1-butene Reaction Research Articles

Rational solvent selection for the preparation of industrial monolithic supported liquid-phase (SLP) olefin hydroformylation catalyst

Heterogenisation of the hydroformylation (HyFo) process converting C4 olefins and syngas (CO/H2) to n-pentanal can substantially reduce its carbon footprint by simplifying downstream processing. Current upscaling efforts include constructing a pilot plant containing a Rh-diphosphite-stabilized supported liquid-phase (SLP) catalyst. The air-sensitive nature of the catalyst requires in-situ impregnation of the porous support material with the liquid phase components (Rh-precursor, ligand, stabiliser) entailing the use of large quantities of an organic solvent. Environment, health, and safety (EHS) as well as regulatory aspects prompt the search for an alternative to dichloromethane (DCM), which was used as standard solvent for lab-scale studies. To obtain alternatives to DCM, the replacement solvent methyl tert-butyl ether (MTBE) and in-silico screening of more than 5000 solvent candidates has been performed covering boiling points and solubility predictions by COSMO-RS as well as carcinogenicity- and mutagenicity predictions by quantitative structure–activity relationship (QSAR) models. The final list of solvent candidates contained unsaturated compounds (alkenes, alkynes) in addition to ether- and ester-functionalized​ solvents, which are typically recommended as DCM replacements. Sufficiently high solubilities of ligand and stabiliser to prepare the desired SLP catalyst were experimentally determined in the following solvents: methyl propionate (MP), dimethoxymethane (DMM), MTBE, tetrahydrofuran (THF) and DCM for benchmarking, and a monolithic SLP catalyst prepared with MTBE demonstrated to perform equally well in the HyFo reaction of 1-butene as the benchmark catalyst prepared using DCM solvent. Overall, the study demonstrates a practical approach for selecting solvents with a greener profile for making catalyst systems applicable for large-scale production.

Unit cell distortion of ferrierite induced by carbonaceous deposits during skeletal isomerization of 1-butene

In this study, high temperature and ambient X-ray powder diffraction (XRD) are employed to differentiate the impacts of temperature and carbon deposition on the catalytic activity of the zeolite H-ferrierite (H-FER) via changes in the unit cell structure. XRD serves as a straightforward tool to distinguish these influences on the lattice geometry of H-FER, which ultimately affects catalytic activity. Due to its industrial relevance, the isomerization reaction of 1-butene to iso-butene is selected. Pristine H-FER undergoes a thermal contraction when heated from room temperature to 450 °C. However, internal carbonaceous deposits (i.e., deposits inside the micropores of the zeolite) counterbalance this effect, and the unit cell expands anisotropically during the reaction startup phase. Internal carbon deposits act as the driving force for this expansion and counteract external forces. During catalyst deactivation (time on stream >100 h), a slight unit cell contraction (i.e., ΔV = −6 Å3) is observed that stems from external carbon deposit condensation (i.e., deposits on the crystal surface). Characterization of an oxidatively regenerated catalyst supports this finding by proving this structural distortion to be nearly reversible. This study concludes that internal carbon species are primarily responsible for structural distortion and counteract thermal contraction, whereas external coke species are the driving force for catalyst deactivation.

Konwersja etanolu do acetonu na katalizatorze ZnO-CaO w obecności pary wodnej

The main product of the conversion of ethanol to acetone on a ZnO-CaO catalyst is acetone, the yield of which strongly depends on the composition of the reaction environment. When oxygen is present, the yield of products of destructive and complete oxidation increases greatly. In contrast, when water vapor is present, both the selectivity and conversion of ethanol increase. Therefore, the conversion of ethanol is the limiting step in the overall process, which determines the selectivity of the conversion of ethanol to acetone. In this regard, it appeared suitable to investigate the effect of introducing water to the contact zone. As experiments indicated, the addition of water caused a significant effect on the conversion, selectivity, and acetone yield on the ZnO-CaO catalyst. As the partial pressure of water vapor increases, the conversion of ethanol and the acetone yield increase, while the yield of carbon dioxide decreases. The decrease in carbon dioxide is associated not only with the inhibition of the conversion of ethanol to CO2. In this study, the adsorption of water vapor and ammonia on the surface of the ZnO-CaO catalyst was examined by infrared spectroscopy method. It has been shown that water vapor at low temperatures is adsorbed on the catalyst surface in the molecular form, while at higher temperatures it is adsorbed in the dissociative form. Co-transformation reactions of ethanol with acetic acid, acetaldehyde with ethylene, and acetaldehyde with acetic acid have been studied. The obtained results indicated that acetone is formed mainly through the stage of complexation of acetaldehyde with ethylene. The isomerization reaction of 1-butene to 2-butene has been investigated. It was found that the yield of cis-2-butene in the absence of water vapor is higher, likely attributed to the molecular adsorption of water on Lewis centers. Based on these findings, a scheme for the vapor-phase conversion of ethanol into acetone on the studied catalysts was formulated.

