the FCCU is the true way make great contribution to meet the demand for propylene consumption, saving fossil fuel and lowing impacts of the greenhouse effect by cutting down exhaust fumes emission In the next ten years, the FCCU which is also an alternative method of Steam crackers produces even higher propylene yields

Optimizations can be acquired by changes in the reaction conditions, i.e raising riser temperature, residence time or the cat/oil-ratio, where total conversion is primarily increased [2] HZSM-5 additive using without any post-modification accounts for 25 wt.% of FCC catalyst, the propylene yield is only 8.8 at C/O=2.3 and Conversion is about 70% [3]

Figure 1-1: The propylene supply and demand [4]

Figure 1-1 shows the propylene supply and demand for past summaries and the forecast from now until 2021, maximization of propylene production has become the focus of most refineries because it is in high demand and there is a supply shortage from modern steam crackers, which now produce relatively less propylene

The flexibility of the fluid catalytic cracking (FCC) to various reaction conditions makes it possible as one of the means to close the gap between supply and demand, not exceed 5% under regular operating in the FCC unit [4]

LE TRUNG NGHIA’S MASTER THESIS 3 The world Propylene demand is bigger than the total of Propylene yield from both Steam Cracker and FCC method production route Although the gap can easily fill Propylene yield from steam cracker route which is not perfect with inflexibility operating conditions as well as high rate energy loss, so the FCC solution is potentially chosen by those later reasons

• Firstly, the use of lower activation energy for C-C bonds leads to the new naphtha cracking process is 150-250°C lower than those for steam crackers;

• Secondly, catalysts improve selectivity to the desired product as propylene for instance even in the same conditions as those of steam cracker, the olefin yield is determined higher than all;

• Thirdly, the generator unit solves the coke formation on the surface of the catalysts;

• Fourth, the flexibility of the FCC is higher than a steam cracker

Additionally, the circulating fluidized bed is equipped by FCC technology, which has originally efficiency heat, mass transfer, and catalyst generation that go forward the upgrading of heavy feed to gasoline In term of olefin production, the remarkable principle has based on the interaction of feed and one or more crystalline microporous molecular sieves to selectively the feed into an olefin After excluding the energy content of final products, it is supported that Steam Cracker is also most of the energy- consuming process reached approximately about 8 % energy consumption of the global primary energy use [4]

Zeolite applications

The main duty of FCC transforms the high-boiling feedstocks, a low-value fraction as residue from Atmospheric Distillation Column or Vacuum Distillation Column into the valuable product such as Gasoline, LPG, Diesel The catalytic cracking is more efficient in energy use and gives high yields of propylene and ethylene at relatively low temperatures [5-7]

LE TRUNG NGHIA’S MASTER THESIS 4 Under the severe regenerator condition in order to maintain the activity of catalysts for cracking heavy oils, the high hydrothermal stability is the important property impact on Catalyst lifespan, the cost of changing catalyst [8] It can be solved by the post-synthesis treatments with Phosphorus, enhancing stability was anticipated along with the Propylene selectivity in term of Phosphorus impregnation

Catalysts for cracking heavy oils or atmospheric residue must have high hydrothermal stability in order to maintain activity under severe condition of regenerator and selectivity for light and high-valuable outputs’ production such as olefin, gasoline or diesel Steam catalytic cracking operating in the FCC mode could be an interesting approach for cracking heavy crude oil into light olefins [9]

The cracking reaction temperature is about 950°F (510°C) in the reactor [10] , whereas the generator temperature is severely performed more than 700°C [11] together with the presence of steam) [8,12]

Table 1-1 : Properties of major synthetic zeolites [10]

Xylene isomerization, benzene alkylation, catalytic cracking, catalyst dewaxing, and methanol conversion

According to Table 1-1, the properties information shows the high acidity of Faujasite zeolite type compared to ZSM-5 which has the lower Aluminum ingredient

In other words, the lower activity belongs to ZSM-5 in the application

LE TRUNG NGHIA’S MASTER THESIS 5 Figure 1-2 : Schematic depiction of the typical fluid catalytic cracking FCCU [12]

Figure 1-2 shows the schematic depiction of the typical fluid catalytic cracking (FCC) process, including reactor and regenerator [12] A regeneration step in the FCC process, the recycling of catalyst is performed in the severe condition at the high temperature together with the presence of steam [8] For the industrial application, zeolite needs to be processed to improve the hydrothermal stabilization which is the most essential properties of zeolites [13]

LE TRUNG NGHIA’S MASTER THESIS 6

Many components consist of zeolite, matrix, filler, and binder need to build a typical FCC catalyst [14]

Figure 1-3: Schematic representation of FCC catalysts [15]

Figure 1-4 : Incorporated FCC catalyst production process [14]

Both the Figure 1-3 and Figure 1-4 point out the ZSM-5 belongs to part of FCC catalyst, whereas the positive benefits of Phosphorus modifying have been investigated not only Zeolite component, but Binder in FCC catalyst also [16] Unlike ZSM-5 main role contributing cracking reaction, Binder is a substance added to the mixture to make all parts stick together Using in the combination with Ultra Stable

LE TRUNG NGHIA’S MASTER THESIS 7 Y Zeolite in FCC catalysts, ZSM-5 cracks low octane gasoline range material formed primary cracking with Ultra Stable Y [17] Steam treatment condition is also an important part in the first phase and synthesized ZSM-5 with various Si/Al ratio and its application to improve Motor octane number in my engineer thesis which plays an important role of this research

Figure 1-5: Mechanism of coke formation for several reactant molecules

Figure 1-5 shows the mechanism of coke formation for several reactant molecules such as Oligomerization (OL), hydrogen transfer (HT) and cyclization (Cyc) [18]

In the comparison, the possibility of Coke deposition on ZSM-5 is lower than zeolite Y due to its narrow pore which makes limitation of bulky coke One more evidence to prove that the ZSM-5 need to be added to the FCC catalysts instead of the absolutely 100 percent Y zeolite and other components [4]

ZSM-5 additives in FCC catalysts

When P-impregnated ZSM-5 sample is used as an additive for cracking industrial feeds, selectivity to propylene increases [19] The family of MFI type zeolites, especially ZSM-5 thanks the invention of Mobil Oil company, has used in Petrochemical industry and Refinery processes widely since 1967 [20] The commercialization of ZSM-5 additive which plays a preferential cracking selectivity

LE TRUNG NGHIA’S MASTER THESIS 8 obtains increasing C2-C5 olefins yield from in general and to Propylene yield in particular [9]

