基团保护法1，3-二氯丙烯制备1，3-丙二醇工艺研究
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摘要
本文对基团保护法1,3-二氯丙烯制备1,3-丙二醇工艺的研究主要集中在催化剂制备工艺及加氢机理的探讨，主要分为以下三个部分：
第一部分在常压加氢反应器中进行。首先采用浸渍还原法制备了一系列的Pd／C催化剂，研究活性炭活化方法、负载量、改性剂种类以及用量和溶剂对醋酸-3-氯丙烯酯加氢性能的影响。结果表明：磷酸活化过的活性炭为载体可以获得较高的选择性；高负载量会降低选择性，但是下降到5％以后选择性变化不大；少量亚磷酸可以提高15％～20％的选择性，但是活性下降到15％～20％；非极性溶剂中可以保持较高的选择性40％～50％。并通过实验证明加氢脱氯并非是由于产物发生氢解所致，加氢和氢解是两个平行发生的反应。
第二部分首先用GC—MS对产物进行了定性分析，得出了反应的网络图，由于C—O键也发生了氢解，利用内标校正面积归一法代替面积归一法，对反应产物进行了更加准确的跟踪。之后，集中研究Pd／γ-Al_2O_3制备工艺对反应的影响。评价结果表明，催化剂在如下条件主选择性最优(40.53％)：
最后，提出选择性降低的可能原因：C—Cl氢解可能是通过乙烯基氯和烯丙基氯和活性中心相互作用两种机理来进行；C—O键氢解一方面可能由于O原子被活性中心吸附进而发生断裂，另一方面可能是由于生成氯化氢可以促进C—O键断裂。
最后一部分中自行搭建了一套高压釜(＜1.5MPa)，在排除内外扩散的影响之后，进行了动力学实验。采用Langmuir-Hinshelwood动力学方程并结合一级平行
浙江大学硕士学位论文
反应速率方程，建立了一套参数求取方法，并最终得到了本征反应速率方程:
、·鲁
伙·令
、一令
0 .5433 x 10‘xe即(-
48064
RT
)P 0843吼
·3 .5809 x 108 Xe二(j粤奖)尸。‘，sc月
大1
=0 .0592 x 10‘xe却(-
44048
RT
、P08255C，
，J，
实验值和模型值比较的结果表明，相对误差在5%以内。同时还深入分析了温度、
压力和反应进程对选择性的影响。
In this thesis, hydrogenation of 3-chloroallylacetate, which is the key step in the process of 1,3-propanediol from 1,3-dichloropropene by group-protecting technology, is studied.
Experiments can be divided into three parts, as follows:
In the first part, tentative evaluation experiments were carried out in hydrogenation reactor at atmospheric pressure and 293.15K. Firstly, a series of Pd/C catalysts were prepared by impregnation-reduction method, and effects of activation method of activated carbon, Pd loadings, modifiers and quantity of one of them were investigated. Findings were as follows: carbon activated by phosphoric acid achieved the highest selectivity among all the kinds of carbons; selectivity dropped slightly from the loading of 10%, but stopped at 5%; phosphorous acid elevated selectivity by up to 15%~20%, but activity dropped sharply down to 15%~20% or so; non-polar solvents improved selectivity. Initial conclusion was drawn that hydrodehalogenaion didn't happen to the main product, thus hydrogenation and hydrodehalogenaion were parallel.
In the second part, qualitative analysis of the products was carried out by GC-MS, which led to the buildup of the reaction network, it showed that hydrogenolysis of C-O bond took place.apart from that of C-C1 bond. Based on the reaction network, corrected area normalization method using octane as internal standard was adopted in order to give more accurate data. After that, emphasizes were concentrated on the process of the preparation of Pd/y-Al2O3, in which we found that the highest selectivity was achieved under the following conditions:
Meanwhile, the reason of low selectivity were further discussed: hydrogenolysis of C-C1 bond might come from the interaction of active sites with vinyl chlorine and allyl chlorine; and that of C-0 bond might result from either strong adsorption of 0 atoms on the active sites or improving effect of resulting HCI.
In the Last part, the entire steps of this multiphase catalytic reaction were analyzed, and then internal diffusion and external diffusion were eliminated respectively by improving stirring speed and adopting little particles (r<34um accounted for 93% ), and then a Langmuir-Hinshelwood type kinetic model was evaluated and further simplified.
