Deactivation mechanism of beta-zeolite catalyst for synthesis of cumene by
benzene alkylation with isopropanol

Yefei Liu, Yang Zou, Hong Jiang, Huanxin Gao, Rizhi Chen

PII: S1004-9541(16)30703-0
DOI: doi:10.1016/j.cjche.2016.11.001
Reference: CJCHE 705

To appear in:

Received date: 21 July 2016

Revised date: 8 November 2016
Accepted date: 9 November 2016

Please cite this article as: Yefei Liu, Yang Zou, Hong Jiang, Huanxin Gao, Rizhi Chen,
Deactivation mechanism of beta-zeolite catalyst for synthesis of cumene by benzene alky-
lation with isopropanol, (2016), doi:10.1016/j.cjche.2016.11.001

This is a PDF file of an unedited manuscript that has been accepted for publication.
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 ACCEPTED MANUSCRIPT

Catalysis, kinetics and reaction engineering

Graphical abstract

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Some organic matters including 1-ethyl-3-(1-methyl) benzene could be produced during the

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benzene alkylation with isopropanol over beta-zeolite and deposit in the catalyst, resulting the

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deactivation of beta-zeolite.

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Deactivation mechanism of beta-zeolite catalyst for synthesis

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of cumene by benzene alkylation with isopropanol

Yefei Liu1, Yang Zou1, Hong Jiang1, Huanxin Gao2, Rizhi Chen1,*

Supports by the National Key Research and Development Plan (2016YFB0301503), the
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Jiangsu Natural Science Foundation for Distinguished Young Scholars (BK20150044),

the National Natural Science Foundation of China (91534110, 21606124), the Natural

Science Foundation of the Higher Education Institutions of Jiangsu Province

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(14KJB530004), the Foundation from State Key Laboratory of Materials-Oriented

Chemical Engineering (ZK201402, ZK201407), and the Technology Innovation

Foundation for Science and Technology Enterprises in Jiangsu Province (BC2015008).

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1 State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University,

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Nanjing 210009, China

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2 SINOPEC Shanghai Research Institute of Petrochemical Technology,
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Shanghai 201208, China

*Corresponding author. Tel.:+86-25-83172286, E-mail: rizhichen@njtech.edu.cn

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Abstract: The alkylation of benzene with isopropanol over beta-zeolite is a more cost-effective

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solution to cumene production. During the benzene alkylation cycles, the cumene selectivity

slowly increased, while the benzene conversion presented the sharp decrease due to catalyst

deactivation. The deactivation mechanism of beta-zeolite catalyst was investigated by

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characterizing the fresh and used catalysts. The XRD, SEM and TEM results show that the

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crystalline and particle size of the beta-zeolite catalyst almost remained stable during the

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alkylation cycles. The drop in catalytic activity and benzene conversion could be explained by the

TG, BET, NH3-TPD and GC-MS results. The organic matters mainly consisted of ethylbenzene,

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p-xylene and 1-ethyl-3-(1-methyl) benzene produced in the benzene alkylation deposited in the
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catalyst, which strongly reduced the specific surface area of beta-zeolite catalyst. Moreover,

during the reaction cycles, the amount of acidity also significantly decreased. As a result, the
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catalyst deactivation occurred. To maintain the catalytic performance, the catalyst regeneration
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was carried out by using ethanol rinse and calcination. The deactivated catalyst could be
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effectively regenerated by the calcination method and the good catalytic performance was
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obtained.
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Keywords: Cumene; Benzene; Isopropanol; Alkylation; Beta-zeolite; Catalyst deactivation

1. Introduction

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Cumene is an important chemical feedstock for the production of phenol and acetone in

industry. Cumene is firstly oxidized to cumene hydroperoxide, and then phenol and acetone are

produced by the acid arrangement of cumene hydroperoxide. The cumene-to-phenol route

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contributes more than 90% of phenol capacity in the world [1, 2]. In recent years, the rapidly

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growing market of phenol increases the demand for cumene [3, 4].

