CN1520420A - 用含磷杂环戊烷基烷烃配体的催化剂从环氧乙烷和合成气单步骤生产1,3-丙二醇的方法 - Google Patents
用含磷杂环戊烷基烷烃配体的催化剂从环氧乙烷和合成气单步骤生产1,3-丙二醇的方法 Download PDFInfo
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- CN1520420A CN1520420A CNA028112725A CN02811272A CN1520420A CN 1520420 A CN1520420 A CN 1520420A CN A028112725 A CNA028112725 A CN A028112725A CN 02811272 A CN02811272 A CN 02811272A CN 1520420 A CN1520420 A CN 1520420A
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- ruthenium
- phospholane base
- cobalt
- ethane
- catalyst
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- 239000003446 ligand Substances 0.000 title abstract description 7
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title abstract 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 title abstract 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title description 11
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- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- KOUOYBLNBHOXFR-WDSKDSINSA-N (2s,5s)-2,5-dimethylphospholane Chemical compound C[C@H]1CC[C@H](C)P1 KOUOYBLNBHOXFR-WDSKDSINSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
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- 238000005660 chlorination reaction Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 abstract description 2
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- 238000005984 hydrogenation reaction Methods 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 7
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- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- JXRMCWSOTOKXSP-UHFFFAOYSA-N P1CCCC1.[Ru].[Co] Chemical compound P1CCCC1.[Ru].[Co] JXRMCWSOTOKXSP-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- KOUOYBLNBHOXFR-PHDIDXHHSA-N (2r,5r)-2,5-dimethylphospholane Chemical compound C[C@@H]1CC[C@@H](C)P1 KOUOYBLNBHOXFR-PHDIDXHHSA-N 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
