MESOPOROUS ZEOLITES AND USES THEREOF IN DEWAXING HYDROCARBON FEEDS

Abstract

The present invention relates to the field of dewaxing of hydrocarbon feeds. More in particular, it relates to the use of alkaline-treated mesoporous zeolites and catalysts encompassing the same for the dewaxing of hydrocarbon feeds. It was found that the zeolites and catalysts of the present invention can significantly reduce cracking of the hydrocarbon feed, and accordingly significantly reduce liquid hydrocarbon feed loss during processes such as dewaxing.

Claims

1. A method for dewaxing a hydrocarbon feedstock under dewaxing conditions, comprising the steps of: providing a hydrocarbon feedstock to a reactor; providing a catalyst to the reactor, and contacting the hydrocarbon feedstock with the catalyst, wherein the catalyst comprises at least 300 ppm of a hydrogenation metal and an alkaline-treated mesoporous zeolite, wherein the alkaline-treated mesoporous zeolite comprises a framework density (FD.sub.Si) of 17 to 20 T/nm.sup.3, a molar Si/Al ratio of 20 to 400, and a mesopore volume of 0.05 to 1.2 ml/g, and wherein the alkaline-treated mesoporous zeolite is prepared by an alkaline treatment comprising the steps of: providing a parent zeolite to an aqueous solution, wherein the aqueous solution has a pH of at most 8, and comprises at least one salt comprising an element selected from the group of Mg, Ca, Ti, V, Cr, Ni, Co, Fe, Cu, Mn, La, Ce, W, Mo; adding a base to the reaction mixture, wherein the pH of the aqueous reaction mixture is increased to at least 10; reacting the base and the parent zeolite thereby obtaining said alkaline-treated mesoporous zeolite; and separating the alkaline-treated mesoporous zeolite.

2. The method according to claim 1, further comprising that the alkaline-treated mesoporous zeolite features a magnesium content in the range of 0.3 wt % to 10 wt %.

3. The method according to claim 2, wherein the magnesium dispersion is at least 50% as measured with oxalic acid chemisorption.

4. (canceled)

5. The method according to claim 1, further comprising that the alkaline-treated mesoporous zeolite features a mesopore volume of 0.4 to 1.2 ml/g.

6. The method according to claim 1, wherein said alkaline treatment further comprises performing a subsequent acid treatment.

7. The method according to claim 1, wherein the hydrocarbon feedstock is selected from the group consisting of: wax, hydrowax, diesel, lube oil, base oil, vegetable oil, Fischer-Tropsch derived oil, and er any combination thereof.

8. (canceled)

9. The method according to claim 1, wherein the method reduces diesel and/or lube losses to less than 0.2% per degree Celsius of Cloud Point improvement.

10. The method according to claim 1, wherein the dewaxing conditions comprise a temperature in the range of 200 C. to 450 C.

11. The method according to claim 1, wherein the dewaxing conditions comprise a hydrogen partial pressure in the range of 15 bar to 350 bar.

12. The method according to claim 1, wherein the dewaxing conditions comprise a hydrogen treat gas rate in the range of 100 Nl/l to 1000 N/l.

13. The method according to claim 1, wherein the catalyst comprises at least 5 wt % of metal oxide support, wherein the metal oxide support is one or more selected from the group consisting of: alumina, silica, silica-alumina, magnesium oxide, and titania.

14. The method according to claim 1, wherein the hydrogenation metal is one or more selected from the group consisting of: Pt, Pd, Ni, Co, Mo, W, and Fe.

15. The method according to claim 1, wherein the alkaline-treated zeolite has the framework topology of MTT, TON, AEL, MRE, MTW, MFI, FER, or MEL.

16. The method according to claim 1, wherein the alkaline-treated zeolite has a unidirectional micropore structure and 10 member rings.

17. The method according to claim 1, wherein the alkaline treatment is executed gradually.

18. The method according to claim 1, wherein the alkaline treatment is executed by flowing an alkaline solution through a stationary membrane containing the parent zeolite.

19. The method according to claim 1, wherein the preparation of the alkaline-treated mesoporous zeolite using an alkaline treatment at a pH>10 comprises the steps of: providing a suspension of a parent zeolite in an aqueous solution, wherein the aqueous solution has a pH of at most 8 and comprises at least one salt comprising an element selected from the group consisting of: Mg, Ca, Ti, V, Cr, Ni, Co, Fe, Cu, Mn, La, Ce, W, Mo; adding a base to the suspension, thereby forming a reaction mixture, wherein the pH of the aqueous solution is increased to at least 10; reacting the base and the parent zeolite in the suspension, thereby obtaining said alkaline-treated mesoporous zeolite; and separating the alkaline-treated mesoporous zeolite from the suspension.

20.-24. (canceled)

25. The method according to claim 1, wherein the preparation of the catalyst further comprises the step of: performing an ion exchange treatment on the alkaline-treated mesoporous zeolite; and/or performing a calcination treatment on the alkaline-treated mesoporous zeolite; and/or shaping the alkaline-treated mesoporous zeolite into a macroscopic shaped catalyst particle.

26. (canceled)

27. A dewaxing catalyst comprising an alkaline-treated mesoporous zeolite with the MTT framework topology and at least 300 ppm of Pt or Pd, wherein the alkaline-treated mesoporous zeolite further comprises a molar Si/Al ratio of at least 20, a mesopore volume in the range of 0.4 to 1.2 ml/g and/or external surface in the range of 100 to 350 m.sup.2/g, and a Bronsted acidity as measured using pyridine of at least 50 mol/g.

