The Prins condensation between i-butene and formaldehyde over modified BEA and MFI zeolites in liquid phase

Journal Pre-proof The Prins condensation between i-butene and formaldehyde over modified BEA and MFI zeolites in liquid phase

Stanislav P. Bedenko, Andrei A. Kozhevnikov, Konstantin I. Dement'ev, Valentin F. Tret'yakov, Anton L. Maximov PII:

S1566-7367(20)30041-8

DOI:

https://doi.org/10.1016/j.catcom.2020.105965

Reference:

CATCOM 105965

To appear in:

Catalysis Communications

Received date:

23 November 2019

Revised date:

3 February 2020

Accepted date:

17 February 2020

Please cite this article as: S.P. Bedenko, A.A. Kozhevnikov, K.I. Dement'ev, et al., The Prins condensation between i-butene and formaldehyde over modified BEA and MFI zeolites in liquid phase, Catalysis Communications (2020), https://doi.org/10.1016/ j.catcom.2020.105965

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© 2020 Published by Elsevier.

Journal Pre-proof The Prins condensation between i-butene and formaldehyde over modified BEA and MFI zeolites in liquid phase. Stanislav P. Bedenko*, Andrei A. Kozhevnikov, Konstantin I. Dement’ev, Valentin F. Tret’yakov, Anton L. Maximov A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia *Corresponding author at: Moscow 119991, Leninsky Ave 29, Russia e-mail address: [email protected] Abstract

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The liquid-phase Prins condensation between i-butene and formaldehyde was studied over parent

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and Mg-modified MFI and BEA zeolites with low Si/Al ratios. High catalytic activity and selectivity toward isoprene were obtained using the H-BEA zeolite. The H-MFI zeolite was

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confirmed as a highly selective catalyst for 3-methylbut-3-ene-1-ol production via Prins

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condensation. The influence of Mg-ion-exchange treatment on the catalytic behavior of the zeolites was studied; modification of BEA led to significant changes in the catalytic behavior,

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while Mg-MFI and H-MFI showed similar conversion of formaldehyde and similar product distribution.

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Keywords: Prins reaction, isoprene, i-butene, formaldehyde, MFI, BEA

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1. Introduction

Isoprene is a very important and widely used semiproduct obtained in the production of

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synthetic rubbers (in 2018, approximately 212 thousand tons were produced in the US

[1]

).

Currently, naphtha steam cracking is the basic industrial process for isoprene production, but the yield

from this method

is relatively low.

Prins condensation between isobutene and

formaldehyde is an alternative reaction for high-yield isoprene production, and there are some additional industrial applications for this reaction

[3]

. For example, the condensation between

propylene and formaldehyde can be used for butadiene production synthesis via dimethyl ether conversion source of formaldehyde

[6-8]

[5]

[4]

, including butadiene

, where oxygenates (such as dimethyl ether) act as a

.

The Prins reaction is usually catalyzed by mineral acids such as H2 SO 4 and H3 PO4, or by Lewis acids (ZnCl2 , SnCl4 , etc.), which have significant drawbacks: they are extremely corrosive, suffer from poor selectivity and cannot be reused. These problems can be solved by using heterogeneous catalysts such as metal-organic frameworks (MOFs) [12-15]

, phosphates

[16]

and heteropolyacids

[17-18]

1

[9]

, CeO 2

[10-11]

,

zeolites

. For instance, zeolites are used as catalysts for

Journal Pre-proof isoprene production via the Prins reaction; however, the necessity of extreme conditions (approximately 300°C)

[12-15]

and low yield of isoprene are problematic for their application in

industry. Vasiliadou and coauthors

[4,

19]

have recently shown that MFI-type zeolites are

promising catalysts for the Prins reaction under mild conditions. Theoretical studies