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- 230000008901 benefit Effects 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 description 3
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- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
- B01J31/2428—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom
- B01J31/2433—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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Abstract
一种催化剂组合物,包括:(a)包括一种或多种非配位的钴化合物的钴组分;和(b)以主要部分包括与磷杂环戊烷基烷烃配体配位的羰基钌化合物的钌组分;和使用这样的催化剂组合物制备1,3-丙二醇的方法。
Description
发明领域
本发明涉及在一个步骤中从环氧乙烷和合成气合成脂族1,3-二醇,特别是1,3-丙二醇的方法。更特别地,本发明涉及一种催化剂,该催化剂在1,3-丙二醇的单步骤合成中的缓和条件下提供良好的收率和展示关于成本和性能的优点。本发明的催化剂包括在醚溶剂中溶解的,与双(磷杂环戊烷基(phospholano))烷烃类别配体结合的均相双金属钴-钌催化剂。
发明背景
脂族1,3-二醇,特别是1,3-丙二醇具有作为聚酯和聚氨酯的单体单元,和作为环状化合物合成的起始材料的许多应用。例如,CORTERRA(商标)聚合物是特征为突出性能的聚酯,它由1,3-丙二醇(以下称1,3-PD)和对苯二甲酸组成。在本领域中引起极大兴趣的是发现用于合成1,3-PD的有效的,经济的,和展示工艺优点的新途径。
US-A-3463819和US-A-3456017教导了使用叔膦改性的羰基钴催化剂对环氧乙烷加氢甲酰化以生产1,3-丙二醇和3-羟基丙醛(以下称3-HPA)。
US-A5304691公开了在单步骤中,使用包括与钌催化剂结合的钴-叔膦配体的改进催化剂体系,将环氧乙烷加氢甲酰化成3-羟基丙醛和1,3-丙二醇的方法。在US-A-5304691中,通过在惰性反应溶剂中,在加氢甲酰化反应条件下,充分接触环氧烷(oxirane),特别是环氧乙烷(以下称EO),二叔膦改性的羰基钴催化剂,钌催化剂促进剂,和合成气(一氧化碳和氢气)生产1,3-PDO和3-HPA。使用包括如下物质的催化剂,报导至多86-87%的PDO收率:与作为双齿配体的1,2-双(9-磷杂双环壬基)乙烷配位的钴,和作为助催化剂的十二羰基三钌(0)或双[二氯化三羰基钌]。同样参见US-A-5304686,它公开了使用二叔膦改性的羰基钴催化剂和催化剂促进剂合成3-羟基丙醛。
具有最小杂质和副产物的在单步骤中的1,3-PDO生产包括循环并在1,3-PDO合成和在产物回收和循环期间,都要求具有良好稳定性的催化剂体系。在本领域需要识别另外的催化剂体系,该催化剂体系在1,3-PDO的单步骤生产中展示潜在的优点。
概述
根据上面所述,本发明提供用于加氢甲酰化/氢化催化剂组合物的新类型配体。本发明的配体提供关于成本和性能的潜在优点。本发明提供一种催化剂组合物,该组合物包括:
(a)包括一种或多种非配位钴化合物的钴组分;和
(b)以主要部分包括与磷杂环戊烷基烷烃配体配位的羰基钌化合物的钌组分。
