污泥热解制油
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学校代码： 10286 分类号： 密 X705
级： 公开 620
U D C：
学 号： 120478
工程硕士学位论文 城市污泥低温催化热解制油 实验研究及装置设计
研究生姓名： 导 师 姓 名：
申请学位类别 工程领域名称 研究方向 答辩委员会主席
工程硕士 动力工程 新能源技术
学位授予单位 论文答辩日期 学位授予日期 评 阅 人
本人声明所呈交的学位论文是我个人在导师指导下进行的研究工作及取得的研究 成果。尽我所知，除了文中特别加以标注和致谢的地方外，论文中不包含其他人已经发 表或撰写过的研究成果， 也不包含为获得东南大学或其它教育机构的学位或证书而使用 过的材料。 与我一同工作的同志对本研究所做的任何贡献均已在论文中作了明确的说明 并表示了谢意。
研究生签名：
日期：
东 南 大 学 学 位 论 文 使 用 授 权 声 明
东南大学、中国科学技术信息研究所、国家图书馆有权保留本人所送交学位论文的 复印件和电子文档，可以采用影印、缩印或其他复制手段保存论文。本人电子文档的内 容和纸质论文的内容相一致。除在保密期内的保密论文外，允许论文被查阅和借阅，可 以公布（包括刊登）论文的全部或部分内容。论文的公布（包括刊登）授权东南大学研 究生院办理。
I
Abstract
Abstract
The production the municipal sludge is becoming huge. Due to its complex composition and great harm to environment, municipal sludge must be managed properly. Thermochemical process such as pyrolysis is gaining academic attention for the valorisation and reduction of this waste. The pyrolysis liquids of sewage sludge contain large amounts of oxygen compounds with high viscosity, catalytic pyrolysis may be a solution for the improvement of its quality. Studies have shown that the mineral elements in ashes of sludge have catalytic effects. In this paper, sludge char was used as the catalysts for pyrolysis of municipal sludge to investigate the effect of different catalytic methods. Several kinds of metals were supported on sludge char to improve the catalytic effect. The reactor of catalytic treatment of vapors of sludge pyrolysis was designed. Thermogravimetric analysis was conducted first, it was found that weightless range of lipids, carbohydrates and proteins overlapped with the heating rate of 100℃/min. A horizontal tube reactor was used to research the pyrolysis of sludge for bio-oil with the addition of char. The influences of temperature as well as proportion of char to the yield, composition and physicochemical properties of pyrolysis liquid were considered. After that, Fe、 Cu、 Al and Ni were supported on the char respectively. Results showed that sludge char promote the hydrodeoxygenation and benzene’s ring-opening reaction of organic phase (OP) in pyrolysis liquids. The heating value and viscosity of OP were also improved. The char-supported Fe which was best for the hydrodeoxygenation favored the highest HHV (higher heating value) of OP for 35.48MJ/kg. The char-supported Ni favored the lowest viscosity with 64.29 cSt@20℃. A vertical fixed bed catalytic reactor was designed and produced, hot pyrolysis vapors coming from sludge ptrolysis in a horizontal tube reactor passed through the catalytic reactor filled with sludge char. The experiments have been done in different temperature matching and height of catalysts to determine optimum experimental conditions. The results showed that the suitable temperature matching for maximum yield of OP was 500/400 ℃. Comparing the condition