Production of Liquid Hydrocarbon Fuel from Catalytic Cracking of

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The Production of Liquid Hydrocarbon Fuel from Catalytic Cracking of Rubber Seed Oil Using New Mesoporous Molecular Sieves Zhiping Wang, and Shi-Tao Yu ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.6b01441 • Publication Date (Web): 22 Aug 2016 Downloaded from http://pubs.acs.org on August 23, 2016

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ACS Sustainable Chemistry & Engineering

The Production of Liquid Hydrocarbon Fuel from Catalytic Cracking of Rubber Seed Oil Using New Mesoporous Molecular Sieves Zhiping Wang, Shitao Yu* College of Chemical Engineering, Qingdao University of Science and Technology, 53 Zhengzhou Road, 266042 Qingdao, People’s Republic of China

*E-mail: [email protected]

KEYWORDS: Rubber seed oil, Catalytic cracking, Mesoporous molecular sieve, Liquid hydrocarbon fuels, Heterogeneous

ABSTRACT: New mesoporous molecular sieves MMS-11, MMP-12, MNS-16, MNP-10, and MNC-13 were synthesized successfully using zeolite β as a silica-alumina source and different ionic liquid as a template. The structure and catalytic activity of the mesoporous molecular sieves as heterogeneous catalysts for the cracking of rubber seed oil (RSO) were studied in detail. MNC-13 exhibited excellent catalytic performance for the cracking of RSO, and the cracked oil had a chemical composition and properties similar to those of diesel-based fuels. Furthermore, the catalyst MNC-13 is of such outstanding stability that it retains high activity even after being

ACS Paragon Plus Environment

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used five times. Therefore, this research provides a new type of catalytic results for the same type of high-temperature cracking reaction.



INTRODUCTION

The rubber tree is an important economic crop

[1, 2]

. In addition to producing natural rubber,

the tree also provides a variety of ancillary products. Rubber seed, from which rubber seed oil (RSO) can be extracted, figures prominently among these products. Research on sources of renewable energy for the replacement of fossil fuels has been stimulated by the challenges of non-availability of fuels in the future, instability in prices of crude oil and negative environmental impacts

[3,4]

. The extraction method and properties of RSO were studied, and it

has been investigated as a potential source for biodiesel production

[5]

. As a fuel, RSO can

produce the same power output as diesel but has reduced thermal efficiency and increased smoke emission because of its high viscosity (more than 50 cSt), which leads to sluggish combustion 7]

[6,

. Some important properties of RSO, shown in Table 1, are given by the Institute of Chemical

Industry of Forest Products.

Table 1 Properties of RSO Property

RSO

Density

Cetane

Viscosity

Calorific

Acid value/

Iodine value

Flash

/kg m-3

number

/mm2 s-1

value/MJ kg-1

mg KOH g-1

/g/100 g

point/℃

925

40

57.9

37.2

25.1

135.8

240


2

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There has been an increasing interest in producing bio-fuel by catalytic cracking in recent years [8, 9]. Na2CO3 or K2CO3 was chosen for use as the traditional basic catalyst. Members of our team have reported the catalytic cracking of soybean oil using Na2CO3 or K2CO3 as a basic [10, 11]

catalyst in a continuous mode

. However, this catalyst would be exhausted, and the

corresponding salts would be present in the bio-fuel, which could lead to the corrosion of equipment. To solve this problem, finding the right type of solid catalyst is a new and important area of research.

Zeolite has been widely used due to its high thermal stability, good shape-selective properties and ability to concentrate reactants inside the pores, but it has been restricted to relatively small molecules

[12]

. For example, USY (ultrastable Y zeolite) has been reported to catalyze the

cracking reactions of palm oil

[13]

, soybean oil

[14]

, RSO

[15]

and waste cooking oil

[16]

.

Mesoporous molecular sieves of the M41S- type can help to overcome these limitations due to their large pore sizes [17]. K2O/Ba-MCM-41, K2O/Ca-MCM-41 and K2O/Mg-MCM-41 have been reported to catalyze the cracking reactions of soybean oil

[18]

, RSO [19] and waste cooking oil [20].