本发明的新颖环氧烷加氢甲酰化催化剂包括一种配合物,该配合物假定为钴-钌-磷杂环戊烷基烷烃配合物。新催化剂的一个特性特征是配位到钌的磷杂环戊烷基烷烃配体的使用,而不是如在US-A-5304691中配位到钴。许多磷杂环戊烷基烷烃配体是有效的,特别是双齿配体,双(磷杂环戊烷基)烷烃。
本发明也提供制备1,3-二醇的单步骤方法,该方法包括在加氢甲酰化条件下,在惰性溶剂中,在本发明催化剂组合物存在下,环氧烷与合成气的反应。
特别地,本发明提供一种制备1,3-丙二醇的方法,该方法包括如下步骤:
(a)在反应混合物中接触环氧乙烷,一氧化碳,氢气,和惰性反应溶剂,和催化剂组合物,该催化剂组合物包括:
(i)一种或多种非配位羰基钴化合物;和
(iii)与磷杂环戊烷基烷烃部分配位的羰基钌化合物;和
(b)加热该混合物到30-150℃的温度和至少100psi(690kPa)的压力下有效生产两相反应产物混合物的时间,该产物混合物包括上部相和下部相,上部相包括大部分的溶剂,至少50wt%催化剂组合物加上未反应的环氧乙烷,下部相包括大部分的1,3-丙二醇。
附图简述
现在通过实施例,参考附图描述本发明,其中:
图1是在EO对1,3-PDO合成的单步骤转化期间,钴-钌-1,2-双[(2R,5R)-2,5-二甲基磷杂环戊烷基]乙烷(BDMPE)催化剂的典型IR光谱,其中初始Co-Ru-BDMPE比是1∶0.67∶1.2;和
图2是在EO到1,3-PDO合成期间,相同钴-钌-1,2-双[(2R,5R)-2,5-二甲基磷杂环戊烷基]乙烷(BDMPE)催化剂的层叠图。
发明详述
已经使用在惰性反应溶剂中溶解的,与双(磷杂环戊烷基)烷烃类型配体结合的双金属钴-钌均相催化剂体系,展示由如下反应式表示的在单步骤中的环氧乙烷到1,3-PDO的选择性加氢甲酰化/氢化反应:
例如,在它从EO加合成气的产生期间,在甲基叔丁基醚中溶解的钴-钌-1,2-双(2,5-二甲基磷杂环戊烷基)乙烷催化剂可提供至多70mol%的1,3-PDO收率,基于加入的EO。
一般情况下合成1,3-PDO的单步骤方法包括在液相溶液中,在惰性反应溶剂中,在30-150℃的温度,和高压,优选100-4000psi(690-27580kPa)下,充分接触环氧乙烷,一氧化碳和氢气(合成气),和双金属催化剂。在此化学中,重要的因素包括从粗羰化产物溶液的有效PDO回收,和活性双金属催化剂配合物的循环。
在本发明中,在加氢甲酰化条件下,通过向压力反应器加入环氧烷,Co-Ru-磷烷并烷烃配合物,反应溶剂,和非必要的助催化剂和/或催化剂促进剂,及合适地以1∶1-8;1,优选2∶1-6∶1的H2∶CO比例引入合成气(氢气和一氧化碳的混合物),而制备1,3-二醇。
本发明的方法可以作为间歇类型方法、连续方法、或其组合方法进行。
在本发明的优选实施方案中,将EO,合成气和催化剂的单独、结合或分段物流加入到反应容器中,反应容器可以是间歇地或以连续方式操作的压力容器如泡罩塔或搅拌高压釜。
在本发明催化剂配合物存在下,通过与合成气的加氢加酰化反应,至多10个碳原子,优选至多6个碳原子的环氧烷,和特别是环氧乙烷可以转化成它们的相应1,3-二醇。
本发明的必要部分是Co-Ru-磷烷并烷烃配合物的使用。据信本发明的配合物包括新类别的钌改性催化剂。此新颖类别的特性特征包括配位到磷杂环戊烷基烷烃配体上的氧化的钌金属,与作为反荷离子的钴化合物。
钌原子的氧化态不是完全确定的(理论上,钌可具有0-8的价数),和可甚至在加氢甲酰化反应过程中改变。因此,钌对钴的摩尔比可以在相对宽范围内变化。应当加入足够的钴(0)以完全氧化加入的所有配合钌。可以加入过量钴,但不具有特定的价值。合适地,Ru∶Co的摩尔比为4∶1-1∶4,优选2∶1-1∶4,更优选1∶1-1∶2。
许多磷杂环戊烷基烷烃配体已识别为对使用钴-钌催化剂对的单步骤PDO合成是有效的。合适的磷杂环戊烷基烷烃包括以下通式I和II的膦烷取代的烷烃化合物:
其中,在通式I和II两者中,R是低级烷基、三氟甲基、苯基、取代苯基、芳烷基、或环取代的芳烷基;和n是1-12的整数;和对于通式II,A是CCH3、CH、N或P。优选是通式I和II的化合物,其中R是C1-C6烷基的低级烷基和n是1-3。最优选的是通式I和II的那些化合物,其中R是甲基和n是1-3。
这样化合物的例子包括,但不限于,1,2-双(磷杂环戊烷基)乙烷、1,2-双(2,5-二甲基磷杂环戊烷基)乙烷、1,2-双[(2R,5R)-2,5-二甲基磷杂环戊烷基]乙烷、1,2-双[(2S,5S)-2,5-二甲基磷杂环戊烷基]乙烷、1,3-双(2,5-二甲基磷杂环戊烷基)丙烷、三[(2,5-二甲基磷杂环戊烷基)甲基]甲烷、三[(2,5-二甲基磷杂环戊烷基)乙基]胺、和1,1,1-三[(2,5-二甲基磷杂环戊烷基)乙基]乙烷。
在本发明中特别有用的,如在实施例中显示的那样,是双齿,双(磷杂环戊烷基)烷烃,例如,1,2-双[(2R,5R)-2,5-二甲基磷杂环戊烷基]乙烷(BDMPE)、1,2-双[(2S,5S)-2,5-二甲基磷杂环戊烷基]乙烷、两者的外消旋混合物、加上1,2双(磷杂环戊烷基)乙烷。
合适的钴源包括在氢气和一氧化碳气氛中,由热处理还原到零价数的盐。这样盐的例子包括,例如,羧酸钴如乙酸钴和6-12个碳原子的链烷酸钴如辛酸钴,它是优选的,以及无机酸的钴盐如氯化钴、氟化钴、硫酸钴和磺酸钴。也可操作的是这些钴盐的混合物。然而优选当使用混合物时,混合物的至少一种组分是6-12个碳原子的链烷酸钴,优选锌酸钴。还原可以在催化剂的使用之前进行,或它可以在加氢甲酰化区中与加氢甲酰化工艺同时完成。
为了最好的结果,据信反荷离子是羰基钴,如四羰基钴阴离子,[Co(CO)4]-,它在1875-1900cm-1区域中,特别是在1888cm-1区域中具有特征IR谱带。然而,活性催化剂中的此离子可以是其改性物。羰基钴可以由起始钴源如辛酸钴与合成气的反应产生。
钴∶钌∶磷杂环戊烷基烷烃配体的摩尔化学计量比合适地为0.5-4摩尔钴∶0.25-2摩尔钌∶0.4-3摩尔磷杂环戊烷基烷烃配体。优选的范围是1-3摩尔钴∶0.3-1.5摩尔钌∶0.5-2摩尔磷杂环戊烷基烷烃配体,例如,1∶0.7∶1.2。例如表现较好的配制剂是分别以1∶0.67∶1.2摩尔化学计量的钴∶钌∶1,2-双(2,5-二甲基磷杂环戊烷基)乙烷。据信未配位的羰基钌不太有效,和因此催化剂制备探索以配位每一个钌原子。优选钌对钴的摩尔比是1∶4-4∶1。
在本发明中,制备钴-钌-磷杂环戊烷基烷烃配合物的优选方法是自组配方法,其中同时将所有的催化剂组分加到一起。如在实施例1中所示,当在合成气条件下在合适的醚溶剂中溶解时,钴-钌-磷杂环戊烷基烷烃配合物可以在单步骤中由自组配产生。选择条件,特别是溶剂以有利于配位钌物质,而不是配位钴物质的形成。Ru-配位物质而不是Co-配体物质的存在可以由例如IR分析确认。
同样在本发明范围内的是以下的催化剂的逐步或顺序设计制备。在逐步制备中的第一步骤是Ru-磷杂环戊烷基烷烃配合物的合成。这可通过将合适的钌源,如十二羰基三钌与选择的配体接触而进行。或者,可以采用其它容易得到的羰基钌衍生物,如乙酸二羰基钌聚合物和二氯化三羰基钌、二聚体代替十二羰基三钌。进一步的选择方案包括不太昂贵钌源的使用,该钌源在合成气气氛下原位形成羰基钌物质。这些不太昂贵的钌源可包括,例如,氧化钌(IV)、水合物、氯化钌(III)、和在碳上的钌。
磷杂环戊烷基烷烃配体对钌的摩尔比可以是4∶1-1∶2,优选大约2∶1。
例如,可以在溶剂中,在25-150℃,合适地100-110℃的温度下,在一氧化碳或合成气气氛下,将十二羰基三钌与化学计量数量的选择配体反应1-24小时(即,直到完全),而制备钌-磷杂环戊烷基烷烃配合物。在此点,该钌-配体配合物非必要地,可以分离为离散材料。
其次,在逐步方法中,再次在上述(非关键)条件下,通过氧化还原反应将Ru-配体配合物与合适的钴化合物接触,以形成Ru-Co-配体配合物。合适的钴源是辛酸钴,但也可以使用其它钴配合物和盐。例如,将选择的辛酸钴,和如果存在的非必要促进剂加入到溶液中,然后将溶液保持在高温(25-150℃)下15分钟-24小时的时间。再次,非必要地,可以分离和表征新钴-钌-磷杂环戊烷基烷烃配合物。
