CN1045605C - 从硅烷中除去链烯烃的方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
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Abstract
本发明涉及一种从在甲基氯硅烷合成过程所得硅烷或硅烷混合物中除去链烯烃的方法，在该方法中使链烯烃在氢化催化剂存在下与氢气进行反应。
Description
本发明涉及一种从直接合成甲基氯硅烷过程所得硅烷或硅烷混合物中除去链烯烃的方法。
链烯烃(olefins)与饱和烃、芳族化合物和含氯烃一样，是Muller-Rochow法即在250-300℃下使用铜催化剂、用硅和氯代甲烷直接合成甲基氯硅烷过程中的副产物。与烷烃不同之处在于，链烯烃由于存在碳-碳双键而具有反应活性，并且能够破坏一系列后续的反应过程。例如，它们能够加上HCl，然后当受热时又会被消去。HCl的消去会使催化剂受到抑制，容器和设备遭受腐蚀，以及可能导致在反应过程中或实际上不应有HCl参与的地方发生酸催化副反应。链烯烃本身也具有一定的抑制作用，例如对氢化硅烷化过程中的贵金属催化剂具有抑制作用。
迄今为止，业已通过蒸馏来尽可能地除去链烯烃。但是，链烯烃的沸点通常很接近单体有机氯硅烷的沸点，因此不可能在可接受的消耗前提下进行所说的除去步骤。
EP-A-310258描述了一种降低甲基硅烷中链烯烃含量的方法，在该方法中，链烯烃与甲基氯硅烷在溶解的铂催化剂存在下进行反应得到硅杂烷烃，其中所说的甲基氯硅烷含有直接连接在硅上的氢原子(H-硅烷)。为了达到完全转化的目的，该方法需要使用过量的H-硅烷，如果所说的H-硅烷是另外加入到原始硅烷物料流中的，还必须再除去它。由于硅杂烷烃一般仍含有反应活性基团，如Si-Cl，还必须再除去硅杂烷烃。
本发明的目的是提供一种从在甲基氯硅烷合成过程中所得到的硅烷或硅烷混合物中除去链烯烃的方法，在该方法中只有易于除去的物质被引入到硅烷或硅烷混合物中。
本发明涉及一种从在甲基氯硅烷合成过程中所得到的硅烷或硅烷混合物中除去链烯烃的方法，在该方法中，链烯烃与氢气在氢化催化剂存在下进行反应。
链烯烃将转化成相应的烷烃，例如，3-甲基-2-戊烯被转化成3-甲基戊烷。由于烷烃具有反应慢这一特性且通常它们的浓度很低，因此可以保留在硅烷或硅烷混合物中。如果必须除去烷烃的话，可以采用简单的蒸馏法而将其除去。
链烯烃中每摩尔的双键需用至少1摩尔的氢气。氢气的用量优选是过量，以每摩尔双键计，使用至少2摩尔氢气。由于氢气在所述的温度和压力下是以气体存在的，因此在反应后可以很容易地从硅烷或硅烷混合物中除去。可以采用商购的氢气来进行氢化。优选的是，将氢气以尽可能均匀的方式分散于催化剂床上游的硅烷或硅烷混合物中。
术语“在甲基氯硅烷合成过程中所得到的硅烷或硅烷混合物”还包括合成后经过分离、浓缩或进一步处理的硅烷或硅烷混合物，也包括例如苯基氯硅烷。
甲基氯硅烷合成过程中所得到的硅烷或硅烷混合物是，或者基本上包含通式Ⅰ的硅烷：RxCl3-xSi-[SiRyCl2-y]n-A(Ⅰ)其中R是氢原子或甲基、苯基或乙基，A是氯原子或基团R,x是数值0、1、2或3,y是数值0、1或2,n是数值0或1。
通式Ⅰ硅烷的实例是甲基氯硅烷如甲基三氯硅烷、甲基二氯硅烷、二甲基二氯硅烷、三甲基氯硅烷、三甲基硅烷以及四甲基硅烷；乙基氯硅烷如乙基三氯硅烷；苯基氯硅烷如苯基三氯硅烷和苯基甲基二氯硅烷；氯硅烷如三氯硅烷和四氯硅烷；以及低聚硅烷如六氯二硅烷、六甲基二硅烷和甲基氯二硅烷。硅烷混合物最好不含H-硅烷或低聚硅烷。
待除去的链烯烃是具有2-10个碳原子的所有直链或支链烯烃。引起干扰的链烯烃主要是具有5-7个碳原子的链烯烃，其沸点为20-100℃，并且可能具有各种区域-和立体化学异构体，例如，甲基丁烯异构体、2,3-二甲基丁烯异构体、2,3,3-三甲基-1-丁烯、甲基戊烯异构体、二甲基戊烯异构体、己烯异构体、甲基己烯异构体和庚烯异构体。
在硅烷的大规模工业蒸馏的工业硅烷和硅烷混合物的物流中所存在的链烯烃的含量取决于所述的硅烷和硅烷混合物，还取决于硅烷合成时的条件。特别是在硅烷反应器的启动阶段和逐渐停止阶段(run-downphase)副产物的含量会增加，因此链烯烃的含量有可能高达10,000ppm。
含有1-10个碳原子的直链或支链烷烃、含有1-10个碳原子及1-3个氯原子的含氯烃以及含有6-10个碳原子的芳香烃经常作为另一些硅烷和硅烷混合物中的杂质存在。
本发明适用的催化剂是所有已知的氢化催化剂。氢化催化剂分为均相和多相催化剂。
均相氢化催化剂是过渡金属，尤其是第8副族金属的配位化合物，特别优选的实例是(Ph3P)3RuCl或威尔金森(Wilkinson)催化剂。
许多粉末状的过渡金属、过渡金属氧化物和过渡金属硫化物能够作为多相氢化催化剂。过渡金属优选第1、2、6和8副族的金属，例如铜、锌、铬、铁、镍、钴、铑、钌、铂和钯。适用的氧化物的实例是铬铜矿(CuO·Cr2O3) (copper chromite)和铬锌矿(ZnO·Cr2O3)。适用的硫化物的实例是硫化钼和硫化钨。