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The production of cumene in industry is usually conducted by using the alkylation of benzene

with propylene as the alkylating agent in fixed bed reactors. Since the solid phosphoric acid and

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aluminium chloride catalysts cause corrosion and environmental problems, several zeolite-based
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catalysts have been developed for producing cumene [5-7]. At present, some cumene production

processes have been commercialized with success, e.g. Dow/Kellogg process, UOP/Q-Max
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process, EniChem process and Mobil/Badger process [7]. For example, in the Dow/Kellogg
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process, the dealuminated mordenite was firstly used as the alkylation catalyst, in which a large
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number of meso-scale pores enhanced the mass diffusion and reduced the tar formation [8]. The
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UOP/Q-Max process used the metal ion-containing beta-zeolite as the alkylation catalyst. By
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adjusting the content of metal ions in beta-zeolite, the n-propylbenzene formation was reduced and

the catalyst functioned with good stability [9]. Although the alkylation of benzene with propylene

is an industrially important reaction for the cumene production, the use of propylene as the

alkylating agent readily results in the coke deposits on alkylation catalysts. Besides, the presence

of acidic catalysts promotes the polymerization of propylene and thus large excess of benzene is

needed to prevent propylene polymerization [10].

Instead of using propylene as the alkylating agent, the use of isopropanol to alkylate benzene

has been studied as a promising route to produce cumene [11]. Acetone as the byproduct in the

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cumene-to-phenol route can be recycled by reduction reaction to isopropanol, and then

isopropanol directly reacts with benzene to produce cumene. The economy of this process can be

improved due to the recycling of acetone. Moreover, the alkylation of benzene with isopropanol is

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more energy-efficient than that using propylene.

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Unfortunately, there are few reports on the alkylation of benzene with isopropanol. Girotti et

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al. [12] used isopropanol as the alkylating agent in the direct alkylation of benzene to cumene over

the beta-zeolite catalyst, and achieved similar reaction performance with the propylene route. It

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was also found that the catalyst activity and catalyst deactivation rate were influenced by the water
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content in the reaction mixture, and high water content was not favorable for maintaining the

catalytic performance. Deactivation of beta-zeolite catalyst was observed in some catalytic

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reactions [12-16], however, the catalytic stability and deactivation mechanism of beta-zeolite
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catalyst in the alkylation of benzene with isopropanol were still not investigated in detail.
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In this study, the catalytic stability of the beta-zeolite catalyst for benzene alkylation was
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investigated by using a submerged ceramic membrane reactor operated in a semi-batch mode. The
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deactivation mechanism of beta-zeolite catalyst was explored based on a series of characterization

techniques including XRD, SEM, TEM, TG, BET, NH3-TPD and GC-MS. And, the catalyst

regeneration was carried out.

2. Experimental

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2.1. Materials

The beta-zeolite catalyst was provided by SINOPEC Shanghai Research Institute of

Petrochemical Technology, China. Benzene was purchased from Shanghai Lingfeng Chemical

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Reagent Co., Ltd., China. Isopropanol was obtained from Shanghai Shenbo Chemical Co., Ltd.,

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China. Methanol (>99.9% chromatography grade) was supplied by Yuwang Group, China. Ethanol

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was provided by Wuxi Yasheng Chemical Co., Ltd., China. n-Hexane was purchased from

Shanghai Shisihewei Chemical Co., Ltd., China. All materials were used without further

treatment.
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2.2. Benzene alkylation

