复合氧化物催化微晶纤维素/蔗渣液化研究
摘要
石油、煤炭、天然气等不可再生资源日益枯竭,导致世界能源危机日趋严峻。生物质具有可再生、零净碳排放等优点,其开发利用符合低碳经济的理念,因此随着新能源研究的深入,生物质等可再生资源的开发研究成了当今世界面临的重大课题。
本文采用共沉淀法制备了MgMOx(M=Cr、Ni、Al、Mn、Zn、Fe)系列二元金属复合氧化物催化剂。以微晶纤维素及蔗渣为原料,采用高压反应釜对其在热压水条件下的催化液化过程工艺进行了研究。同时,将生物质液化反应产物分为气相、水溶相、四氢呋喃(THF)溶相和残渣四部分,对水溶相的主要化合物组成及相对含量采用气相色谱质谱(GC-MS)进行了分析,并分析了液化反应温度、时间对蔗渣液化水溶相产物酸、羟值的影响;利用凝胶渗透色谱(GPC)对四氢呋喃溶相化合物的分子量分布进行了表征,并采用傅利叶红外光谱(FT-IR)对其主要特征官能团进行了分析;采用元素分析仪对液化残渣的化学元素组成和热值(HHV)进行了分析与表征。探讨了反应温度、时间、液固比、液化气氛、催化剂等因素对微晶纤维素、蔗渣液化转化率以及各相产物分布的影响。结果表明,当以二元金属复合氧化物MgMnOx作为催化剂时,在250℃,30 min,液固比为10条件下,微晶纤维素转化率达96.2%;在270℃,5 min,液固比为10条件下,蔗渣的转化率为90.4%,其中水溶相产率达51.5%。
以MgMnOx作为液化催化剂时,微晶纤维素液化水溶相主要产物为环戊烯酮及其衍生物、2-羟基丙酸、及少量酸、醇、醚,其四氢呋喃萃取相的质均分子量(Mw)为659 g·mol-1;蔗渣液化时,四氢呋喃萃取相的质均分子量为802 g·mol-1,较无催化剂时降低了219 g·mol-1。催化剂对蔗渣液化各相产率分布及水溶相主要组成有很大影响,当以MgMnOx等系列复合金属氧化物作为催化剂时,其水溶相产物主要为环戊烯酮衍生物、2,5-己二酮、苯酚及衍生物、乙酰丙酸、对羟基苯醛等;无催化剂条件下,其液化水溶相主要为糠醛及其衍生物5-羟甲基-2-呋喃甲醛。
复合金属氧化物催化剂MgMnOx能有效促进微晶纤维素、蔗渣的液化降解,且环境友好,本研究结果对生物质催化液化具有较好的借鉴意义。
With the depletion of petroleum, coal, natural gas and other fossil fuels, the global energy crisis is increasing fairly rapidly. Biomass is one of renewable energy form with zero net carbon emission; the utilization of biomass is in accordance well with the concept of low carbon economy. Studying on the transformation of biomass has been paid great interesting for the exploitation of new energy and renewable resources.
In this dissertation, coprecipitation method was adopted for the preparation of a series of mixed metallic oxides MgMOx(M=Cr、Ni、Al、Mn、Zn、Fe) and their catalytic properties were investigated for the liquefaction of microcellulose and bagasse in the thermal compressed water. The liquefied products of biomass feedstock were separated into gas phase, water and THF extraction fractions and solid residues. The main chemical compositions and relative content of water extraction products were characterized by GC-MS and the effects of reaction temperature and time on acid/hydroxide number of aqueous phase were analyzed as well. GPC was used to measure the molecular weight distribution of polymers dissolved in THF and the qualitative analysis of functional groups was carried out by FT-IR. Simultaneously, the chemical element composition and high heat valve of the solid residue were characterized by element analyzer and calculated. The effects of reaction temperature, time, ratio of liquid to solid (L/S), atmosphere and catalysts on liquefaction of microcellulose and bagasse were investigated in detail. Experimental results indicated that 96.2% of microcellulose was converted when the MgMnOx was used as catalyst at 250℃for 30 min with L/S ratio 10, while 90.4% of baggase was converted at an elevated temperature of 270℃for 5 min with L/S ratio 10 and more than of 51.5% products dissolved in water phase.
Water dissolving phase were mainly composed of cyclopentyl ketene and its derivatives, 2-hydroxypropanoic acid and a small amount of acid, alcohol and ether with the mass-average molecular weight of THF extraction phase was 659 g·mol-1 while MgMnOx was used as catalyst for the liquefaction of microcellulose. As for the liquefaction of bagasse, the average number of molecular weight in tetrahydrofuran (THF) dissolving fractions decreased from 1021 g·mol-1 to 802 g·mol-1 while the same catalyst was adopted. The results demonstrated that the bagasse liquefaction products distribution and composition were significantly affected by the catalyst. For example, water soluble phase in catalytic liquefaction of bagasse were mainly composed of cyclopentenone, 2, 5-Hexanedione, phenol and its derivatives, 4-oxo-pentanoic acid, p-hydroxy-Benzaldehyde but, the aqueous phase were mainly composed of furfural and its derivatives when no catalyst was used.