However, the weak hydrothermal stability of these materials greatly limits the extensive applications of mesoporous molecular sieves [21].

In this paper, new types of mesoporous molecular sieves named MMS-11, MMP-12, MNS-16, MNP-10, and MNC-13 were synthesized using zeolite β as a silica-alumina source and different


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ionic liquids, [HSO3-(CH2)3-mim] [HSO4], [HSO3-(CH2)3-mim] [H2PO4], [HSO3-(CH2)3-NEt3] [HSO4], [HSO3-(CH2)3-NEt3] [H2PO4], and [HSO3- (CH2)3-NEt3] [Cl], as a template. The structure, catalytic activity and stability of the catalysts have been examined. To the best of our knowledge, this is the first report on the synthesis and use of MNC-13 as a heterogeneous catalyst for the cracking of RSO. 

EXPERIMENTAL

Materials. RSO was obtained from commercial sources (Institute of Chemical Industry of Forest Products) and used without further purification. Other materials, such as hydrochloric acid, sulfuric acid, phosphoric acid, tetraethyl ammonium hydroxide (TEAOH), sodium aluminate, triethylamine, hexadecyl trimethyl ammonium bromide (CTAMBr) and sodium hydroxide, ethyl acetate, 1,3-propanesultone, and N-methylimidazole, were all purchased from Aldrich, and all materials were directly used after drying without further purification.

Characterization of Mesoporous Molecular Sieves. X-ray powder diffraction patterns of the samples were obtained on an XD-610 instrument using monochromatic Cu Kα radiation. Py-FTIR

spectra were recorded with a Nicolet NEXUS470 FTIR spectrometer in the range of 4000 to 500 cm-1. N2 physical adsorption/desorption isotherms were measured at the temperature of liquid nitrogen using a Micromeritics Tristar 3000 system. NH3-TPD was performed by a DLUT-1 automatic temperature programmed desorption apparatus. Detailed information can be found in the Supporting Information.


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Catalytic Cracking of RSO. Catalytic cracking experiments were carried out at temperatures ranging from 390 to 420℃ using a 250 ml glass vessel. The RSO and catalysts were introduced into the reactor and then heated by external electrical resistance at a heating rate of 20℃ min−1. The temperature was measured at two positions (column temperature and bottom temperature) using calibrated thermocouples. When the temperature inside the reactor reached 390℃, the RSO cracked and vaporized. The vapor left the reactor through the rectification column at temperatures ranging from 390 to 420℃, and then entered the heat exchanger. Finally, the liquid fractions were weighed and analyzed by GC-MS. The residue in the reactor including the coke and catalysts was weighed. The reaction was repeated three times, and the results exhibited excellent stability. The conversion (wt%) for RSO and yields (wt%) for bio-oil were as follows:

Conversion (%) =

W 1 +W 2 −W 4 W1

× 100%

Equation (1) W

Yield (bio-oil) (%) = W 3 × 100% 1

Equation (2)

Yield (coke) (%) =

W 4 −W 2 W1

× 100%

Equation (3)

where W1 = weight of RSO, W2 = weight of catalyst, W3 = weight of liquid fraction, and W4 = weight of residue.


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The gas fractions can be obtained by mass balance. To collect the gas product, we used 50 g of RSO as the feed. The obtained gas product was also analyzed by GC-MS. The results show that the main components were CH4, C2H6, H2, and CO. Preparation of New Mesoporous Molecular Sieves. The βprecursor solution and β/AlMCM-41were synthesized under autogenous pressure according to ref. 22. The molar ratio was 1:(80, 60, 40, or 20):2.5:22:800 Al2O3:SiO2:Na2O:TEAOH:H2O. The detailed preparation process is given in the Supporting Information. The ionic liquid was synthesized according to ref. 23. The obtained βprecursor solution was added to the ionic liquids ([HSO3-(CH2)3-mim][HSO4], [HSO3-(CH2)3-mim][H2PO4], [HSO3-(CH2)3-NEt3] [HSO4], [HSO3-(CH2)3-NEt3][H2PO4] or [HSO3-(CH2)3-NEt3][Cl]) at a molar ratio of 1:75 ionic liquid:H2O, mixed and then agitated for 30 min. The solution was stirred for 12 h at 40℃ after adding alcohol. Finally, the mixed solution was crystallized, vacuum filtered, washed, dried and calcined for 8 h at 550℃ to prepare the new molecular sieves MMS-11, MMP-12, MNS-16, MNP-10, or MNC-13. The structure of MMS-11, MMP-12, MNS-16, MNP-10, and MNC-13 was characterized by XRD, FT-IR and N2 adsorption-desorption (see the Supporting Information).