Improved Catalytic Performances of the NaOH-Treated ZSM-22 Zeolite in the 1-Butene Skeletal Isomerization Reaction: Effect of External Acid Sites.

In this paper, a series of alkaline-treated ZSM-22 zeolite samples were prepared by treating the parent ZSM-22 zeolite using NaOH aqueous solution with different concentrations. By investigating the effects of alkaline treatment on the parent ZSM-22 zeolite, we discovered that the alkaline treatment contributed to the reduction of Brønsted acid sites due to the coverage of extra-framework Al on its external surface. In addition, it was found that the alkaline-treated samples were favorable to the improvement of the isobutene yield and selectivity, while these features appeared to be low for the subsequent acid-washed counterparts in the skeletal isomerization reaction of 1-butene. These results indicate that the catalytic performance of ZSM-22 zeolite is related to reduced amounts of Brønsted acid sites in it. To further reveal the reasons for the promoted catalytic performances of the alkaline-treated ZSM-22 series zeolites, we studied the properties of coke deposited on the two series of samples using Raman spectroscopy and thermogravimetric analysis and mass spectrometry (TG/MS-TPO). It was shown that the carbon deposited on the alkaline-treated series samples was mainly distributed at the outer surface, while the coke was distributed to a relatively lesser extent at the exterior surface for the acid-washed series samples. Moreover, by partially passivating outer acid sites of the parent zeolite, the selected alkaline-treated zeolite, and acid-washed zeolite, their isobutene selectivities were all improved with the decrease in outer acid sites. These phenomena confirmed that the improved catalytic performances of the alkaline-treated samples are related to their decreased external Brønsted acid site density, which further demonstrated that the high isobutene yield and selectivity in the skeletal isomerization reaction of 1-butene is realized via the monomolecular reaction pathway of 1-butene.

A study of the acidity on catalyst surface to control 1-butene reaction mechanism of metallosilicate catalysts

The metallosilicate catalysts (H-M-silicate, when M = Al, Fe, Cu, and Ni and Si/metal = 20) were synthesized and characterized by XRD, SEM-EDX, XRF, N2 adsorption and desorption, 27Al MAS NMR, XANES, EXAFS, NH3-TPD, NH3-IR, and TPO methods to investigate the effect of transition metals substitution in zeolite structure for 1-butene reaction. Only Fe3+ of H-Fe-silicate bonded in the MFI structure like H-ZSM-5, whereas transition metals of H-Cu-silicate and H-Ni-silicate embedded in zeolite matrix over catalyst surface; therefore: the reduction reaction occurred over metal of H-M-silicate catalyst during the reaction. There were two different roles of Brønsted acid site, detected by NH3-IR (B1 at ca. 1470 cm−1 and B2 at ca. 1660 cm−1). The B1 Brønsted acid site over micropore surface of catalyst (Si-OH-M) favored oligomerization-cracking route of 1-butene reaction, while butene isomerization route reacted on B2 Brønsted acid site (Si-OH) over external surface of catalyst (Acid strength: B1 > B2)

The study of ferrierite zeolite synthesized by using silica sol modified by HCl as silica source for the skeletal isomerization reaction of 1-butene

The study of ferrierite zeolite synthesized by using silica sol modified by HCl as silica source for the skeletal isomerization reaction of 1-butene

Insight into the Effect of Lewis Acid of W/Al-MCM-41 Catalyst on Metathesis of 1-Butene and Ethylene

Elucidating the role of support nature of the W catalyst is of great importance for the metathesis reaction of 1-butene and ethene to propene. Herein, a series of highly dispersed W/Al-MCM-41 catalysts were prepared by impregnating W on the Al-MCM-41 supports with different Si/Al ratios. Multi-characterizations together with DFT calculations revealed that the Lewis Acid formed by framework Al could strength the interaction between W metal and Al-MCM-41 support and promote the formation of the W-(O-Si)n species, which are the main active sites in the metathesis reaction. Through the optimization of various parameters (such as Si/Al ratio, W metal loading, pretreatment atmosphere and reaction temperature), optimal 1-butene conversion (94%) and propene selectivity (81%) are obtained on the N2-pretreated 10W/70-MCM-41 catalyst at 350°C under atmospheric pressure. This work may provide some new insights for the rational design of W based catalysts in the olefin metathesis system.