of sludge pyrolysis with the addition of char, the content of oxygen compounds in OP reduced significantly. The catalytic effects of char performed in two aspects, the promotion of hydrodeoxygenation of OP as well as the transformation of aromatic hydrocarbons into phenol. the promoting effect for hydrodeoxygenation increased With metal supported, the physicochemical properties of OP improved significantly. The char-supported Ni favored the highest heating value of OP for 40.27MJ/kg, while the char-supported Ni favored the lowest viscosity of OP for 18.75cSt@20℃. In addition, the catalytic activity of sludge char was relatively stable. Based on the catalytic effects of sludge char on the vapors from municipal sludge
BY ZHANG Ya
Supervised by Prof. JIN Bao-sheng
School of Energy and Environment Southeast University September 2014
东南大Baidu Nhomakorabea学位论文独创性声明
东 南 大 学 学 位 论 文 独 创 性 声 明
东 南大学 2014 年 2014 年 月 月 日 日
2014 年 6 月
Experimental research and design of low-temperature catalytic pyrolysis of municipal sludge for bio-oil
A Thesis Submitted to SoutheastUniversity For the Academic Degree of Master of Engineering
研究生签名：
导师签名：
日期：
摘要
摘 要
城市污泥产量巨大且组成复杂，环境危害大，必须进行减量化无害化处置。低温热 解制油技术作为一种城市污泥资源化利用方式，正日益受到学术界的重视。污泥热解油 高热值有机相的氧含量高且粘度大， 催化热解是改善热解油品质的一个方向。 研究表明， 污泥灰分中富含具有催化作用的矿物质元素。本文以污泥残炭作为污泥热解催化剂，考 察不同催化方式对污泥热解制油的影响。利用残炭作为载体负载不同金属元素，考察改 性后残炭的催化制油效果，并开展残炭催化污泥热解气提质反应器的设计计算。 首先对污泥进行热重分析，发现在快速热解条件下（ 100℃/min） ，污泥中的脂质、 糖类和蛋白质的失重区间交叠。 利用水平管式炉开展残炭与污泥混合热解制油实验研究， 考察了热解温度，残炭添加比例对热解油产率、组分分布及理化特性的影响。并在残炭 上负载 Fe、Cu、Al、Ni 等金属元素，研究不同金属元素与残炭中固有矿物质对污泥热 解的协同催化作用。结果表明：残炭能够促进热解液有机相的加氢脱氧反应，并催化苯 环发生加氢开环反应。经残炭催化后，热解液有机相热值和粘度均得到改善。负载 Fe 的残炭对有机相加氢脱氧的促进效果最好，所得有机相高位热值最高为 35.48MJ/kg，负 载 Ni 的残炭催化所得有机相粘度最低为 64.29cSt@20℃。 利用自制立式固定床催化炉， 污泥在水平管式炉内热解产生的高温热解气穿催化炉 内残炭料层，考察双炉温度匹配、催化炉床料种类及残炭填装高度等参数对污泥热解制 油的影响。结果表明：双炉温度匹配为 500/400℃时有机相产率最大；相比残炭与污泥 混合热解工况，有机相含氧化合物含量显著降低。残炭对污泥热解气的催化作用主要表 现为：一是促进有机相加氢脱氧，二是促进芳烃的环化和芳构化反应生成 PAHs。残炭 负载金属后，对热解气加氢脱氧的促进作用增强，热解液的理化特性显著改善。其中负 载 Fe 的残炭催化所得有机相高位热值达 40.27MJ/kg， 负载 Ni 的残炭催化所得有机相粘 度仅为 18.75cSt@20℃。通过多次重复实验发现，残炭的催化活性稳定，不易失活。 基于污泥残炭对污泥热解气优异的催化特性， 提出了一种利用残炭催化污泥热解气 提质的循环流化床热解反应装置。在现有 50t/d 双床交互循环式污泥低温热解制油工业 示范系统的热解反应装置基础上，开展残炭催化污泥热解气提质反应器的设计计算，以 期为后续工程应用中污泥热解油的进一步提质提供参考。 关键词：城市污泥；催化热解；残炭；有机相；设计计算
II
Abstract
pyrolysis, the circulating fluidized bed reactor was developed to improve the quality of vapors from sludge pyrolysis with sludge char. For “50t/d interact circulation configuration of sludge low-temperature pyrolysis for bio-oil demonstration project” in Jurong of Jiangsu province, the design of the catalytic treatment reactor of vapors from sludge pyrolysis for quality improvement was conducted on the basis of pyrolysis reaction device, the design was conducted with the purpose of providing the references for future engineering applications. Key words: Municipal sludge; Catalytic pyrolysis; Char; Organic phase; Design calculation