Stability Measurement. The stability of the catalyst was studied as follows: after completion of the reaction, the catalyst was reused without further treatment. That is, the residue in the reactor was used as the catalyst, and RSO was only added to the reactor to carry out the next reaction.


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

RESULTS AND DISCUSSION

Choice of Catalysts. The activities of the different catalysts for the cracking of RSO were investigated. The performances of the catalysts were evaluated in terms of yields of liquid product, gas product, and coke. The detailed results are shown in Table 2, from which it can be seen that when using MNC-13 as the catalyst, the conversion was 95.1% and the yield of liquid product (liquid fuel + water) was 74.9% (No.10), higher than that using the traditional catalyst Na2CO3 or K2CO3 (No.2~3) or using Al-MCM-41 or β/Al-MCM-41 (No.4~5), synthesized by the hydrothermal method, as the catalyst. When using MMS-11, MMP-12, MNS-16 or MNP-10 as the catalyst, the conversions and yields were all lower (No.6~9).

Table 2 Effect of Different Catalysts on Yield of Liquid Product* No.

Catalyst

Conversion/%

Yield of Biooil/%

Yield of Biogas/%

Yield of coke/%

1

Blank

76.8±0.5

54.9±0.4

21.9±0.5

23.2±0.4

2

K2CO3

89.7±0.3

68.8±0.4

20.9±0.3

10.3±0.3

3

Na2CO3

90.5±0.4

66.3±0.5

24.2±0.4

9.5±0.5

4

Si-MCM-41

82.2±0.3

57.8±0.4

24.4±0.4

17.8±0.3

5

β/Al-MCM-41

83.1±0.5

61.3±0.4

21.8±0.3

16.9±0.4

6

MMS-11

88.3±0.3

66.3±0.5

22.0±0.4

11.8±0.3

7

MMP-12

71.0±0.5

42.2±0.3

28.8±0.4

29.0±0.4

8

MNS-16

72.1±0.2

43.5±0.3

28.6±0.4

27.9±0.3

9

MNP-10

75.2±0.4

43.8±0.5

31.4±0.3

24.8±0.4

10

MNC-13

95.1±0.5

74.9±0.3

20.2±0.4

4.9±0.4

*Reaction conditions: RSO 10g, m(cat):m(RSO)=1:30, 410℃, 100min.


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Fig. 1 shows the NH3-TPD patterns of MMS-11, MMP-12, MNS-16, MNP-10 and MNC-13 within the range of 100~1000℃. The presence of the bands at approximately 100~200℃, 300~400℃ and 700~800℃ indicated a weak acid, a medium strong acid and a strong acid, respectively

[24]

. From Fig. 1, it can be observed that there are weak and strong acid sites co-

existing on the surface of all the new molecular sieves. However, the absorption peaks of MNS16 and MNC-13 are situated at higher temperature positions than those of MMS-11, MMP-12, and MNP-10, which means that the acidities of MNS-16 and MNC-13 are stronger than those of the other three. Moreover, there are weak, medium strong and strong acid sites co-existing on the surface of the MNC-13 molecular sieves. This indicates that the acidity of MNC-13 is stronger than those of other four. The acid amounts of each catalyst were determined by quantitative analysis and are shown in Table 3. According to the amount of the total acid, the acid centers of MNC-13 are more plentiful than those of the other four. The activity of the catalyst was affected by the amount of acid, which is why MNC-13 shows a higher activity.