Multichannel dynamics in the OH+ n-butane reaction revealed by crossed-beam slice imaging and quasiclassical trajectory calculations

Multidimensional reactions present various channels that can exhibit very different dynamics and give products of varying subsequent reactivity. Here, we present a combination of experiment and theory to reveal the dynamics of hydrogen abstraction by OH radical at primary and secondary sites in n-butane at a collision energy of 8 kcal/mol. Crossed molecular beam slice imaging experiments unequivocally probe the secondary abstraction channel showing backward angular distributions with mild energy release to product translation, which are accurately captured by trajectory calculations using a specific-reaction-parameter Hamiltonian. Experiments containing both reaction channels indicate a less marked backward character in the angular distribution, whose origin is shown by trajectory calculations to appear as an evolution toward more sideways scattering from the secondary to primary channel. While the two channels have markedly different angular distributions, their energy release is largely comparable, showing ample energy release into the water product. The synergistic combination of crossed-beam imaging and trajectories opens the door to detailed reaction-dynamics studies of chemical reactions with ever-increasing complexity.

Differences in acid and catalytic properties of W incorporated spherical SiO2 and 1%Al-doped SiO2 in propene metathesis

Propene self-metathesis to ethylene and 2-butene was investigated over tungsten-based catalysts (9 wt.% W) supported on silica and 1%Al-doped SiO2, prepared by different processes. On pure SiO2, incorporating WOx improved tungsten dispersion and formation of active tetrahedral WOx species, compared to the impregnated ones. However, negative effect was found when tungsten was incorporated in the 1%Al-doped SiO2 as the catalysts contained more crystalline WOx, lower tetrahedral species, and lower Lewis acid sites, compared to the W-imp 1Al2O3/SiO2 prepared by impregnation. Incorporating both W and Al in the SiO2 by sol-gel method may lead to suppression of bridge hydroxyl Si(OH)Al group, as a consequence more crystalline WOx was formed. Nevertheless, the abundance of Bronsted and Lewis acid was found to play important role in the propene metathesis and the secondary metathesis of 1-butene reactions than surface silanol and the presence of tetrahedral tungsten oxide species on the 1%Al-doped SiO2 supported catalysts.

Rate constants and kinetic isotope effects for H-atom abstraction reactions by muonium in the Mu + propane and Mu + n-butane reactions from 300 K to 435 K: challenges for theory.

This paper reports measurements of the temperature dependence of the rate constants for H-atom abstraction reactions from propane and n-butane by the light isotopic H-atom muonium (Mu), kMu(T), over temperatures in the range 300 K to 435 K. Simple Arrhenius fits to these data yield activation energies, E, that are some 2-4 times lower than E found from corresponding fits for the H + propane and H + n-butane reactions studied elsewhere, both experimentally and theoretically, and fit over a similar temperature range. These activation energies E are also much lower than estimated from zero-point-energy corrected vibrationally adiabatic potential barriers, both results suggesting that quantum tunneling plays an important role in determining kMu(T) and for the Mu + propane reaction in particular. The results are expected to pose a considerable challenge to reaction rate theory for isotopic H-atom reactions in alkane systems.

Rate rules for the reactions of oxygen atoms with terminal alkenes

The reaction of ground state atomic oxygen with terminal alkenes plays an important role in both atmospheric and combustion chemistry. Because of its complicated nature, which involves intersystem crossing from the triplet to the singlet potential energy surface, its channel specific reactivity has been explored only for a few species in restricted temperature and pressure ranges. Here, we report results of crossed molecular beam experiments and theoretical computations for the O(3P) + 1-butene reaction. It is found that traditional rate rules methods where the reactivity of larger size molecules is extrapolated from simpler homologues is not valid for this reaction class. A viable alternative is proposed that allows to predict the reactivity of the whole O(3P) + terminal alkenes reaction class across wide temperature and pressure ranges, encompassing atmospheric and combustion conditions. The present results suggest that all O(3P) reactions with unsaturated hydrocarbons implemented with extrapolated rate constants in kinetic mechanisms should be revised.

