CN103804227B - 一种烯腈混合液直接异构化合成2-甲基-2-丁烯腈的方法 - Google Patents
一种烯腈混合液直接异构化合成2-甲基-2-丁烯腈的方法 Download PDFInfo
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- CN103804227B CN103804227B CN201410052751.8A CN201410052751A CN103804227B CN 103804227 B CN103804227 B CN 103804227B CN 201410052751 A CN201410052751 A CN 201410052751A CN 103804227 B CN103804227 B CN 103804227B
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- nitrile
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- -1 alkene nitrile Chemical class 0.000 title claims abstract description 25
- 239000011259 mixed solution Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 22
- IHXNSHZBFXGOJM-UHFFFAOYSA-N 2-methylbut-2-enenitrile Chemical compound CC=C(C)C#N IHXNSHZBFXGOJM-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 11
- 239000011707 mineral Substances 0.000 claims abstract description 11
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 claims abstract description 7
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 21
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 2
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 5
- IHXNSHZBFXGOJM-HWKANZROSA-N (e)-2-methylbut-2-enenitrile Chemical compound C\C=C(/C)C#N IHXNSHZBFXGOJM-HWKANZROSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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Abstract
本发明公开了一种烯腈混合液直接异构化合成2-甲基-2-丁烯腈的方法，往包含2-甲基-3-丁烯腈和3-戊烯腈的烯腈混合液中加入含钙无机碱，发生异构化反应，生成包含2-甲基-2-丁烯腈的产物。本发明省去了减压精馏提纯2M3BN的过程，使用含钙无机碱作催化剂，将包含2M3BN和3PN的烯腈混合液直接异构化为2M2BN，反应转化率和选择性均大于95%；本发明的方法与传统方法相比，省去了烯腈混合液精馏分离过程，使整个工艺路线缩短，简化了工艺流程，降低了设备成本和生产成本，并且使用的催化剂为含钙无机碱，廉价易得且可循环套用，整个工艺过程基本无三废产生。
Description
技术领域
本发明涉及己二腈的生产技术领域，涉及一种烯腈混合液直接异构化合成2-甲基-2-丁烯腈的方法。
背景技术
2-甲基-2-丁烯腈（2M2BN）是一种重要的化工原料，广泛用于涂料、医药、电镀、洗涤、纺织溶剂、分析化学测定等各个方面。
丁二烯法合成己二腈的工艺中，丁二烯与氢氰酸在零价镍催化剂、含磷配体的作用下，一次加成合成3-戊烯腈（3PN），该反应产生副产2-甲基-3-丁烯腈（2M3BN）；其中3PN的选择性为75%，2M3BN的选择性为25%，上述加成反应的方程式如下：
2M2BN现有合成工艺是：先将上述反应液减压精馏，分离出高纯度2M3BN，再将2M3BN异构化为2M2BN。但是，此法需要从包含2M3BN和3PN的烯腈混合液中减压精馏获得高纯度2M3BN，而2M3BN和3PN为同分异构体，常压下沸点相差仅18℃，精馏操作难度较大，能耗较高。
发明内容
有鉴于此，本发明的目的在于提供一种烯腈混合液直接异构化合成2-甲基-2-丁烯腈的方法，简化工艺流程，降低设备成本和生产成本。
为达到上述目的，本发明提供如下技术方案：
本发明的烯腈混合液直接异构化合成2-甲基-2-丁烯腈的方法，往包含2-甲基-3-丁烯腈和3-戊烯腈的烯腈混合液中加入含钙无机碱，发生异构化反应，生成包含2-甲基-2-丁烯腈的产物。
进一步，所述含钙无机碱为氯化钙、氧化钙、氢化钙、氢氧化钙或硫酸钙。
进一步，所述含钙无机碱与烯腈混合液的摩尔比为1:5~15。
进一步，所述异构化反应的反应压力为0.1~0.2Mpa，反应温度为120~160℃，保温反应6~12小时。
进一步，所述异构化反应结束后，过滤回收含钙无机碱循环套用。
本发明的有益效果在于：
本发明省去了减压精馏提纯2M3BN的过程，使用含钙无机碱作催化剂，将包含2M3BN和3PN的烯腈混合液直接异构化为2M2BN，反应转化率和选择性均大于95%，其反应方程式如下：