A submerged ceramic membrane reactor system was developed for alkylation of benzene
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with isopropanol to produce cumene, as shown in Fig. 1. The system mainly consisted of an
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autoclave, a ceramic membrane module and nitrogen source. The autoclave was made of stainless
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steel with a working volume of 1 L. The ceramic membrane made up of a fine layer of ZrO2
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(nominal pore size of 200 nm) was provided by Nanjing Jiusi High-Tech Co., Ltd., China.
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Typically, 3.5 g of beta-zeolite catalyst, 67 mL of benzene, 19.5 mL of isopropanol and 385

mL of n-hexane were introduced into the autoclave reactor in sequence. The autoclave was sealed

and purged with N2 for five times to evacuate air. Subsequently, the sealed autoclave was

pressurized to 1.0 MPa and heated. The stirring rate was controlled to be 800 rpm. When the

temperature reached 180 oC, N2 was fed into the reactor to adjust the pressure to 3.0 MPa and then

the benzene alkylation reaction with isopropanol got started. Each reaction lasted for 3 h. After

reaction, the stirring was stopped and the reactor was cooled down to 60 oC. The pressure was

adjusted to 0.3 MPa to drive the membrane filtration process. The fine beta-zeolite catalyst could

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be separated from the liquid phase mixture [17, 18] and retained in the reactor for next cycle of

alkylation reaction.

To investigate the catalytic stability of the beta-zeolite catalyst, after the membrane filtration,

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the fresh n-hexane solution of benzene and isopropanol were added to the reactor, and the

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processes of benzene alkylation and membrane filtration were repeated. Due to the vertical setting

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of membrane module in the autoclave as shown in Fig. 1, parts of products were remained in the

reactor and could influence the reaction. In further work, we will design horizontal membrane

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module, and make the membrane locate in the bottom of the reactor and more products be
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exported from the reactor. When all reaction tests were finished, the beta-zeolite catalyst used was

collected for various characterizations to analyze the catalyst deactivation mechanism.

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2.3. Analysis
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The reaction products were analyzed by an HPLC system (Agilent 1200 Series, USA). The
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benzene conversion was defined as the ratio of concentration of all products and initial
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concentration of benzene, while the selectivity of cumene was calculated as the concentration ratio
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of cumene in all products.

The X-ray powder diffraction (XRD) patterns of the beta-zeolite catalyst were recorded on a

Rigaku MiniFlex600 diffractometer using CuKα radiation at 40 kV and 15 mA with the 2θ range

of 5-80°. The morphology of the beta-zeolite catalyst was examined by field emission scanning

electron microscope (FESEM, Hitachi S-4800II, Japan). To verify the distribution and

morphology of catalyst particles, the transmission electron microscope (TEM, Philips Tecnai 12,

the Netherlands) was adopted. The thermogravimetric analyzer (TG, NetzschSTA449 F3 Jupiter,

Germany) was used to study the thermal stability of the catalyst. During the TG analysis, the air

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temperature was increased from room temperature to 800 C by 10 C·min-1. The N2

adsorption-desorption isotherms were measured by using an ASAP 2020 analyzer (Micromeritics,

USA) at its normal boiling point (77 K). The specific surface area of beta-zeolite was calculated

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by the Brunauer-Emmett-Teller (BET) method and the pore volume was estimated by the

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Barrett-Joyner-Halenda (BJH) method. The temperature-programmed desorption of ammonia

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(NH3-TPD) was used to determine the acid amount and the acidities of the catalysts by a

BELCAT-A equipment connected to a thermal conductivity detector (TCD). The composition of

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organic matters deposited in the beta-zeolite catalyst during the benzene alkylation was analyzed
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by gas chromatography with mass-spectrometric detection (GC-MS). Typically, 0.06 g of used

catalyst was carefully dissolved in 5 ml of 1 M HF solution. The solution was treated with 5 ml of
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toluene to extract the organic matters, and then the organic extract was analyzed by GC-MS
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(Agilent 7590B-5977A).
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3. Results and discussion

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3.1. Catalytic stability of beta-zeolite catalyst

To investigate the catalytic stability of beta-zeolite catalyst, a number of catalytic reaction

cycles were carried out in the submerged ceramic membrane reactor system. Fig. 2 presents the

relative benzene conversion and cumene selectivity during catalytic reaction cycles, which are

expressed by the ratios of the benzene conversion and cumene selectivity after a certain number of

reaction cycles to those during the first reaction cycle. It is seen that the cumene selectivity

increased through six reaction cycles. This may be due to the fact that the di-isopropylbenzene as

the byproduct further reacts with the excessive benzene to produce cumene [19]. Unfortunately,

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the benzene conversion presented the sharp decrease by 90% through six reaction cycles. It is

indicated that the severe deactivation of the beta-zeolite catalyst took place.