The intrinsic kinetics of catalytic hydrogenation of 3-chloroallylacetate on Pd/gamma-Al2O3 was investigated at temperature from 293.15 K to 313.15 K (l.OMPa) and under pressure from 0.6MPa to 1 .OMPa (303.15K). Based on the experimental data, the parameters in this simplified kinetic model were acquired by data-fitting. The entire intrinsic reaction equations are as follows:
the relative errors between the experiment data and calculated ones were below 5 percents. The evolution of selectivity and the effects of reaction temperature and hydrogen pressure were further investigated.
第一部分在常压加氢反应器中进行。首先采用浸渍还原法制备了一系列的Pd／C催化剂，研究活性炭活化方法、负载量、改性剂种类以及用量和溶剂对醋酸-3-氯丙烯酯加氢性能的影响。结果表明：磷酸活化过的活性炭为载体可以获得较高的选择性；高负载量会降低选择性，但是下降到5％以后选择性变化不大；少量亚磷酸可以提高15％～20％的选择性，但是活性下降到15％～20％；非极性溶剂中可以保持较高的选择性40％～50％。并通过实验证明加氢脱氯并非是由于产物发生氢解所致，加氢和氢解是两个平行发生的反应。
第二部分首先用GC—MS对产物进行了定性分析，得出了反应的网络图，由于C—O键也发生了氢解，利用内标校正面积归一法代替面积归一法，对反应产物进行了更加准确的跟踪。之后，集中研究Pd／γ-Al_2O_3制备工艺对反应的影响。评价结果表明，催化剂在如下条件主选择性最优(40.53％)：
最后，提出选择性降低的可能原因：C—Cl氢解可能是通过乙烯基氯和烯丙基氯和活性中心相互作用两种机理来进行；C—O键氢解一方面可能由于O原子被活性中心吸附进而发生断裂，另一方面可能是由于生成氯化氢可以促进C—O键断裂。
最后一部分中自行搭建了一套高压釜(＜1.5MPa)，在排除内外扩散的影响之后，进行了动力学实验。采用Langmuir-Hinshelwood动力学方程并结合一级平行
浙江大学硕士学位论文
反应速率方程，建立了一套参数求取方法，并最终得到了本征反应速率方程:
、·鲁
伙·令
、一令
0 .5433 x 10‘xe即(-
48064
RT
)P 0843吼
·3 .5809 x 108 Xe二(j粤奖)尸。‘，sc月
大1
=0 .0592 x 10‘xe却(-
44048
RT
、P08255C，
，J，
实验值和模型值比较的结果表明，相对误差在5%以内。同时还深入分析了温度、
压力和反应进程对选择性的影响。
In this thesis, hydrogenation of 3-chloroallylacetate, which is the key step in the process of 1,3-propanediol from 1,3-dichloropropene by group-protecting technology, is studied.
Experiments can be divided into three parts, as follows:
In the first part, tentative evaluation experiments were carried out in hydrogenation reactor at atmospheric pressure and 293.15K. Firstly, a series of Pd/C catalysts were prepared by impregnation-reduction method, and effects of activation method of activated carbon, Pd loadings, modifiers and quantity of one of them were investigated. Findings were as follows: carbon activated by phosphoric acid achieved the highest selectivity among all the kinds of carbons; selectivity dropped slightly from the loading of 10%, but stopped at 5%; phosphorous acid elevated selectivity by up to 15%~20%, but activity dropped sharply down to 15%~20% or so; non-polar solvents improved selectivity. Initial conclusion was drawn that hydrodehalogenaion didn't happen to the main product, thus hydrogenation and hydrodehalogenaion were parallel.
In the second part, qualitative analysis of the products was carried out by GC-MS, which led to the buildup of the reaction network, it showed that hydrogenolysis of C-O bond took place.apart from that of C-C1 bond. Based on the reaction network, corrected area normalization method using octane as internal standard was adopted in order to give more accurate data. After that, emphasizes were concentrated on the process of the preparation of Pd/y-Al2O3, in which we found that the highest selectivity was achieved under the following conditions:
Meanwhile, the reason of low selectivity were further discussed: hydrogenolysis of C-C1 bond might come from the interaction of active sites with vinyl chlorine and allyl chlorine; and that of C-0 bond might result from either strong adsorption of 0 atoms on the active sites or improving effect of resulting HCI.