28. An alkaline-treated mesoporous zeolite with the MTT framework topology, wherein the alkaline-treated mesoporous zeolite further comprises a molar Si/Al ratio of at least 20, a mesopore volume in the range of 0.4 to 1.2 ml/g and/or external surface in the range of 100 to 350 m.sup.2/g, and a Bronsted acidity as measured using pyridine of at least 50 mol/g.

29. The dewaxing catalyst according to claim 27, further comprising a magnesium content in the range of 0.3 wt % to 10 wt %.

30.-32. (canceled)

33. The method claim 1, wherein the hydrogenation metal is one or more selected from the group consisting of: Pt, Pd, Ni, Co, and Fe.

34. The alkaline-treated mesoporous zeolite according to claim 28, further comprising a magnesium content in the range of 0.3 wt % to 10 wt %.

Description

FIGURES

[0182] FIG. 1: BJH mesopore size distributions of the Reference (parent) Zeolite, the comparative Zeolite 1, and Zeolites 2 and 3 according to the invention;

[0183] FIG. 2: Diesel yield loss (DYL) as a function of cloud point (CP) improvement (FIG. 2A) or pour point (PP) improvement (FIG. 2B) for the Reference (parent) Catalyst, comparative Catalyst 1, and Catalysts 2 and 3 according to the invention;

[0184] FIG. 3: Distribution of the C1-C8 fraction as a function of the carbon number and type of molecule (linear alkane, branched alkane, aromatics, naphthenes, and olefins) for the Reference (parent) Catalyst, comparative Catalyst 1, and Catalysts 2 and 3 according to the invention at fixed cloud point improvement;

[0185] FIG. 4: Distribution of the C1-C8 fraction as a function of the carbon number and type of molecule (linear alkane, branched alkane, aromatics, naphthenes, and olefins) for the Reference (parent) Catalyst, comparative Catalyst 1, and Catalysts 2 and 3 according to the invention at fixed diesel loss;

[0186] FIG. 5: Total aromatic content versus reaction temperature for the product stream coming after dewaxing using the Reference (parent) Catalyst, comparative Catalyst 1, and Catalysts 2 and 3 according to the invention;

[0187] FIG. 6: Total aromatic content versus density for the product stream coming after dewaxing using the Reference (parent) Catalyst, comparative Catalyst 1, and Catalysts 2 and 3 according to the invention; and

[0188] FIG. 7: Total aromatic content versus cloud point improvement for the product stream coming after dewaxing using the Reference (parent) Catalyst, comparative Catalyst 1, and Catalysts 2 and 3 according to the invention.

EXAMPLES

Methods

N.SUB.2 .Adsorption Technique

[0189] The properties of the zeolite (catalysts) may be assessed using nitrogen sorption at 77 K as it is a well-established technique to quantify the intrinsic zeotypical properties (relevant for crystalline microporous solids), as well as the secondary (meso)porosity in the solid. A descriptor that is derived from the nitrogen isotherm is the total surface area (S.sub.BET), as it gives an indication of the overall porosity (micropores and mesopores) of the solids. The intrinsic zeotypical properties can be examined using the micropore volume (V.sub.micro), which is derived from application of the t-plot to the adsorption branch of the isotherm. The t-plot method simultaneously yields an external surface (referred to S.sub.meso) which is used as an indication for the degree of secondary porosity. The total pore volume (V.sub.pore) is used as an indicator for the overall porosity. The mesopore volume is also an indicator of the amount of generated secondary porosity, and (V.sub.meso) is defined as V.sub.meso=V.sub.poreV.sub.micro. It is generally thought most desirable to attain solids with the highest microporosity (V.sub.micro) and mesoporosity (S.sub.meso, V.sub.meso), yielding in turn the high overall porosity (S.sub.BET, V.sub.pore).

[0190] Pore volume for the D1 (3-4 nm), D2 (4-20 nm) and D3 (>20 nm) diameter ranges (as determined in Table 2) were calculated using the integration of the BJH Adsorption dV/dD Pore Volume curves in the specified pore size ranges (see FIG. 1). These ranges are used to further quantify the mesoporosity formed in the zeolites. BJH Adsorption dV/dD Pore Volume curves were derived from the N.sub.2-isotherm using the Harkins and Jura method with Faas correction.

Acidity

[0191] Acidity measurements are instrumental as they enable to monitor the amount and type of acid sites present in the zeolite. Acidity assessment using pyridine-probed infrared spectroscopy can be executed as reported previously in WO2017148852 using a desorption temperature and time of 150 C. and 20 min, resulting in a concentration of Bronsted sites (B) and Lewis sites (L), both in gmol per gram, which can be combined to give an overall acidity (B+L) and a relatively Lewis acidity, L/(B+L).

[0192] In more detail, Pyridine FTIR measurements were performed by using a Nicolet 6700 spectrometer equipped with a DTGS detector. Samples were pressed into self-supporting wafers and degassed at 400 C. for 1 h in vacuo before measurements. Bronsted and Lewis acid sites were analysed by using a pyridine probe. After evacuation, the samples were subjected to 4-5 pulses of at least 25 mbar of pyridine at 50 C. for 1 min (until saturation), after which the system was heated to 150 C. in 20 min, followed by the acquisition of the spectra at the same temperature. The absorptions at 1550 and 1450 cm.sup.1 corresponded to the amount of Bronsted and Lewis acid sites, respectively. The extinction coefficients were determined by Emeis, J. Catal. 1993, 141, 347-354.