典型地,不管该活性Co-Ru-磷杂环戊烷基烷烃配合物由自组配产生,或逐步产生,它显示特征IR谱带,特别是由于[Co(CO)4]-阴离子,在1875-1900cm-1区域中的强羰基钴谱带,加上在1900-2200cm-1区域中一系列的三或四个钌-羰基谱带,该钌-羰基谱带假定是由于阳离子羰基钌物质。
允许这些化合物形成配合物的条件不是关键的。温度和压力可以在以下关于加氢甲酰化反应给出的范围内变化,例如25-150℃。在配合物形成期间合成气可以用作气封。优选使用溶剂,优选用于加氢甲酰化反应的溶剂。显然地,此溶剂应当能够溶解活性催化剂,而不影响它的性能。合适的溶剂包括用于加氢甲酰化工艺的下述醚,特别是支化烷基醚,例如MTBE。
在使用本发明催化剂组合物的单步骤加氢甲酰化/氢化反应中,进料中环氧烷对Co-Ru-配体配合物的最优比例,部分依赖于采用的特定配合物。然而,2∶1-10,000∶1的环氧烷对Co-Ru-配体配合物中钴的摩尔比一般是令人满意的,优选是50∶1-500∶1的摩尔比。
当环氧烷是EO时,在整个反应中优选以如下浓度保持EO:不小于0.2wt%,一般0.2-20wt%,优选1-10wt%,基于反应混合物的总重量。
反应溶剂应当是惰性的,意味着它在反应过程中并不消耗。用于本发明方法的理想溶剂会在反应过程中溶解进料和产物,但允许在降低的温度下发生相分离。合适的溶剂描述于US-A-5304691。可以采用烷基醚,特别是支化烷基醚,和更特别地含叔碳原子的烷基醚,达到良好的结果。用于展示本发明的溶剂是甲基叔丁基醚。
可以采用促进剂。合适的促进剂描述于先前引用的US-A-5304691。表现较好,容易获得和展示EO转化的促进的促进剂的例子是叔胺如N,N-二甲基十二烷胺和三乙胺,以及碱金属盐如乙酸钠。
在本发明催化剂配合物存在下,在合适的反应溶剂中接触进料物流的组分。例如通过分段EO加入,本发明的方法可以采用连续方式进行,同时保持该EO浓度。
为了最好的结果,在高温和高压的条件下进行单步骤加氢甲酰化/氢化。反应温度为30-150℃,优选50-125℃,和最优选60-110℃。
反应压力(总压力,或如果使用惰性气体稀释剂,分压)应当至少为100psi(690kPa)。合适的操作压力是100psi(690kPa)-4000psi(27,580kPa),优选1000psi(6900kPa)-2000psi(13,790kPa),和最优选约1500psi(10,340kPa)±250psi(1725kPa)。在间歇方法中,反应一般在1-5小时内完成。
在加氢加酰化反应结束时,通过常规方法如选择性萃取、分馏、相分离和选择性结晶从产物混合物回收1,3-PDO。未反应的起始材料以及催化剂和反应溶剂可以,和优选被循环用于进一步的用途。
可以通过加入分相诱导剂促进反应混合物的分隔。合适的试剂包括二醇如乙二醇和线性烷烃,例如,十二烷。以2-10wt%,优选4-8wt%的数量将这样的试剂加入到反应混合物中,基于总反应混合物。另外的方法包括向反应混合物中加入1,3-丙二醇以将产物浓度达到目标比例。同样,可以将具有相似极性的混溶醇和试剂如乙醇、丙醇和异丙醇初始加入,然后在随后的相分离诱导之前除去。
商业操作要求有效的催化剂回收与催化剂对反应的基本完全循环的多个循环。优选的催化剂回收工艺包括先前所述两种液相混合物的分离和本体溶剂相对反应器的循环和至少60-90wt%起始催化剂与其的返回。
在运行工艺的优选方式中,选择反应条件如环氧烷浓度,催化剂浓度,溶剂,产物浓度,和反应温度以在高温下达到均相反应混合物和在冷却混合物时,引起反应混合物分配成包含较多催化剂的上溶剂相,和包含大多数1,3-丙二醇的下部相。这样的分配促进产物的分离和回收,催化剂的循环,和重尾馏分从溶剂系统的脱除。此工艺称为相分离催化剂循环/产物回收方法。
在此方法中,允许反应器内容物在从大气压到接近反应压力的压力下沉降或转移到合适的容器,其中在轻微或相当大的冷却时,形成基本不同的区别相,该区别相相当富含1,3-丙二醇产物,或富含催化剂和溶剂。将富含钴-钌-磷杂环戊烷基烷烃配合物和溶剂的相直接循环用于与进料材料的进一步反应。由常规方法从产物富集相回收产物1,3-PDO。
