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Enhanced reaction performances for light olefin production from butene through co-feeding reaction with methanol Zhongren Wang, Binbo Jiang, Zuwei Liao, Jingdai Wang, Yongrong Yang, and Xieqing Wang Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b03614 • Publication Date (Web): 05 Dec 2017 Downloaded from http://pubs.acs.org on December 9, 2017

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Enhanced reaction performances for light olefin production from butene through co-feeding reaction with methanol Zhongren Wanga, Binbo Jianga*, Zuwei Liaoa, Jingdai Wang, Yongrong Yanga, Xieqing Wangb,a a

College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China b

Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, People’s Republic of China Abstract

The effects of methanol co-feeding on reaction performances and reaction pathways for light olefin production from butene were investigated. Reactions under different conditions were carried out, and the kinetics of butene consumption was established using the integration method. Based on kinetic study, the reaction pathways for butene conversion changed due to the co-feeding, much higher conversion of butene was found in co-feeding reaction than butene cracking when extrapolating to space time was 0, indicating that conversion of butene was promoted when methanol joined the reaction due to the co-reaction of butene and methanol. The reaction activity was improve due the co-feeding, leading to significant improvements on reaction performances for light olefin production from butene, especially under condition of high WHSV and low concentration of butene or on stream treated catalysts. The results indicated that

co-feeding reaction

was a feasible way to raise throughput and cope with hydrothermal deactivation for feeds

ACS Paragon Plus Environment

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with low butene concentrations. 1. Introduction Light olefins, especially ethene and propene, are key building blocks in petrochemical and organic chemical industry. Driven by the boom of light olefins consumption, research on promising techniques for light olefin production has attracted considerable interests. C4 hydrocarbon, mainly produced by naphtha pyrolysis and FCC, is an attractive feedstock with an abundant supply. Thereinto, butene is considered as a suitable feedstock for light olefin production.1-3 Consequently, catalytic cracking of butene becomes one of the most popular issues. Butene cracking follows the ‘dimerization-cracking’ mechanism, which contains three main reaction pathways (2C=4 →2C=4 , 2C=4 →C=3 +C=5 and 2C=4 →C=2 +C=6 ).3-5 Reaction pathways of butene cracking were influenced by acid strength of the zeolite catalyst (ZSM-5). A relatively low amount of total acid sites and strong-weak acid sites ratio (SA/WA) was propitious for propene production.3, 6 However, there is a conflict between catalytic activity and selectivity of target products. Catalysts with a low amount of total acid sites and SA/WA are less reactive, which should struggle with high WHSV and low concentration of butene. In addition, hydrothermal deactivation is avoidless for catalysts in industrial reactors, leading to even weaker activities, which greatly hindered the reaction performances in butene cracking. Thus, it is necessary to find a way to improve the reaction activity for butene conversion on these catalysts. Methanol, mainly produced from coal and natural gas, is another attractive feedstock


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for light olefin production. Methanol to olefins (MTO) has been widely investigated in recent years.7-13 The MTO reaction on zeolite catalysts (ZSM-5 or SAPO-34) follows the ‘dual-cycle’ mechanism, olefin methylation is the key step in olefin-based cycle.8,

14

Lighter olefins could be methylated into higher olefins, then cracking to ethene and propene,8, 15, 16 which provides another pathway for light olefin production from butene. Due to similar target products and catalysts, complementary heat of reaction (endothermic for butene cracking, exothermic for MTO), combing butene cracking and MTO reaction in a single reactor is feasible and profitable. Thus, co-feeding reaction of butene and methanol was proposed for light olefin production.17-20 Nowak et al. proposed coupled methanol and hydrocarbon cracking (CMHC) in early times.17 Several hydrocarbons (including butene) and catalysts were investigated, near thermal neutral reaction and a high space-time yield were realized in CMHC process. Wang et al. studied co-reaction of methanol and 1-butene over P-doped HZSM-5.18 Propene yield of 44% was reached, higher than 1-butene cracking and MTO on the same catalysts. Gong et al. focused on influence of the Brønsted-Lewis acid sites ratio of the catalyst in CMHC, a high propene yield of 46% was reached on La-doped HZSM-5 due to a proper Brønsted-Lewis acid sites ratio.19, 20 Although there was a necessary to find a way for better reaction activity for light olefin production from butene, previous investigations on co-feeding reaction of butene and methanol mostly fall on improving yield of the target products by optimizing catalyst structures and reaction conditions. Seldom investigation focused on benefits for butene