Figure 1-6: Effect of ZSM-5 contents on propylene yield by wt.% [4,9]

The figure 1-6 showed the effect of ZSM-5 contents on propylene yield by wt.%, supposing the ZSM-5 loading higher than 10% has no considerable increase of propylene, so it is not necessary the high existence of ZSM-5 in order to produce high propylene yield

There are many types of research using ZSM-5 which produces Propylene from raw-materials [21] The well-known application to improve motor octanes of gasoline produced via Fluid catalytic cracking process [17]

LE TRUNG NGHIA’S MASTER THESIS 9 Table 1-2 : Landmark in the history of zeolites and related materials [20]

1962 Zeolites as FCC catalysts Mobil Oil

1967 Syntheses of zeolite beta and ZSM-5 Mobil Oil 1982 Aluminum phosphate molecular sieves Union Carbide 1983 First commercial use of ZSM-5 octane/ olefins additive in FCC [10]

Table 1-2 lists the timeline of ZSM-5 invention and olefins produce an application in reality

As figure 1-9 and figure 1-12, ZSM-5 and silicalite have two types of channels

The Zig-zag channels 5.4 × 5.6 Å interconnecting with the Straight channels 5.2×5.8 Å

Figure 1-7: Molecular traffic control in the Straight elliptical and Zig-zag circular channels of ZSM-5 zeolite [22,23]

According to the figure 1-7, catalytic properties of ZSM-5 zeolites completely depends on the topology of zeolite structure, for example; it can understand that the molecules are bigger than the entrance route cannot go through the sinus system of ZSM-5 to transform into new forms Besides, the other scientists called these porous systems by the other names

Figure 1-8: Channel structures of ZSM-5 and ZSM-11 [24]

According to the figure 1-8 as the Sato (1997) ‘ s summarization [24] , the prospects of Pentasil zeolite as ZSM-5 has never become obsolete relying on a variety of applications The ratio of solid acidity over substrates affinity is widely available, especially; that of Silica per Aluminum can be freely controlled in a range of 6 to infinity In other words, the activity of the catalyst can be changed for specific reactions

Like Figure 1-9, the model of a porous system showed the way that the molecules connect together to become the porous system

LE TRUNG NGHIA’S MASTER THESIS 11 Figure 1-10: Schematic of the intergrowth structure of a ZSM-5 crystal and the relative pore orientations [26]

Figure 1-10 shows the crystal structure of typical ZSM-5, the major activity and selectivity effects are caused by the nature and content of the zeolites present

The pore size and shape in a zeolite may affect the selectivity of a reaction in three ways [27] :

Firstly, reactant selectivity occurs when the aperture size of the zeolite is such it admits only certain smaller molecules and excludes larger molecules; hence, in a mixture, effectively only the smaller molecules react;

Secondly, product selectivity occurs when bulkier product molecules cannot diffuse out, and, it formed, they are converted to smaller molecules or to carbonaceous deposits within the pore These eventually may cause pore blockage;

Thirdly, Spaciospecific selectivity was proposed [28] The conclusion is insufficient space was available in the pores for two molecules of the dialkyl benzene to come together This type of behavior is sometimes also termed restricted transition-state selectivity Unlike reactant or product selectivity, spaciospecific;

The mechanism from the intake of feedstocks to propylene

Limited the rate hydro transfer reaction which promotes the olefin hydrogenation makes the olefins regeneration or increased rate of hydrogen transfer reactions decreased the yield of propylene [3] Furthermore, cutting down hydrogen transfer activity as low as possible which tailors by the based-Y-zeolite catalysts of FCCU prevents the coke formation The recommendation to increase light olefins yield in the FCC process is adding ZSM-5 zeolite as additive Besides, not only adding ZSM-5 zeolite additive but also these methods: Using ZSM-5 with optimized Si/Al (low acidity), hydrothermally deactivated ZSM-5, treatment with phosphorus

Figure 1-21: FCC reactions pathways to produce olefins [64]

Figure 1-21 shows the ZSM-5 contribution for boosting C3,4,5= yield in the FCC unit, and the naphtha olefins yield is in the inversely proportional to olefin output

LE TRUNG NGHIA’S MASTER THESIS 23 Figure 1-22: Gasoline turning into a gas by FCC catalyst with Zeolite additive [3]

On the other hand, there is some research giving the recommendation of the role of elimination of hydro transfer to produce naphtha olefin leading to olefin [38] In other words, depending on the shape selectivity structure of ZSM-5, mostly C3- C5 are selectively cracked from low linear low octane compounds in the gasoline boiling range [38,59,65-66] The key feature to increase the production of light olefins in the FCC process is to preserve the olefinic products resulting from beta scission primary cracking reaction [38,67] Besides, primary olefins are less stable and can be easily consumed through bimolecular reactions such as cyclization and hydrogen transfer reactions [68]

Scheme 1-1: Dominant pathways for FCC paraffin production [38]

Scheme 1-1 shows the influence of Hydro transfer on products from Gasoil or Distillate input In term of Catalytic Cracking of Paraffins, carbonium ion formation was recommended as the main source in the primary step of catalytic reaction in both mechanisms

LE TRUNG NGHIA’S MASTER THESIS 24 Under the observation, the carbon-catalyst linkage formed in the first step of the cracking According to the research of Taylor in 1948, this thing was proven by the easy exchange of CD4 and CH4 The simultaneous loss of a hydride ion (H:) from the paraffin molecular and a proton from the acidic catalyst surface In the first step of cracking reaction, a carbonium ion generates in the combination of the acid anion (A) and molecular hydrogen:

Before the olefin and new carbonium ion are generated by the second step of catalytic cracking, either carbonium ion or activated molecular decomposes The carbon-carbon cleavage occurs at the position one carbon atom away from the carbonium-ion carbon atom, which can be understood as the same as Markovnikov’s rule

Scheme 1-2: Forming Propylene from Alkanes reaction [69]

Following Scheme 1-2, the well-known Beta-scission principle was developed by F.C Whitmore which recommends the shifting of electrons only in the carbonium systems While the priority tendency of transforming to the stable configuration is a principle of the reactions, the next carbonium ion is higher level than the previous one [69]

Consequently, this step explains the presence of the olefin product from the Catalytic Cracking process as FCC Catalytic cracking is a vital process giving both the side chain hydrocarbon and the olefin generation from the primary n-paraffin in the FCC

On the other hand, four major types of hydrocarbons react in the primary cracking step, which can be seen from the following type reactions [70] :