3.2. Catalyst characterizations

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To explore the deactivation mechanism of beta-zeolite catalyst, the fresh and used catalysts

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were characterized by XRD, SEM, TEM, TG, BET and NH3-TPD techniques.

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The XRD technique was adopted to analyze the microscopic crystalline structures. In Fig. 3,

no obvious differences were observed for the crystal structure, crystalline size and peak intensity

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before and after reactions. The (101) and (302) diffraction peaks were presented at 2 = 7.8o and
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22.5o, respectively. These peaks are characteristic of beta-zeolite that is obtained from the

tetragonal and monoclinic intergrowth crystals [20]. The XRD pattern shows that the crystallinity
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and skeletal structure of the beta-zeolite catalyst were well maintained and the catalyst still had
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good hydrothermal stability through six reaction cycles.

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Figs. 4 and 5 show the SEM and TEM images of the fresh beta-zeolite catalyst, the catalyst
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after the first cycle and the catalyst after the sixth cycle. By comparing with the fresh catalyst
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under different magnifications, the morphology of the catalysts after the first and sixth cycles had

no obvious change. The nanoparticles and their agglomerates were observed. The TEM image

with high resolution presents that the zeolite was composed of particles of approximately 20 nm in

diameter, and the lamellar nanocrystals stacked randomly. This TEM finding was consistent with

that reported in the literature [21]. By the XRD, SEM and TEM analyses, the alkylation of

benzene with isopropanol did not affect the crystalline and particle size of the beta-zeolite catalyst.

Therefore, it is concluded that the catalyst deactivation was not attributed to the changes in

crystalline and particle size of the catalyst.

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The thermogravimetric analysis curves of the fresh and used catalysts are presented in Fig. 6.

The weight loss of all catalyst samples below 150 oC was due to the desorption of water. The

minor weight loss of the fresh catalyst was observed when the temperature was increased from

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200 to 800 oC, which resulted from the residual water in the catalyst [12]. However, the used

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catalysts presented pronounced weight loss and the weight loss of the catalyst after the sixth cycle

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was larger than that after the first cycle. Clearly, the difference in weight loss was caused by the

decomposition of organic materials having different amount [22]. Meanwhile, from Fig. 7, the

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color of the catalyst became deepened as the number of reaction cycles increased, indicating that
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the organic matters like polycyclic aromatic hydrocarbons were produced in the alkylation of

benzene with isopropanol [23]. As a result, the catalyst was deactivated due to the deposition of
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carbonaceous materials on the catalyst.

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To further verify the finding from the thermogravimetric analysis, the BET tests were carried
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out to check the changes in catalyst pores. Fig. 8 gives the isotherms of nitrogen
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adsorption-desorption on different catalysts. At the low pressure, all the samples exhibited the
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I-type isotherms typical of microporous materials [24]. At the high pressure, i.e. p/p0>0.7, the

obvious hysteresis loops appeared, which was the characteristic of mesoporous materials [25]. The

results showed that the fresh and used beta-zeolite catalysts had well-developed microporous and

mesoporous structures. In Fig. 9, the pore size distribution also indicated that the beta-zeolite had

good crystalline and hydrothermal stability during the alkylation cycles. However, compared to

the fresh catalyst, the catalysts after the first and sixth cycle had drastic drop in the N2 adsorption

amount. In contrast to the fresh catalyst, the specific surface area and pore volume of the used

catalysts significantly decreased, and the decrease trend was more obvious by increasing the

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number of reaction cycles (Table 1). For example, after the sixth cycle, the specific surface area

and pore volume decreased by 33.2% and 29.2%, respectively. These results suggested that some

organic matters would deposit on the beta-zeolite catalyst during the alkylation cycles, leading to

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small specific surface area and few catalytic active sites. As a result, the catalyst deactivation

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occurred and the benzene conversion decreased.

