CN111417617B - 通过使用非均相催化剂进行氧化酯化来生产甲基丙烯酸甲酯的方法 - Google Patents
通过使用非均相催化剂进行氧化酯化来生产甲基丙烯酸甲酯的方法 Download PDFInfo
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 6
- 238000006709 oxidative esterification reaction Methods 0.000 title description 6
- 238000004519 manufacturing process Methods 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 24
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
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- 150000003839 salts Chemical class 0.000 description 7
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
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- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
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- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
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- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
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Abstract
一种从甲基丙烯醛和甲醇制备甲基丙烯酸甲酯的方法。所述方法包含使包含甲基丙烯醛、甲醇和氧气的混合物与包含载体和贵金属的非均相催化剂接触，其中反应器出口处的氧浓度为1至7.5mol％且其中反应器出口处的pH为不超过7.5。
Description
背景技术
本发明涉及一种使用非均相催化剂从甲基丙烯醛和甲醇制备甲基丙烯酸甲酯的方法。
已知在相对较低pH下氧化酯化甲基丙烯醛以产生甲基丙烯酸甲酯，参见例如JP3408700(B2)。但是，此参考文件使用钯和铅催化剂且教示极低氧气分压是优选的。需要可在氧化酯化反应中提供改进的选择性的方法，尤其是在副产物异丁酸甲酯的水平方面。
发明内容
本发明涉及一种从甲基丙烯醛和甲醇制备甲基丙烯酸甲酯的方法；所述方法包含使包含甲基丙烯醛、甲醇和氧气的混合物与包含载体和贵金属的非均相催化剂在反应器中接触，其中反应器出口处的氧浓度为1至7.5mol％且其中反应器出口处的pH为不超过7.5。
具体实施方式
除非另外指示，否则所有百分比组成都是重量百分比(wt％)，并且所有温度都是以℃为单位。贵金属是金、铂、铱、锇、银、钯、铑和钌中的任一种。催化剂中可存在超过一种贵金属，在这种情况下，限制适用于所有贵金属的总量。“催化剂中心”是催化剂粒子的质心，即在所有坐标方向上所有点的平均位置。直径是穿过催化剂中心的任何线性尺寸，且平均直径是所有可能直径的算术平均值。纵横比是最长与最短直径的比。
优选地，载体是氧化物材料的粒子；优选地，γ-、δ-或θ-氧化铝、二氧化硅、氧化镁、二氧化钛、氧化锆、氧化铪、氧化钒、氧化铌、氧化钽、二氧化铈、氧化钇、氧化镧或其组合；优选地，γ-、δ-或θ-氧化铝。优选地，在包含贵金属的催化剂的部分中，载体的表面积为大于10m2/g，优选地大于30m2/g，优选地大于50m2/g，优选地大于100m2/g，优选地大于120m2/g。在几乎不包含或不包含贵金属的催化剂的部分中，载体的表面积可为小于50m2/g，优选地小于20m2/g。
