脱硅重组装法制备 ZSM-5/MCM-41 复合分子筛及其催化裂解性能研究

报告人：那金丹指导老师：王莅 教授

Alkali Treatment

CTAB Crystallize

2011 年实验总结

目前工作

计划与展望

报告内容

2011 年实验总结

椭圆形孔，直通道0.51×0.53nm

圆形孔，弯曲通道 0.53×0.56nm

≥1.5nm

ZSM-5 MCM-41

优点：比表面积大 稳性 ,活性好 择形性缺点：孔径小 阻碍扩散

优点：孔径均一 , 可调缺点：孔壁不定型 稳定性 , 酸性差

ZSM-5/MCM-41制备过程

Alkali Treatment

CTAB Crystallize

变量 影响

主要工作：

NaOH Concentration

Crystallization Time

Amount of Silica source

Thickness and PSD of MCM-41 shell

Effect of NaOH Concentration

1 2 3 4 5 6 7

A

c

a

b

Inte

nsi

ty

2 theta/degrees

a: ZMC-OH1.0-C12 b: ZMC-OH1.5-C12 c: ZMC-OH2.0-C12

0 10 20 30 40 50

B

a

c

bInte

ns

ity

2 theta /degrees

a: ZMC-OH1.0-C12 b: ZMC-OH1.5-C12 c: ZMC-OH2.0-C12

Fig.1 (A) Small-angle XRD patterns and (B) wide-angle XRD patterns of the ZSM-5/MCM-41 composite

XRD

Effect of NaOH Concentration

Sample S total (m2/g) S external (m2/g) V total (cm3/g) V micro (cm3/g) d (nm)

ZSM-5 370 69 0.189 0.130 0.54

ZCM-OH1.0-C12 401 219 0.26 0.083 2.6

ZCM-OH1.5-C12 568 363 0.43 0.093 3.0

ZCM-OH2.0-C12 463 341 0.35 0.054 3.0

0.0 0.2 0.4 0.6 0.8 1.0

0

50

100

150

200

250

300 A

d

c

b

a

Vo

lum

e A

ds

orb

ed

cm

3 /g

P/P0

1 2 3 4 5 6 7 8

B

0.0 0.5 1.0 1.5 2.0

a

d/nm

c

d

b

PS

D

d/nm

Fig. 2 N2 adsorption-desorption isotherms (A) and pore size distributions (B) of ZSM-5 (a), ZMC-OH1.0-C12 (b), ZMC-OH1.5-C12 (c) and ZMC-OH- 2.0 -C12

(d)

BET & PSD

Table 1 Physicochemical properties of ZSM-5 and

Effect of Crystallization Time

0.0 0.2 0.4 0.6 0.8 1.0

0

100

200

300

400

500

A

f

c

e

g

b d

a

Vo

lum

n A

dso

rped

/ cm

3/g

P/P0

0 1 2 3 4 5 6 7 8 9 10

B

0.0 0.5 1.0 1.5 2.0

a

d/nm

g

f

e

dc

b

PS

D

d/nm

Fig.3 (A) N2 adsorption-desorption isotherms and (B) pore size distributions of a: ZSM-5, b: ZMC-OH1.5-C12, c: ZMC-OH1.5-C24, d: ZMC-OH1.5–C36,

e: ZMC-OH1.5–C48, f: ZMC-OH1.5–C60, g: ZMC-OH1.5–C72 Sample S total (m2/g) S external (m2/g) V total (cm3/g) V micro (cm3/g) d(nm)

ZSM-5 370 69 0.189 0.130 0.54

ZCM-OH1.5-C12 568 363 0.43 0.093 3.0

ZCM-OH1.5-C24 700 595 0.65 0.110 3.7

ZCM-OH1.5-C36 567 361 0.50 0.094 3.5

ZCM-OH1.5-C48 422 195 0.31 0.100 2.9

ZCM-OH1.5-C60 390 153 0.27 0.110 2.8

ZCM-OH1.5-C72 380 148 0.25 0.110 2.6

TEM images

15 nm

50 nm 18nm

a b

c d

Fig.4 TEM images for a: ZSM-5, b: ZMC-OH1.5-C12, c: ZMC-OH1.5-C24, d: ZMC-OH1.5–C48