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The acidities of the fresh and used catalysts were detected by NH3-TPD, as shown in Fig. 10.

For the fresh catalyst, two NH3 desorption peaks were observed in the range of 260-450 oC and

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500-650 oC, respectively, indicating the weak and medium acid sites existed on the catalyst [26].
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Furthermore, the number of the weak acid sites was much larger than that of the medium acid sites.

Obvious differences could be observed in the NH3-TPD patterns of the three samples. By
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calculating peak areas, it was found that the amount of beta-zeolite catalyst acidity gradually
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decreased from 14.88 mmol/g of the fresh catalyst to 8.55 mmol/g of the catalyst after the sixth
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cycle (Table 2). In particular, the decrease by 33.7% was so pronounced for the catalyst after the
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first cycle. In addition, the desorption peak temperature became lower when the number of
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reaction cycles increased as presented in Table 2. These changes might be related with the

adsorption of organic matters on the catalyst and/or the thermal deactivation of catalyst at high

reaction temperatures [27]. From the NH3-TPD tests, it was confirmed that the decrease in the

amount of acidity was also responsible for the poor catalytic performance of beta-zeolite catalyst

during the alkylation cycles.

To understand well the deactivation mechanism of the beta-zeolite catalyst, the exact

composition of the organic matters deposited in the used catalyst after the sixth cycle was

analyzed by GC-MS after dissolution of catalyst framework and extraction of the organics [28, 29].

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As shown in Fig. 11, the deposited organic matters mainly consisted of ethylbenzene, p-xylene

and 1-ethyl-3-(1-methyl) benzene. These matters were possibly responsible for the deactivation of

benzene alkylation over beta-zeolite catalyst.

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3.3. Regeneration of beta-zeolite catalyst

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Since the deactivation mechanism of beta-zeolite catalyst has been found owing to the

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adsorption of organic matters on the catalyst surface, the catalyst regeneration was carried out by

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ethanol rinse and calcination, respectively to remove the organic matters [22, 30]. The deactivated

catalyst was rinsed repeatedly for three times by ethanol solution, and then the rinsed catalyst was
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filtered and dried at 150 oC overnight to get the regenerated catalyst. With regard to the catalyst

calcination, the deactivated catalyst was directly calcinated in air atmosphere at 500 oC for 10 h to
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get the regenerated catalyst. The BET and NH3-TPD were performed to analyze the regenerated

catalysts. Also, the benzene alkylation was carried out by using the regenerated catalysts to
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evaluate the validity of the regeneration methods.

It is seen from Table 1 that the catalyst regenerated by calcination had similar surface area
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and pore volume with the fresh one. However, the ethanol rinse did not effectively recover the

surface area and pore volume. Correspondingly, as shown in Fig. 10, the amount of acidity could

be easily recovered by calcination as compared to ethanol rinse. The catalytic properties of

regenerated catalysts were presented in Fig. 12. With respect to the catalyst regenerated by

calcination, the benzene conversion had been increased to 23.6% and the selectivity of cumene

had reached 90.5%, which were similar with the values for the fresh catalyst. However, the

catalyst regenerated by ethanol rinse still had poor catalytic performance in the benzene alkylation

reaction. By comparison, the calcination method could effectively regenerate the beta-zeolite

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catalyst, in agreement with the reported results [31]. It is also observed form Table 1 that

calcination could recover the micropores, and ethanol rinse could regenerate the mesopores.

Together with the results in Fig. 12, we might hypothesize that the benzene alkylation and the

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deactivation occurred in the micropores of beta-zeolite catalyst.

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4. Conclusions

The physicochemical properties of the fresh and used beta-zeolite catalysts were

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characterized to explore the deactivation mechanism for the alkylation of benzene with
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isopropanol. The organic matters mainly consisted of ethylbenzene, p-xylene and

1-ethyl-3-(1-methyl) benzene formed in the benzene alkylation deposited in the catalyst and
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reduced the specific surface area. Meanwhile, the amount of acidity largely decreased during the
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reaction. Thus, the decrease in specific surface area and acidity resulted in the catalyst
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deactivation and the decrease in benzene conversion. Based on the understanding on catalyst
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deactivation mechanism, the catalyst regeneration by the calcination method was found to be an
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effective way to maintain high catalyst activity and benzene conversion.

