乙醇为烷基化剂的工艺研究.doc
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乙醇为烷基化剂的工艺研究,53页,41660个字,摘要:本文主要对由乙醇脱水制取乙烯，再由产物乙烯直接与苯烷基化反应制取乙苯的连续化工艺路线展开研究，找到其适肩{的工艺条件。并对催化剂中所含微量水对反应结果的影响进行了考察。论文主要包括以下几个方面:分子筛催化剂上进行的乙醇脱水反应制取乙烯气体，其中主要考察温度和空速对反应的影响，最终确定适肩{...
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53页,41660个字,
摘要:
本文主要对由乙醇脱水制取乙烯，再由产物乙烯直接与苯烷基化反应制取乙苯的连续化工艺路线展开研究，找到其适肩{的工艺条件。并对催化剂中所含微量水对反应结果的影响进行了考察。论文主要包括以下几个方面:
分子筛催化剂上进行的乙醇脱水反应制取乙烯气体，其中主要考察温度和空速对反应的影响，最终确定适肩{的工艺条件为:温度2500C、反应空速1 h-1,反应压力为常压。在此条件下进行脱水反应，乙醇的转化率可以达到94%以上，乙醇的利用率可以达到91%以上。
利用响应面分析实验法(RSM，对p沸石改性催化剂及MCM-22改性催化
剂上进行的苯的烷基化反应进行工艺探究，通过计算机模拟和实验验证，最终确定适,{的工艺条件。以p改性分子筛作为催化剂时的适肩{条件为温度154 0C;空速2 h-1;乙烯和苯的物料摩尔比1:3。在此条件下进行烷基化反应，得到苯的转化率为56.274%，乙苯的选择性为86. 592%。以MCM-22改性分子筛作为催化剂时的适肩{条件为温度150 0C;空速3.8 h-1;乙烯和苯的物料摩尔比1:6。在此条件下进行烷基化反应，得到苯的转化率为20.142%，乙苯的选择性为94.673% o所得实验值与计算机模拟结果相差极小，故采用RSM法优化模拟的苯与乙烯在p沸石改性催化剂及MCM-22改性催化剂条件下的烷基化反应实验条件参数准确可靠，具有实用价值。
原料1中的微量水对催化剂的活性有很大的影响，微量水会在反应进行过程中占据催化剂的酸活性位，使得催化剂迅速失活，故在生产中要确保物料的纯度。
关键词:乙醇；乙烯；苯；乙苯；烷基化；β沸石催化剂；MCM-22催化剂；响应面法
IIETHANOL AS ALKYLATING AGENT OF TECHNOLOGY
Abstract
Continuous Process Route between the dehydration of ethanol produces ethylene And the reaction of alkylation of benzene with ethylbenzene directly was investigated
in this paper.in order to find out proper Process Route.At the same time,the impaction of reaction results from trace water contained in the catalyst were studied.
The paper content several facets as follows：
The dehydration of ethanol produces ethylene on Zeolite Catalyst,effects of temperature and space velocity on the reaction were mainly studied.ultimately
suitable process conditions were determined.they were:temperature:250℃,space
velocity:1h-1,reaction pressure is atmospheric pressure.Under these conditions,
dehydration reaction were carried out,and ethanol conversion rate can reach above
94%,utilization of ethanol can reach 91%.
The parameters ofβ-zeolite-base catalyst and MCM-22 modified catalyst for
preparing ethylbenzene from benzene and ethylene by alkylation were optimized
using response surface method(RSM).Forβ-zeolite-base catalyst,a response surface
method was conducted to get the following optimal parameters:reaction temperature:
154℃,reaction airspeed:2 h
-1
and reaction molar ratio:1/3.The conversion of
benzene and selection of ethylbenzene under these optimal parameters respectively
are 56.274%and 86.592%.For MCM-22 modified catalyst,a response surface
method was conducted to get the following optimal parameters:reaction temperature:
150℃,reaction airspeed:3.8 h
-1
and reaction molar ratio:1/6.The conversion of
benzene and selection of ethylbenzene under these optimal parameters respectively
are 20.142%and 94.673%.The experimental values are very similar to the computer
simulation values,consequently,β-zeolite-base catalyst and MCM-22 modified
catalyst for preparing ethylbenzene from benzene and ethylene by alkylation using
response surface method is not only accurate and reliable,but also has practical
III
values.
The impaction of the catalytic activity of trace water in the Raw.Trace water
would occupy the acid catalyst active site in the process,in the result,catalyst
deactivated rapidly,so it was ensured the purity of materials in production.