As an environmental friendly liquefaction catalyst, MgMnOx can effectively promoted liquefied degradation of microcellulose and baggase. So reported result is significant for the reference of biomass liquefaction process.
本文采用共沉淀法制备了MgMOx(M=Cr、Ni、Al、Mn、Zn、Fe)系列二元金属复合氧化物催化剂。以微晶纤维素及蔗渣为原料,采用高压反应釜对其在热压水条件下的催化液化过程工艺进行了研究。同时,将生物质液化反应产物分为气相、水溶相、四氢呋喃(THF)溶相和残渣四部分,对水溶相的主要化合物组成及相对含量采用气相色谱质谱(GC-MS)进行了分析,并分析了液化反应温度、时间对蔗渣液化水溶相产物酸、羟值的影响;利用凝胶渗透色谱(GPC)对四氢呋喃溶相化合物的分子量分布进行了表征,并采用傅利叶红外光谱(FT-IR)对其主要特征官能团进行了分析;采用元素分析仪对液化残渣的化学元素组成和热值(HHV)进行了分析与表征。探讨了反应温度、时间、液固比、液化气氛、催化剂等因素对微晶纤维素、蔗渣液化转化率以及各相产物分布的影响。结果表明,当以二元金属复合氧化物MgMnOx作为催化剂时,在250℃,30 min,液固比为10条件下,微晶纤维素转化率达96.2%;在270℃,5 min,液固比为10条件下,蔗渣的转化率为90.4%,其中水溶相产率达51.5%。
以MgMnOx作为液化催化剂时,微晶纤维素液化水溶相主要产物为环戊烯酮及其衍生物、2-羟基丙酸、及少量酸、醇、醚,其四氢呋喃萃取相的质均分子量(Mw)为659 g·mol-1;蔗渣液化时,四氢呋喃萃取相的质均分子量为802 g·mol-1,较无催化剂时降低了219 g·mol-1。催化剂对蔗渣液化各相产率分布及水溶相主要组成有很大影响,当以MgMnOx等系列复合金属氧化物作为催化剂时,其水溶相产物主要为环戊烯酮衍生物、2,5-己二酮、苯酚及衍生物、乙酰丙酸、对羟基苯醛等;无催化剂条件下,其液化水溶相主要为糠醛及其衍生物5-羟甲基-2-呋喃甲醛。
复合金属氧化物催化剂MgMnOx能有效促进微晶纤维素、蔗渣的液化降解,且环境友好,本研究结果对生物质催化液化具有较好的借鉴意义。
With the depletion of petroleum, coal, natural gas and other fossil fuels, the global energy crisis is increasing fairly rapidly. Biomass is one of renewable energy form with zero net carbon emission; the utilization of biomass is in accordance well with the concept of low carbon economy. Studying on the transformation of biomass has been paid great interesting for the exploitation of new energy and renewable resources.
In this dissertation, coprecipitation method was adopted for the preparation of a series of mixed metallic oxides MgMOx(M=Cr、Ni、Al、Mn、Zn、Fe) and their catalytic properties were investigated for the liquefaction of microcellulose and bagasse in the thermal compressed water. The liquefied products of biomass feedstock were separated into gas phase, water and THF extraction fractions and solid residues. The main chemical compositions and relative content of water extraction products were characterized by GC-MS and the effects of reaction temperature and time on acid/hydroxide number of aqueous phase were analyzed as well. GPC was used to measure the molecular weight distribution of polymers dissolved in THF and the qualitative analysis of functional groups was carried out by FT-IR. Simultaneously, the chemical element composition and high heat valve of the solid residue were characterized by element analyzer and calculated. The effects of reaction temperature, time, ratio of liquid to solid (L/S), atmosphere and catalysts on liquefaction of microcellulose and bagasse were investigated in detail. Experimental results indicated that 96.2% of microcellulose was converted when the MgMnOx was used as catalyst at 250℃for 30 min with L/S ratio 10, while 90.4% of baggase was converted at an elevated temperature of 270℃for 5 min with L/S ratio 10 and more than of 51.5% products dissolved in water phase.
Water dissolving phase were mainly composed of cyclopentyl ketene and its derivatives, 2-hydroxypropanoic acid and a small amount of acid, alcohol and ether with the mass-average molecular weight of THF extraction phase was 659 g·mol-1 while MgMnOx was used as catalyst for the liquefaction of microcellulose. As for the liquefaction of bagasse, the average number of molecular weight in tetrahydrofuran (THF) dissolving fractions decreased from 1021 g·mol-1 to 802 g·mol-1 while the same catalyst was adopted. The results demonstrated that the bagasse liquefaction products distribution and composition were significantly affected by the catalyst. For example, water soluble phase in catalytic liquefaction of bagasse were mainly composed of cyclopentenone, 2, 5-Hexanedione, phenol and its derivatives, 4-oxo-pentanoic acid, p-hydroxy-Benzaldehyde but, the aqueous phase were mainly composed of furfural and its derivatives when no catalyst was used.
As an environmental friendly liquefaction catalyst, MgMnOx can effectively promoted liquefied degradation of microcellulose and baggase. So reported result is significant for the reference of biomass liquefaction process.
引文
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