多相氢化催化剂，尤其是第8副族的过渡金属如铁、镍、钴、铑、钌、铂和钯是优选使用的，其中铂和钯是特别优选的。
优选将多相氢化催化剂负载于载体上，这样它们则可以用于如允许混合物流过的固定床反应器中，例如蒸馏塔或流通式(flow-through)反应器。
由于使硅烷或硅烷混合物尽可能慢地流过，为了保持压力降，优选使用块状载体。可以使用的载体材料是所有的常规材料，如木炭和陶瓷载体。载体的实例为活性炭和无机氧化物如二氧化硅、氧化铝(Ⅲ)、硅酸盐、二氧化钛和二氧化锆；以及碳化物如碳化硅；其中活性炭和二氧化硅是优选使用的。负载在块状碳上的钯作为氢化催化剂是特别优选的。
在载体的存在下将金属化合物还原可以制得所说的在载体上负载有粉末状金属的氢化催化剂。
在催化剂的总重量计，金属在载体上的浓度优选为0.5-5％(重量)，但是浓度高一些和低一些也是可以的。
所说的催化剂可以用于液相或气相中。
为了尽可能长时间地保持催化剂的活性，硅烷或硅烷混合物应不含固体或糊状杂质并且应不含重金属如铅，因为重金属能使催化剂中毒。上述会引起麻烦的杂质可以通过简单的蒸馏除去。
在室温，大约20℃，以及环境压力，大约0.1MPa，下氢化作用已经发生。随着温度的升高，氢化作用的结果可以改善，即达到＞95％去除率所需的滞留时间缩短。优选的温度为20-90℃，特别是40-80℃。温度的上限是由混合物的沸点决定的。可以在不同的压力下进行氢化反应。优选的压力为0.1-0.5MPa，特别优选的是0.1-0.3MPa。
在反应器中的滞留时间为1秒至1小时，优选小于10分钟，所说的反应器优选是连续操作的。
本发明的方法可以间歇地、半连续地或完全连续地进行，完全连续法是优选的。
实施例
该实施例除了说明温度的影响外，还说明了链烯烃的去除和烷烃的增加情况。使含链烯烃的甲基三氯硅烷在0.1MPa的压力及不同的温度下从底部引入通过一直径为50mm，长度为500mm的立式反应器，该反应器内填装有负载在块状活性炭上的金属钯催化剂(5％重量的Pd，由W.C.Heraus GmbH获得，品名为K-0219,Hanau)。氢气被并流(co-current)送入催化剂床。滞留时间为5分钟，氢气的体积流速为1.3升/小时。
表：甲基氯硅烷中链烯烃的氢化
| 成 分 | 20℃ | 50℃ | ||
| 反应前 | 反应后 | 反应前 | 反应后 | |
| [ppm] | [ppm] | [ppm] | [ppm] | |
| 反-2-己烯 | 15 | 1 | 15 | 0 |
| 顺-3-甲基-2-戊烯 | 18 | 1 | 18 | 0 |
| 顺-2-己烯 | 25 | 0 | 25 | 0 |
| 反-3-甲基-2-戊烯 | 6 | 1 | 6 | 0 |
| 2,3-二甲基-2-丁烯 | 14 | 6 | 14 | 1 |
| 2-甲基戊烷 | 0 | 5 | 0 | 15 |
| 顺-3-甲基-23-甲基戊烷 | 0 | 11 | 1 | 47 |
Claims (3)
1、一种从在甲基氯硅烷合成过程所得到的硅烷或硅烷混合物中除去链烯烃的方法，其中使链烯烃在氢化催化剂存在下与氢气进行反应。
2、根据权利要求1的方法，其中除去含2-10个碳原子的直链或支链链烯烃。
3、根据权利要求1或2的方法，其中采用铁、镍、钴、铑、钌、铂或钯作为氢化催化剂。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4415924A DE4415924A1 (de) | 1994-05-05 | 1994-05-05 | Verfahren zur Entfernung von Olefinen aus Silanen |
| DEP4415924.2 | 1994-05-05 |
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| Publication Number | Publication Date |
|---|---|
| CN1120542A CN1120542A (zh) | 1996-04-17 |
| CN1045605C true CN1045605C (zh) | 1999-10-13 |
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| CN95105024A Expired - Fee Related CN1045605C (zh) | 1994-05-05 | 1995-05-04 | 从硅烷中除去链烯烃的方法 |
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| Country | Link |
|---|---|
| US (1) | US5476958A (zh) |
| EP (1) | EP0680965A1 (zh) |
| JP (1) | JPH0848691A (zh) |