Paraffin → Paraffin + Olefin Olefin → Olefin + Olefin Naphthene → Saturate + Olefin or Olefin + Olefin Aromatic → Aromatic + Olefin

Interest needs to be considered that is the control of hydro transfer can be limited the Propylene molecular consuming in the alkene hydrogenation reaction from the catalytic cracking products, as a consequence of:

CH2=CH−CH3 + H + → CH3−C + H−CH3 [70]

After that, two ions can be combined to become a new ion bigger than the original one:

CH3−C + H−CH3 + CH3−C + H−CH3 → CH3-CH(CH3)-CH2−C + H−CH3

The effect of increased octane rating is most pronounced with paraffinic feeds and stems primarily from increased olefin content The key is the effect of the catalyst to control the ratio of hydrogen transfer to cracking In a highly siliceous zeolite, acid sites are more widely dispersed, and this minimizes hydrogen transfer by:

Formation of coke, which proceeds from H-deficient polyaromatics, is also reduced for the same reason, example the acid sites in Ultra Stable Zeolite Y are also stronger than the rare-earth modified zeolite Y, which enhances cracking instead of H transfer

Incorporation of shape-selective zeolites into the final catalyst, usually in a small amount such as ZSM-5, also increases the octane number of the gasoline produced by selectively cracking paraffin However, this decreases gasoline yield [71] The stronger Brứnsted acid sites might be generated by the steaming for short times, resulting in the enhancement in the catalytic activity On the other hand, the activation energy for the cracking of heptane decreased with a decrease in the Si/Al atomic ratio

LE TRUNG NGHIA’S MASTER THESIS 26 of the parent H-ZSM-5 [72] Wielers et al have reported that the H-ZSM-5 containing the lower aluminum concentration exhibits the higher activation energies for the cracking of hexane [72,73] However, it has been reported that the Brứnsted acid strength is constant or slightly weakened by increasing Al contents [72,74, 75].

Phosphorus post-modification of ZSM-5

The most practiced Phosphorus penetration to modify the ZSM-5 additive is Wet-impregnation which chose as a priority in state-of-the-art research [19,53,76-85] There are several common precursors, which can be applied for modifying ZSM-5 additive purpose to upgrade Propylene yield including Phosphoric acid [19,42,47,49,60,76-

, as well as less acidity precursors such as NH4H2PO4 [19,60,83] and (NH4)2HPO4 [81,85,89].were used in catalyst preparation The most remarkable phosphorus precursor choosing for a wet-impregnation method on ZSM-5 is H3PO4 [13,19,39,41,90,91], but investigating the affections of various precursors belongs to this project

The phosphorus treatment effects have already published lead to a decrease in the coke cover in the surface of the catalysts including micropores area and external surface area [50,52,76,78,87,92,93] Before the steaming treatment, there are some counterproductive effects which impact by the phosphorus impregnation, but it can make positive impacts on any By-products like Propylene instead of intensifying gasoline production normally [18] :

• The decrease in microporous volume, thus even if the microporous volume is in lower value after Phosphorus modification, which proves that interacting P species with ZSM-5 lattice in any way;

• Finally, reversible decrease in activity due to the interacting effects In addition, there are several consequences such as cracking activity or conversion

LE TRUNG NGHIA’S MASTER THESIS 27 Although there are some counterproductive effects remains after modifying, it also likely suitable for hydrothermal stability, diversifying functional post- modification zeolite and feedstock flexibility processing In other words, Phosphorus plays as a promoter when it is parts of ZSM-5 additive With the examination on n- Decane by Phosphorus modified ZSM-5 The cracking activity and acidity was found an optimum in term of steamed sample for P/Al ratios in range 0.5 to 0.7, an optimum in acidity for an overall P/Al ratio of 0.5, in any Si/Al ratio which as well as model reaction used originally affections on the highest activity via optimum Phosphorus content [19]

In the methanol-to-hydrocarbons reaction, the presence of Phosphorus boots selectivity toward light olefins and especially towards propylene[94] Additionally, the necessity of post-modification on ZSM-5 zeolite by Phosphorus precursors was made a change in acidic and shape-selective catalytic properties Moreover, the hydrothermal stability was found increasing after impregnating treatment with a Phosphorus [54,95-97], in order to produce Propylene yield from various feeding sources instead of the Atmospheric residue by (NH4)2HPO4 precursor [85] , H3PO4 precursor [78]

The activity of the catalyst was changed clearly with the loading amount of Phosphorus, and the catalytic cracking activity decreased with the loading amount of Phosphorus Moreover, Phosphorus low loadings getting the most effective selectivity for Propylene production was obtained at the limited to 1.0 wt.% in the P over H-ZSM-5 catalysts [85] , and the high P content to 3 wt.% or more in the catalyst was not brought more Propylene Afterward, the high Phosphorus content in the catalyst was not recognized directly proportional to the Propylene yield On the other hand, a range of Phosphorus weight loadings of 1.3-1.9 wt.%, the selectivity towards propylene has been reported to reach the maximum and can be as high as 33 percent at temperatures between 400°C and 500°C [13,41]

Impregnation with phosphoric acid protects the zeolite framework against dealumination by hydrothermal treatment [91]

LE TRUNG NGHIA’S MASTER THESIS 28 Furthermore, an intensive Phosphorus penetration into ZSM-5 micropore leads to a lower acid site strength improving higher selectivity toward propylene [98] In the Phosphorus mass percentage, more than 2% makes a downtrend in Propylene selectivity [48,78,99] The amount of Phosphorus loading on the Zeolites has detailly examined the activity, so it is not necessary to check this aspect

After hydrothermal treatment of phosphate zeolite, the Brứnsted acid sites better remained in the samples modified by Phosphorus than in the non-phosphate modified respectively [19,60,91,93] In term of steam treatment in a short time on the phosphates, the loss of acid sites corresponding to the removal of Aluminum is lower in comparison with non-phosphates Nevertheless, the absolute number of acid sites of the non-phosphate samples treating in Steam only is still higher than the steam-treated and phosphate-treated for samples Consequently, the evidence of the acid sites reduction of Phosphorus reagent on Zeolites [13]

The presence of weak acid sites owing to P-modification over the ZSM-5 [76] The presence of phosphorus in both external surface and internal surface cause the decrease of in micropore volume and surface area Adding phosphorus in high weights of loadings obtains the penetration into an inner lattice, but the opposite effects happen with the increase in phosphorus content Longer diffusion pathways for reactants and products as a consequence of decreasing pore dimensions and openings [13]