级： 公开 620
U D C：
学 号： 120478
工程硕士学位论文 城市污泥低温催化热解制油 实验研究及装置设计
研究生姓名： 导 师 姓 名：
申请学位类别 工程领域名称 研究方向 答辩委员会主席
工程硕士 动力工程 新能源技术
学位授予单位 论文答辩日期 学位授予日期 评 阅 人
本人声明所呈交的学位论文是我个人在导师指导下进行的研究工作及取得的研究 成果。尽我所知，除了文中特别加以标注和致谢的地方外，论文中不包含其他人已经发 表或撰写过的研究成果， 也不包含为获得东南大学或其它教育机构的学位或证书而使用 过的材料。 与我一同工作的同志对本研究所做的任何贡献均已在论文中作了明确的说明 并表示了谢意。
研究生签名：
日期：
东 南 大 学 学 位 论 文 使 用 授 权 声 明
东南大学、中国科学技术信息研究所、国家图书馆有权保留本人所送交学位论文的 复印件和电子文档，可以采用影印、缩印或其他复制手段保存论文。本人电子文档的内 容和纸质论文的内容相一致。除在保密期内的保密论文外，允许论文被查阅和借阅，可 以公布（包括刊登）论文的全部或部分内容。论文的公布（包括刊登）授权东南大学研 究生院办理。
I
Abstract
Abstract
The production the municipal sludge is becoming huge. Due to its complex composition and great harm to environment, municipal sludge must be managed properly. Thermochemical process such as pyrolysis is gaining academic attention for the valorisation and reduction of this waste. The pyrolysis liquids of sewage sludge contain large amounts of oxygen compounds with high viscosity, catalytic pyrolysis may be a solution for the improvement of its quality. Studies have shown that the mineral elements in ashes of sludge have catalytic effects. In this paper, sludge char was used as the catalysts for pyrolysis of municipal sludge to investigate the effect of different catalytic methods. Several kinds of metals were supported on sludge char to improve the catalytic effect. The reactor of catalytic treatment of vapors of sludge pyrolysis was designed. Thermogravimetric analysis was conducted first, it was found that weightless range of lipids, carbohydrates and proteins overlapped with the heating rate of 100℃/min. A horizontal tube reactor was used to research the pyrolysis of sludge for bio-oil with the addition of char. The influences of temperature as well as proportion of char to the yield, composition and physicochemical properties of pyrolysis liquid were considered. After that, Fe、 Cu、 Al and Ni were supported on the char respectively. Results showed that sludge char promote the hydrodeoxygenation and benzene’s ring-opening reaction of organic phase (OP) in pyrolysis liquids. The heating value and viscosity of OP were also improved. The char-supported Fe which was best for the hydrodeoxygenation favored the highest HHV (higher heating value) of OP for 35.48MJ/kg. The char-supported Ni favored the lowest viscosity with 64.29 cSt@20℃. A vertical fixed bed catalytic reactor was designed and produced, hot pyrolysis vapors coming from sludge ptrolysis in a horizontal tube reactor passed through the catalytic reactor filled with sludge char. The experiments have been done in different temperature matching and height of catalysts to determine optimum experimental conditions. The results showed that the suitable temperature matching for maximum yield of OP was 500/400 ℃. Comparing the condition of sludge pyrolysis with the addition