In the Last part, the entire steps of this multiphase catalytic reaction were analyzed, and then internal diffusion and external diffusion were eliminated respectively by improving stirring speed and adopting little particles (r<34um accounted for 93% ), and then a Langmuir-Hinshelwood type kinetic model was evaluated and further simplified.
The intrinsic kinetics of catalytic hydrogenation of 3-chloroallylacetate on Pd/gamma-Al2O3 was investigated at temperature from 293.15 K to 313.15 K (l.OMPa) and under pressure from 0.6MPa to 1 .OMPa (303.15K). Based on the experimental data, the parameters in this simplified kinetic model were acquired by data-fitting. The entire intrinsic reaction equations are as follows:
the relative errors between the experiment data and calculated ones were below 5 percents. The evolution of selectivity and the effects of reaction temperature and hydrogen pressure were further investigated.
引文
1．世界PPT生产状况，精细化工原料及中间体，2003．1
2．PTT塑料市场前景广阔，浙江化工，2003
3．PTT聚酯市场有待扩大，中国塑料信息，2002
4．郭青松，羰基合成1，3-PDO催化剂和工艺研究，浙江大学硕士学位论文，2002．1
5．王剑锋，李慧，1，3-丙二醇的工业应用和生产，发展论坛
6．杨菊群，王幸宜，1，3-丙二醇的合成工艺研究 化学工业与工程技术
7. Wiu u,Muller R J,Widdeeke H,Deckwer W D.Syntheses,properties and biodegradability of polyesters based on 1,3-propanediol.Makromol.Chem.Phys. 1994, 195:793～802
8．姜兴茂，1，3-丙二醇的合成，第六期《上海化工》
9．杨佳庆，黄象安，顾利霞，1，3—丙二醇合成新进展，1999，Vol．22合成纤维工业
10．王熙庭，陈曼华，1，3-丙二醇生产方法及用途，煤化工，2000，第四期
11．浙江化工，2003，34(2)，31-32
12．甲醛与甲醇，2003(1)，40-40
13. http://www.hnrcsc.com
14．丁士均，丁红育，DD混剂的综合利用，氯碱工业，1994
15．农药，1973．3，24—26
16. United States Patent:5,914,432
17. UK Patent Application GB2,108,953A
18．恽魁宏，《有机化学》，高等教育出版社，1982，p175
19. G.E.Ham,et al.,J.Org.Chem.,29,194 (1964)
20. U.S.P. 3,179,705
21. GB1008175
22. U.S.E 4,899,001
23. U.S.E 5914432 (1999年)
24. Thomas Allmendinger ; Christian Dandois & Bernhard Walliser, Tetrahedron
Lett.32(1991),2735
25. E.J.Mcmullen, et al., J.Am.Chem.Soc. 76,5636(1954)
26. J.Org.Chem.1979,44(8),1348～9(eng)
27．姜麟忠，《催化氢化在有机合成中的应用》，化学工业出版社，p123
28．Morris Freifelder，《有机合成中的催化氢化》，安徽省化工研究所
29．张杰，Cu,Ni/γ-Al2O3催化加氢动力学与应用研究，浙江大学博士论文，2001．6
30. United States Patent:3,179,705
31. Mozingo, R ;Org.Synth.Coll.Vol.1955,3,685
32. Alexander, E. R .;Cope,A.C.;J.Am.Chem.Soc.1944,66,886
33．单绍军等，催化加氢制备对氯邻氨基苯酚，染料工业，Vol38(2001)，p5
34．宋东明，李树德，霍世勇，邻硝基氯苯催化加氢的选择性，大连理工大学学报，Vol35(1)，330
35．自彦兵，6-氯-3-硝基甲苯4-磺酸液相加氢制备CLT酸的研究，化工科技，1998，6(3)：34～39