[20-23]

propose Mg- and Au-metal-exchanged FAU zeolites as promising catalysts for the Prins condensation between propylene and formaldehyde due to their ability to preserve formaldehyde in a monomeric form and stabilize formaldehyde-olefin coadsorption complexes, but there is no practical evidence of their efficiency. Vakulin and coauthors

[24]

used the molecular dynamics method to show that the size and

topology of the zeolite pores influence the activation energy in the Prins reaction toward 4-

oo

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substituted-1,3-dioxanes. Condensation of relatively voluminous species such as arylalkenes with formaldehyde is catalyzed by the H-BEA zeolite, with high selectivity toward Prins reaction [25]

. At

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products, while narrowly porous H-MFI has both poor activity and selectivity in this case

the same time, MFI zeolites are very promising in the reaction between lower alkenes and [4, 12-15, 19]

. In other words, the topology of zeolite channels has a pronounced

e-

formaldehyde

influence on the activity and product distribution. In addition to topology, the acid properties of

Pr

catalysts impact the reaction rate and selectivity; according to previous reports

[12-15]

, the

formation of isoprene and 3-methylbut-3-ene-1-ol in the Prins reaction is controlled by weak

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Brønsted acid sites (BAS), while strong BAS and Lewis acid sites (LAS) contribute to side reactions (aromatization, oligomerization, etc.). [4]

have studied the condensation between propylene and formaldehyde over

rn

The authors

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Zn-MFI and Zn-BEA zeolites and demonstrated that Zn-MFI zeolites are selective catalysts for 3-butenol-1 production, while Zn-BEA catalyzes the reaction toward 1,3-butadiene and 5,6dihydro-2H-pyrane. According to previous research

[19]

, H-MFI zeolites are a promising catalyst

for one-pot isoprene synthesis while H-BEA is not an efficient catalyst for this aim, although HBEA with a Si/Al ratio of 19.0 had high selectivity toward isoprene production (44.1%). Moreover, experimental data showed that increasing the Si/Al ratio in MFI led to a decrease in the reaction selectivity toward isoprene. We took these circumstances into account and decided to explore the Prins reaction between i-butene and formaldehyde over parent and Mg-modified MFI and BEA zeolites with a lower Si/Al ratio than that previously used

[19]

. Here, we publish our experimental data about the

Prins reaction between formaldehyde and i-butene under mild conditions over parent and Mgmodified MFI with a Si/Al ratio of 15.0 and BEA zeolites with a ratio of 12.5.

2

Journal Pre-proof

2. Experimental 2.1. Catalyst Preparation All zeolite powders were commercially available samples in the ammonium form. The parent forms (H-forms) of MFI (Novosibirsk Chemical Concentrates Plant, Si/Al=15.0) and BEA (Angarsk Catalysts and Organic Synthesis Plant Si/Al=12.5) zeolites for catalytic experiments and ion exchange were obtained after calcination at 600°C overnight. Mg-MFI and Mg-BEA were prepared by the ion-exchange technique: zeolite powders were processed using a 1 M aqueous solution of Mg(NO 3 )2 *6H2 O at 80°C for 12 h (zeolite ratio mass per volume of

oo

f

solution was 1 g per 100 mL), and afterwards, the samples were washed with distilled water, filtered and dried overnight at room temperature, after which they were calcined at 600°C for 12

pr

h.

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2.2. Catalyst Characterization

BET, XRF, XRD, and TPD-NH3 methods and FTIR spectral analysis of adsorbed pyridine

Pr

were used to characterize the samples. Nitrogen physisorption isotherms were obtained using ASAP-2020. Specific area was determined by BET and Langmuir models. Micropore volume

al

was measured by the t-plot method. The elemental compositions were identified by the XRF technique (ARL Perform’x Sequential XFR with 2.5 kW power). The phase composition was

rn

determined by XRD analysis (Rigaku Rotaflex RU-200, CuKα radiation). The acid properties