本发明的方法与传统方法相比，省去了烯腈混合液精馏分离过程，使整个工艺路线缩短，简化了工艺流程，降低了设备成本和生产成本，并且使用的催化剂为含钙无机碱，廉价易得且可循环套用，整个工艺过程基本无三废产生。
具体实施方式
为了使本发明的目的、技术方案和有益效果更加清楚，下面将对本发明的优选实施例进行详细的描述。
实施例1
往包含2-甲基-3-丁烯腈和3-戊烯腈的烯腈混合液中加入氢氧化钙，氢氧化钙与烯腈混合液的摩尔比为1:5，控制反应压力为0.1Mpa，反应温度为140℃，保温反应8小时；反应结束后，过滤回收氢氧化钙循环套用，滤液中2-甲基-2-丁烯腈的含量为96%，经精馏分离得到含量大于99%的2-甲基-2-丁烯腈。
实施例2
往包含2-甲基-3-丁烯腈和3-戊烯腈的烯腈混合液中加入氢化钙，氢化钙与烯腈混合液的摩尔比为1:10，控制反应压力为0.1Mpa，反应温度为150℃，保温反应12小时；反应结束后，过滤回收氢化钙循环套用，滤液中2-甲基-2-丁烯腈的含量为96%，经精馏分离得到含量大于99%的2-甲基-2-丁烯腈。
实施例3
往包含2-甲基-3-丁烯腈和3-戊烯腈的烯腈混合液中加入氯化钙，氯化钙与烯腈混合液的摩尔比为1:15，控制反应压力为0.1Mpa，反应温度为120℃，保温反应12小时；反应结束后，过滤回收氯化钙循环套用，滤液中2-甲基-2-丁烯腈的含量为93%，经精馏分离得到含量大于99%的2-甲基-2-丁烯腈。
最后说明的是，以上优选实施例仅用以说明本发明的技术方案而非限制，尽管通过上述优选实施例已经对本发明进行了详细的描述，但本领域技术人员应当理解，可以在形式上和细节上对其作出各种各样的改变，而不偏离本发明权利要求书所限定的范围。
Claims (2)
1.一种烯腈混合液直接异构化合成2-甲基-2-丁烯腈的方法，其特征在于：包含2-甲基-3-丁烯腈和3-戊烯腈的烯腈混合液中加入含钙无机碱，发生异构化反应，生成包含2-甲基-2-丁烯腈的产物；所述含钙无机碱为氧化钙、氢化钙或氢氧化钙；所述含钙无机碱与烯腈混合液的摩尔比为1:5~15；所述异构化反应的反应压力为0.1~0.2Mpa，反应温度为120~160℃，保温反应6~12小时。
2.据权利要求1的烯腈混合液直接异构化合成2-甲基-2-丁烯腈的方法，其特征在于：所述异构化反应结束后，过滤回收含钙无机碱循环套用。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852325A (en) * | 1973-08-29 | 1974-12-03 | Du Pont | Selective isomerization of pentenenitriles |
| CN1333745A (zh) * | 1998-12-22 | 2002-01-30 | 罗狄亚聚酰胺中间体公司 | 烯属不饱和有机化合物的氢氰化方法 |
| EP2041075A2 (en) * | 2006-07-14 | 2009-04-01 | Invista Technologies S.a.r.l. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
| CN102341358A (zh) * | 2009-07-21 | 2012-02-01 | 鲁姆斯科技公司 | 用于乙烯和2-丁烯的复分解和/或双键异构化的催化剂 |
| CN103396340A (zh) * | 2013-08-16 | 2013-11-20 | 山东海力化工股份有限公司 | 2-甲基-3丁烯腈的异构化方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3676481A (en) * | 1970-06-29 | 1972-07-11 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles in the presence of certain metal salt and/or tri(hydrocarbyl)boron promoters |
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- 2014-02-17 CN CN201410052751.8A patent/CN103804227B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852325A (en) * | 1973-08-29 | 1974-12-03 | Du Pont | Selective isomerization of pentenenitriles |
| CN1333745A (zh) * | 1998-12-22 | 2002-01-30 | 罗狄亚聚酰胺中间体公司 | 烯属不饱和有机化合物的氢氰化方法 |
| EP2041075A2 (en) * | 2006-07-14 | 2009-04-01 | Invista Technologies S.a.r.l. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
| CN102341358A (zh) * | 2009-07-21 | 2012-02-01 | 鲁姆斯科技公司 | 用于乙烯和2-丁烯的复分解和/或双键异构化的催化剂 |
| CN103396340A (zh) * | 2013-08-16 | 2013-11-20 | 山东海力化工股份有限公司 | 2-甲基-3丁烯腈的异构化方法 |
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