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Figure 1. NH3-TPD patterns of new molecular sieves 1. MMS-11; 2.MMP-12; 3.MNS-16; 4.MNP-10; 5.MNC-13 Table 3 Acid Amounts of Different New Catalysts

Weak acid

Medium strong acid

Strong acid

Total acid

Relative intensity of Brönsted acid/Lewis acid (B/L)

MMS-11

0.192

-

0.459

0.651

0.997

MMP-12

0.046

-

0.105

0.151

1.54

MNS-16

0.089

-

0.436

0.525

1.67

MNP-10

0.184

-

0.376

0.56

1.54

MNC-13

0.162

0.160

0.836

1.158

0.912

Catalysts

Acid amounts (mmol/g)

The Py-FTIR studies of the catalysts are shown in Fig. 2. The presence of the band at approximately 1450 cm-1 indicated Lewis acid sites, and the band at approximately 1540 cm-1 indicated characteristic Brönsted acid sites

[25]

. The data showed that Brönsted acid and Lewis


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acid sites co-existed on the surfaces of the five catalysts. The relative intensity of Brönsted acid/Lewis acid (B/L) over MMS-11, MMP-12, MNS-16, MNP-10 and MNC-13 was determined and is shown in Table 3. The results show that the Brönsted and Lewis acid sites are basically equivalent over MMS-11and MNC-13, while over MMP-12, MNS-16 and MNP-10, the intensity of the Brönsted acid is higher than that of the Lewis acid. Compared with the activity (Table 2), the Lewis acid sites play a key role in the activity of the catalyst.

According to the mechanism of acid-catalyzed pyrolysis

[26]

, a large amount of fatty acids is

produced during the pyrolysis of RSO, most of which may be rapidly decarboxylated, especially when using a typical acidic catalyst such as MNC-13. In summary, MNC-13 showed better catalytic activity than the traditional basic catalysts Na2CO3 or K2CO3, according to Table 2. For this reason, MNC-13 was taken as an example to research its pyrolysis reaction in detail.


10

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Figure 2. Py-FTIR spectra of new molecular sieves 1. MMS-11; 2.MMP-12; 3.MNS-16; 4.MNP-10; 5.MNC-13 The effect of different n(Si)/n(Al) values on the catalyst was also investigated. The XRD data are shown in Fig. 3. It can be noted that spectrum peaks appear at approximately 2θ = 2º, which is characteristic of the hexagonally symmetric MCM-41 mesoporous structure

[17]

. However,

note the poor order and crystallinity in MNC-13 with n(Si)/n(Al) = 40.


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Figure 3. X-ray diffraction patterns of MNC-13 with different n(Si)/n(Al) a. n(Si):n(Al) = 10; b. n(Si):n(Al) = 20; c. n(Si):n(Al) = 30; d. n(Si):n(Al) = 40

The activity of the catalysts was greatly affected by the amount of Al elements. Table 4 shows the activity of MNC-13 with different n(Si)/n(Al). It can be noted that the conversion and yield of the reaction increased with n(Si)/n(Al). When n(Si)/n(Al) was 30, the catalyst showed the highest activity. Subsequently, the activity of the catalyst decreased with increasing n(Si)/n(Al). This result can be explained by NH3-TPD (Fig. 4).

Table 4 Effect of MNC-13 with Different n(Si)/n(Al) on Yield of Liquid Product* n(Si)/n(Al)

Conversion/%

Yield of Bio-oil/%

Yield of Bio-gas/%

Yield of coke/%

10

82.3±0.3

56.2±0.2

26.1±0.4

17.7±0.3


12

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20

88.3±0.3

66.8±0.4

21.5±0.3

11.7±0.4

30

95.1±0.2

74.9±0.3

20.2±0.5

4.9±0.4

40

83.1±0.4

61.3±0.3

21.8±0.4

16.9±0.3

*Reaction conditions: RSO 10g, m(cat):m(RSO)=1:30, 410℃, 100min.

