MeMo/USY催化剂对神东煤热解产物的调控

doi:10.16085/j.issn.1000-6613.2018-0082

摘要/Abstract

摘要：

以USY分子筛为载体，通过等体积浸渍MoO₃、Fe₂O₃、Co₃O₄、NiO四种过渡金属氧化物，制备了Mo/USY、FeMo/USY、CoMo/USY、NiMo/USY催化剂，并借助ICP、XRD、BET、NH₃-TPD、TG等手段对催化剂进行表征。使用粉-粒流化床进行神东煤的催化热解实验，考察了过渡金属氧化物对USY的改性作用及其对热解产物的影响。结果表明：不同催化剂作用下，半焦收率基本保持在65%左右；与SiO₂相比，USY分子筛使焦油中酚类化合物含量从36.95%减少到5.08%，萘类化合物含量从8.24%增加到72.76%；与USY相比，Mo/USY使气体、液体产物的收率分别降低了4.4个百分点、30.0个百分点，萘类含量减少了18.5个百分点；Fe₂O₃、Co₃O₄、NiO对Mo/USY的改性作用明显，降低了催化剂的积炭率，提高了CH₄、C₂、C₃、CO₂的收率和气体总收率；FeMo/USY促进了产物的芳构化和萘类的生成；CoMo/USY促进了产物的芳构化反应，抑制了萘类的生成反应；NiMo/USY抑制了产物的芳构化反应、萘类的生成反应。

关键词: 流化床, 分子筛, 过渡金属氧化物, 改性作用, 催化, 热解, 产物调控

Abstract:

Four transition metal oxides, MoO₃, Fe₂O₃, Co₃O₄, and NiO, were supported on USY molecular sieves by equal volume impregnation to prepare Mo/USY, FeMo/USY, CoMo/USY and NiMo/USY catalysts, and characterized by ICP, XRD, BET, NH₃-TPD, TG. The pyrolysis experiments of Shendong coal were conducted in a powder-particle fluidized bed reactor. The results showed that the yield of the semi coke was basically around 65% with different catalysts. Compared with SiO₂, the content of phenols was reduced from 36.95% to 5.08%, and the content of naphthalenes was increased from 8.24% to 72.76% in tar by USY molecular sieve. Compared with USY molecular sieve, gas product yield, liquid product yield, and content of naphthalenes was decreased by 4.4%, 30.0% and 18.5% by Mo/USY, respectively. The effects of Fe₂O₃, Co₃O₄ and NiO on the modification of Mo/USY were obvious, which reduced the carbon accumulation rate of the catalyst and increased the yield of CH₄, C₂, C₃, CO₂ and the total gas. The aromatization of the products and the formation of naphthalenes were enhanced by FeMo/USY. The aromatization reaction of the product was enhanced, but the formation reaction of naphthalenes was inhibited by CoMo/USY. The aromatization reaction of the products and the formation reaction of naphthalenes were inhibited by NiMo/USY.

Key words: fluidized bed, molecular sieves, transition metals oxide, modification, pyrolysis, catalysis, product regulation

中图分类号:

TQ 53

李刚,张穗穗,张妮娜,高婷,兰婷玮,马晓迅. MeMo/USY催化剂对神东煤热解产物的调控[J]. 化工进展, 2019, 38(03): 1329-1337.

Gang LI,Suisui ZHANG,Nina ZHANG,Ting GAO,Tingwei LAN,Xiaoxun MA. Regulation of Shendong coal pyrolysis products based on MeMo/USY catalyst[J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1329-1337.

图/表 16

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气体	质量/g		气体流量/L?min^?1		温度控制/℃
气体	煤样	催化剂	进料气	流化气	反应器	旋风分离器	冷凝管
N₂	6.0	18.0	1.2	0.6	600	350	?42±2

气体	质量/g		气体流量/L?min^?1		温度控制/℃
气体	煤样	催化剂	进料气	流化气	反应器	旋风分离器	冷凝管
N₂	6.0	18.0	1.2	0.6	600	350	?42±2

工业分析w/%				元素分析w/%
M _ad	A _d	V _daf	FC _daf	N_daf	C_daf	H_daf	S_t,daf	O_daf
15.32	9.53	35.61	64.39	1.04	77.84	4.47	0.39	16.26

工业分析w/%				元素分析w/%
M _ad	A _d	V _daf	FC _daf	N_daf	C_daf	H_daf	S_t,daf	O_daf
15.32	9.53	35.61	64.39	1.04	77.84	4.47	0.39	16.26

催化剂	Si /mg?g^?1	Al /mg?g^?1	Si/Al	Mo			Me
催化剂	Si /mg?g^?1	Al /mg?g^?1	Si/Al	X ₁/mg?g^?1	X ₂/mg?g^?1	X ₂?X ₁ ^?1/%	X ₁/mg?g^?1	X ₂/mg?g^?1	X ₂?X ₁ ^?1/%
USY	405.80	65.46	6.2		—	—	—	—	—
Mo/USY	357.56	57.63	6.2	79.98	72.94	91.2	—	—	—
FeMo/USY	355.68	57.39	6.2	53.33	48.72	91.4	28.00	25.32	90.4
CoMo/USY	359.37	57.93	6.2	53.33	48.85	91.6	29.37	26.73	91.0
NiMo/USY	354.88	57.30	6.2	53.33	48.61	91.2	31.43	28.36	90.2