Catalytic Cracking of n-dodecane

5 10 15 20 25 300.0

0.1

0.2

0.3

0.4

0.5

0.6 ZSM-5ZMC-OH1.5-C24 Desilicated ZSM-5

Con

vers

ion

TOS/min

Temperature: 550 0C Pressure: 4MPa

Fig.5 Conversion versus TOS for coatings of ZSM-5, ZSM-5/MCM-41 and desilicated ZSM-5

目前工作：不同模板剂制备 ZSM-5/MCM-41复合分子筛

10 20 30 40 50

303151501020

101B

C16

TAB

C14

TAB

C12

TAB

C10

TAB

2 theta /degrees

1 2 3 4 5 6 7

A

200101

100

2 theta/ degrees

C14

TAB & C16

TAB

C12

TAB & C16

TAB

C10

TAB & C16

TAB

C16

TAB

C14

TAB

C12

TAB

C10

TAB

Inte

ns

ity

Fig. 6 (A) Small-angle XRD patterns and (B) wide-angle XRD patterns of the ZSM-5/MCM-41 composite prepared with different templates

N2-adsorption

Fig. 7 N2 adsorption-desorption isotherms (A) and pore size distributions (B) of ZSM-5/MCM-41 samples

0.0 0.2 0.4 0.6 0.8 1.0 1.2

C14

& C16

C12

& C16

C16

TAB

C10

& C16

C14

TAB

C12

TAB

C10

TAB

Vo

lum

n A

ds

orp

ed

/ cm

3 /g

P/P0

A

1 2 3 4 5 6 7

PS

D

d / nm

B

Fig. 8 pore size distributions of ZSM-5 /MCM-41 samples with single template (C)

and dual-template (D)

1 2 3 4 5 6 7

B C14

TAB

C12

TAB

C10

TAB

C16

TAB

PS

D

d / nm

1 2 3 4 5 6 7

C

PS

D

d / nm

C10

& C16

C12

& C16

C14

& C16

D

0.4 0.8 1.2 1.6 2.0

dV

/dW

d/nm

ZSM-5

Sample (Si / Al) SBET (m2/g) Sexter

(m2/g)

Vtotal

(cm3/g)

Vmicro

(cm3/g)

d(nm)

HF

ZSM-5 (54) 370.3756 68.9759 0.185403 0.1345 0.8260 0.1351

HZM-C10 (46.4) 538.8080 359.0552 0.3616 0.0761 2.6847 0.1402

HZM-C12 (49.1) 549.7440 443.0477 0.4239 0.0534 3.0847 0.1015

HZM-C14 (48.0) 668.6308 539.9349 0.6238 0.0539 3.7320 0.0700

HZM-C16 739.4984 609.7680 0.7189 0.0539 3.9000 0.0618

HZM-C10&C16 (46.9) 739.2631 607.6090 0.7912 0.0557 4.2810 0.0579

HZM-C12&C16 779.0871 683.0062 0.7790 0.0572 4.0000 0.0644

HZM-C14&C16 685.4143 546.7326 0.6495 0.0592 3.7904 0.0727

BET 数据总结

TEM images of samples

C16TAB

C10TAB C12TAB C14TAB

C10 & C16 C12 & C16

谢谢！请提出批评指正

0.0 0.2 0.4 0.6 0.8 1.0 1.2

A C14

& C16

C12

& C16

C10

& C16

C16

TAB

C14

TAB

C12

TAB

C10

TAB

ZSM-5

Volu

mn

Adso

rped

/ cm

3 /g

P/P0

1 2 3 4 5 6 7

B C14

TAB

C12

TAB

C10

TAB

C16

TAB

PSD

d / nm

1 2 3 4 5 6 7

C

PSD

d / nm

C10

& C16

C12

& C16

C14

& C16

a b c

50 nm

50 nm

d

e