It can be noted from Fig. 4 and Table 5 that the amount of acid increased with n(Si)/n(Al). The activity of the catalyst also increased (Table 4). When n(Si)/n(Al) (feed ratio) was 30, the acidity of the catalyst was the highest and showed the highest activity. Subsequently, the acidity and activity of the catalyst decreased with increasing n(Si)/n(Al). Although the metal element Al can enhance the catalytic activity, the active centers will be covered if Al is too abundant, which will decrease the activity. Thus the n(Si)/n(Al) of MNC-13 was determined to be 30.

Figure 4. NH3-TPD patterns of MNC-13 with different n(Si)/n(Al) Table 5 Acid Amounts of MNC-13 with Different n(Si)/n(Al)


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Catalysts

Page 14 of 24

Acid amounts (mmol/g)

/Feed ratio

Weak acid

Medium strong acid

Strong acid

Total acid

ICP/ n(Si):n(Al)

n(Si):n(Al)=10

0.168

-

0.454

0.622

0.07

n(Si):n(Al)=20

0.204

-

0.740

0.944

0.085

n(Si):n(Al)=30

0.162

0.160

0.836

1.158

0.213

n(Si):n(Al)=40

0.176

0.577

0.753

0.188

There was a significant difference in the compositions of the liquid fuels obtained using MNC13 compared with Na2CO3 or K2CO3 as the catalyst. The liquid fuels were analyzed by GC–MS, and the results are summarized in Table 6. It can be seen that the main components of the products change with the different catalysts. Using MNC-13 as the catalyst, the main ingredients of the cracked oils were alkanes with a carbon atom number of approximately 15-17, and the total content was more than 70%, which is similar to diesel fuel. However, when using Na2CO3 or K2CO3 as the catalyst, the distribution of the carbon atom number was very wide for the pyrolysis oil, and the highest content of any one ingredient was not more than 17%. The properties of the pyrolysis oil from different catalysts were rigorously studied, and the results are shown in Table 7. For comparison purposes, Table 7 also displays the specified values for the petroleum-based fuel. The results showed that the fuels derived from RSO using MNC-13 as the catalyst possess acceptable values for the given properties when compared with those of the petroleum-based fuel. Therefore, MNC-13 is an excellent catalyst for the cracking of RSO; its typical mesoporous structure could focus the distribution of product and improve the properties of fuels. The catalytic performance and catalytic stability of MNC-13 were studied as follows.


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Table 6 Main Components of CrackedOil from RSO Catalysts

Yield of Bio-oil/%

Components

Content/%

Blank

57.4

1-Octylene

8.04

Octane

5.36

Nonane

5.32

4-Decene

6.17

Hendecane

10.44

Nonane

5.53

Decane

5.36

Dodecane

10.13

1-Tridecylene

16.28

Cetane

8.6

Nonane

5.05

Cetane

11.75

8-Heptadecene

6.19

Heptadecene

12.57

6-Laurylene

2.88

Dodecane

4.00

Tridecane

4.41

Tetradecane

5.84

Pentadecane

10.04

Cetane

26.11

Heptadecane

17.31

Na2CO3

67.9

K2CO3

69.0

MNC-13

74.9

Table 7 Properties of Oils Fuel properties

Cracked oil, blank*

Cracked oil, Na2CO3*

Cracked oil, K2CO3*

Cracked oil, MNC13

Biodiesel*

0# diesel*

93# gasoline*

Density/g cm-3

0.89

0.88

0.87

0.83

0.89

0.84

0.82

Dynamic viscosity,40℃/mm2

3.98

3.97

4.12

3.42

4.5

–

–


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s-1 Moisture content/%

0.59

0.38

0.39

0.31

–

–

–

Calorific value/MJ kg-1

37.44

39.72

39.34

43.14

39

43.56

44

Color

Brown

Yellow

Yellow

Faint yellow

–

Faint yellow

–

*Literature value from ref 19.