Metal Dispersion

[0193] The dispersion of non-noble metals, such as Mg and/or Ni, can be suitably assessed using chemisorption of oxalic acid. Oxalic acid displays a unique interaction with many metals, and metal dispersion can be determined by relating the amount of metal complexes (formed when contacted with oxalic acid) with the total amount of metal on the solid. The deposition of oxalic acid on the solid herein was performed in the vapour phase. Hereto, 0.5 g of solid was prepared into a sieve fraction, and was mixed with 0.5 g of oxalic acid. This mixture was placed into a metal cup, coupled to a heating gun, heated to a temperature of 200 C., and left at this temperature for 30 min. During this period, the heating of the metal parts results in the vaporization of the oxalic acid and the formation of metaloxalate species. Simultaneously, the airflow provided by the heat gun ensures that excess oxalic acid (hence those not present in a metal oxalate complex) is evacuated from the solid. The amount of metal oxalate on the solid was subsequently determined using thermogravimetric analysis (TGA). Hereto, about 5-10 mg of sample was put in a crucible and placed in a TGA apparatus. Next, an analysis was started under nitrogen atmosphere (10 ml/min) and a heating rate of 20 C./min in the temperature range of room temperature to 900 C. Next, the weight loss in the range of 275 C. to 800 C. was quantified, yielding an amount of metal oxalate complex by relation of the weight loss to that of the pure metal oxalate compound in the same range determined using the same protocol.

Mesoporous Zeolite MTT Preparation

[0194] The examples feature the synthesis of comparative and inventive zeolite treatments, which can be generally classified as follows: [0195] Process A: Alkaline treatment in the absence of suitable salts, followed by an acid and ion exchange treatments. This is a comparative process based on the absence of suitable salts in the alkaline treatment. [0196] Process B: Alkaline treatment in the presence of suitable salts, followed by an acid and ion exchange treatments. This is an inventive process based on the presence of suitable salts in the alkaline treatment. [0197] Process C: Alkaline treatment in the presence of suitable salts, followed by ion exchange treatments. This is an inventive process based on the presence of suitable salts in the alkaline treatment.

a) Reference (Parent) Zeolite

[0198] The parent zeolite, featuring the MTT framework and a molar Si/Al of 43 (hence molar SAR or Si/Al.sub.2 of 86), was not in an active protonic form and needed to be ion exchanged (to NH.sub.4 form) and calcined (to remove NH.sub.3) to yield the active protonic form: [0199] Hereto, in Step 0, 10 g was introduced in one go in a round-bottom flask containing a stirred 1000 ml solution of a 0.05 M (NH.sub.4).sub.2SO.sub.4 (10 mmol NH.sub.4.sup.+ per gram of zeolite). The resulting suspension was stirred and maintained at 25 C. for 8 h. Afterwards, the suspension was transferred to a one stage deep bed cylindrical filter (filter media: SK100 d=14 cm, separation limit 7.0-18 m), in order to separate the solid from the suspension. Afterwards, the resulting wet zeolite was dried overnight in an oven at 100 C. This procedure was repeated an extra two times. [0200] The dried solid obtained after the 3.sup.rd IE (ion exchange) was calcined under air at a temperature of 550 C. for 15 h with an initial heating ramp of 1.5 C./min.

B) Zeolite 1 (Comparative, Process a)

[0201] Zeolite 1 is mesoporized via base-acid treatment in the absence of inventive salts and is considered a comparative example. [0202] 33 g of the parent MTT zeolite was added to 900 ml of water which was stirred and maintained at 85 C. in a round bottom flask (forming suspension of Step 1A). [0203] Then, in Step 1B, 100 ml of a 4 M NaOH solution was added dropwise to the suspension of Step 1A over the course of 120 min. Afterwards, in Step 1C, the suspension filtered and dried as mentioned in Step 0. [0204] In step 1D, the dried solid obtained after Step 1C was exposed to a subsequent acid treatment. Hereto, 20 g of the dried solid obtained after Step 1C was introduced in one go in a round-bottom flask containing a stirred 2000 ml solution of a 0.1 M HCl (10 mmol HCl per gram of alkaline-treated mesoporous zeolite). The resulting suspension was stirred and maintained at 65 C. for 6 h. Afterwards, the solid was separated using the above described filtration, dried overnight in an oven at 100 C. [0205] Zeolite sample was then ion exchanged and calcined following the above described procedure for the reference material.

C) Zeolite 2 (According to the Invention, Process B)

[0206] 50 mmol of magnesium nitrate (salt) was added in one go to 900 ml of water, which was stirred and maintained at 85 C. in a round-bottom flask. Next, within several minutes, 33 g of the parent MTT zeolite was added to the solution, stirred, and maintained at 85 C. for about 5 minutes (forming suspension of step 2A). [0207] Then, in Step 2B, 100 ml of a 4 M NaOH solution was added dropwise to the suspension of Step 2A over the course of 60 min. Afterwards, in Step 2C, the suspension was filtered and dried as mentioned in Step 0. The molar metal(Mg)-to-aluminium ratio in the obtained alkaline-treated solid was 2.3 mol/mol. Then, an additional subsequent acid treatment was performed as described in Step 1D. [0208] Zeolite sample was then ion exchanged and calcined following the above described procedure for the reference material.

