不同固定床位置生物质热解挥发物蒸汽催化重整反应中焦炭的形成和演化

doi:10.1016/S1872-2067(23)64407-9

摘要/Abstract

摘要：

对生物质热解挥发物蒸汽重整反应过程中催化剂的失活过程和主要机理进行了研究. 在圆锥形喷动床反应器中于500 °C进行生物质热解, 随后在固定床反应器中于600 °C进行重整反应; 同时在不同轴向位置分析了催化剂位置对重整反应器的影响. 采用N₂吸附-脱附、X射线衍射、扫描电镜、透射电镜、程序升温氧化、拉曼光谱和傅里叶变换红外光谱对失活样品进行表征. 结果表明, 焦炭沉积是初始催化剂活性衰减的主要原因, 且没有观察到镍位点的烧结或氧化. 随着反应的进行, 沿着重整催化床观察到失活情况, 焦炭沉积于催化剂内, 其性质和组成取决于到达床中每个轴向位置的挥发物组成. 在催化床的入口部分, 焦炭沉积在Ni位点上, 并且具有一定的含氧量. 在更深的轴向床位置, 催化剂与挥发性物质接触, 该挥发性物质的组成已经明显改变, 从而形成具有石墨化程度更高的焦炭, 并且形成更多的缩合聚芳烃化合物. 此外, 沉积在所有失活样品上的焦炭没有呈现任何特定的形态, 这也表明, 无论所处的催化床位置和反应时间, 焦炭均呈现无定形结构.

关键词: 生物质, 热解, 蒸汽重整, 失活, 积碳, 氢气, 生物油

Abstract:

The evolution and the main mechanisms of catalyst deactivation have been assessed throughout continuous operation in the steam reforming of biomass pyrolysis volatiles. Biomass pyrolysis was conducted in a conical spouted bed reactor at 500 °C and the subsequent reforming step in a fixed bed reactor at 600 °C. The influence of catalyst location on the reforming reactor is also analyzed at different axial positions. Deactivated samples have been characterized by N₂ adsorption-desorption, XRD, SEM and TEM images, TPO, Raman and FTIR spectroscopies. Coke deposition is the main cause of initial catalyst decay, with no sintering or oxidation of Ni sites being observed. As reaction proceeds, a deactivation front is observed along the reforming catalytic bed, with coke location within the catalyst, and its nature and composition depending on the volatile composition reaching each axial position in the bed. At the inlet section of the catalytic bed (A1), the coke is deposited on Ni sites and is of rather oxygenated nature. At further axial bed locations, the catalyst is in contact with a volatile stream whose composition has been considerably modified, which leads to the formation of a more structured coke with higher graphitization degree and made up of more condensed polyaromatic compounds. Moreover, the coke deposited on all deactivated samples does not present any specific morphology, which is evidence of its amorphous structure regardless the bed location and reaction time.

Key words: Biomass, Pyrolysis, Steam reforming, Deactivation, Coke deposition, Hydrogen, Bio-oil

Enara Fernandez, Laura Santamaria, Irati García, Maider Amutio, Maite Artetxe, Gartzen Lopez, Javier Bilbao, Martin Olazar. 不同固定床位置生物质热解挥发物蒸汽催化重整反应中焦炭的形成和演化[J]. 催化学报, 2023, 48: 101-116.

Enara Fernandez, Laura Santamaria, Irati García, Maider Amutio, Maite Artetxe, Gartzen Lopez, Javier Bilbao, Martin Olazar. Elucidating coke formation and evolution in the catalytic steam reforming of biomass pyrolysis volatiles at different fixed bed locations[J]. Chinese Journal of Catalysis, 2023, 48: 101-116.

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https://www.cjcatal.com/CN/Y2023/V48/I5/101

图/表 13

Fig. 1. Scheme of the laboratory scale plant.

Table 1 Characterization techniques and information obtained.

Technique	Information obtained
N₂ adsorption-desorption	surface area pore volume pore diameter
TPR	reduction temperature of metallic phases
XRD	crystallographic structure Ni⁰ particle size (scherrer Eq.)
TPO	coke content coke structure coke composition
SEM	coke morphology coke nature coke location
TEM	coke morphology coke nature coke location
RAMAN	structure, composition
FTIR	structure, composition

Fig. 2. Evolution of the volatile conversion (a) and individual product yields (b) with time on stream. Reforming conditions: 600 °C, space time 20 gcat min gvolatiles-1, S/B ratio 4.

Table 2 Evolution of the textural properties and Ni crystallite size of the Ni/Al2O3 catalyst with TOS at different axial locations in the catalytic bed.

