53頁,41660個(gè)字,

摘要:
本文主要對由乙醇脫水制取乙烯，再由產(chǎn)物乙烯直接與苯烷基化反應(yīng)制取乙苯的連續(xù)化工藝路線展開研究，找到其適肩{的工藝條件。并對催化劑中所含微量水對反應(yīng)結(jié)果的影響進(jìn)行了考察。論文主要包括以下幾個(gè)方面:
分子篩催化劑上進(jìn)行的乙醇脫水反應(yīng)制取乙烯氣體，其中主要考察溫度和空速對反應(yīng)的影響，最終確定適肩{的工藝條件為:溫度2500C、反應(yīng)空速1 h-1,反應(yīng)壓力為常壓。在此條件下進(jìn)行脫水反應(yīng)，乙醇的轉(zhuǎn)化率可以達(dá)到94%以上，乙醇的利用率可以達(dá)到91%以上。
利用響應(yīng)面分析實(shí)驗(yàn)法(RSM，對p沸石改性催化劑及MCM-22改性催化
劑上進(jìn)行的苯的烷基化反應(yīng)進(jìn)行工藝探究，通過計(jì)算機(jī)模擬和實(shí)驗(yàn)驗(yàn)證，最終確定適,{的工藝條件。以p改性分子篩作為催化劑時(shí)的適肩{條件為溫度154 0C;空速2 h-1;乙烯和苯的物料摩爾比1:3。在此條件下進(jìn)行烷基化反應(yīng)，得到苯的轉(zhuǎn)化率為56.274%，乙苯的選擇性為86. 592%。以MCM-22改性分子篩作為催化劑時(shí)的適肩{條件為溫度150 0C;空速3.8 h-1;乙烯和苯的物料摩爾比1:6。在此條件下進(jìn)行烷基化反應(yīng)，得到苯的轉(zhuǎn)化率為20.142%，乙苯的選擇性為94.673% o所得實(shí)驗(yàn)值與計(jì)算機(jī)模擬結(jié)果相差極小，故采用RSM法優(yōu)化模擬的苯與乙烯在p沸石改性催化劑及MCM-22改性催化劑條件下的烷基化反應(yīng)實(shí)驗(yàn)條件參數(shù)準(zhǔn)確可靠，具有實(shí)用價(jià)值。
原料1中的微量水對催化劑的活性有很大的影響，微量水會(huì)在反應(yīng)進(jìn)行過程中占據(jù)催化劑的酸活性位，使得催化劑迅速失活，故在生產(chǎn)中要確保物料的純度。

關(guān)鍵詞:乙醇；乙烯；苯；乙苯；烷基化；β沸石催化劑；MCM-22催化劑；響應(yīng)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
目錄
摘要..............................................................................................................................I
ABSTRACT.................................................................................................................II
第1章文獻(xiàn)綜述.........................................................................................................1
1.1乙苯的相關(guān)概況...............................................................................................2
1.1.1 AlCl3法.....................................................................................................2
1.1.2分子篩烴化法.............................................................................................2
1.1.3催化精餾工藝
[15,16]
.....................................................................................5
1.1.4 Alene工藝.................................................................................................5
1.1.5 Dow化學(xué)稀乙烯工藝...............................................................................5
1.2乙醇脫水制乙烯的相關(guān)概況...........................................................................6
1.2.1乙醇法乙烯與石油裂解乙烯比較.............................................................6
1.2.2乙醇脫水制乙烯工藝比較.........................................................................6
1.3烷基化反應(yīng)的催化劑.......................................................................................7
1.3.1 AlCl3催化劑.............................................................................................7
1.3.2分子篩類催化劑.........................................................................................8
1.3.3催化劑的失活與再生.................................................................................9
1.4反應(yīng)器.............................................................................................................10
1.5烷基化劑.........................................................................................................11
1.6烷基化反應(yīng)機(jī)理
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.........................................................................................11
第2章實(shí)驗(yàn)部分.....................................................................................................13
2.1實(shí)驗(yàn)原料及來源.............................................................................................13
2.1.1催化劑.......................................................................................................13
2.1.2試劑...........................................................................................................13
2.2反應(yīng)裝置與設(shè)備.............................................................................................14
2.2.1實(shí)驗(yàn)用微型反應(yīng)器...................................................................................14
2.2.2催化劑酸性測定裝置...............................................................................15
2.3組成定量分析及轉(zhuǎn)化率和選擇性的計(jì)算.....................................................15
V
2.3.1組成定量分析...........................................................................................15
2.3.2相對校正因子的測定...............................................................................17
2.4乙醇在分子篩上脫水反應(yīng)的研究.................................................................18
2.4.1實(shí)驗(yàn)步驟...................................................................................................18
2.4.2分析及計(jì)算結(jié)果.......................................................................................19
2.5苯和乙烯在分子篩上的烷基化反應(yīng)研究.....................................................19
2.5.1實(shí)驗(yàn)步驟.....................................................................................................19
2.5.2分析及計(jì)算結(jié)果.........................................................................................19
2.6水對烷基化反應(yīng)的影響.................................................................................20