D) Zeolite 3 (According to the Invention, Process C)

[0209] Preparation of Zeolite 3 is similar to Zeolite 2, with the exception that after the base contacting in Step 2B, no subsequent acid treatment was performed. The resulting material featured a significant amount of magnesium. This is unique to the invention as metals deposited used other metal deposition technologies (such as IWI or ion exchange) would have been completely washed out during the 3-step ion exchange.

E) Zeolite 4 (According to the Invention, Process B)

[0210] Preparation of Zeolite 4 is similar to Zeolite 2, with the exception that 2.5 mmol HCl per g of alkaline-treated mesoporous zeolite was used instead of 10 mmol HCl per g of alkaline-treated mesoporous zeolite.

F) Zeolite 5 (According to the Invention, Process B)

[0211] Preparation of Zeolite 5 is similar to Zeolite 2, with the exception that the alkaline treatment was performed in a fixed-bed configuration, with the parent MTT zeolite present as a cake/membrane through which the alkaline solution was fed. To this end, the zeolite was first formed into a cake membrane by slurrying the 33 g of parent ZSM-23 in one liter of demi-water and filtering this suspension on a Buchner filtration set-up, of which the upper filtration cup had cylindrical shape, a volume of about 300 ml, and a diameter of about 12 cm, resulting in an average (wet) filter cake thickness of about 10-20 mm. Subsequently, 1 L of a preheated and stirred suspension of 50 mmol of Mg(NO.sub.3).sub.2 in 400 mmol of NaOH was gradually dripped over the cake over a period of 75 minutes. After the alkaline treatment was completed, the solid was washed and dried as mentioned for Zeolite 2. The resulting material featured, like Zeolite 2, increased mesoporosity over the parent zeolite and no significant amounts of Mg.

Mesoporous Zeolite MTT Properties

[0212] Table 1 and 2 provide the properties of the reference (parent) zeolite and Zeolite 1-5, as well as details on the used mesoporization process.

TABLE-US-00002 TABLE 1 Process for SBETb Smeso.sup.c, Vmicro.sup.d, Vmeso.sup.e, Entry Type mesopor. SAR.sup.a m2 .Math. g1 m2 .Math. g1 ml .Math. g1 ml .Math. g1 Reference Parent None 86 172 57 0.06 0.33 zeolite Zeolite 1 Mesoporous Process A 94 281 162 0.06 0.68 Zeolite 2 Mesoporous Process B 104 275 177 0.05 0.79 Zeolite 3 Mesoporous Process C 52 281 173 0.02 0.74 Zeolite 4 Mesoporous Process B 48 231 160 0.04 0.65 Zeolite 5 Mesoporous Process B 91 262 111 0.08 0.47 .sup.aMolar silica to Alumina ratio measured by elemental analysis: ICP (Inductively Coupled Plasma) bBET (total) surface area measured by N2-physisorption using the BET model .sup.cMesopore surface area measured by N2-physisorption using the t-plot model .sup.dMicropore volume measured by N2-Physisorption using the t-plot model .sup.eVpore-Vmicro

TABLE-US-00003 TABLE 2 Process Mesopores Mesopores Mesopores for D1 30-40 D2 40-200 D3 >200 A Entry Type mesopor. A/ml/g A/ml/g ml/g D2/D3 Reference Parent None 0.000 0.029 0.127 0.228 zeolite Zeolite 1 Mesoporous Process A 0.010 0.091 0.309 0.294 Zeolite 2 Mesoporous Process B 0.009 0.113 0.417 0.271 Zeolite 3 Mesoporous Process C 0.013 0.143 0.426 0.336

[0213] N.sub.2-Physisorption was used to determine isotherm, adsorption and desorption properties of the zeolites used herein. The data (FIG. 1) revealed that the type of mesoporosity was largely similar between the 3 displayed mesoporous samples, while varying mesopore size distribution between the different mesoporous zeolites was observed. These size distributions can be used to define a specific type of mesopore volume. Table 2 evidences a large porosity increase in each of D1, D2 and D3 for the zeolites of the present invention compared to the reference zeolite, without a significant change in the ratio of D2/D3. The similarity between the porosity and composition of Zeolite 1 and Zeolite 2 is emphasized.

[0214] The treated zeolites 1-5 comprised, like the parent reference zeolite, the MTT framework as could be discerned using powder X-ray diffraction.

Preparation of MTT Catalysts 1-4 (Metal Containing Sieve Fraction)

[0215] The mesoporous zeolites as defined herein were subsequently used to prepare catalysts using the below defined process: [0216] Step 1: zeolites were tableted under 28 ton to produce 40 mm pellets [0217] Step 2: pellets were sieved to 315-500 m sieve fraction [0218] Step 3: the sieve fraction was dried at 450 C. in air for 1-3 hours [0219] Step 4: the dried sieve fraction was impregnated with 90% soaking volume by dropwise addition at room temperature for 60-120 min with agitation, with a target of 1 wt % Pt [0220] Step 5: the impregnated sieve fraction was dried at 80 C. for 15 h [0221] Step 6: the dried sieve fraction of step 5 was calcinated at 190 C. (ramp 5 C./min, 1 h hold) under air flow [0222] Step 7: the fraction of step 6 was calcinated ate 300 C. (ramp 5-10 C./min, 5 h hold) under air flow [0223] Step 8: the fraction of step 8 was cooled down to room temperature

[0224] In further detail step 4 of the above process was performed using the following: [0225] Impregnation solution consisted of x mmol of tetraammineplatinum(II) nitrate solubilized in a pH 10 buffer solution containing 0.1 M ammonia and 0.02 M ammonium nitrate. [0226] The x mmol amount tetraammineplatinum(II) nitrate is dependent on the targeted Pt amount and the water soaking volume of the sieve fraction.