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conversion from the co-reaction of butene and methanol. Effects of the co-feeding on reaction performances and pathways for butene remained lacking of research. Thus, a series of investigations were carried out to figure out the benefits of co-feeding for light olefin production from butene. The results showed that the reaction activity for butene conversion was improved when methanol joined the reaction, leading to improvements on reaction performances for light olefin production from butene. Based on the kinetic study, the improvements could be ascribed to the co-reaction of butene and methanol. 2. Experimental Section 2.1. Catalyst Preparation. The commercial HZSM-5 catalyst for butene cracking (obtained from Shanghai Fuxu Molecular Sieve Co., Ltd. in extruded column form) was crushed to 20-40 mesh, calcined at 823K in air for 2h, donated as FX. To simulate the hydrothermal deactivated catalysts, FX samples were treated with 100% steam in a quartz tube (80mm i.d.) at 973K and 1073K for 4h, donated as ST700 and ST800. 2.2. Catalyst Characterization. The surface areas and pore volumes of the samples were measured by nitrogen sorption at 77K using Quantachrome Autosorb IQ after evacuation at 623K for 12h. The acidic properties were measured by temperature programmed desorption of ammonia (NH3-TPD) using Quantachrome Autosorb IQ equipped with a thermal conductivity detector (TCD). Samples were pretreated with helium at 773K for 1h. NH3 was adsorbed in a helium stream containing 10% vol of NH3 at 373K. Samples were flushed with helium at 393K after to remove weakly adsorbed NH3. Then TPD program started at a heating rate of 10K/min from 393K to 823K in a


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helium flow. 2.3. Catalytic Testing. 1-Butene (>99.5%, obtained from Hangzhou Minxing Chemical Technology Co., Ltd.) and methanol (>99.5%, obtained from Sinopharm Chemical Reagent Co., Ltd.) were used as reactants. Catalytic cracking of 1-butene and co-feeding reaction of 1-butene and methanol were carried out at ambient pressure using a continuous flow fixed-bed system (8mm i.d.). The catalyst was pretreated at the reaction temperature for 30min in a nitrogen flow. 1-Butene and methanol were fed into the preheated zone of the reactor using a mass flow controller (MFC) and a HPLC pump respectively. Nitrogen (>99.99%) was used to adjust partial pressure of the reactants. The products were analyzed using an on-line Agilent 7890A gas chromatography (GC) equipped with a HP-PLOT Q column and a flame ionization detector (FID). The conversion, selectivity and yield were calculated by following equations respectively. Conversion of total reactants = (1 − ω ( Butene ) outlet ) × 100%

Conversion of butene =

Selectivity of i =

ω ( Butene ) inlet − ω ( Butene ) outlet × 100% ω ( Butene ) inlet

ω ( i ) outlet Conversion of total reactants

× 100%

Yield of i = Selectivity of i × Conversion of total reactants × 100%

(1) (2)

(3) (4)

Butene isomers (1-Butene, cis-2-butene, trans-2-butene and i-butene) in the outlet stream were all considered as reactants. ω(Butene)outlet in the Equation 1 and 2 represents the CH2-based mass fraction of total butene isomers in the outlet stream. The content of methanol was neglected in the outlet stream (0.98) in co-feeding reaction (1:1 mole ratio) at investigated space times (Fig. 5b). Notably, methanol was fully converted under investigated conditions. Apparent rate constants of butene consumption were 1.45g/h·g cat, 1.73g/h·g cat, 1.89g/h·g cat, 2.19g/h·g cat at 763K, 783K, 803K, 823K respectively, lower than butene cracking due to a portion of acid sites were occupied by methanol. The intercepts of kinetic regression line were much greater than 1. Conversion of butene was 53.67%, 52.23%, 52.45%, 51.52% at 763K, 783K, 803K, 823K respectively when extrapolating to space time was 0, much higher than those of butene cracking (7.41%, 2.45%, 0%, 0% at 763K, 783K, 803K, 823K respectively), indicating that a large portion of butene was converted rapidly before investigated space times through co-reaction of butene and methanol. According to previous investigations on MTO reaction12,