当在合适的醚溶剂中溶解时,包含与十二羰基三钌和双(磷杂环戊烷基)烷烃配体结合的辛酸钴的配制剂提供1,3-PDO的单步骤合成。在MTBE中溶解的辛酸钴-十二羰基三钌-1,2-双(2,5-二甲基磷杂环戊烷基)乙烷催化剂前体,允许以大于70mol%的收率(基于加入的EO),从EO加合成气产生1,3-PDO。在此,在90℃和1500psi(10,340kPa)下,使用4∶1(H2/CO)气体进行加氢甲酰化。典型地,液体产物包括两相,其中所需的1,3-PDO在重相(B)(参见表的“相”列)中浓缩。对于此重相,在实施例1中,预测的1,3-PDO/HPA产物比是约52,1,3-PDO/EtOH比是83,和乙醛含量仅为0.2%。
该羰化活性溶液典型地在如下区域显示某些标记红外谱带:1850-1900cm-1,1900-2200cm-1。对于在EO到1,3-PDO合成期间在MTBE中的Co-Ru-BDMPE体系,这些光谱说明于图1和2。PDO合成说明于实施例15。
过量BDMPE向该Co-Ru催化剂溶液中的加入导致不显著的1,3-PDO生产和在1900-2200cm-1光谱区域中没有标记红外谱带。
以下实施例用于说明在此公开的本发明。实施例仅认为是说明的措施和不应当解释为以任何方式限制本发明的范围。本领域技术人员将会认识到可以进行许多变化而不背离公开的本发明的精神。
实施例1
1,3-PDO的制备
向装配有必须的温度和压力控制件的100ml,搅拌的Parr高压釜中加入228mg(0.66毫摩尔)辛酸钴,207mg(0.80毫摩尔)1,2-双[(2R,5R)-2,5-二甲基磷杂环戊烷基]乙烷,23ml干燥的氮气冲洗的甲基叔丁基醚(MTBE),93mg(0.48毫摩尔Ru)十二羰基三钌,和17mg(0.21毫摩尔)乙酸钠。将高压釜密封和采用4/1(H2∶CO)合成气加压到1300psi(8960kPa),和采用搅拌在1500psi(10,340kPa)下加热到130℃下三小时。在此时,将反应器和内容物冷却到5℃和排出气体。将环氧乙烷(3.6gm,82毫摩尔)加入到反应器系统中,在采用4/1(H2∶CO)合成气再加压到1300psi(8960kPa)之后,将反应器在1500psi(10,340kPa)下加热到90℃下5-6小时。根据需要提供另外的合成气。
在冷却到约4℃和脱气之后,收集21.07gm两相液体产物,该产物包括16.00gm的MTBE溶剂富集相和5.07gm的1,3-丙二醇富集相。由gc对这两种产物液体相(T和B)的分析,加入反应器的随后水洗涤(24.1gm)显示71mol%的1,3-PDO收率,基于加入的EO。从重相(B)的进一步gc分析,得出的结论是预测的PDO/HPA产物比是约52,PDO/EtOH比是83,和乙醛含量仅为0.2%。
实施例2-17
根据实施例1的步骤进行实施例2-17。在这些试验中,钴-钌均相催化剂用于与一系列双(磷杂环戊烷基)烷烃配体结合使用。试验总结数据在附表1-4中提供,其中W/W表示Parr反应器的后水洗涤,和ND表示未检测。
使用如下条件展示1,3-PDO合成:
a)一系列P-配体,包括1,2-双[(2R,5R)-2,5-二甲基磷杂环戊烷基]乙烷[BDMPE(R,R)]、1,2-双[(2S,5S)-2,5-二甲基磷杂环戊烷基]乙烷[BDMPE(S,S)]、它们的外消旋混合物、以及1,2-双(磷杂环戊烷基)乙烷(BPE)。
b)钴∶钌∶磷杂环戊烷基初始催化剂比例的范围。
c)操作温度(80-100℃),和压力(500-1500psi,3550-10,340kPa)的范围。
d)合成气(H2/CO)组成的范围。
表1
实施例 | 催化剂 | 溶剂 | 温度℃ | 时间EO吸收(小时) | 产物相 wt(g) | 浓度(%)PDO HPA | PDO生气(毫摩尔) | PDO选择性(%) | PDO收率(mol%) |