Preparation of MTT Catalysts 5-7 (Metal Containing Sieve Fraction)

[0227] Catalyst 5 was prepared following the same procedure as for Catalyst 1-4 with the exception that a targeted amount of 0.3 wt % Pt was used instead of 1 wt % Pt in Step 4. [0228] Catalysts 6 and 7 were prepared following the same procedure as for Catalyst 1-4 with the exception that tetraaminepalladium(II) nitrate was used instead of tetraammineplatinum(II) nitrate.

Preparation of MTT Catalysts 8 and 9 (Metal Containing Extrudates)

[0229] Catalysts 8 and 9 were prepared following the same procedure as for Catalysts 1-4 with the exception that, the zeolite powder was first extruded with an alumina binder (Catapal B) in a 50/50 weight ratio to form cylindrical extrudates (diameter 0.9 mm, length 3-4 mm), Steps 1 and 2 were not performed, and Step 3 was performed at 550 C. instead for 450 C.

MTT Catalyst Properties

[0230] Table 3 provides the properties of the several catalysts as used herein. Reference catalyst is derived from the Reference (parent) zeolite, while catalysts 1, 2, 3, and 4 were derived from zeolites 1, 2, 3, and 4, respectively. Reference Catalysts 6 and 8 are made from the Reference (parent) Zeolite, whereas Catalysts 5, 7 and 9 are made from Zeolite 3.

TABLE-US-00004 TABLE 3 Mg Pt Acidity Zeolite content.sup.h, content.sup.j, pyridine.sup.k, Entry sample Type Wt % Wt % mol .Math. g1 Reference Reference Parent 0.01 0.75 346 Catalyst zeolite Catalyst 1 Zeolite 1 Mesoporous 0.02 0.63 247 (comparative) Catalyst 2 Zeolite 2 Mesoporous 0.02 0.82 281 Catalyst 3 Zeolite 3 Mesoporous 4.40 0.72 92 Catalyst 4 Zeolite 4 Mesoporous 1.11 0.96 na Catalyst 5 Zeolite 3 Mesoporous 3.13 0.30 na Reference Reference Parent 0.01 0.71 (Pd).sup.l na Catalyst 6 zeolite Catalyst 7 Zeolite 3 Mesoporous 3.15 0.71 (Pd).sup.l na Reference Reference Parent 0.05 1.00 na Catalyst 8 zeolite extrudate Catalyst 9 Zeolite 3 Mesoporous 1.68 0.93 na extrudate .sup.hMagnesium content measured by ICP .sup.jPt content measured by ICP .sup.kTotal acidity measured using pyridine-probed FTIR (Fourier Transform InfraRed spectroscopy) .sup.lPd was used as hydrogenation metal instead of Pt.

[0231] From Table 3 it is evident that the catalysts of the invention contain sufficient Pt (or Pd), which ensures that the metal function for hydrogenation is not limiting. Catalyst 3 contains a large amount of Mg compared to the other catalysts, as well as limited (accessible) micropores and a low acidity.

Hydrocarbon Feedstock Used for the Catalytic Test

[0232] Table 4 provides the properties of the hydrocarbon feedstock used in the below experiments:

TABLE-US-00005 TABLE 4 Feed properties Sulfur, ppm (ASTM D5453) 13 Nitrogen, ppm (ASTM D4629) 0.9 Cloud Point, C. (ASTM D7689) 5 Pour Point, C. (ASTM D7346) 8 Density, g/ml (ASTM D4052) 0.8389 API Gravity (ASTM D4052) 37.17 Kinematic viscosity at 30 C., mm2 .Math. s1 4.76 (ASTM D7042) Naphtha (IBP-150 C.), wt % (ASTM D7213) 1.4 Diesel (150 C.-370 C.), wt % (ASTM D7213) 93.8 Lube (370 + C.), wt % (ASTM D7213) 4.8 SimDist (ASTM D7213) C. 0.5% 113 5% 195 10% 221 20% 254 30% 274 40% 290 50% 303 60% 313 70% 323 80% 336 90% 355 95% 369 99% 400 99.5% 412 SimDist refers to simulated distillation which is the industry standard method to characterize feeds in refining.