Catalytic Cracking of RSO by MNC-13. The effects of reaction conditions on the hydrolysis results are shown in Table 8. Temperature had a significant effect on the RSO cracking results. At 390℃, the conversion was 85.4% under the given conditions. The conversion and yield gradually increased with increasing reaction temperature. When the temperature was increased to 410℃ under otherwise identical conditions, the conversion reached 95.1%, and the yield of liquid product was 74.9%. Moreover, when the time was increased, the conversion increased. However, when the time was further increased from 100 to 120 min, the yield was almost unchanged. When the MNC-13 dosage was increased, both the conversion and the yield of liquid product increased. When m(MNC-13):m(RSO) was increased from 1:50 to 1:30, the conversion increased from 89.4% to 95.1%, and the yield of liquid product increased from 69.3% to 74.9%. However, when the MNC-13 dosage was further increased, the conversion was almost unchanged, but the yield of liquid product decreased. In summary, the optimum operating conditions for the catalytic cracking of RSO were as follows: RSO 10 g, m(MNC13):m(RSO) = 1:30, 410℃ for 100 min. Under the above conditions, the cracking conversion and yield of liquid product were 95.1% and 74.9%, respectively. Table 8 Effect of Reaction Conditions on Reaction Result


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No.

Temperature/℃

Time/min

m(MNC-13):m(RSO)

Conversion/%

Yield of liquid product/%

1

390

100

1:30

85.4±0.3

60.6±0.4

2

400

100

1:30

92.9±0.2

62.2±0.3

3

410

100

1:30

95.1±0.3

74.9±0.5

4

420

100

1:30

95.4±0.5

74.5±0.4

5

410

80

1:30

91.9±0.2

72.0±0.4

6

410

90

1:30

94.0±0.4

74.6±0.6

7

410

100

1:30

95.1±0.5

74.9±0.4

8

410

110

1:30

95.5±0.5

74.5±0.5

9

410

120

1:30

95.7±0.4

74.5±0.3

10

410

100

1:50

89.4±0.4

69.3±0.5

11

410

100

1:40

92.1±0.3

72.5±0.4

12

410

100

1:30

95.1±0.4

74.9±0.5

13

410

100

1:20

95.5±0.2

74.3±0.4

14

410

100

1:20

95.5±0.5

73.2±0.4

Stability of MCN-13. Recycling of the catalyst is a crucial aspect affecting the cost of cracking production. Thus, the stability of MCN-13 was studied, and the results are shown in Fig. 5. MNC-13 could be reused without further treatment after the reaction. The conversion of the RSO still reached 94.4% and the yield of liquid product could reach 74.5% even after five successive cycles of reuse. Moreover, MNC-13 still retained an excellent mesoporous structure after the fifth use (Fig. 6). Thus, MNC-13 can be recycled and reused with negligible loss in activity.


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Figure 5. Stability of MNC-13(RSO 10g, m(cat):m(RSO)=1:30, 410℃, 100min)

Figure 6. X-ray diffraction patterns of reused MNC-13

 CONCLUSION


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The new molecular sieve MNC-13 synthesized in the ionic liquid [HSO3-(CH2)3-NEt3] [Cl] exhibited excellent catalytic activity and stability for the cracking of RSO. Therefore, this research provides a new preparation method for acidic molecular sieves and points to a highly effective way to further utilize inedible biolipids.

 ASSOCIATED CONTENT Supporting Information

Preparation of β/Al-MCM-41, characterization equipment, characterization of molecular sieves, characterization of ionic liquids. This material is available free of charge via the Internet at http://pubs.acs.org.

 AUTHOR INFORMATION *Corresponding Author: Shitao Yu, Fax: +86-532-84022864; Tel: +86-532-84022864; E-mail: [email protected]

Zhiping

Wang,

Fax:

+86-532-84022864;

Tel:

+86-532-84022864;

E-mail:

[email protected] Notes The authors declare no competing financial interest.

 ACKNOWLEDGMENT ACKNOWLEDGMENT


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This research was supported by the Taishan Scholar Program of Shandong and the National Science Foundation of China (31570573).

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TOC GRAPHIC

Title: The Production of Liquid Hydrocarbon Fuel from Catalytic Cracking of Rubber Seed Oil Using New Mesoporous Molecular Sieves Authors: Zhiping Wang, Shitao Yu Synopsis: A production method of biofuel from inedible oil RSO by deep processing using new mesoporous molecular sieves.


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Production of Liquid Hydrocarbon Fuel from Catalytic Cracking of

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