Combined Experimental and Theoretical Studies of the O(3P) + 1-Butene Reaction Dynamics: Primary Products, Branching Fractions, and Role of Intersystem Crossing.

Information on the detailed mechanism and dynamics (primary products, branching fractions (BFs), and channel specific rate constants as a function of temperature) for many important combustion reactions of O(3P) with unsaturated hydrocarbons is still lacking. We report synergistic experimental/theoretical studies on the mechanism and dynamics of the O(3P) + 1-C4H8 (1-butene) reaction by combining crossed molecular beam (CMB) experiments with soft electron ionization mass-spectrometric detection and time-of-flight analysis at 10.5 kcal/mol collision energy (Ec) to high-level ab initio electronic structure calculations of the underlying triplet and singlet potential energy surfaces (PESs) and statistical Rice-Ramsperger-Kassel-Marcus/Master Equation (RRKM/ME) computations of BFs including intersystem crossing (ISC). The reactive interaction of O(3P) with 1-butene is found to mainly break apart the 4-carbon atom chain, leading to the radical product channels ethyl + vinoxy (BF = 0.34 ± 0.11), methyl + C3H5O (BF = 0.28 ± 0.09), formyl + propyl (BF = 0.17 ± 0.05), ethyl + acetyl (BF = 0.014 ± 0.007), and butanal radical (ethylvinoxy) + H (BF = 0.013 ± 0.004), and molecular product channels formaldehyde + propenylidene/propene (BF = 0.15 ± 0.05) and butenone (ethyl ketene) + H2 (BF = 0.037 ± 0.015). As some of these products can only be formed via ISC from triplet to singlet PESs, from BFs an extent of ISC of 50% is inferred. This value is significantly larger than that recently observed for O(3P) + propene (22%) at similar Ec, underlying the question of how important it is to consider nonadiabatic effects for these and similar combustion reactions. Comparison of the derived BFs with those of statistical (RRKM/ME) simulations on the ab initio coupled triplet/singlet PESs shows good agreement, warranting the use of the RRKM/ME approach to provide information on the variation of BFs with temperature and to derive channel specific rate constants as a function of temperature (T) and pressure (p). Notably, ISC is predicted to decrease strongly with increasing temperature (from about 70% at 300 K to 46% at Ec = 10.5 kcal/mol, and about 1% at 2000 K). The present results lead to a detailed understanding of the complex reaction mechanism of O(3P) + 1-butene and, by providing channel specific rate constants as a function of T and p, should facilitate the improvement of current fossil-fuel (1-butene) as well as biofuel (1-butanol) combustion models.

Influence of acidity on the performance of silica supported tungsten oxide catalysts assessed by in situ and Operando DRIFTS

The types of acidity on WOx/SiO2 catalysts prepared with different tungsten loadings (5 and 9 wt.% W) and pretreatment atmospheres (N2 and H2) were clarified by using the in situ diffuse reflectance infrared Fourier transform spectroscopy with temperature-programmed desorption (in situ DRIFTS-TPD) technique. Ammonia (NH3) acted as probe molecules that could block Lewis acid site type II (1620 cm−1) on the studied catalysts. The reactant feed containing 2% trans-2-butene or mixed feed of 2% trans-2-butene and 4% ethylene were used to investigate the reaction pathway on the WOx/SiO2 catalysts. Combining the Operando DRIFTS with gas chromatography-flame ionization detector (Operando DRIFTS-GC-FID) technique and in situ DRIFTS-TPD led to more deeply understanding of the correlation of acid sites and the primary cross metathesis reaction as the main reaction with isomerization of trans-2-butene as the side reaction. The adsorption energy of pulse chemisorption of 1-butene on catalyst by in situ DSC, confirmed the presence of the Lewis acid site type II related to the opportunity of 1-butene adsorption. The results confirmed that the Lewis acid site at 1620 cm−1 was crucial for the secondary metathesis reaction of 1-butene.