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using Mg-Al hydrotalcite derived catalysts, Appl. Catal. A-Gen. 331 (1) (2007) 138-148.
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Table 1 Specific surface area and pore volume of beta-zeolite catalysts

Surface area (m2∙g-1) Pore volume (cm3∙g-1)

Beta-zeolite
Smeso Smicro Vmeso Vmicro

Fresh 247 420.4 0.769 0.234

Used (after the first cycle) 214.9 347.5 0.696 0.196

Used (after the sixth cycle) 170.6 275.3 0.553 0.157

Regenerated (calcination) 187.2 419.3 0.751 0.212

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Regenerated (ethanol rinse) 229.7 121.7 0.612 0.113

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Table 2 NH3-TPD test of beta-zeolite catalysts

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Beta-zeolite Fresh After the first cycle After the sixth cycle

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Desorption peak temperature (oC) 278 250 240

Adsorption capacity (mmol∙g-1) 14.88 9.86 8.55

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Captions of Figures
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Fig. 1 Schematic diagram of the submerged ceramic membrane reactor system

Fig. 2 Change of benzene alkylation reaction performance with the number of catalytic reaction

cycle

Fig. 3 XRD patterns of beta-zeolite catalysts: (a) fresh; (b) after the first cycle; (c) after the sixth

cycle

Fig. 4 SEM images of beta-zeolite catalysts: (a, d) fresh; (b, e) after the first cycle; (c, f) after the

sixth cycle

Fig. 5 TEM images of beta-zeolite catalysts: (a) fresh; (b) after the first cycle; (c) after the sixth

cycle

Fig. 6 TG curves of beta-zeolite catalysts: (a) fresh; (b) after the first cycle; (c) after the sixth

cycle

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Fig.7 Powders of beta-zeolite catalysts: (a) fresh; (b) after the first cycle; (c) after the sixth cycle

Fig. 8 Adsorption-desorption isotherms of beta-zeolite catalysts: (a) fresh; (b) after the first cycle;

(c) after the sixth cycle

Fig. 9 Pore size distribution of beta-zeolite catalysts: (a) mesopores; (b) micropores

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Fig. 10 NH3-TPD diagrams of beta-zeolite catalysts: (a) fresh; (b) used after the first cycle; (c)

used after the sixth cycle; (d) regenerated with calcination; (e) regenerated with ethanol rinse

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Fig. 11 GC-MS analysis of the organic matters deposited in the beta-zeolite catalyst after the sixth

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cycle

Fig. 12 Effect of catalyst regeneration on the conversion and selectivity of benzene alkylation

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Fig. 1

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Relative conversion or selectivity

1.2
D

1.0
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0.8 Benzene conversion

Cumene selectivity
P

0.6
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0.4

0.2
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0.0
1 2 3 4 5 6
Number of catalytic reaction cycle

Fig. 2

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(a)
Intensity
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(c)

0 20 40 60 80
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2θ/(o)

Fig. 3

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Fig. 4
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Fig. 5
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95 (a)
TG /%

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90
(b)

85 (c)
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80
100 200 300 400 500 600 700 800

Temperature /oC

Fig. 6
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Fig. 7

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700

-1

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Quantity adsorbed (STP) /cm3·g
600
Adsorption

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500 Desorption

400

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300
(a)
200

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100 (c) (b)

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0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (P/P0)

Fig. 8
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Fig. 9

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(a)

(d)

(e)

Intensity

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(b)

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(c)

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0 100 200 300 400 500 600
Temperature /C

Fig. 10

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Fig. 11
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100
Benzene conversion

Conversion & Selectivity/%

IPB selectivity
90

80

70

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0

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Fresh Calcination Ethanol rinse

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Fig. 12

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