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were investigated with the TPD-NH3 method using USGA-101 equipped with a TCD; the samples were placed into a quartz reactor, heated under He flow to 500°C, calcined at this temperature for 1 h and finally cooled to 60°C. Ammonia adsorption was carried out using a dry NH3 /N 2 gas mixture (1/9) for 15 min, and then, physically adsorbed NH3 was removed at 100°C in a He flow for 1 h, after which the temperature in the reactor was linearly increased to 600°C (rate 8°C/min). FTIR analysis of the adsorbed pyridine (FTIR) was carried out to determine the BAS and LAS distribution using a Protege 460 instrument (Nicolet) equipped with a Fourier converter at 4000-400 cm-1 ; the samples were pressed into wafers (20 mg with diameter 20 mm), activated under a vacuum of 5*10-4 Pa, heated for 2 h to 450°C and calcined at this temperature for 1 h. After cooling the samples to 150°C, pyridine was injected into the IR cell for 30 min; then, the samples were subjected to vacuum for 1 h at the same temperature. The difference spectra were calculated using Omnic software. 2.3. Catalytic tests 3

Journal Pre-proof The Prins reaction between formaldehyde and i-butene was carried out in a 250 mL stainless steel batch reactor (SKB TIPS RAS) with stirring. The temperature was controlled by a band heater with a controller (OVEN TRM-1). In a typical experiment, the reactor was loaded with the required amount of the reactants (10.0 g of i-butene and 1.0 g of paraformaldehyde as the formaldehyde source, with an i-butene/formaldehyde molar ratio of 5.3) in the presence of a solvent (1,4-dioxane, 20.0 mL) with the appropriate amount of catalyst (0.25 g). The reaction temperature was set to be constant at 150°C. The liquid products were collected in a glass separator after the reaction, and then cooled, filtered, and analyzed by the GC method using a Chromatec Crystal 2000, equipped with a HP-PLOT Q column (15 m length and 0.32 mm diameter) and an FID. Gaseous products were collected in a gas bag after separation and were

oo

f

analyzed with a Chromatec Crystal 2000 system equipped with a SE-30 column (20 m length and 0.32 mm diameter) and an FID. The conversion of the substrate and selectivity toward

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products were calculated on the basis of formaldehyde, since i-butene was taken in excess, using the following equations:

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moles of CH2 O converted into all products ∗ 100% moles of CH2 O initially loaded

Pr

conversion =

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3. Results and discussion

moles of CH2 O converted into this product ∗ 100% moles of CH2 O converted into all products

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selectivity toward product =

3.1. Catalyst Characterization

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The textural and acid properties of catalysts are shown in table 1. The specific area (SBET , SLM) and microporous volume (Vmicro ) of the samples obtained from nitrogen physisorption isotherms (S.2-5) were consistent with the structure of the parent zeolites, although the Mg-ionexchange samples had slightly lower values than did the parent zeolites. Additionally, the treatment led to changes in the pore size distribution (S.6-9). The Si/Al ratio value of the MFI zeolite, obtained by the XRF method (15.5), was close to the nominal value (15.0), while that of the BEA zeolite showed a small deviation (9.4 instead of 11.5). The Mg-exchanged samples had different amounts of Mg in their structure; according to XRF, the degree of ion exchange for the Mg-BEA sample was 44%, while that of the Mg-MFI sample was only 20%. These differences can be explained by the different micropore volumes of the samples and their topology as well as the Si/Al ratios of the samples; according to previous research

[26]

, the degree of ion exchange for alkaline-earth metal cations increases with a

decreasing ratio. The XRD patterns (S.10, S.12) showed high values for the degree of 4

Journal Pre-proof crystallinity in the samples, and the Mg-ion-exchanged samples had no MgO phase in their structure. We exclude the possibility of amorphous Mg-containing species on the zeolite surface, which is consistent with previous work regarding both Mg-ion-exchanged zeolites

[27,28]

.