The decrease in acid sites strength

Figure 1-23: Relative amount of Brứnsted acid sites vs P/Al ratio [13,19]

Figure 1-23 shows how big the importance of P/Al ratio affects the Bronsted acid sites of ZSM-5 and some relative interactions Where:

(a) Relative amount of Brứnsted acid sites vs P/Al ratio, as determined by adsorption of pyridine at 150°C The concentration is relative to the parent material (b) Relative acid sites strength of Brứnsted acid sites vs P/Al ratio, as determined by adsorption of pyridine at 150°C and 350°C The percentage is the concentration of protonated pyridinium ions of a sample at 350°C, divided by the concentration of protonated pyridinium ions of the same sample at 150°C The markers of each line represented:

(green dot) = H-ZSM-5 + NH4H2PO4 (Si/Al) (blue dot) = H-ZSM-5 +NH4H2PO4 (Si/Al%) (black dot) = H-ZSM-5+ H3PO4 (Si/Al%) (gray dot) = H-ZSM-5+ NH4H2PO4 (Si/Al@) Infographic was designed by [13] Data obtained from the study of [19]

LE TRUNG NGHIA’S MASTER THESIS 30 Naturally, there are three types of solid acid sites in the zeolite The strongest one is formed by the protons present in framework bridging hydroxyl groups, whereas the remaining acid sites are very weak include surface terminal silanol and aluminol groups as the name called by Hendrik E van der Bij (2015)

There is a correlation between Brứnsted acid sites and P/Al ratio [19] Modified by phosphorus affects Brứnsted acid sites much higher than Lewis acid sites Recent research pointed out that all Brứnsted acid sites completely disappeared at above 5 wt.% weight loadings of Phosphorus, strong Brứnsted acid sites is particularly converted into weal Brứnsted acid site without changing acid-base properties by Phosphorus acid [41] Moreover, the ultimate effect of the phosphorus treatment was the removal of the strong Brứnsted acid sites as well as the density of the weak Brứnsted acid sites was found to increase after treatment with phosphoric acid [35] This hypothesis can be used to explain TPD-NH3 results of non-phosphate HZSM-5 and Phosphorus modified HZSM-5

Figure 1-24: Relative concentration of acid sites (%) versus P/Al ratio [13] Figure 1-24 shows the correlation between P/Al ratio and the concentration of acid sites Where: (a) Relative concentration of weak site (%) versus P/Al ratio (b)

LE TRUNG NGHIA’S MASTER THESIS 31 weak/strong acid site ratio versus P/Al ratio Concentrations are relative to the respective parent H-ZSM-5 material [13]

Figure 1-25: Model of the interaction of H 3 PO 4 with Brứnsted acid sites [41]

Figure1-25 shows the model of the modified additives containing Phosphorus species forming new transformation impregnated zeolite with different properties

Figure 1-26: Model was proposed for the interaction of Phosphorus with Brứnsted acid sites of ZSM-5 [19,100]

LE TRUNG NGHIA’S MASTER THESIS 32 In Figure 1-26, model was proposed for the interaction of Phosphorus with Brứnsted acid sites of ZSM-5 prepared by impregnation with Phosphoric acid under recommendation of Blasco et al (2006) [19,100]

EXPERIMENTS

Material

Acid Phosphoric (85%, Merk); Diammonium Hydro Phosphate (powder, China); Ammonia solution (25%, China); HNO3 (65%, China), ZSM-5 zeolite (power, China Commercial company); Distilled water (twice-time distilled by Biofuel laboratory of VPI, glass wool, Glass bead to take on heat transfer internal components in the FCC catalyst mixture for testing catalytic activity purpose.

Tools and equipment

• Tools: Magnetic stirrer, burette, volumetric flask, pH paper test, beaker, glass stirring rod, 1-ml volumetric pipette, 3-valve pipette filler, petri dish, porcelain crucible, pestle and mortar, polypropylene centrifugal test tube

• Equipment: Centrifuge, Magnetic stirrer mixer with Heater, pH meter, Calcination oven, Dryer, Steaming Quartz Tube.

ZSM-5 modification procedure

100 grams NaZSM-5 parent ZSM-5 was converted to NH4-form by two-fold ion-exchange The first batch using 500 ml of 1 M NH4NO3 solution per 1.5-hour batch in a beaker with aluminum foil film cover to stop excessive water removal was left under agitation at 80°C After the first ion-exchange step, the suspension was filtrated to remove the solvent out of the mixture, then the solid part was washed twice with demineralized water Following the first ion-exchange step’s procedure, the first ion-exchange step’s solid was added to another 500 ml of 1 M NH4NO3 solution for the second ion-exchange step [112] The suspension was centrifugated at 6000 rpm for 5 minutes and washed twice with demineralized water The sample was put into the Dry oven at 110°C overnight to get 86.274 gram of NH4-ZSM-5 sample at the end

Ion-exchange (second time) NH 4 NO 3

Figure 2-1: The preparation of H-form ZSM-5 Figure 2-1 summarizes the protocols for the preparation of H-form ZSM-5

Wet impregnation by Phosphorus precursors

The H3PO4 solution and China commercial ZSM-5 zeolites were used for the impregnation procedure [113] A suspension containing 30 wt.% of zeolite and 70 wt.% of the demineralized water was prepared by 6 grams of NH4 form-ZSM-5, 14 ml of demineralized water The ammonia solution was added to maintain pH around 8, after stirred steps for 3 hours under a room temperature range of 30-40°C The suspension was then left under agitation 1 hour at around 75°C to remove excess water in suspension, then dried at 110°C overnight and calcinated in Fume Hood at 550°C for 5 hours [60]

Figure 2-2 summarizes the protocols for wet impregnation by 2 different Phosphorus precursors

DAP & H3PO4 precursors, P/Al ratio based, room temperature

At 550°C, for 5 hrs, fume hood 3 hrs agitation, 1 hr at 75-80°C water excess removal

6 gram pH electronic calibration, pH paper

LE TRUNG NGHIA’S MASTER THESIS 41 Figure 2-3: Both pH paper method and electronic pH calibration were applied to check the pH value in impregnation steps and adjusting pH value

Figure 2-3 shows two ways to check the pH of the solution including pH paper and pH electronic calibration in the pH adjusting step