Key words:ethanol;ethylene;benzene;ethylbenzene;alkylation;β-zeolite-base;
MCM-22 catalyst;Response Surface Methodology
IV
目录
摘要..............................................................................................................................I
ABSTRACT.................................................................................................................II
第1章文献综述.........................................................................................................1
1.1乙苯的相关概况...............................................................................................2
1.1.1 AlCl3法.....................................................................................................2
1.1.2分子筛烃化法.............................................................................................2
1.1.3催化精馏工艺
[15,16]
.....................................................................................5
1.1.4 Alene工艺.................................................................................................5
1.1.5 Dow化学稀乙烯工艺...............................................................................5
1.2乙醇脱水制乙烯的相关概况...........................................................................6
1.2.1乙醇法乙烯与石油裂解乙烯比较.............................................................6
1.2.2乙醇脱水制乙烯工艺比较.........................................................................6
1.3烷基化反应的催化剂.......................................................................................7
1.3.1 AlCl3催化剂.............................................................................................7
1.3.2分子筛类催化剂.........................................................................................8
1.3.3催化剂的失活与再生.................................................................................9
1.4反应器.............................................................................................................10
1.5烷基化剂.........................................................................................................11
1.6烷基化反应机理
[30]
.........................................................................................11
第2章实验部分.....................................................................................................13
2.1实验原料及来源.............................................................................................13
2.1.1催化剂.......................................................................................................13
2.1.2试剂...........................................................................................................13
2.2反应装置与设备.............................................................................................14
2.2.1实验用微型反应器...................................................................................14
2.2.2催化剂酸性测定装置...............................................................................15
2.3组成定量分析及转化率和选择性的计算.....................................................15
V
2.3.1组成定量分析...........................................................................................15
2.3.2相对校正因子的测定...............................................................................17
2.4乙醇在分子筛上脱水反应的研究.................................................................18
2.4.1实验步骤...................................................................................................18
2.4.2分析及计算结果.......................................................................................19
2.5苯和乙烯在分子筛上的烷基化反应研究.....................................................19
2.5.1实验步骤.....................................................................................................19
2.5.2分析及计算结果.........................................................................................19
2.6水对烷基化反应的影响.................................................................................20
2.7催化剂稳定性粗探.........................................................................................20
2.7.1 XRD检测.................................................................................................20
2.7.2热重和差热分析.......................................................................................20
第3章乙醇脱水制乙烯.........................................................................................22
3.1催化反应预实验.............................................................................................22
3.2气体产物定量分析近似处理..........................................................................22
3.3乙醇在分子筛上脱水制乙烯..........................................................................23
3.3.1反应温度对脱水反应的影响...................................................................23
3.3.2反应空速对脱水反应的影响...................................................................24
3.4乙醇的脱水反应工艺小结..............................................................................25
第4章烷基化实验方法的选择...............................................................................26
4.1实验方法介绍.................................................................................................26
4.1.1正交实验法...............................................................................................26
4.1.2响应面实验法
[35]
......................................................................................26
4.1.3方法的确立...............................................................................................27
4.2实验部分介绍..................................................................................................27
4.2.1影响因素的确定.......................................................................................27
4.2.2响应面实验...............................................................................................27