The TPD-NH3 curves for the catalysts are shown in the supporting information (S.13S.17). There are two peaks present in all of the curves: in the 100-250°C (TI) and 350-450°C (TII) ranges. The first peak (TI) corresponds with weak acid sites, while the second peak (TII) refers to medium and strong acid sites. Mg treatment led to the displacement of peaks I and II in both samples into the low-temperature region and increased the I/II peak ratio, which indicated the lower strength of the acid sites in Mg-BEA and Mg-MFI than those in H-BEA and H-MFI,

SLM, m2 /g

Vmicro , m3 /g

CAM, µmol/g

H-BEA

585

771

0.189

1125.0

H-MFI

332

445

0.113

1323.0

Mg-BEA

571

764

0.172

1076.0

Mg-MFI

326

440

0.103

1088.0

TI, °C

TII, °C

e-

SBET, m2 /g

Table 1. Properties of catalysts

TI/TII ratio

CAS, µmol/g

Distribution of BAS and LAS, % BAS LAS

DAS, µmol/m2

210.3

368.1

2.03

967.0

55.1

44.9

1.25

233.0

442.2

1.31

1072.4

82.9

21.1

2.41

203.5

360.5

3.16

917.6

49.6

50.4

1.20

223.6

425.3

1.85

993.3

70.0

30.0

2.26

al

Pr

Sample

pr

oo

f

respectively.

The FTIR spectra of adsorbed pyridine (S.18) were used to calculate the concentration of

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acid sites (CAM) and percentage distribution of BAS and LAS in the samples. The values for the

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concentrations of acid sites obtained by FTIR analysis of adsorbed pyridine and the total amount of desorbed ammonia determined by TPD-NH3 (CAM) analysis were comparable, which indicates the availability of major acid sites for pyridine and ammonia. The total acidity and BAS-LAS distribution were altered after the Mg-ion exchange; compared to the Mg-modified samples, both parent zeolites have a higher total concentration of acid sites and more BAS. Mg-ion-exchange treatment led to an increase in the number of weak LAS in both samples, as shown in S.19 and S.20; according to the FTIR ratio of weak/strong sites, that of the LAS was close to 1 for the parent zeolites, while Mg-BEA and Mg-MFI had ratios of 4.55 and 2.73, respectively. The total concentration of acid sites decreased in the order H-MFI > H-BEA > Mg-MFI > Mg-BEA, which is consistent with the TPD data, while the BAS concentration declined in the following order: H-MFI > Mg-MFI > H-BEA > Mg-BEA. The concentration of weak LAS increased in the order of H-BEA ≈ H-MFI < Mg-MFI < Mg-BEA. The density of acid sites (DAS) was calculated as the ratio of the acid site concentration (C AS) to the value of the Langmuir specific area. Both Mg-ion-exchanged samples had slightly lower DAS values than the parent zeolites did. 5

Journal Pre-proof 3.2. The Prins reaction over H-BEA and H-MFI The Prins condensation is an acid-catalyzed addition of a formaldehyde to alkenes. The product distribution depends on the reaction conditions as well as the catalyst. In all cases, the first step is an electrophilic attack by a protonated formaldehyde on an unsaturated alkene bond. As a result, a carbocation intermediate is formed. The second step can vary: if we use anhydrous solvents, the intermediate loses a proton to generate an unsaturated alcohol; with water, the carbocation forms a diol; and 4-substituted-1,3-dioxanes are formed if formaldehyde is provided in excess. Based on these facts, we carried out our experiments using 1,4-dioxane as a solvent to prevent hydration of the intermediate. Scheme 1 illustrates the reaction pathways.

f

First, we tested the activity of parent zeolites in the Prins condensation. The values of

oo

formaldehyde conversion and selectivity toward the reaction products are shown in Table 2. Both zeolites were catalytically active, but the conversion of formaldehyde over H-BEA was

pr

twice that of the reaction carried out over H-MFI. Isoprene was the main product over H-BEA; however, undesired 4DMD, M2HP and terpenes were obtained, while 3MBO was produced over

e-

H-MFI with high selectivity (approximately 96%). Our experimental data over H-MFI are [19]

, while the H-BEA sample was more active. We

Pr

consistent with previously reported results

propose that the activity of H-BEA was mainly due to the higher acidity of the low Si/Al ratio

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rn

al

zeolite than that of the sample from previous experiments.