Wet impregnation by Diammonium Hydro phosphate precursor

Applying the same procedure as a Phosphoric acid treatment for 6 grams of NH4ZSM-5 along with 14ml of demineralized water The pH correction step is not necessary as a consequence of the non-corrosive property of the Diammonium hydro phosphate solution on ZSM-5 Moreover, the originally negative charge of the phosphate group reacts to become new chemical in the acidity solution The maximize Phosphorus penetration method concerning electrostatic field is not useful in this precursor treatment [114] After washing, drying overnight at 110°C, calcination at 550°C for 5 hours in atmospheric pressure to get the DAP modified catalyst [57,115]

The deactivation of Phosphorus modified ZSM-5 additives

Figure 2-4: Modified ZSM-5 additive was steamed at 1500 Kelvin (816°C) for 20 hours before the MAT test

The Figure 2-4 showed the deactivated progress, the ZSM-5 was simulated by the 20-hour steaming with 100% steam to test the activity of Phosphorus modified ZSM-5 as an additive in FCC catalysts with Atmospheric residue, as well as the hydrothermal stability of Phosphorus modified catalysts compared to original HZSM- 5 in the severity conditions in MAT systems [65]

CATALYST EVALUATION METHOD

In general, the synthesized sodium form ZSM-5 is originally pretty good at hydrothermal but have no acidity properties, so they are inactive for hydrocarbon cracking, so the preparation of sodium form ZSM-5 need to be processed to H-from

[19] The interaction between Phosphorus and ZSM-5 has been found a variety of studies which recommended phosphorus added in the form of H3PO4 reacted with the framework and extra-framework aluminum lead to the aluminophosphates changing the acid properties in the final products About ZSM-5, the forming of bridged OH groups owing to P compound interaction creates the zeolite acidity decrease which consequently reduces catalytic activity and modifying shape selectivity In the case of modifying shape selectivity, the decrease of pore volume affects directly to shape selectivity as well [59]

Figure 2-5 summarizes all procedure for additives characterization

The Si/Al ratios of all Modified samples were determined using X-ray fluorescence XRF analysis, which was in good agreement with that of parent purchased ZSM-5 [105] In the X-ray fluorescence process, a liquid or solid sample is irradiated with high energy X-rays from a controlled X-ray tube, when an atom in the sample is stuck with an -ray of sufficient energy (greater than the atom’s K or L shell binding energy), an electron from one of the atom’s inner orbital shells is dislodged

The atom regains stability, filling the vacancy left in the inner orbital shell with an electron from one of the atom’s higher energy orbital shells The electron drops to the lower energy state by releasing a fluorescent X-ray The energy of this X-ray is equal

LE TRUNG NGHIA’S MASTER THESIS 45 to the specific difference in energy between two quantum states of the electron The measurement of this energy is the basis of XRF analysis [106]

Figure 2-6 : The X-ray fluorescence process [106]

Figure 2-7: A standard XRD pattern of MFI-group zeolite [107]

Figure 2-7 shows clearly two typical peaks representing for ZSM-5 zeolite

LE TRUNG NGHIA’S MASTER THESIS 46 Figure 2-8: XRD pattern of fully crystalline MFI, Si/Al = 12 to 13.5 [108,109]

2.4.2.3 Brunauer–Emmett–Teller method (BET)

Adsorption-desorption isotherms were recorded using a Micromeritics TriStar II 3020 setup operating at minus 196°C (77K) Prior to physisorption measurements, all samples were cleaned overnight at 500°C under Nitrogen flow with a temperature ramp of 10K/min up to 673K The micropores characterization, as well as the total surface area, were determined by the BET method and t-plot method which also have named by Harkin-Jura plots In all BET analysis of this research, BET surface areas are illustrated as the sum of micropore and external surface area determined by the t- plot method

2.4.2.4 Temperature Programmed Desorption-Ammonia (TPD-NH 3 )

Figure 2-9: AMI—902 (Altamira) TPD-NH 3 analysis equipment

This model of TPD-NH3 analysis equipment in Figure 2-9 supplied by VPI for TPD-NH3 results of this thesis

LE TRUNG NGHIA’S MASTER THESIS 48 Figure 2-10 : TPD spectrum of ammonia desorbing from H-ZSM-5, Volume desorption short by V des [103]

Figure 2-10 shows ZSM-5 TPD-ammonia Desorbing from HZSM-5 with the range of temperature Previous research used TPD-NH3 as a characterization of HZSM-5 modified with Phosphorus precursors [80] and obviously, that monitored the degree of conversion in the modified sample [41] , Phosphoric acid precursor [39,41,91] , DAP precursor [57]

LE TRUNG NGHIA’S MASTER THESIS 49 Figure 2-11: The TPD-NH 3 peaks of ammonia trace and acidity of phosphate modified samples [39]

Figure 2-11 shows the TPD-NH3 peaks of ammonia trace and acidity of phosphate modified hierarchical porous ZSM-5 catalysts (SiO2 /Al2O3 60) [39]

LE TRUNG NGHIA’S MASTER THESIS 50 Figure 2-12: ZSM-5 P1, ZSM-5 P2, ZSM-5 P5, ZSM-5 P8 represented for 1% ,

2%, 5%, 8% P on the Modified Samples, 673 K approximately 400°C [41]

In Figure 2-12, the higher amount of Phosphorus loading in wt.% the lower density of strong acid sites

Figure 2-13: TPD-NH 3 plots with total acidity, mmol NH 3 /g

In Figure 2-13, this phosphate modified ZSM-5 is designated as XPZSM-5(w) where X is wt.% of P (as phosphate) added during preparation and (w) indicates water treatment wherever applicable

Figure 2-14: Temperature-programmed desorption of NH 3 from thermally nontreated H-ZSM-5

Figure 2-14 shows separately two humps representing for strong and weak acid sites of ZSM-5 in picture A and the disappearance of strong acid sites in the Phosphorus modified ZSM-5 samples Where:

Sample A: parent sample Sample F: sample A after H3PO4 impregnation (content of phosphorus: 2.5 wt.%) [91]

LE TRUNG NGHIA’S MASTER THESIS 52 The comparison of TPD-NH3 in the result of this research and previous studies was explained in the below part

Figure 2-15: TPD-profiles of parent and phosphorus modified H-ZSM-5 samples

(P-content increases from top-down)

The list of P content was explained by the table relying on Figure 2-16 below

Figure 2-16: Textural, structural and acidic properties of parent and phosphorus modified H-ZSM5 samples [101]

According to information from Figure 2-15 and Figure 2-16, the lower acidity ZSM-5 is influenced by the higher Phosphorus loading amount Where:

LE TRUNG NGHIA’S MASTER THESIS 53 Washed samples were indexed with ‘‘w’’ and after calcination with ‘‘cw’’

[101] The figure above showed that the H3PO4 was used to decrease the acid strength of ZSM5 similar to others [41] , but the stable performance was obtained after DAP precursor modification in specific or Phosphorus modification in general [57]

On behalf of this research, phosphorus weight loading is about 1.97 wt.% of the final impregnating sample in order to compare Phosphorus precursors impacts on HZSM-5 TPD of ammonia showed that the stronger acid sites were replaced with weaker acid sites after phosphate modification [59]

The result of TPD-NH3 of M Gửhlich et al between 373°K and 823°K (about 100 and 550°C) was shown that the decrease of acidity on HZSM-5 Another effect of phosphoric acid impregnation is the modification of the acidic properties by number and strength NH3-TPD profiles of parent and phosphorus modified samples between 373 and 823°K Without modification, TPD-profile consists of an intensive peak in the low temperature (550ºK corresponds approximately to 276.85°C, LTP) and a shoulder in the high-temperature region (700°K corresponds approximately to 426.85°C, HTP) according to weak and strong acid sites, respectively [101] On the other hand, in the other studies, the first peak- LT stand for the low-temperature peak, assigns to NH3 desorbing from weak acid or non-acidic sites such as that build from silicalite Secondly, the desorption spectrum peak representing the amount of ammonia desorbed from a strong acid in HT stands for the high-temperature peak

Nonetheless, this technique is not a choice to discriminate between Lewis Acid and Brứnsted Acid centers, but the IR transmission absorption spectrum of pyridine can be able to do that According to previous studies, some figures have used to determine the acid type, the first peak (low-temperature peak) is assigned to NH3 desorbing from weak acid in range 400-600°K equivalent to 127-327°C, the second peak (high- temperature peak) was built by Ammonia desorbed pattern from strong acid sites in range 700-800°K equivalent to 427-527°C [110]

LE TRUNG NGHIA’S MASTER THESIS 54 The IR spectroscopy of pyridine adsorbed was used to evaluate the effect of different sequences of treatments with H3PO4 on the concentration of strong Brứnsted acid sites [77]

Catalyst activity testing 2.4.3.1 Micro activity test (MAT)

Figure 2-17 shows the detail of the MAT system where the catalyst is tested by various feedstock In the system, the feedstock is pumped into the reactor containg testing catalyst and the liquid and gas product is collected by the container

LE TRUNG NGHIA’S MASTER THESIS 55 a) b) e) f) c) d)

Figure 2-18: MAT protocol and system

Figure 2-18 shows the MAT system in VPI which has some components including (a) Reactor furnace (b) Pre-heating furnace (c) Feedstock springe is injected by Nitrogen flow (d) Condensation chamber by dried ice (e) Products collector (f) SCT-MAT protocols and notepaper

2.4.3.2 Micro activity test procedure (MAT)

By following the ASTM D5154/D5154, the SCT-MAT procedure was conducted on the Grace Davison system with modified catalysts at 520ºC The E-Cat was calcined at 550°C for 3h before the MAT test, while the temperature was increased at 5°C/min during calcination Modified ZSM-5 was deactivated by

RESULTS AND DISCUSSION

Catalyst properties testing

The XRD results in Figure 3-1 and Figure 3-2 cannot be used to make an explanation for the difference of acidity of modified additives compared to unmodified additives Additionally, these of modified additive or not showed the similarity of crystallinity level on the lattice, whereas these of steam treatment or not are dissimilar

Figure 3-1: The XRD pattern of HZSM-5 impregnated with Phosphoric acid precursor without steam treatment

In the comparison with the XRD pattern of standard ZSM-5, modified catalysts XRD patterns by Phosphorus precursors are striking resemblance the

LE TRUNG NGHIA’S MASTER THESIS 59 standard ZSM-5 zeolite XRD spectrum, even after the considerable affected by post- modification treatment

Figure 3-2: The XRD pattern of HZSM-5 impregnated with Phosphoric acid precursor after steam treatment

In Figure 3-1 and 3-2, the intensity of steaming treatment samples decreases considerably compared to that of un-steaming treatment XRD patterns of Phosphate modified ZSM-5 similarly matches with the unmodified ZSM-5 indistinct broad diffraction peaks in 8°-10° and 20-25° (2𝜃) ranges, which recommend that Phosphorus species remained after Phosphate modification in structural integrity

[39,116] X-ray powder diffraction showed no additional phases present in HZSM-5 samples treated with both DAP and H3PO4 precursor by which correspondents to other studies [61] XRD patterns of all Phosphorus precursors are presented in the Appendix

The XRF was applied to exam the Si/Al ratio of parent China commercial ZSM-5 additive which is realistic at Si/Al ration value at 23.4

Figure 3-3: The characterization of acid property on catalysts by the TPD-NH 3 method

In Figure 3-3, 4 different lines represented 4 additive samples Where:

The orange is depicted non-steamed or before steam DAP precursor modified catalyst The blue is represented non-steamed or before steam acid Phosphoric precursor wet-impregnated catalyst, while the gray line illustrated parent-H form ZSM-5 and the yellow was using to draw steamed catalyst modified with Phosphoric acid precursor

As the results of TPD-NH3 in Figure 3-3, the decrease of acid sites strength property of Phosphorus modification, the spectrum of ammonia adsorption contributing by the Brứnsted acid site exists in the TPD-NH3 results of the original H-ZSM-5 and disappears in the Phosphorus modified samples

Temperature,°CPhosphoric acid, BSt DAP, BStHZSM-5, BSt Phosphoric acid, ASt

Activity testing result

Figure 3-4: Influence of various concentrations on Micropore area

In the Figure 3-4, the influence of various concentrations created by different precursors relying on the t-Plot Micropore Area of modified HZSM-5 samples impregnated with different Precursors solution concentrations of (m 2 /g), at the same stirring time at 3 hours in the impregnation process, before steam

• The solution containing 14 ml demineralized water was prepared for DAP modified sample (at P/Al ratio=1) bst

• The solution containing 50 ml demineralized water was prepared for DAP modified sample (at P/Al ratio=1) bst

• The solution containing 14 ml demineralized water was prepared for Phosphoric acid-modified sample (at P/Al ratio=1) bst

The volumes of precursor solutions (ml) and Precursors (at the same ratio P/Al=1), respectively. t-Plot Micropore Area (m²/g ) bst