| CN (1) | CN1045605C (zh) |
| DE (1) | DE4415924A1 (zh) |
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| US6217147B1 (en) | 1999-01-07 | 2001-04-17 | Hewlett-Packard Company | Printer having media advance coordinated with primitive size |
| US7939693B2 (en) * | 2007-08-22 | 2011-05-10 | Exxonmobil Chemical Patents Inc. | Process for producing sec-butylbenzene |
| US8436213B2 (en) | 2008-10-10 | 2013-05-07 | Exxonmobil Chemical Patents Inc. | Process for producing phenol and methyl ethyl ketone |
| CN108948063B (zh) * | 2018-08-09 | 2020-10-02 | 洛阳中硅高科技有限公司 | 四甲基硅烷的制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0310258A2 (en) * | 1987-10-01 | 1989-04-05 | Dow Corning Corporation | Removalof olefins from organohalosilanes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4181673A (en) * | 1979-01-23 | 1980-01-01 | Veb Chemiewerk Nunchritz | Process for preparing dimethylhydrogenchlorosilane |
| EP0383793A4 (en) * | 1987-09-21 | 1990-09-26 | The Dow Chemical Company | Process to produce aromatics of low acid-wash color |
| US5210250A (en) * | 1991-08-28 | 1993-05-11 | Shin-Etsu Chemical Co. Ltd. | Method for decolorizing purification of halogenated silane |
| DE4130790A1 (de) * | 1991-09-16 | 1993-03-18 | Wacker Chemie Gmbh | Verfahren zur abtrennung von alkenen bei der methylchlorsilan-destillation |
-
1994
- 1994-05-05 DE DE4415924A patent/DE4415924A1/de not_active Withdrawn
-
1995
- 1995-04-06 US US08/418,218 patent/US5476958A/en not_active Expired - Fee Related
- 1995-05-01 JP JP7107578A patent/JPH0848691A/ja active Pending
- 1995-05-04 CN CN95105024A patent/CN1045605C/zh not_active Expired - Fee Related
- 1995-05-04 EP EP95106758A patent/EP0680965A1/de not_active Ceased
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0310258A2 (en) * | 1987-10-01 | 1989-04-05 | Dow Corning Corporation | Removalof olefins from organohalosilanes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1120542A (zh) | 1996-04-17 |
| EP0680965A1 (de) | 1995-11-08 |
| JPH0848691A (ja) | 1996-02-20 |
| DE4415924A1 (de) | 1995-11-09 |
| US5476958A (en) | 1995-12-19 |
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