Scheme 1. Reaction network Table 2. Formaldehyde conversion and product selectivity after 1 h of reaction at 150°C CH2 O to product selectivity, % CH2 O TON* conversion, % 3MBO isoprene M2HP 4DMD other** H-BEA 64.6 8.2 15.3 47.7 15.8 14.1 7.1 H-MFI 32.1 3.5 95.8 0.7 2.3 1.2 Mg-BEA 54.5 6.6 36.9 18.7 25.5 15.2 3.7 Mg-MFI 28.0 3.6 98.6 0.2 1.2 0.1 * - TON was calculated on the basis of the sum of product moles and the number of acid sites; ** - other products were predominantly terpenes. Catalyst

6

Journal Pre-proof The experiments with different residence times (0.5, 1 and 2 h) were carried out over HBEA (fig. 1) and H-MFI (fig. 2) to quantify the evolution of the product distribution. According to fig. 1, isoprene was the main product over H-BEA, but its selectivity decreased as the reaction progressed. This decrease is due to the reaction of isoprene with formaldehyde, yielding M2HP and undergoing an oligomerization reaction. The curve of 3MBO selectivity also slightly decreased because 3MBO was dehydrated into isoprene and cyclized with formaldehyde to produce 4DMD. Selectivity toward M2HP and 4DMD increased as the reaction progressed because M2HP and 4DMD had no reactivity under these experimental conditions, which is in agreement with the literature

[19]

. 3MBO was the main product in all experiments over H-MFI

(fig. 2), but its selectivity decreased as the reaction progressed, while the selectivity curves

oo

f

toward isoprene, 4DMD and M2HP insignificantly increased in parallel. It seems that the difference in the catalytic behavior of these zeolites is mainly related to

pr

their topology; BEA zeolites have 12-T-membered ring linear and tortuous channels MFI-type zeolites have 10-T-membered straight and sinusoidal channels

[30]

[29]

while

. Porous topology

e-

influences the mass transfer of reactants and intermediates; since BEA pores are wider than MFI channels, acid sites in BEA pores are more available for relatively voluminous species

Pr

as isoprene, 4DMD and M2HP, as shown in previous work

[12-15]

[25]

, such

, so the narrow pores of MFI

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rn

al

inhibit the formation of 4DMD and M2HP, while the wide BEA pores permit the side reaction.

Fig. 1. Conversion and product selectivity

Fig. 2. Conversion and product selectivity

versus residence time upon H-BEA at 150°C

versus residence time upon H-MFI at 150°C

The second reason for the variation in sample behavior is acidity. According to previous research

[12-17]

, weak BAS catalyze the Prins reaction toward 3MBO and 4DMD. Dehydration of

alcohols may proceed over strong BAS

[31-32]

and LAS

[33]

, depending on the reaction conditions,

while the side hetero-Diels-Alder reaction is controlled by weak LAS

[34]

. According to the FTIR

spectra of adsorbed pyridine and the TPD-NH3 data, the H-BEA sample had a higher weak LAS 7

Journal Pre-proof concentration than H-MFI did, which resulted in the higher selectivity toward M2HP over HBEA than over H-MFI. The obtained data confirmed that H-MFI with a low Si/Al ratio is not a promising catalyst because the H-MFI had high selectivity toward 3MBO and low selectivity toward isoprene, while H-BEA with a ratio of 11.5 may be used for that aim. 3.3. Prins reaction upon Mg-BEA and Mg-MFI The effect of Mg-ion-exchange treatment on the catalytic behavior of the samples is shown in table 2. The modification by Mg had a strong influence on the BEA behavior; formaldehyde conversion over Mg-BEA was lower than that over H-BEA, and 3MBO became the main product. Moreover, in the case of Mg-BEA, M2HP selectivity increased by 10% compared to

oo

f

that in the experiment when catalyzed by H-BEA. The amounts of 4DMD remained constant, and the amount of terpenes was reduced by 2 times. The catalytic behavior of Mg-MFI was similar to that of H-MFI, with a formaldehyde conversion established at 28% and 3MBO as the

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rn

al

Pr

e-

pr

main product (selectivity approximately 99%). Side products were observed in trace amounts.