36. J.R.Kosak: Hydrogenation of Haloaromatic Nitro Compound, Catalysis in Organic Synthesis
37. J.Catalysis, 83,238-241(1983)
38．金松寿等，《有机催化》，上海科学技术出版社，1986
39．A．P．G．凯布默，F．范兰特威克，《合成有机化学中的氢化与氢解》，科学出版社，p160；p4
40．姚蒙正，陈侣柏，王家儒，《精细化工产品合成原理》，中国石化出版社，p180
41．吴越，《催化化学》，科学出版社，2000，上册 p9
42．李绍芬，《反应工程》，化学工业出版社，2002．6
43．李绍芬，《化学与催化反应工程》，化学工业出版社，1986．5
44．陈甘棠，《化学反应工程》，化学工业出版社，1990．11
45．钟邦克，《精细化工过程催化作用》，中国石化出版社，2002．8
46．陈怀九，1，2-二氯丙烷和1，3-二氯丙烯混合物氯化新工艺，石油化工，1993
2．PTT塑料市场前景广阔，浙江化工，2003
3．PTT聚酯市场有待扩大，中国塑料信息，2002
4．郭青松，羰基合成1，3-PDO催化剂和工艺研究，浙江大学硕士学位论文，2002．1
5．王剑锋，李慧，1，3-丙二醇的工业应用和生产，发展论坛
6．杨菊群，王幸宜，1，3-丙二醇的合成工艺研究 化学工业与工程技术
7. Wiu u,Muller R J,Widdeeke H,Deckwer W D.Syntheses,properties and biodegradability of polyesters based on 1,3-propanediol.Makromol.Chem.Phys. 1994, 195:793～802
8．姜兴茂，1，3-丙二醇的合成，第六期《上海化工》
9．杨佳庆，黄象安，顾利霞，1，3—丙二醇合成新进展，1999，Vol．22合成纤维工业
10．王熙庭，陈曼华，1，3-丙二醇生产方法及用途，煤化工，2000，第四期
11．浙江化工，2003，34(2)，31-32
12．甲醛与甲醇，2003(1)，40-40
13. http://www.hnrcsc.com
14．丁士均，丁红育，DD混剂的综合利用，氯碱工业，1994
15．农药，1973．3，24—26
16. United States Patent:5,914,432
17. UK Patent Application GB2,108,953A
18．恽魁宏，《有机化学》，高等教育出版社，1982，p175
19. G.E.Ham,et al.,J.Org.Chem.,29,194 (1964)
20. U.S.P. 3,179,705
21. GB1008175
22. U.S.E 4,899,001
23. U.S.E 5914432 (1999年)
24. Thomas Allmendinger ; Christian Dandois & Bernhard Walliser, Tetrahedron
Lett.32(1991),2735
25. E.J.Mcmullen, et al., J.Am.Chem.Soc. 76,5636(1954)
26. J.Org.Chem.1979,44(8),1348～9(eng)
27．姜麟忠，《催化氢化在有机合成中的应用》，化学工业出版社，p123
28．Morris Freifelder，《有机合成中的催化氢化》，安徽省化工研究所
29．张杰，Cu,Ni/γ-Al2O3催化加氢动力学与应用研究，浙江大学博士论文，2001．6
30. United States Patent:3,179,705
31. Mozingo, R ;Org.Synth.Coll.Vol.1955,3,685
32. Alexander, E. R .;Cope,A.C.;J.Am.Chem.Soc.1944,66,886
33．单绍军等，催化加氢制备对氯邻氨基苯酚，染料工业，Vol38(2001)，p5
34．宋东明，李树德，霍世勇，邻硝基氯苯催化加氢的选择性，大连理工大学学报，Vol35(1)，330
35．自彦兵，6-氯-3-硝基甲苯4-磺酸液相加氢制备CLT酸的研究，化工科技，1998，6(3)：34～39
36. J.R.Kosak: Hydrogenation of Haloaromatic Nitro Compound, Catalysis in Organic Synthesis
37. J.Catalysis, 83,238-241(1983)
38．金松寿等，《有机催化》，上海科学技术出版社，1986
39．A．P．G．凯布默，F．范兰特威克，《合成有机化学中的氢化与氢解》，科学出版社，p160；p4
40．姚蒙正，陈侣柏，王家儒，《精细化工产品合成原理》，中国石化出版社，p180
41．吴越，《催化化学》，科学出版社，2000，上册 p9
42．李绍芬，《反应工程》，化学工业出版社，2002．6
43．李绍芬，《化学与催化反应工程》，化学工业出版社，1986．5
44．陈甘棠，《化学反应工程》，化学工业出版社，1990．11
45．钟邦克，《精细化工过程催化作用》，中国石化出版社，2002．8
46．陈怀九，1，2-二氯丙烷和1，3-二氯丙烯混合物氯化新工艺，石油化工，1993
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