Catalytic Tests on MTT Zeolites

[0233] The conditions of the catalytic tests used herein were as follows: [0234] LHSV (liquid hourly space velocity, space times): 0.9 and 1.8 h.sup.1 [0235] Temperatures: 270-315 C. [0236] Pressure: 30 bar (total pressure) [0237] Hydrogen treat gas rate: 300 NI/1

Catalytic Tests on MTT Zeolites

[0238] As evident from FIG. 2, both the Cloud Point (CP) and Pour Point (PP) improved with at least a factor 4 for the catalysts of the invention compared to the reference catalyst, indicating that mesoporisation has a significant impact on these parameters. Moreover, the order of best performing catalysts is as follows: Catalyst 3>Catalyst 2>Catalyst 1; indicating that the mesoporization sequence in the presence of salts (Process B/Catalyst 2 and Process C/Catalyst 3) yields a much superior dewaxing compared to the mesoporization sequence in the absence of the salts (Process A/Catalyst 1). Since also in the state of the art (Catalysis Today, Volumes 218-219, December 2013, Pages 135-142) base-acid mesoporization sequences have thus far been only executed in the absence of salts (like Process A/Catalyst 1), the salt-containing mesoporization Process B and Process C enable a significantly improved dewaxing performance over the state of the art. Moreover, the superior performance of Catalyst 2 over Catalyst 1 is surprising as the properties of catalysts and related alkaline-treated mesoporous zeolites were largely similar.

[0239] Next, as Catalyst 3 is superior over Catalyst 2, it proves that the presence of the salt (Mg in this case) on the alkaline-treated mesoporous zeolite can be of high value to yield an optimal dewaxing performance.

[0240] Further experimental details for these catalysts at a fixed cloud point improvement of 30 C. (vertical line in FIG. 2), can be found in Table 5.

TABLE-US-00006 TABLE 5 Processing conditions and results Reference Feed catalyst Catalyst 1 Catalyst 2 Catalyst 3 Temperature, C. 295 290 295 295 LHSV, hr1 1.8 1.8 1.8 1.8 Pressure, barg 30 30 30 30 Cloud point improvement, C. 30 27 32 29 Pour point improvement, C. 30 30 36 32 Density, g/ml 0.8389 0.8366 0.8321 0.831 0.8274 API gravity 37.17 37.64 38.55 38.78 39.52 Kinematic viscosity 4.76 4.33 4.41 4.45 4.46 at 30 C., mm2 .Math. s1 Diesel Yield Loss, % 9.3 5.4 4.4 1.8 Naphtha (IBP-150 C.), wt % 1.4 8.2 6.0 5.4 3.6 Diesel (150 C.-370 C.), wt % 93.8 84.6 88.4 89.4 92.0 Lube (370 + C.), wt % 4.8 4.0 4.0 3.8 3.8 C1-C4, wt % 3.3 1.7 1.4 0.5 C5-C8, wt % 3.3 1.7 1.4 0.5 Average carbon number in 5.1 5.3 5.4 5.8 total C1-C8, a.u. Paraffinicity C4-C8, % 57.5 51.6 50.1 43.3 Paraffinicity C4-C8, is the percentage of paraffin (linear alkanes) vs the total hydrocarbon amount of C4-C8.

[0241] As evident from Table 5, at fixed cloud point improvement (30 C.), the catalysts of the present invention showed lower diesel yield loss (which is highly desirable), and a lower liquid density (i.e. higher API gravity).

[0242] FIG. 3 and Table 5 show a comparison of the composition of the C.sub.1 to C.sub.8 fraction of the different catalysts at similar cloud point improvement. The catalysts in accordance with the present invention produce less small carbon numbers, compared to the reference catalyst. In particular, the catalysts of the present invention (Catalyst 2 and Catalyst 3) yield higher average carbon numbers and a lower degree of paraffinicity (hence more branching).

[0243] Further experimental details for these catalysts at a similar diesel yield (horizontal line in FIG. 2), can be found in Tables 6 and 7.

TABLE-US-00007 TABLE 6 Processing conditions and results Reference Feed catalyst Catalyst 1 Catalyst 2 Catalyst 3 Temperature, C. 270 270 280 290 LHSV, hr1 0.9 0.9 0.9 0.9 Pressure, barg 30 30 30 30 Cloud point improvement, C. 9 18 33 37 Pour point improvement, C. 8 18 32 36 Density, g/ml 0.8389 0.8349 0.8303 0.8293 0.8267 API gravity 37.17 37.98 38.92 39.13 39.66 Kinematic viscosity 4.76 4.70 4.53 4.51 4.35 at 30 C., mm2 .Math. s1 Diesel Yield Loss, % 3.6 2.8 3.3 2.6 Naphtha (IBP-150 C.), wt % 1.4 4.4 4.2 4.7 4.4 Diesel (150 C.-370 C.), wt % 93.8 90.2 91.0 90.5 91.2 Lube (370 + C.), wt % 4.8 4.1 3.9 3.8 3.6

TABLE-US-00008 TABLE 7 Product quality at 3 wt % Diesel yield loss Reference Feed catalyst Catalyst 3 Cloud Point, C. 5 14 42 Pour Point, C. 8 16 44 Density, g/ml 0.8389 0.8349 0.8267 API Gravity 37.17 37.98 39.66 Kinematic viscosity at 30 C., 4.76 4.70 4.35 mm2 .Math. s1 Naphtha (IBP-150 C.), wt % 1.4 4.4 4.4 Diesel (150 C.-370 C.), wt % 93.8 90.2 91.2 Lube (370 + C.), wt % 4.8 4.1 3.6 Simdist C. 0.5% 113 102 102 5% 195 186 180 10% 221 215 208 20% 254 248 240 30% 274 270 264 40% 290 288 281 50% 303 300 296 60% 313 310 306 70% 323 321 318 80% 336 334 331 90% 355 353 350 95% 369 367 364 99% 400 397 394 99.5% 412 410 407

[0244] These data evidence that at fixed diesel yield loss (horizontal line in FIG. 2), catalysts of the present invention enable a much better product specification, higher Cloud Point and Pour Point improvement and a lower density. This density can be suitable related to the degree of aromatics in the feed and product streams (FIGS. 5 and 6). The aromatic content of the liquid samples is measured by High Performance Liquid Chromatography Method with Refractive Index Detection according to ASTM D6591. FIGS. 5 and 6 show that, using the inventive Catalyst 2 and 3, much lower aromatics levels can be attained. Moreover, the aromatic content (hence density) is much less sensitive to temperature, enabling to yield a desired density/aromatics level at any cloud point improvement (FIG. 7), being of clear commercial value.