Fig. 3. Conversion and product selectivity

Fig. 4. Conversion and product selectivity

versus residence time over Mg-BEA at 150°C

versus residence time over Mg-MFI at 150°C

Since zeolite treatment by Mg can influence the evolution of the product distribution, we carried out experiments with 3 residence times to quantify evolution over the Mg-BEA (fig. 3) and Mg-MFI (fig. 4) catalysts. 3MBO was the main product in all experiments over Mg-BEA (fig. 3), unlike H-BEA (fig. 1). The selectivity curves had the same trends as those observed for H-BEA; the 3MBO and isoprene curves slightly decreased with time, while the amounts of undesired products increased. It is important to note that the hetero-Diels-Alder reaction rate over Mg-BEA is higher than that over H-BEA (M2HP curves shown in fig. 1 and fig. 3). A short residence time is preferred for 3MBO and isoprene production because they are consumed by 8

Journal Pre-proof side reactions, yielding M2HP, 4DMD and terpenes. Changes in the catalytic behavior of the BEA samples are due to the reduced micropore volume and the occurrence of steric difficulties for the transition state of the dehydration reaction. Moreover, the treatment caused a change in the acidity of the samples and the BAS-LAS ratio. According to references

[27-28]

, the Mg-ion-

exchange treatment causes a narrowing of the pores and a reduction in the number of strong BAS on the zeolite surface; these factors caused the decrease in the formaldehyde conversion and explained the changes in the selectivity trends over Mg-BEA in comparison to H-BEA. The reduction in the number of strong BAS and LAS on the Mg-BEA surface resulted in the decreased selectivity toward isoprene, while the increase in the number of weak LAS caused the rise in M2HP selectivity.

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f

The Mg-MFI selectivity curves (fig. 4) were similar to those of H-MFI (fig. 2), and all the trends were the same; however, the acidity, strength and BAS/LAS ratio were different. The

pr

experimental data confirmed that MFI predominantly catalyzed the reaction by external acidic sites and that the slight decrease in formaldehyde conversion was caused by the decrease in the

e-

specific area and the number of external acid sites.

The calculated geometry of substrates and products is shown in S.21-S.22. All molecular

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sizes allow these molecules to diffuse over pores of both zeolites (S.6-7). However, the transition state (TS) of 3MBO dehydrogenation as well as the formation of 4DMD and M2HP probably

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requires a greater volume than the reagent particle sizes, so these reactions may be prohibited in the MFI micropores, and undesired products (4DMD and M2HP) are formed on the external

rn

surface. The topology of the BEA channels allowed the side reaction that caused the obtained

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product distribution. Ion-exchange treatment led to a change in the pore size distribution (S.8-9), especially in the Mg-BEA case, which together with the reduced BAS concentration on the surface caused reduced activity and changed the product distribution. 4. Conclusions:

The Prins reaction between formaldehyde and i-butene was examined over parent and Mgmodified MFI and BEA zeolites with low Si/Al ratios. It was found that H-BEA with a ratio of 12.5 is a promising catalyst for isoprene one-pot synthesis via the Prins reaction with high selectivity (55%), while H-MFI with a ratio of 15 can be used as a high-selectivity (97%) catalyst for 3MBO production under the same conditions. For the first time, Mg-BEA and MgMFI were used as catalysts for i-butene:formaldehyde condensation. According to our experimental data, the Mg-ion-exchange treatment affected the catalytic behavior of BEA zeolites in the Prins reaction; the change in the product distribution has been pointed out, while the effect of Mg2+ treatment on MFI was negligible. It was proposed that both zeolite topology 9

Journal Pre-proof and acidity influence the catalytic performance: for wide-porous BEA, acidity greatly affects selectivity toward target products, while the reaction over narrowly porous MFI is predominantly controlled by the external specific area and acid sites.