LE TRUNG NGHIA’S MASTER THESIS 62 Phosphorus species place on the external surface before entering the zeolite channel Increasing loading helps phosphorus easily enters the zeolite channel, but the limitation on diffusion leads to a distribution gradient with a higher concentration of phosphorus at the outer space Consequently, phosphorus in the lower concentration can effectively enter the micropore better than high concentration as well as depositing on the external surface 4 units different of micropore area exists in the sample volume between DAP and H3PO4 It seems that Phosphoric precursor is more impact on Zeolite Micropore than the other Not only the acidity of precursors needs to be considered, but the dialuminium also has been recommended in the current studies

The explanation of this test was completed relying on the inclusion of state- of-the-art studies Phosphorus performance on zeolite framework can easily observe by the sign of a decrease in surface area and micropore volume which implied with an increase of phosphorus content There are several theories about the excess phosphorus forming as orthro-, pyro-, and polyphosphates, excess phosphorus particularly dehydration happens at high temperature to transform condensed polyphosphates This process is reversible, so the rehydration leads to small phosphate species which do not interact with the zeolite framework and can easily be eluted by washing with hot water [13]

Figure 3-5: Influence of various concentrations on external surface

As a result of Figure 3-5, the influence of various concentrations created on the external surface area by different precursors The t-Plot External Surface Area of modified HZSM-5 samples impregnated with different Precursors solution concentration of (m 2 /g), at the same stirring time for 3 hours in the impregnation process, before steam

The external surface of each concentration is depicted in the figure above In the lower concentration of 50ml water is compared to other samples with a higher concentration in the preparation step with 14 ml of water, the lower Phosphorus wet- impregnating precursor solution impacted the External surface area higher than the higher concentration others However, there was insignificant in other to change external surface area characterization with various precursors, the values of 14 ml solution volume on both DAP precursor and acid Phosphoric precursor were 75.02 and 75.03, respectively Finally, the error analysis in BET result is about 2-3% which needs to be considered

The volumes of precursors solutions (ml) and Precursors (at the same ratio P/Al=1), respectively. t-Plot External Surface Area (m²/g ) bst

The influence of P/Al ratio on the pore system of ZSM-5 additive

Figure 3-6: Influence of P/Al ratio on t-Plot micropore area bst

In Figure 3-6, the influence of P/Al ratio on the Micropore area of Phosphorus modified HZSM-5 additives

• Additive HZSM-5 treated with 14 ml of water in H3PO4 solution

• Additive HZSM-5 treated with different concentration solutions of DAP precursor at different {

• Additive HZSM-5 treated with 14 ml of water in H3PO4 solutionat P/Al ratio=1

In the comparison of precursors at the same P/Al ratio =1, there was insignificant change, but the higher concentration has approximately as same as impact on HZSM- 5 with low concentration in the same of P/Al ratio

P/Al ratios and Precursors , respectively, 3 HRS stirringP/Al ratio t-Plot Micropore Area (m²/g ) bst

LE TRUNG NGHIA’S MASTER THESIS 65 Figure 3-7: Influence of P/Al ratio on t-Plot external surface area bst

As a result of Figure 3-7, the influence of P/Al ratio on the External surface area of Phosphorus modified HZSM-5 additives Where:

• Additive HZSM-5 treated with 14 ml of water in H3PO4 solution

• Additive HZSM-5 treated with different concentration solutions of DAP precursor at different {

• Additive HZSM-5 treated with 14 ml of water in H3PO4 solutionat P/Al ratio=1

HZSM-5 DAP Phosphoric acid External surface area (m2 /g)

P/Al ratios and Precursors, respectively, 3 HRS stirring t-Plot External surface Area (m²/g ) BSt

Figure 3-8: MAT Conversion before steam (%)

Following Figure 3-8, micro activity testing result of parent HZSM-5 and HZSM-5 samples modified by DAP, Phosphorus acid precursor at various P/Al ratio before steam Where:

• Additive HZSM-5 treated with DAP precursor at different ratio {

P/Al=0 P/Al=0.25 P/Al=0.5 P/Al=1 P/Al= 1

P/Al ratiosMAT Conversion before steam (%)

Figure 3-9: MAT Conversion after steam (%)

According to Figure 3-9, micro activity testing result of parent HZSM-5 and HZSM-5 samples modified by DAP, Phosphoric acid precursor at various P/Al ratio after steam Where:

• Additive HZSM-5 treated with DAP precursor at different ratio {

P/Al=0 P/Al=0.25 P/Al=0.5 P/Al=1 P/Al= 1

P/Al ratiosMAT Conversion after steam (%)

The influence stirring time step of impregnation time on the micropore

Figure 3-10: MAT conversion after steam (%)

As a result of Figure 3-10, the chart illustrated the impact of total impregnating time and water removal step on the micropore surface area Where:

Most of the samples are non-steamed, Blank Additive HZSM-5, Additive HZSM-5 treated with HNO3 at pH 2, Additive HZSM-5 treated with H3PO4 at the different impregnating time including water elimination 1hr, 2 hrs., 3hrs., 24 hrs., Additive HZSM-5 treated with DAP at P/Al ratio=1 at 3hrs

The t-Plot Micropore area decreases considerably only in 1 hour stirring of the P impregnation progress from 315 m 2 /gram in parent H-ZSM-5 to 260.13 m 2 /gram

It can be seen in the figure, Phosphorus impregnating blocked significantly the micropore area which compared to Blank ZSM-5 sample or HNO3 treatment

However, the impregnating time did not affect substantially on the micropore area even in the 24 hours condition of impregnating test with DAP precursor The micropore area declines as a consequence of the penetration of Phosphorus species

HZSM-5 HZSM-5 1 hr 2 hrs 3 hrs 24 hrs DAP-3hrs

Precursors and time units (hr), respectively t-Plot Micropore Area (m²/g )

LE TRUNG NGHIA’S MASTER THESIS 69 into Micropore in ZSM-5 lattice Additionally, the 3 hours stirring in impregnation steps in other studies [19] which also a peak of Phosphorus effects on ZSM-5 micropore surface with the lowest 250.6 m 2 /gram in this case Obviously, this condition is properly with various Phosphorus precursors in Impregnation step

The influence of different precursors on the stabilization

Figure 3-11: Influence of P precursors on hydrothermal stability

As a result of Figure 3-11, the impacts of different precursors on hydrothermal stability relying on Micropore surface area All the samples were examined in order to check the Hydrothermal stability under severe Condition with 100% steam, higher than 700°C