Inhibition effect of Na+ form in ZSM-5 zeolite on hydrogen transfer reaction via 1-butene cracking

The Na+ and H+ of ZSM-5 having three Si/Al molar ratios (20, 35, and 50) were synthesized to investigate and illustrate 1-butene cracking mechanism. The physical and chemical properties of ZSM-5 were described by XRD, SEM-EDX, N2 physicsorption, FT-IR, pyridine-IR, 1H MAS NMR, TPO, and NH3-TPD techniques. For the characterization, the Na-ZSM-5 consisted of two main types of acid sites (weak and medium acid sites), whereas strong, medium, and weak acid sites were detected on H-ZSM-5. For H-ZSM-5, the Si-(OH)-Al site (strong Brønsted site) was an active site for 1-butene cracking reaction, while the active site of Na-ZSM-5 in the reaction was silanol nest (moderate Brønsted site). The 1-butene cracking reaction on H-ZSM-5 and Na-ZSM-5 was studied under the operating condition of temperature =500 °C, pressure =1 atm, and WHSV =3 h−1. The oligomerization, cracking, and hydrogen transfer were three main reactions in the 1-butene cracking mechanism. The alkenes excluding propylene occurred on weak acid site, while the formation of propylene underwent on medium acid site of ZSM-5 catalyst. The presence of strong acid site on ZSM-5 catalyst promoted the hydrogen transfer reaction, which provoked the alkane formation. The hydrogen transfer index in 1-butene reaction of Na-ZSM-5 was less than H-ZSM-5 in all Si/Al molar ratios because of the absence of strong acid. The Na-ZSM-5 (Si/Al molar ratio = 20) reached the highest propylene selectivity at 31.73 C-wt.% and the Na+ ion could block the strong acid site. At low Si/Al molar ratio, the stability of Na-ZSM-5 was higher than H-ZSM-5 because of the lower coke formation. Therefore, the Na-ZSM-5 was more suitable catalyst than H-ZSM-5 for propylene formation in 1-butene cracking reaction.

The influence of different monodentate P-ligand mixtures on Rh-catalyzed 1-butene hydroformylation

Abstract Four monodentate P-ligands and their mixtures (six groups of double-ligand systems, four groups of triple-ligand systems and one group of tetra-ligand system) were used with Rh(acac)(CO)2 (acac = acetylacetonate) or Rh(acac)CO(PPh3) as the catalyst in the hydroformylation reaction of 1-butene. It was found that different Rh catalysts showed little difference in the catalysis performance. The general order of catalysis performance is double-ligand system > single-ligand system > triple-ligand system > tetra-ligand system. Some synergistic effect in the double-ligand system was detected which needs a further investigation.

Lanthanum-mediated dehydrogenation of butenes: Spectroscopy and formation of La(C4H6) isomers.

La atom reactions with 1-butene, 2-butene, and isobutene are carried out in a laser-vaporization molecular beam source. The three reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butenes. The dehydrogenated species La(C4H6) is the major product, which is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectrum of La(C4H6) produced from the La+1-butene reaction exhibits two band systems, whereas the MATI spectra produced from the La+2-butene and isobutene reactions display only a single band system. Each of these spectra shows a strong origin band and several vibrational progressions. The two band systems from the spectrum of the 1-butene reaction are assigned to the ionization of two isomers: La[C(CH2)3] (Iso A) and La(CH2CHCHCH2) (Iso B), and the single band system from the spectra of the 2-butene and isobutene reactions is attributed to Iso B and Iso A, respectively. The ground electronic states are 2A1 (C3v) for Iso A and 2A' (Cs) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and leads to the 1A1 ion of Iso A and the 1A' ion of Iso B. The formation of both isomers consists of La addition to the C=C double bond, La insertion into two C(sp3)-H bonds, and H2 elimination. In addition to these steps, the formation of Iso A from the La+1-butene reaction may involve the isomerization of 1-butene to isobutene prior to the C-H bond activation, whereas the formation of Iso B from the La+trans-2-butene reaction may include the trans- to cis-butene isomerization after the C-H bond activation.