Axial position	TOS (min)	S_BET (m² g^-1)	V_pore (cm³ g^-1)	d_pore (Å)	d_Ni^{0 a} (nm)	d_Ni^{0 b} (nm)
A1	0	19.0	0.040	122	25	24
	50	9.3	0.033	288	25	25
	100	7.4	0.025	259	27	28
	150	5.9	0.020	178	28	28
A2	50	9.5	0.039	185	26	26
	100	10.2	0.032	160	29	30
	150	8.9	0.031	187	29	30
A3	50	10.6	0.042	199	26	27
	100	11.0	0.039	174	32	33
	150	11.3	0.036	152	33	33

Fig. 3. XRD patterns of the fresh reduced catalyst and those deactivated for 150 min on stream at different axial positions (A1, A2, and A3). Crystalline phases: () CaO(Al2O3)2, () Ni0, () CaAl2O4, () CaAl12O19, and () Al2O3.

Fig. 4. Evolution of TPO profiles with time on stream in the catalysts deactivated at different axial positions in the fixed bed reactor: (a) A1; (b) A2; (c) A3.

Fig. 5. Evolution with time on stream of the coke content deposited at different axial positions and average coke deposition rates in different axial positions. (a,d) A1; (b,e) A2; (c,f) A3.

Fig. 6. (a) SEM images of the fresh reduced catalyst; the catalysts deactivated at different axial positions and for different times on stream. TOS 50 min: A1 (b), A2 (c) and A3 (d); TOS 100 min: A1 (e), A2 (f) and A3 (g); TOS 150 min: A1 (h), A2 (i) and A3 (j).

Fig. 7. TEM images of the catalyst deactivated at different axial positions and different times on stream. TOS 50 min: A1 (a), A2 (b), A3 (c); TOS 100 min: A1 (d), A2 (e) and A3 (f); TOS 150 min: A1 (g), A2 (h) and A3 (i).

Fig. 8. Evolution of the Raman spectra (1000-1800 cm-1 region) of the coke deposited on the catalysts deactivated at different axial positions in the fixed bed reactor. (a) A1; (b) A2; (c) A3.

Table 3 Evolution of deconvolution parameters of the Raman spectra with time on stream at different axial positions in the fixed bed reactor.

Axial Position	TOS (min)	σ_D (cm^-1)	σ_G (cm^-1)	Γ_D (cm^-1)	Γ_G (cm^-1)	I_D1/I_G	La (nm)
A1	50	1348	1593	174	65	0.66	1.09
	100	1348	1595	137	65	0.67	1.10
	150	1346	1590	161	71	0.65	1.09
A2	50	1344	1592	175	65	0.64	1.08
	100	1343	1592	157	63	0.66	1.10
	150	1348	1599	169	63	0.63	1.07
A3	50	1345	1597	147	62	0.68	1.11
	100	1346	1595	167	64	0.66	1.10
	150	1351	1597	100	61	0.78	1.19

Table 4 Functional groups associated with IR bands.

IR band (cm⁻¹)	Functional group
1260	stretching vibration of C-O bonds in alcohols, ethers or related compounds, and/or stretching asymmetric vibrational mode of C-O-C bonds C-O bonds in acetate groups (AC), phenolic esters (P,ES) and/or ethers (ET) bonded to aliphatic compounds and/or alkenes
1390	C-H in aliphatic compounds (AL)
1420	O=C-O in acetate groups (AC) // methoxyl group or C-H in aliphatic compounds, 1420-1490 cm⁻¹
1450	bending vibrations in -CH2 and -CH3 aliphatic groups, alkylaromatic compounds and/or symmetric stretching vibrations of O=C-O bonds in acetate groups (AC, AL, AA)
1505	Symmetric stretching vibrations of O=C-O bonds in carbonate groups and/or C=C in low condensed aromatic compounds
1525	O=C-O in carbonates (CA)
1580	C=C in polycondensed aromatic compounds or asymmetric stretching vibrations of O=C-O bonds in acetate groups
1610	dienes and/or conjugated double bonds (DI)
2850, 2925 and 2960	stretching vibration of C-H in -CH_n aliphatic groups (AL)

Fig. 9. Evolution with time on stream of the relative intensities of several representative FTIR bands corresponding to functional groups of the coke deposited at different axial positions in the fixed bed reactor: (a) A1; (b) A2; (c) A3. Abbreviations: aromatics (A), alkyl aromatics (AA), acetates (AC), aliphatics (AL), carbonates (CA), dienes (DI), esters (ES), ethers (ET), phenols (P), polyaromatics (PA).

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