Steamed status, at the same ratio P/Al =1

LE TRUNG NGHIA’S MASTER THESIS 70 Table 3-1: The influence of precursors on the external and micropore surface

Surface Area (m 2 /gram) External Micropore

Following Table 3-1, the precursor influences impact on both the external and Micropore surface area at P/Al ratio=1 in impregnating method Before steam treatment, the state of Micropore system of ZSM-5 zeolite, the reduction of the surface from 316 m 2 /gram to 252 m 2 /gram of DAP precursor or 250 m 2 /gram of H3PO4 precursor was also happened by the occupation of Phosphorus groups after wet-impregnation treatment

The sample explanation in order to External system of Phosphorus treatment ZSM-5 zeolite, the external surface went down from 102 m 2 /gram to 83 m 2 /gram with DAP and 75 m 2 /gram with H3PO4 precursor However, according to the Phosphorus elution phenomenon by the water in steam flow recommending in few studies which can apply in the rise of External surface area to 175 m 2 /gram of DAP, 140 m 2 /gram of H3PO4 precursor According to this analysis with after steam samples, the surface area of H3PO4 precursor after steam sample with a lower rise of external surface area than DAP which can possibly declare that the remaining of Phosphorus in the outer space of H3PO4 treatment’s sample better than DAP precursor treating route in this aspect

Nevertheless, it is not a substantial interaction with the zeolite phase, the cover of Phosphorus species in the external edge of zeolite made a deterioration of surface hydroxyl groups after Phosphorus impregnation

The influence of different precursors on the Gasoline yield

According to Figure 3-12, the influence of precursors on gasoline yield in the activity test of FCC catalyst with modified HZSM-5 before steam Where:

• FCC catalyst with additive HZSM-5 treated with HNO3 at pH 2

• FCC catalyst with additive HZSM-5 treated with DAP at different {

• FCC catalyst with additive HZSM-5 treated with H3PO4 at P/Al ratio=1

As depicted in figure about the result in a range of P/Al ratio and different precursors, the propylene yield gap between before and after the steam treatment is the outstanding characterization which is small in the high P/Al ratio

Nitric acid DAP-50ml Phosphoric acid

P/Al molar ratio and Precursor, respectively before steam, wt.% after steam, wt.%

LE TRUNG NGHIA’S MASTER THESIS 72 The gasoline yield decreases gradually in correlation with the increase of Propylene yield as a result of the cracking of Gasoline olefins as well as the limitation of Hydro transfer It was also explained in a few studies [38]

CONCLUSION AND RECOMMENDATION

Conclusion

HZSM-5 was impregnated with 2 Precursor types include Phosphoric acid and DAP For testing the Hydrothermal stability, all Phosphorus modification additives mixing with E-cat was tested under severe steaming condition and then reacted with Atmospheric residue feedstock After activity testing, all products were analyzed to evaluate the difference of different Precursors on impregnating function and characterizations of each type Physical characterization was used simultaneously for evaluating the additive properties

According to the results of TPD-NH3 analysis and the MAT test, the before steaming samples treated with H3PO4 precursor performs a total of acid sites lower than those of DAP precursors along with Parent H-ZSM-5 in general Consequently, the propylene yield of the sample treated with H3PO4 precursor is slightly lower than that of DAP precursor because of the higher hydride transfer and the lower acidity

In Phosphoric acid-treated sample, strong acid sites decrease significantly, whereas the number of weak acid sites went higher than both original HZSM-5 and sample treated with DAP precursor It is a behavior of the strong acid sites which has affected in DAP samples was weaker than in H3PO4 precursor sample, whereas hydride transfer phenomenon was proposed as a consequence of the increase of weak acid sites as well as the reduction of strong acid sites Higher Propylene yield of DAP precursor than H3PO4 precursor was proper evidence for the lower acid sites state in DAP compared to H3PO4 sample before steam, but it makes the Zeolite more stable under hydrothermal condition

The presence of water in steam flow in the steaming system and heat effect after steaming treatment creating the elution Phosphorus species from impregnation treatment may lead to the recovery of concentration of acid sites may about 42% that of parent material which leads the strength of acid site recovery It heals the hydride

LE TRUNG NGHIA’S MASTER THESIS 89 transfer affection which decrease the propylene yield in all Phosphorus modified sample throughout various P/Al ratios

Overall, although all steamed samples had the decrease of activity compared to non-steamed samples, the additive treated with phosphorus performed better activity under severe FCC condition which proven the Phosphorus role in modification purpose for enhancing Propylene production ability and improving hydrothermal stabilization of additive In the comparison with other previous research, despite testing with heavier intake like Atmospheric residue, but Propylene yield tested by post-modified samples also was softly lower in both precursors

Although the DAP precursors performed predominantly better than H3PO4 precursor due to the reduction of acid activity about important product yield such as Gasoline, the hydrothermal stabilization and activity stabilization of HZSM-5 modified with Phosphoric acid precursor was higher than DAP.

Future perspectives

Furthermore, the future studies on the phosphorus application as a promoter in zeolite-based pyrolysis of biomass to produce environmentally friendly biofuel

Besides, the FCC catalysts recycling process need to be completed to protect the environment as well as saving the zeolite resources for a sustainable economy, especially rare-earth elements recycle from used FCC catalyst to reuse in new applications

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Appendix 1: HZSM-5 impregnated with DAP for 3 HRS bst

Appendix 2: HZSM-5 impregnated with H 3 PO 4 for 1 HR bst

Appendix 4: HZSM-5 treated with HNO 3 for 3 HRS at pH 2 bst

Appendix 5: HZSM-5 impregnated with H 3 PO 4 for 3 HRS ast

Appendix 6: HZSM-5 impregnated with H 3 PO 4 for 2 HRS bst

Appendix 9: The TPD-NH 3 analysis of post-modification ZSM-5 zeolite

Appendix 10: Calculating procedure of parent ZSM-5 TPD-NH 3

Appendix 9: Procedure of physical adsorption

Appendix 10: Procedure of chemical adsorption

Tiêu đề	Investigating Catalysts Based On ZSM-5 Modified By Phosphorus For Propylene Production From Atmospheric Residue
Tác giả	Le Trung Nghia
Người hướng dẫn	Le Phuc Nguyen, PTS, Huynh Quyen, PGS, TS
Trường học	Ho Chi Minh City University of Technology
Chuyên ngành	Petrochemical Engineering
Thể loại	Master Thesis
Năm xuất bản	2019
Thành phố	Ho Chi Minh City

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Số trang	138
Dung lượng	3,01 MB