19, 20

, butene could be

converted through methylation reaction, which made essential differences between


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butene cracking and co-feeding reaction. Butene conversion was promoted in the initial stage of co-feeding reactions when space time of butene was low due to the methylation reaction. However, rate constants in co-feeding reaction (1:1 mole ratio) were lower than butene cracking after methanol was fully converted. Thus, greater improvements on conversion of butene were observed at higher WHSVbutene (Fig. 1a). In addition, methanol and butene reacted on a mole ratio of 1:1 in methylation reaction. Based on the kinetic study, only a portion of the methanol was consumed by the butene methylation in co-feeding reaction. The methylation reactions of hydrocarbon products occurred simultaneously along with the butene methylation. Lower hydrocarbons were methylated into higher hydrocarbons, which were easier to crack into ethene and propene15,

16

,

resulting in higher selectivities of ethene and propene (Fig. 1b). On the other hand, methylation reaction was first order reaction for butene,21, 22 while butene cracking was second order reaction for butene. Thus, greater improvements on conversion of butene were observed under lower butene conversions (Fig. 2a). 1.20 1.15

0.9

(a)

(b)

0.8

1.10 1.05

0.7

Ln(k)

1.00

Ln(k)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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0.95 0.90

0.5

0.85

Arrhenius Plot for 1-Butene Cracking Regression of Arrhenius Plot

0.80

0.4

0.75 0.70 0.00120

0.6

Arrhenius Plot for Co-feeding Reaction Linear Regression of Arrhenius Plot

0.3 0.00122

0.00124

0.00126

0.00128 -1

0.00130

0.00132

0.00120

0.00122

-1

0.00124

0.00126

0.00128 -1

Temperature (K )

0.00130

0.00132

-1

Temperature (K )

Figure 6. Arrhenius plot for butene consumption in (a) 1-butene cracking and (b)


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co-feeding reaction (1:1 mole ratio) The apparent activation energies for 1-butene cracking and co-feeding reaction (1:1 mole ratio) were derived from Arrhenius plots. The apparent activation energies for 1-butene cracking and co-feeding reaction were -29.73kJ/mol (Fig. 6a) and 34.58kJ/mol (Fig. 6b) under investigated conditions respectively. Although second order reaction for consumption of butene was realized in both two reactions under investigated conditions, the reaction pathways were different due to the co-feeding. Other than butene cracking, a portion of acid sites were occupied by methanol in co-feeding reaction, for which the reaction pathways changed, resulting in positive activation energy.

Table 1. Surface areas and pore volumes tested by nitrogen sorption. Sample

BET Surface

Micropore Surface

Total Pore

Micropore

Area (m2/g)

Area (m2/g)

Volume (ml/g)

Volume (ml/g)

FX

366

299

0.265

0.146

ST700

322

258

0.27

0.144

ST800

311

249

0.27

0.144

3.3. Effects of Co-feeding on Reaction Performances on Steam-treated Catalysts. To investigate the effects of hydrothermal deactivation, steam treated samples ST700 and ST800 were prepared to simulate the hydrothermal deactivated catalysts. Nitrogen sorption and NH3-TPD were carried out to characterize the fresh and steam treated catalysts. Results were shown in Tab. 1 and Fig. 7. BET surface areas decreased after steam treatments, and evident decreases of micropore areas were observed (Tab. 1). Total


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pore volume increased slightly after steam treatments, but micropore volume decreased. Strong and weak acid sites both reduced evidently after steam treatments (Fig. 7). 50

FX (Fresh Catalyst) ST700 (923K Treated) ST800 (1023K Treated)

40

Desorbed NH3 (a.u)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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30

20

10

0 400

450

500

550

600

650

700

750

800

Temperature (K)

Figure 7. Result of NH3-TPD tests for fresh catalyst FX and steam treated catalysts ST700 and ST800 To investigate the benefits of co-feeding for hydrothermal deactivation catalysts, reactions for different n(methanol):n(butene) and WHSVbutene were carried out on ST700 and ST800 under condition of T=823K, Pbutene=14.1kPa. Results were shown in Fig. 8. Comparing with the results on fresh catalyst, conversion of butene decreased evidently on ST700 and ST800 due to the losses of acid sites and micropores (Fig. 8a). Much greater improvements on conversion of butene along with selectivity of target products were observed on FX700 and FX800 than fresh FX catalysts when methanol joined the reaction (Fig. 8a and 8b), indicating that the promotion of butene conversion through co-feeding was more significant. Particularly, conversion of butene was only 10.01% for butene cracking on ST800, but 54.76% when n(methanol):n(butene) was 1. Selectivity of


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C5+ hydrocarbons decreased when methanol joined the reaction (Fig. 8c). 90%

70%

80%

Selectivity of Ethene and Propene

80%

60%

Conversion of Butene

50%

(a)