2 | Co-Ru3(CO)12-BDMPE(R,R)(1∶0.44∶1) | MTBE | 100 | 4 | T 17.2B 3.7W/W | 2.3 1.744.9 16.36.3 3.4 | 7.819.43.430.6 | 3561 | 38 |
3 | Co-Ru3(CO)12-BDMPE(R,R)(1∶0.67∶1.21) | MTBE | 100 | 4 | T 16.8B 4.7W/W | 2.7 0.954.7 7.67.9 1.9 | 8.731.75.145.5 | 4678 | 51 |
4 | Co-Ru3(CO)12-BDMPE(R,R)(1∶0.88∶1.47) | MTBE | 100 | 4.25 | T 17.1B 4.2W/W | 2.7 0.458.1 5.36.6 N.D. | 8.728.84.141.6 | 5381 | 48 |
5 | Co-Ru3(CO)12-BDMPE(R,R)(1∶0.67∶1.21) | MTBE | 100 | 3.75a | T 16.9B 3.6W/W | 2.4 1.155.0 9.59.4 3.0 | 6.120.57.233.8 | 4275 | 40 |
6 | Co-Ru3(CO)12-BDMPE(R,R)(1∶0.67∶1.21) | MTBE | 80 | 5+a | T 12.9bB 4.9W/W | 3.0 0.561.8 67.05.7 N.D. | 6.1b37.33.446.8 | 6384 | 56 |
7 | Co-Ru3(CO)12-BDMPE(R,R)b | MTBE | 80 | 6a | T 16.3B 4.7W/W | 2.2 0.462.4 6.86.0 1.1 | 8.533.74.146.3 | 6285 | 56 |
a使用2∶1 H2/CO气体
b实施例6的重复
表2
实施例 | 催化剂 | 溶剂 | 温度℃ | 时间EO吸收(小时) | 产物相 wt(g) | 浓度(%)PDO HPA | PDO生产(毫摩尔) | PDO选择性(%) | PDO收率(mol%) |
8 | Co-Ru3(CO)12-BDMPE(S,S)(1∶0.67∶1.21) | MTBE | 80 | 6a | T 17.3B 4.0W/W | 2.1 0.561.7 7.63.9 1.1 | 7.529.12.539.1 | 6583 | 45 |
9 | Co-Ru3(CO)12-BDMPE(R,R)(1∶0.44∶0.2) | MTBE | 100 | 1.25a | P 20.5W/W | N.D. 1.4N.D. N.D. | N.D.N.D.<0.1 | <0.1<0.1 | |
10 | Co-Ru3(CO)12-BDMPE(R,R)(1∶0.67∶1.21) | MTBE | 80 | 6b | T 16.0B 5.6W/W | 2.2 N.D.72.6 1.44.5 N.D. | 7.348.22.958.4 | 7595 | 71 |
11 | Co-Ru3(CO)12-BDMPE(R,R)c(1∶0.67∶1.21) | MTBE | 80 | 5b | T 16.3B 4.7W/W | 1.9 0.265.2 5.49.7 N.D. | 71.037.16.450.6 | 6389 | 60 |
12 | Co-Ru3(CO)12-BDMPE(R,R)(1∶0.67∶1.21) | MTBE | 80 | 4.25d | T 16.4B 4.8W/W | 1.3 0.458.8 6.68.3 1.6 | 3.730.95.640.2 | 4678 | 47 |
13 | Co-Ru3(CO)12-BDMPE(R,R)(1∶0.67∶1.21) | MTBE | 80 | 0.75e | T 19.7B 0.4W/W | 3.9 0.361.8 2.63.7 N.D. | 8.12.22.412.7 | 6980 | 15 |
a使用2∶1 H2/CO气体 b使用4∶1 H2/CO气体