4.3数据处理部分介绍..........................................................................................27
4.3.1计算机数据处理
[35]
..................................................................................28
VI
4.3.2模型的建立及方差分析...........................................................................28
4.3.3模型的验证...............................................................................................29
第5章苯和乙烯的烷基化反应...............................................................................30
5.1组成定量分析.................................................................................................30
5.1.1校正因子的测定.......................................................................................30
5.1.2校正因子的检验.......................................................................................32
5.2苯和乙烯在Β沸石改性催化剂上的烷基化反应.........................................33
5.2.1单因素实验...............................................................................................33
5.2.2响应面实验...............................................................................................36
5.3苯和乙烯在MCM-22沸石改性催化剂上的烷基化反应.............................42
5.3.1单因素实验...............................................................................................42
5.3.2响应面实验...............................................................................................46
5.4苯与乙烯的烷基化反应工艺小结.................................................................52
5.4.1苯与乙烯在β改性沸石上的烷基化反应小结.......................................52
5.4.2苯与乙烯在MCM-22改性沸石上的烷基化反应小结.........................52
5.5水对烷基化反应的影响.................................................................................53
5.5.1吸附区间与温度关系的确定...................................................................53
5.5.2考察对象的确定.......................................................................................53
5.5.3考察水对烷基化反应的影响...................................................................55
5.5.4检验及小结...............................................................................................57
5.6催化剂稳定性粗探.........................................................................................57
5.6.1 XRD检测.................................................................................................57
5.6.2热重和差热分析.......................................................................................59
第6章结论...............................................................................................................60
参考文献.....................................................................................................................61
硕士论文期间发表的论文.........................................................................................63
致谢..............................................................................................................................64
摘要:
本文主要对由乙醇脱水制取乙烯，再由产物乙烯直接与苯烷基化反应制取乙苯的连续化工艺路线展开研究，找到其适肩{的工艺条件。并对催化剂中所含微量水对反应结果的影响进行了考察。论文主要包括以下几个方面:
分子筛催化剂上进行的乙醇脱水反应制取乙烯气体，其中主要考察温度和空速对反应的影响，最终确定适肩{的工艺条件为:温度2500C、反应空速1 h-1,反应压力为常压。在此条件下进行脱水反应，乙醇的转化率可以达到94%以上，乙醇的利用率可以达到91%以上。
利用响应面分析实验法(RSM，对p沸石改性催化剂及MCM-22改性催化
剂上进行的苯的烷基化反应进行工艺探究，通过计算机模拟和实验验证，最终确定适,{的工艺条件。以p改性分子筛作为催化剂时的适肩{条件为温度154 0C;空速2 h-1;乙烯和苯的物料摩尔比1:3。在此条件下进行烷基化反应，得到苯的转化率为56.274%，乙苯的选择性为86. 592%。以MCM-22改性分子筛作为催化剂时的适肩{条件为温度150 0C;空速3.8 h-1;乙烯和苯的物料摩尔比1:6。在此条件下进行烷基化反应，得到苯的转化率为20.142%，乙苯的选择性为94.673% o所得实验值与计算机模拟结果相差极小，故采用RSM法优化模拟的苯与乙烯在p沸石改性催化剂及MCM-22改性催化剂条件下的烷基化反应实验条件参数准确可靠，具有实用价值。
原料1中的微量水对催化剂的活性有很大的影响，微量水会在反应进行过程中占据催化剂的酸活性位，使得催化剂迅速失活，故在生产中要确保物料的纯度。
关键词:乙醇；乙烯；苯；乙苯；烷基化；β沸石催化剂；MCM-22催化剂；响应面法
IIETHANOL AS ALKYLATING AGENT OF TECHNOLOGY
Abstract
Continuous Process Route between the dehydration of ethanol produces ethylene And the reaction of alkylation of benzene with ethylbenzene directly was investigated
in this paper.in order to find out proper Process Route.At the same time,the impaction of reaction results from trace water contained in the catalyst were studied.
The paper content several facets as follows：
The dehydration of ethanol produces ethylene on Zeolite Catalyst,effects of temperature and space velocity on the reaction were mainly studied.ultimately
suitable process conditions were determined.they were:temperature:250℃,space
velocity:1h-1,reaction pressure is atmospheric pressure.Under these conditions,
dehydration reaction were carried out,and ethanol conversion rate can reach above
94%,utilization of ethanol can reach 91%.
The parameters ofβ-zeolite-base catalyst and MCM-22 modified catalyst for
preparing ethylbenzene from benzene and ethylene by alkylation were optimized
using response surface method(RSM).Forβ-zeolite-base catalyst,a response surface
method was conducted to get the following optimal parameters:reaction temperature:
154℃,reaction airspeed:2 h
-1
and reaction molar ratio:1/3.The conversion of
benzene and selection of ethylbenzene under these optimal parameters respectively
are 56.274%and 86.592%.For MCM-22 modified catalyst,a response surface
method was conducted to get the following optimal parameters:reaction temperature:
150℃,reaction airspeed:3.8 h
-1
and reaction molar ratio:1/6.The conversion of
benzene and selection of ethylbenzene under these optimal parameters respectively
are 20.142%and 94.673%.The experimental values are very similar to the computer
simulation values,consequently,β-zeolite-base catalyst and MCM-22 modified
catalyst for preparing ethylbenzene from benzene and ethylene by alkylation using
response surface method is not only accurate and reliable,but also has practical
III
values.
The impaction of the catalytic activity of trace water in the Raw.Trace water
would occupy the acid catalyst active site in the process,in the result,catalyst
deactivated rapidly,so it was ensured the purity of materials in production.