[0245] FIG. 4 and Table 8 show a comparison of the C.sub.1-C.sub.s composition of the different catalysts at similar diesel yield loss. The catalysts in accordance with the present invention produce less small carbon numbers, compared to the reference catalyst. In particular, the catalysts of the present invention yield higher average carbon numbers and a lower degree of paraffinicity.

TABLE-US-00009 TABLE 8 Processing conditions and results Reference catalyst Catalyst 1 Catalyst 2 Catalyst 3 Temperature, C. 270 270 280 290 LHSV, hr1 0.9 0.9 0.9 0.9 Pressure, barg 30 30 30 30 Diesel Yield Loss, % 3.6 2.8 3.3 2.6 Average carbon number 5.3 5.5 5.5 5.7 in C1-C8, a.u. C1-C4, wt % 1.3 0.9 1.1 0.8 C5-C8, wt % 2.3 2.0 2.2 1.9 Paraffinicity C4-C8, % 54.2 49.6 48.5 45.0 Paraffinicity C4-C8, is the percentage of paraffin (linear alkanes) vs the total hydrocarbon amount of C4-C8.

[0246] Tables A, B, and C demonstrates that when the Mg content (Catalyst 4), or the amount hydrogenation metal (Catalyst 5), or the type of hydrogenation metal (Catalysts 6 and 7) is varied, or when the alkaline-treated mesoporous zeolites are present in an extrudate (Catalysts 8 and 9), the superior performance (that is, much lower diesel yield loss at fixed cloud point improvement) is maintained for the inventive catalysts.

TABLE-US-00010 TABLE A Processing conditions and results Reference catalyst Catalyst 4 Catalyst 5 Temperature, C. 290 305 315 LHSV, hr1 1.8 1.8 1.8 Pressure, barg 30 30 30 Cloud point improvement, C. 18 18 20 Pour point improvement, C. 20 20 24 Diesel Yield Loss, % 7 1.4 2.5

TABLE-US-00011 TABLE B Processing conditions and results Reference Catalyst 6 Catalyst 7 Temperature, C. 295 295 LHSV, hr1 1.8 1.8 Pressure, barg 30 30 Cloud point improvement, C. 13.6 11.2 Pour point improvement, C. 14 12 Diesel Yield Loss, % 7.9 1.7

TABLE-US-00012 TABLE C Processing conditions and results Reference Catalyst 8 Catalyst 9 Temperature, C. 280 295 LHSV, hr1 1.8 1.8 Pressure, barg 30 30 Cloud point improvement, C. 28.1 25.8 Pour point improvement, C. 28 26 Diesel Yield Loss, % 5.6 2.2

Mesoporous Zeolite MFI Preparation

[0247] To illustrate that the invention is also effective for the MFI framework, a parent ZSM-5 zeolite, featuring a molar Si/Al of 40 (hence molar SAR or Si/Al.sub.2 of 80), was used to make a Reference Zeolite A and two derived mesoporous variants Zeolite A1 and A2.

Reference Zeolite a (Parent)

[0248] The parent zeolite was not in an active protonic form and needed to be calcined following the above described procedure for the Reference (MTT) Zeolite.

Zeolite A1 (Comparative, Process a)

[0249] The mesoporous ZSM-5 Zeolite A1 was prepared according to process A in the same manner as for Zeolite 1 with the exception that: [0250] ZSM-5 parent zeolite was used instead of the MTT parent, during the alkaline treatment 67 g of zeolite instead of 33 g were added to the 900 ml of water which was stirred and maintained at 65 C. in a round bottom flask, then 100 mL of 5 M NaOH solution was added dropwise to the suspension over the course of 30 min. All the other parameters and/or steps are the same as described in Zeolite 1 preparation. Zeolite A1 is a comparative example.

Zeolite A2 (According to the Invention, Process C)

[0251] The mesoporous ZSM-5 Zeolite A2 was prepared according to process C in the following manner: [0252] 200 mmol of magnesium nitrate (salt) was added in one go to 900 ml of water, which was stirred and maintained at 65 C. in a round-bottom flask. Next, within several minutes, 67 g of the zeolite was added to the solution, stirred, and maintained at 65 C. for about 5 minutes (forming Suspension A). [0253] Then, 100 ml of a 6 M NaOH solution was added dropwise to Suspension A over the course of 30 min. Afterwards, the suspension filtered, and dried like for Zeolite 3. [0254] The obtained solid was then ion exchanged and calcined following the above described procedure for the Reference Zeolite, with the exception that 2.5 mmol of (NH.sub.4).sub.2CO.sub.3 per gram of zeolite was used for the first IE step, 5 mmol of (NH.sub.4).sub.2CO.sub.3 per gram of zeolite was used for the second IE step and 5 mmol of (NH.sub.4).sub.2SO.sub.4 per gram of zeolite was used for the third IE step, and for each IE steps the reaction time was 1 h.