c实施例10的重复 d在1000psi(6900kPa)下使用4/1 H2/CO
e在500psi(3550kPa)下使用4/1 H2/CO
表3
实施例 | 催化剂 | 溶剂 | 温度℃ | 时间EO吸收(小时) | 产物相 wt(g) | 浓度(%)PDO HPA | PDO生产(毫摩尔) | PDO选择性(%) | PDO收率(mol%) |
14 | Co-Ru3(CO)12-1,2 BDMPE(RACEMIC)(1∶0.67∶1.21) | MTBE | 80 | 6a | T 16.6B 3.6W/W | 1.3 0.363.8 8.68.1 1.7 | 5.826.05.237.0 | 5483 | 48 |
15 | Co-Ru3(CO)12-BDMPE(R,R)(1∶0.67∶1.21) | MTBE | 80 | b | T 17.0B 2.0 | 1.7 0.560.3 11.9 | 8.119.227.3 | 5978 | 70 |
16 | Co-Ru3(CO)12-BDMPE(R,R)(1∶0.67∶3.64) | MTBE | 80 | b | P 17.4 | <0.1 N.D. | <1 | <1 | <0.1 |
a使用4∶1 H2/CO气体
b在IR池中操作
表4
实施例 | 催化剂 | 溶剂 | 温度℃ | 时间FEO吸收(小时) | 产物相 wt(g) | 浓度(%)PDO HPA | PDO生产(毫摩尔) | PDO选择性(%) | PDO收率(mol%) |
17 | Co-Ru3(CO)12-1,2 BPE(1∶0.67∶1.21) | MTBE | 80 | 4a | T 16.7B 3.7W/W | 4.3 N.D.61.9 0.86.2 0.1 | 14.627.14.346.0 | 6490 | 58 |
a使用4∶1 H2/CO气体
Claims (10)
1.一种催化剂组合物,包括:
(a)包括一种或多种非配位的钴化合物的钴组分;和
(b)以主要部分包括与磷杂环戊烷基烷烃配体配位的羰基钌化合物的钌组分。
2.权利要求1的催化剂组合物,在醚溶剂中溶解。
4.权利要求3的组合物,其中在I和II两者中,R是C1-C6烷基的低级烷基和n是1-3。
5.权利要求4的组合物,其中在通式I和II中,R是甲基。
6.权利要求1的组合物,其中磷杂环戊烷基烷烃选自1,2-双(磷杂环戊烷基)乙烷、1,2-双(2,5-二甲基磷杂环戊烷基)乙烷、1,2-双[(2R,5R)-2,5-二甲基磷杂环戊烷基]乙烷、1,2-双[(2S,5S)-2,5-二甲基磷杂环戊烷基]乙烷、1,3-双(2,5-二甲基磷杂环戊烷基)丙烷、三[(2,5-二甲基磷杂环戊烷基)甲基]甲烷、三[(2,5-二甲基磷杂环戊烷基)乙基]胺、和1,1,1-三[(2,5-二甲基磷杂环戊烷基)乙基]乙烷。
7.权利要求1的组合物,其中钌化合物选自氯化三羰基钌(II)、十二羰基三钌、乙酸二羰基钌聚合物、氯化钌(III)、氧化钌(IV)或它的水合物、和在碳上的钌。
8.一种制备1,3-丙二醇的方法,包括如下步骤:
(a)在反应混合物中接触环氧乙烷,一氧化碳,氢气,和惰性反应溶剂,和催化剂组合物,该催化剂组合物包括:
(i)一种或多种非配位的羰基钴化合物;和
(iii)与磷杂环戊烷基烷烃部分配位的羰基钌化合物;和
(b)加热该混合物到30-150℃的温度和至少100psi(690kPa)的压力下有效生产两相反应产物混合物的时间,该产物混合物包括上部相和下部相,上部相包括大部分的溶剂,至少50wt%催化剂组合物加上未反应的环氧乙烷,下部相包括大部分的1,3-丙二醇。
9.权利要求8的方法,其中催化剂组合物由自组配方法制备,其中在合成气条件下同时将所有组分放在一起。
10.权利要求8的方法,其中催化剂组合物逐步制备,其中在合成气存在下,在25-150℃的温度下将钌化合物与磷杂环戊烷基烷烃反应和随后在25-150℃的温度下,进行与钴化合物的氧化还原反应。
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