of char, the content of oxygen compounds in OP reduced significantly. The catalytic effects of char performed in two aspects, the promotion of hydrodeoxygenation of OP as well as the transformation of aromatic hydrocarbons into phenol. the promoting effect for hydrodeoxygenation increased With metal supported, the physicochemical properties of OP improved significantly. The char-supported Ni favored the highest heating value of OP for 40.27MJ/kg, while the char-supported Ni favored the lowest viscosity of OP for 18.75cSt@20℃. In addition, the catalytic activity of sludge char was relatively stable. Based on the catalytic effects of sludge char on the vapors from municipal sludge
BY ZHANG Ya
Supervised by Prof. JIN Bao-sheng
School of Energy and Environment Southeast University September 2014
东南大Baidu Nhomakorabea学位论文独创性声明
东 南 大 学 学 位 论 文 独 创 性 声 明
东 南大学 2014 年 2014 年 月 月 日 日
2014 年 6 月
Experimental research and design of low-temperature catalytic pyrolysis of municipal sludge for bio-oil
A Thesis Submitted to SoutheastUniversity For the Academic Degree of Master of Engineering
研究生签名：
导师签名：
日期：
摘要
摘 要
城市污泥产量巨大且组成复杂，环境危害大，必须进行减量化无害化处置。低温热 解制油技术作为一种城市污泥资源化利用方式，正日益受到学术界的重视。污泥热解油 高热值有机相的氧含量高且粘度大， 催化热解是改善热解油品质的一个方向。 研究表明， 污泥灰分中富含具有催化作用的矿物质元素。本文以污泥残炭作为污泥热解催化剂，考 察不同催化方式对污泥热解制油的影响。利用残炭作为载体负载不同金属元素，考察改 性后残炭的催化制油效果，并开展残炭催化污泥热解气提质反应器的设计计算。 首先对污泥进行热重分析，发现在快速热解条件下（ 100℃/min） ，污泥中的脂质、 糖类和蛋白质的失重区间交叠。 利用水平管式炉开展残炭与污泥混合热解制油实验研究， 考察了热解温度，残炭添加比例对热解油产率、组分分布及理化特性的影响。并在残炭 上负载 Fe、Cu、Al、Ni 等金属元素，研究不同金属元素与残炭中固有矿物质对污泥热 解的协同催化作用。结果表明：残炭能够促进热解液有机相的加氢脱氧反应，并催化苯 环发生加氢开环反应。经残炭催化后，热解液有机相热值和粘度均得到改善。负载 Fe 的残炭对有机相加氢脱氧的促进效果最好，所得有机相高位热值最高为 35.48MJ/kg，负 载 Ni 的残炭催化所得有机相粘度最低为 64.29cSt@20℃。 利用自制立式固定床催化炉， 污泥在水平管式炉内热解产生的高温热解气穿催化炉 内残炭料层，考察双炉温度匹配、催化炉床料种类及残炭填装高度等参数对污泥热解制 油的影响。结果表明：双炉温度匹配为 500/400℃时有机相产率最大；相比残炭与污泥 混合热解工况，有机相含氧化合物含量显著降低。残炭对污泥热解气的催化作用主要表 现为：一是促进有机相加氢脱氧，二是促进芳烃的环化和芳构化反应生成 PAHs。残炭 负载金属后，对热解气加氢脱氧的促进作用增强，热解液的理化特性显著改善。其中负 载 Fe 的残炭催化所得有机相高位热值达 40.27MJ/kg， 负载 Ni 的残炭催化所得有机相粘 度仅为 18.75cSt@20℃。通过多次重复实验发现，残炭的催化活性稳定，不易失活。 基于污泥残炭对污泥热解气优异的催化特性， 提出了一种利用残炭催化污泥热解气 提质的循环流化床热解反应装置。在现有 50t/d 双床交互循环式污泥低温热解制油工业 示范系统的热解反应装置基础上，开展残炭催化污泥热解气提质反应器的设计计算，以 期为后续工程应用中污泥热解油的进一步提质提供参考。 关键词：城市污泥；催化热解；残炭；有机相；设计计算
II
Abstract
pyrolysis, the circulating fluidized bed reactor was developed to improve the quality of vapors from sludge pyrolysis with sludge char. For “50t/d interact circulation configuration of sludge low-temperature pyrolysis for bio-oil demonstration project” in Jurong of Jiangsu province, the design of the catalytic treatment reactor of vapors from sludge pyrolysis for quality improvement was conducted on the basis of pyrolysis reaction device, the design was conducted with the purpose of providing the references for future engineering applications. Key words: Municipal sludge; Catalytic pyrolysis; Char; Organic phase; Design calculation