Mesoporous Zeolite MFI Properties

[0255] The properties of the parent (Reference Zeolite A) and mesoporous ZSM-5 (Zeolite A1 and A2) zeolites are summarized in Table D, displaying increased mesopore surfaces and volumes combined with the largely preserved micropore volume and total surface area.

[0256] The magnesium dispersion on Zeolite A2 was 73% as assessed using oxalic acid chemisorption. In contrast, when Zeolite A1 was complemented with 3.9 wt % of Mg, using incipient wetness impregnation using a solution of Mg(NO.sub.3).sub.2, a dispersion of merely 14% was obtained, highlighting the advantage of alkaline-induced metal deposition over established metal deposition methods.

TABLE-US-00013 TABLE D Process for SBETb Smeso.sup.c, Vmicro.sup.d, Vmeso.sup.e, Entry Type mesopor. SAR.sup.a m2 .Math. g1 m2 .Math. g1 ml .Math. g1 ml .Math. g1 Reference Parent None 82 386 144 0.12 0.12 zeolite A Zeolite A1 Mesoporous Process A 87 454 244 0.11 0.43 Zeolite A2 Mesoporous Process C 70 417 233 0.09 0.37

Catalytic Tests on MFI Zeolites

[0257] The feedstock and catalytic conditions in the below described tests on MFI, TON, MRE, and MEL frameworks were similar was used for the MTT zeolite.

[0258] All ZSM-5 samples were processed into catalyst following the same procedure as Catalysts 1-4, yielding the below properties (Table E), showing a successful incorporation of Pt and the presence of ca 4 wt % of Mg in Catalyst A2.

[0259] The catalyst results (Table F) show that mesoporization Process A, hence in the absence of additives during the base step, in line with published work (Catal. Sci. Technol., 2016, 6, 6177-6186), yielded only a marginal reduction in diesel yield loss at a fixed cloud point improvement. Surprisingly, using the inventive process C and resulting catalyst, a similar cloud point improvement was combined at a much-reduced diesel yield loss and much reduced temperature.

TABLE-US-00014 TABLE E Zeolite Mg content, Pt content, Entry sample Type Wt % Wt % Reference Reference Parent 0.02 0.96 Catalyst A zeolite A Catalyst Al Zeolite A1 Mesoporous 0.01 0.89 Catalyst A2 Zeolite A2 Mesoporous 3.98 0.94

TABLE-US-00015 TABLE F Processing conditions and results Reference catalyst A Catalyst A1 Catalyst A2 Temperature, C. 295 290 270 LHSV, hr1 1.8 1.8 1.8 Pressure, barg 30 30 30 Cloud point improvement, C. 27.7 29.1 28.5 Pour point improvement, C. 30 28 25 Diesel Yield Loss, % 17.3 16.5 12.3

Catalytic Tests on TON, MRE, and MEL Zeolites

[0260] The effectiveness of the invention was also demonstrated by application of the synthetic approaches as presented for Zeolite 3 or Zeolite A2 to different parent zeolites with frameworks TON (Reference Zeolite B and Zeolite B1), MRE (Reference Zeolite C and Zeolite C1), and MEL (Reference Zeolite D and Zeolite D1, Tables G and H). Adjustments were applied in terms of the used amounts of NaOH and Mg(NO.sub.3).sub.2. In all cases, the parent zeolite was in the protonic form and the catalyst making was done as for Catalysts 1-5.

[0261] The catalytic results, shown in ranges for clarity, prove that the inventive superior catalytic effect (a substantially lower diesel yield loss (DYL) over the cloud point improvement (CPI), that is, DYL/CPI at ca. 30 C. CPI) is obtained in the same order of magnitude (that is, a DYL/CPI reduction larger than 0.1) for different zeolite frameworks over a broad range of Si/Al ratios, mesopore volumes, and Mg contents.

TABLE-US-00016 TABLE G Range classification Si/Al/ DYL/CPI/ Mg in solid/ in Table H mol/mol V.sub.meso/ml/g wt %/C wt % 20-39 0.05-0.14 0.00-0.09 0.0-0.9 40-79 0.15-0.24 0.10-0.19 1.0-2.4 +/ 80-119 0.25-0.39 0.20-0.34 2.4-3.9 + 120-199 0.40-0.79 0.35-0.49 4.0-5.9 ++ 200-400 0.80-1.20 0.50-0.70 6.0-12.0

TABLE-US-00017 TABLE H Mg in Si/Al/ solid/ V.sub.meso/ DYL/CPI/ Mesoporization NaOH/ Mg(NO.sub.3).sub.2/ mol/mol wt % ml/g wt %/ C. Sample Framework Process mmol mmol (described as ranges, see Table G) Reference MTT None None None None +/ +/ Zeolite Zeolite 3 MTT Zeolite 3 400 50 +/ + Reference MFI None None None None ++ Zeolite A Zeolite A2 MFI Zeolite A2 600 200 + +/ + Reference TON None None None None +/ +/ Zeolite B Zeolite B1 TON Zeolite 3 400 50 + Reference MRE None None None ++ None +/ Zeolite C Zeolite C1 MRE Zeolite 3 1000 300 + + + Reference MEL None None None +/ None +/ + Zeolite D Zeolite D1 MEL Zeolite A2 800 250 ++ ++