Self-metathesis of 1-butene to ethene and hexene over molybdenum-based heterogeneous catalysts

A novel route involving self-metathesis of 1-butene under mild conditions that gave high yields of ethene and hexene was proposed. The results of thermodynamic analysis revealed that the Gibbs energy of the target Metathesis I reaction (1-butene → ethene + 3-hexene) was much higher than that of the main side Metathesis II (1-butene + 2-butene → propene + 2-pentene). Suppression of 1-butene double-bond isomerization was the key step to increase the selectivity for the target olefin in the reaction network. The relationship between the catalytic performance and support nature was investigated in detail. On basis of H2-TPR, UV-Vis spectra and HRTEM results, an alumina (Al2O3) support with large surface area was beneficial for the dispersion of molybdenum (Mo) species. Both suitable acidity and sufficient Mo dispersion were important to selectively promote the self-metathesis reaction of 1-butene. On the optimal 6Mo/Al2O3 catalyst, 1-butene conversion reached 47% and ethene selectivity was as high as 42% on the premise of good catalytic stability (80 °C, 1.0 MPa, 3 h−1).

Oxidation of lower alkenes by α-oxygen (FeIII–O•−)α on the FeZSM-5 surface: The epoxidation or the allylic oxidation?

Reactions of anion-radical α-oxygen (FeIII–O•−)α with propylene and 1-butene on sodium-modified FeZSM-5 zeolites were studied in the temperature range from −60 to 25°C. Products were extracted from the zeolite surface and identified. It was found that main reaction pathway was the epoxides formation. Selectivity for epoxides at −60°C was 59–64%. Other products were formed as a result of secondary transformations of epoxides on the zeolite surface. According to IR spectroscopy, the oxidation of propylene over the entire temperature range and 1-butene at −60°C were not accompanied by the formation of (FeIII–OH)α groups, in distinction to methane oxidation. This testifies that hydrogen abstraction does not occur. In case of 1-butene reaction with α-oxygen at 25°C, hydrogen abstraction occurred but was insignificant, ca 7%. According to DFT calculation ferraoxetane intermediate formation is preferable over hydrogen abstraction. Following decomposition of this intermediate leads to the propylene oxide (PO) formation. The results may be relevant to the low selectivity problem of the silver catalyst in propylene epoxidation and raise doubts about the presently accepted mechanism explaining an adverse effect of allylic hydrogen.

TUD-1 type aluminosilicate acid catalysts for 1-butene oligomerisation

TUD-1 type mesoporous aluminosilicates were explored for the acid-catalysed oligomerisation of 1-butene, under high pressure, continuous flow operation, which is an attractive route to produce sulphur-free synthetic fuels with reduced aromatics content. The solid acid catalysts were synthesised via one-pot synthesis (HT) or stepwise approach (PG), without using surfactants as templates, which is an eco-friendly characteristic of the TUD-1 family. While the HT approach may be advantageous in terms of process intensification in relation to the PG one, the latter may lead to relatively low molar ratios Si/Al. The catalysts possessed Si/Al ratios in the range 3–5 and 17–35 for the PG and HT approaches, respectively, pore sizes in the range 10–14nm, and essentially Lewis acidity. To the best of our knowledge, this is the first report of siliceous oxide TUD-1 furnished with acidity via post-synthesis grafting (PG) of Al-species. For comparative studies, an ordered mesoporous aluminosilicate was synthesised via the PG approach using surfactant mixtures. All materials prepared promoted the reaction of 1-butene to higher molar mass products. The best-performing catalyst in terms of space-time yields of the 170–390°C cut (boiling point range) products (of the type middle distillates) was Al-TUD-1(25)-HT synthesised via the HT method. The products were analysed by comprehensive two-dimensional gas chromatography (GC×GC) combined with time-of-flight mass spectrometry (ToFMS). The influence of material properties and process parameters on the catalytic reaction, and catalyst stability were studied. The catalytic performances were benchmarked with ZSM-5 (zeolite used in commercial oligomerisation processes).

Porous Resin Catalyst with Strong Acidity for Hydration Reaction of Butane and Its Catalytic Performance

With nano-alumina modified by the fat acid as an inorganic template for making pores, a new kind of porous resin particle with the large surface was synthesized by emulsion polymerization. Moreover, the sulfonated polystyrene resin was fluorinated to increase its acid strength up to Ho 8.6 and the acid amount of 4.1mmol/g. The ratio of butane to water was increased by packing the catalytic resin with the fixed beds of four stages. Under reaction temperature of 168-174°C, butane to water ratio of 2 mol/mol and WHSV1.0 h-1, hydration reaction conversion was over 15 wt%, with the butyl alcohol selectivity of 99 wt% and a good thermal stability.