Key words:ethanol;ethylene;benzene;ethylbenzene;alkylation;β-zeolite-base;
MCM-22 catalyst;Response Surface Methodology
IV
目录
摘要..............................................................................................................................I
ABSTRACT.................................................................................................................II
第1章文献综述.........................................................................................................1
1.1乙苯的相关概况...............................................................................................2
1.1.1 AlCl3法.....................................................................................................2
1.1.2分子筛烃化法.............................................................................................2
1.1.3催化精馏工艺
[15,16]
.....................................................................................5
1.1.4 Alene工艺.................................................................................................5
1.1.5 Dow化学稀乙烯工艺...............................................................................5
1.2乙醇脱水制乙烯的相关概况...........................................................................6
1.2.1乙醇法乙烯与石油裂解乙烯比较.............................................................6
1.2.2乙醇脱水制乙烯工艺比较.........................................................................6
1.3烷基化反应的催化剂.......................................................................................7
1.3.1 AlCl3催化剂.............................................................................................7
1.3.2分子筛类催化剂.........................................................................................8
1.3.3催化剂的失活与再生.................................................................................9
1.4反应器.............................................................................................................10
1.5烷基化剂.........................................................................................................11
1.6烷基化反应机理
[30]
.........................................................................................11
第2章实验部分.....................................................................................................13
2.1实验原料及来源.............................................................................................13
2.1.1催化剂.......................................................................................................13
2.1.2试剂...........................................................................................................13
2.2反应装置与设备.............................................................................................14
2.2.1实验用微型反应器...................................................................................14
2.2.2催化剂酸性测定装置...............................................................................15
2.3组成定量分析及转化率和选择性的计算.....................................................15
V
2.3.1组成定量分析...........................................................................................15
2.3.2相对校正因子的测定...............................................................................17
2.4乙醇在分子筛上脱水反应的研究.................................................................18
2.4.1实验步骤...................................................................................................18
2.4.2分析及计算结果.......................................................................................19
2.5苯和乙烯在分子筛上的烷基化反应研究.....................................................19
2.5.1实验步骤.....................................................................................................19
2.5.2分析及计算结果.........................................................................................19
2.6水对烷基化反应的影响.................................................................................20
2.7催化剂稳定性粗探.........................................................................................20
2.7.1 XRD检测.................................................................................................20
2.7.2热重和差热分析.......................................................................................20
第3章乙醇脱水制乙烯.........................................................................................22
3.1催化反应预实验.............................................................................................22
3.2气体产物定量分析近似处理..........................................................................22
3.3乙醇在分子筛上脱水制乙烯..........................................................................23
3.3.1反应温度对脱水反应的影响...................................................................23
3.3.2反应空速对脱水反应的影响...................................................................24
3.4乙醇的脱水反应工艺小结..............................................................................25
第4章烷基化实验方法的选择...............................................................................26
4.1实验方法介绍.................................................................................................26
4.1.1正交实验法...............................................................................................26
4.1.2响应面实验法
[35]
......................................................................................26
4.1.3方法的确立...............................................................................................27
4.2实验部分介绍..................................................................................................27
4.2.1影响因素的确定.......................................................................................27
4.2.2响应面实验...............................................................................................27
4.3数据处理部分介绍..........................................................................................27
4.3.1计算机数据处理
[35]
..................................................................................28
VI
4.3.2模型的建立及方差分析...........................................................................28
4.3.3模型的验证...............................................................................................29
第5章苯和乙烯的烷基化反应...............................................................................30
5.1组成定量分析.................................................................................................30
5.1.1校正因子的测定.......................................................................................30
5.1.2校正因子的检验.......................................................................................32
5.2苯和乙烯在Β沸石改性催化剂上的烷基化反应.........................................33
5.2.1单因素实验...............................................................................................33
5.2.2响应面实验...............................................................................................36
5.3苯和乙烯在MCM-22沸石改性催化剂上的烷基化反应.............................42
5.3.1单因素实验...............................................................................................42
5.3.2响应面实验...............................................................................................46
5.4苯与乙烯的烷基化反应工艺小结.................................................................52
5.4.1苯与乙烯在β改性沸石上的烷基化反应小结.......................................52
5.4.2苯与乙烯在MCM-22改性沸石上的烷基化反应小结.........................52
5.5水对烷基化反应的影响.................................................................................53
5.5.1吸附区间与温度关系的确定...................................................................53
5.5.2考察对象的确定.......................................................................................53
5.5.3考察水对烷基化反应的影响...................................................................55
5.5.4检验及小结...............................................................................................57
5.6催化剂稳定性粗探.........................................................................................57
5.6.1 XRD检测.................................................................................................57
5.6.2热重和差热分析.......................................................................................59
第6章结论...............................................................................................................60
参考文献.....................................................................................................................61
硕士论文期间发表的论文.........................................................................................63
致谢..............................................................................................................................64