Abbreviations used: 3MBO – 3-methylbut-3-ene-1-ol; M2HP – 3-methyl-5,6-dihydro-2H-pyran; 4DMD – 4,4dimethyl-1,3-dioxane

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Declaration of interest:

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None

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Acknowledgments:

This work was carried out within the State program of TIPS RAS. The work was

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performed using the equipment of the Shared-Use Center “Analytical Center for Problems of Deep Oil Refining and Petroleum Chemistry” and “New petrochemical process, polymers and

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adhesives” at the TIPS RAS. The authors would like to thank Dr. N.A. Zhilyaeva for help with

The Authors ORCID ID:

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nitrogen physisorption analysis and interpretation of those results.

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Stanislav P. Bedenko https://orcid.org/0000-0001-8926-0818

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Andrei A. Kozhevnikov https://orcid.org/0000-0001-7777-5267 Konstantin I. Dement’ev https://orcid.org/0000-0002-8102-8624 Prof. Valentin F. Tret’yakov https://orcid.org/0000-0001-8891-0866 Prof. Anton L. Maximov https://orcid.org/0000-0001-9297-4950 References [1]

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Journal Pre-proof SLM, m2 /g

Vmicro , m3 /g

CAM, µmol/g

TI, °C

H-BEA

585

771

0.189

1125.0

H-MFI

332

445

0.113

Mg-BEA

571

764

Mg-MFI

326

440

Distribution of BAS and LAS, % BAS LAS

TII, °C

TI/TII ratio

CAS, µmol/g

210.3

368.1

2.03

967.0

55.1

44.9

1.25

1323.0

233.0

442.2

1.31

1072.4

82.9

21.1

2.41

0.172

1076.0

203.5

360.5

3.16

917.6

49.6

50.4

1.20

0.103

1088.0

223.6

425.3

1.85

993.3

70.0

30.0

2.26

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Pr

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Sample

SBET, m2 /g

14

DAS, µmol/m2

Journal Pre-proof CH2O to product selectivity, % CH2 O TON* conversion, % 3MBO isoprene M2HP 4DMD other** H-BEA 80.5 10.2 9.7 36.9 24.7 20.0 8.7 H-MFI 45.1 4.9 94.6 0.9 2.8 1.7 Mg-BEA 69.4 8.4 37.1 15.2 24.6 18.6 4.5 Mg-MFI 43.1 5.7 96.5 0.5 2.7 0.3 * - TON was calculated based on sum of product moles and the number of acid sites; Catalyst

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** - other products were predominantly terpenes,

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Journal Pre-proof Isoprene and 3-methylbut-3-eneol-1 can be produced via Prins reaction over zeolites



Reaction yield can be controlled by topology of zeolites and BAS/LAS distribution



Mg-ion-exchange treatment has strong influence on BEA catalytic behavior



Mg-ion-exchange treatment has a little impact on MFI catalyst performance

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

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Stanislav P. Bedenko: Conceptualization, Methodology, Formal analysis, Investigation, Writing - Original Draft; Andrei A. Kozhevnikov: Formal analysis, Software, Investigation; Konstantin I. Dement’ev: Methodology, Formal analysis, Writing - Original Draft; Valentin F. Tret’yakov: Conceptualization, Writing - Review & Editing; Anton L. Maximov: Conceptualization, Writing - Review & Editing, Supervision.

17

Journal Pre-proof Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:

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Figure 1

Figure 2

Figure 3

Figure 4