2.7催化劑穩(wěn)定性粗探.........................................................................................20
2.7.1 XRD檢測.................................................................................................20
2.7.2熱重和差熱分析.......................................................................................20
第3章乙醇脫水制乙烯.........................................................................................22
3.1催化反應(yīng)預(yù)實(shí)驗(yàn).............................................................................................22
3.2氣體產(chǎn)物定量分析近似處理..........................................................................22
3.3乙醇在分子篩上脫水制乙烯..........................................................................23
3.3.1反應(yīng)溫度對脫水反應(yīng)的影響...................................................................23
3.3.2反應(yīng)空速對脫水反應(yīng)的影響...................................................................24
3.4乙醇的脫水反應(yīng)工藝小結(jié)..............................................................................25
第4章烷基化實(shí)驗(yàn)方法的選擇...............................................................................26
4.1實(shí)驗(yàn)方法介紹.................................................................................................26
4.1.1正交實(shí)驗(yàn)法...............................................................................................26
4.1.2響應(yīng)面實(shí)驗(yàn)法
[35]
......................................................................................26
4.1.3方法的確立...............................................................................................27
4.2實(shí)驗(yàn)部分介紹..................................................................................................27
4.2.1影響因素的確定.......................................................................................27
4.2.2響應(yīng)面實(shí)驗(yàn)...............................................................................................27
4.3數(shù)據(jù)處理部分介紹..........................................................................................27
4.3.1計(jì)算機(jī)數(shù)據(jù)處理
[35]
..................................................................................28
VI
4.3.2模型的建立及方差分析...........................................................................28
4.3.3模型的驗(yàn)證...............................................................................................29
第5章苯和乙烯的烷基化反應(yīng)...............................................................................30
5.1組成定量分析.................................................................................................30
5.1.1校正因子的測定.......................................................................................30
5.1.2校正因子的檢驗(yàn).......................................................................................32
5.2苯和乙烯在Β沸石改性催化劑上的烷基化反應(yīng).........................................33
5.2.1單因素實(shí)驗(yàn)...............................................................................................33
5.2.2響應(yīng)面實(shí)驗(yàn)...............................................................................................36
5.3苯和乙烯在MCM-22沸石改性催化劑上的烷基化反應(yīng).............................42
5.3.1單因素實(shí)驗(yàn)...............................................................................................42
5.3.2響應(yīng)面實(shí)驗(yàn)...............................................................................................46
5.4苯與乙烯的烷基化反應(yīng)工藝小結(jié).................................................................52
5.4.1苯與乙烯在β改性沸石上的烷基化反應(yīng)小結(jié).......................................52
5.4.2苯與乙烯在MCM-22改性沸石上的烷基化反應(yīng)小結(jié).........................52
5.5水對烷基化反應(yīng)的影響.................................................................................53
5.5.1吸附區(qū)間與溫度關(guān)系的確定...................................................................53
5.5.2考察對象的確定.......................................................................................53
5.5.3考察水對烷基化反應(yīng)的影響...................................................................55
5.5.4檢驗(yàn)及小結(jié)...............................................................................................57
5.6催化劑穩(wěn)定性粗探.........................................................................................57
5.6.1 XRD檢測.................................................................................................57
5.6.2熱重和差熱分析.......................................................................................59
第6章結(jié)論...............................................................................................................60
參考文獻(xiàn).....................................................................................................................61
碩士論文期間發(fā)表的論文.........................................................................................63
致謝..............................................................................................................................64