40% 30% -1

WHSVButene=1.75h on FX

20%

-1

WHSVButene=1.75h on ST700 -1

WHSVButene=1.75h on ST800

10% 0%

(b)

70%

-1

WHSVButene=1.75h on FX -1


60%

-1

WHSVButene=1.75h on ST800 50%

40%

30%

20% 0.0

0.2

0.4

0.6

0.8

1.0

0.0

0.2

n(Methanol) : n(Butene)

0.4

0.6

0.8

1.0


70%

60%

Selectivity of C5+ Hydrocarbons

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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(c) 50% -1

WHSVButene=1.75h on FX -1


40%

-1

WHSVButene=1.75h on ST800 30%

20%

10% 0.0

0.2

0.4

0.6

0.8

1.0


Figure 8. (a) Conversion of butene, (b) selectivity of ethene and propene, (c) selectivity of C5+ hydrocarbons for different co-feeding ratios on fresh and steam treated catalysts under condition of T=823K, WHSVbutene=1.75h-1, Pbutene=14.1kPa. Influence of butene concentration on ST700 was investigated in 1-butene cracking and co-feeding reaction (1:1 mole ratio) under condition of T=823K, WHSVbutene=5.25h-1. Results were shown in Fig. 9. Conversion of butene increased with increasing butene concentration in both two reactions, higher in co-feeding reaction (1:1 mole ratio) under Pbutene lower than 42kPa, but a bit lower under Pbutene higher than 42kPa comparing with


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1-butene cracking (Fig. 9a), which was similar to reactions on fresh catalyst. Higher selectivity and yield of ethene and propene was observed in co-feeding reaction (1:1 mole ratio), especially under lower butene concentrations (Fig. 2b and 2c). The results showed that reaction activities were improved evidently when methanol joined the reaction on steam treated samples, indicating that co-feeding reaction was a feasible way to cope with the low catalytic activity caused by hydrothermal deactivation. 80%

72%

(a) Selectivity of Ethene and Propene

70%

60%

Conversion of Butene

50%

40%

30%

Co-feeding (1:1 mole ratio) Butene Cracking

20%

10% 10

15

20

25

30

35

40

45

50

(b)

68%

64%

60%

56%


52%

48% 10

55

15

20

Partial Pressure of Butene (kPa)

25

30

35

40

45

50

55


60%

50%

Yield of Ethene and Propene

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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(c)

40%

30%

20%


10%

0% 10

20

30

40

50

60

70


Figure 9. (a) Conversion, (b) selectivity and (c) yield of ethene and propene for different Pbutene on ST700 under condition of T=823K, WHSVbutene=5.25h-1.

4. Conclusions


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Co-feeding reactions of butene and methanol along with butene cracking as contrast under different conditions were carried out on high-silica HZSM-5 catalyst. Conversion of butene and yield of the target products were improved when methanol joined the reaction, especially under higher WHSV and lower concentration of butene. Particularly, conversion of butene increased from 28.4% to 59.18% when equal mole of methanol joined the reaction under condition of T=823K, Pbutene=14.1kPa, WHSVbutene was 8.75h-1. The kinetics of butene consumption on FX was established to reveal the reason for the improvements. The results showed that reaction pathways changed due to the co-feeding. Both second order reaction was realized in butene cracking and co-feeding reaction under investigated conditions, but conversion of butene was 53.67%, 52.23%, 52.45%, 51.52% at 763K, 783K, 803K, 823K respectively in co-feeding reaction (1:1 mole ratio) when extrapolating to space time was 0, much higher than those of butene cracking (7.41%, 2.45%, 0%, 0% at 763K, 783K, 803K, 823K respectively), indicating that conversion of butene was promoted in the initial stage of the co-feeding reaction due to the co- reaction of butene and methanol. The activation energy changed from negative to positive when methanol joined the reaction, making conversion of butene and selectivity of target products to be both positive correlated to reaction temperature. The results of reactions on stream treated catalysts showed that much greater improvements on reaction performances were observed on steam treated catalysts than fresh catalysts. Particularly, conversion of butene increased from 10.01% to 54.76% when equal mole of methanol joined the reaction on ST800 under condition of T=823K,


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Pbutene=14.1kPa, WHSVbutene was 1.75h-1. In conclusion, the results showed the co-feeding reaction of butene and methanol was a feasible way to improve reaction activity for light olefin production from butene, which could raise throughput and cope with the hydrothermal deactivation for feeds with low butene concentrations, such as FCC C4 fraction.

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Enhanced Reaction Performances for Light Olefin Production from

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