优选地，催化剂粒子的纵横比为不超过10:1，优选地不超过5:1，优选地不超过3:1，优选地不超过2:1，优选地不超过1.5:1，优选地不超过1.1:1。催化剂粒子的优选形状包括球形、圆柱形、矩形固体、环形、多叶形(例如苜蓿叶形横截面)、具有多个孔的形状和“马车车轮”；优选为球形。也可以使用不规则形状。
优选地，至少90重量％的贵金属在催化剂体积(即，平均催化剂粒子的体积)的外部70％、优选地外部60％、优选地外部50％、优选地外部40％、优选地外部35％、优选地外部30％、优选地外部25％中。优选地，对于沿着垂直于外表面的线测量的，从其内表面到其外表面(粒子的表面)具有恒定距离的体积计算任何粒子形状的外部体积。例如，对于球形粒子，体积的外部x％是球形外壳，其外表面是粒子的表面，且其体积为整个球体体积的x％。优选地，至少95重量％、优选地至少97重量％、优选地至少99重量％的贵金属在催化剂的外部体积中。优选地，至少90重量％(优选地至少95重量％、优选地至少97重量％、优选地至少99重量％)的贵金属在距表面不超过催化剂直径的30％、优选地不超过25％、优选地不超过20％、优选地不超过15％、优选地不超过10％、优选地不超过8％的距离内。沿着垂直于表面的线测量距表面的距离。
优选地，贵金属为金或钯，优选为金。优选地，反应混合物(包括催化剂)基本上不含并非贵金属的重金属，例如铅、汞、镉、铬和锰。基本上不含意指具有小于500ppm、优选小于100ppm、优选小于50ppm、优选小于20ppm、优选小于10ppm。
优选地，催化剂粒子的平均直径为至少100微米，优选地至少200微米，优选地至少300微米，优选地至少400微米，优选地至少500微米，优选地至少600微米，优选地至少700微米，优选地至少800微米；优选地不超过30mm，优选地不超过20mm，优选地不超过10mm，优选地不超过7mm，优选地不超过5mm。载体的平均直径和最终催化剂粒子的平均直径没有显著差异。
优选地，呈贵金属和载体的百分比形式的贵金属的量为0.2至5重量％，优选地至少0.5重量％，优选地至少0.8重量％，优选地至少1重量％，优选地至少1.2重量％；优选地不超过4重量％，优选地不超过3重量％，优选地不超过2.5重量％。
优选地，通过在载体的存在下从贵金属盐的水溶液中沉淀贵金属产生催化剂。在本发明的一个实施例中，通过初始润湿产生催化剂，其中将合适的贵金属前体盐的水溶液添加至多孔无机氧化物，使得孔被溶液填充且接着通过干燥去除水。接着通过煅烧、还原或所属领域的技术人员已知的其它预处理将所得材料转化为最终催化剂，以将贵金属盐分解为金属或金属氧化物。优选地，包含至少一个羟基或羧酸取代基的C2-C18硫醇存在于溶液中。优选地，包含至少一个羟基或羧酸取代基的C2-C18硫醇具有2至12个，优选地2至8个，优选地3至6个碳原子。优选地，硫醇化合物包含不超过4个，优选地不超过3个，优选地不超过2个总羟基和羧酸基。优选地，硫醇化合物具有不超过2个，优选地不超过1个硫醇基。如果硫醇化合物包含羧酸取代基，则其可以酸形式、共轭碱形式或其混合物存在。尤其优选的硫醇化合物包括硫代苹果酸、3-巯基丙酸、硫代乙醇酸、2-巯基乙醇和1-硫代甘油，包括其共轭碱。
在本发明的一个实施例中，通过沉积沉淀产生催化剂，其中将多孔无机氧化物浸入含有合适的贵金属前体盐的水溶液中，且接着通过调节溶液的pH而使所述盐与无机氧化物的表面相互作用。接着回收(例如通过过滤)所得处理的固体且接着通过煅烧、还原或所属领域的技术人员已知的其它预处理转化为最终催化剂，以将贵金属盐分解为金属或金属氧化物。
用于生产甲基丙烯酸甲酯(MMA)的方法包含在氧化酯化反应器(OER)中用甲醇和氧气处理甲基丙烯醛。优选地，催化剂粒子在催化剂床中，并且优选地通过固体壁和通过筛网或催化剂载体网格保持在适当的位置。在一些配置中，筛网或网格在催化剂床的相对端上且固体壁在侧面上，尽管在一些配置中，催化剂床可被筛网完全包围。催化剂床的优选的形状包括圆柱体、矩形固体和圆柱形壳体；优选地圆柱体。液相可进一步包含副产物，例如甲基丙烯醛二甲基乙缩醛(MDA)和异丁酸甲酯(MIB)。MIB是特别成问题的副产物，因为其难以去除且其产生异味。优选地，液相的温度为40至120℃；优选地至少50℃，优选地至少60℃；优选地不超过110℃，优选地不超过100℃。优选地，催化剂床的压力为0至2000psig(101.3至13890.8kPa)；优选地不超过2000kPa，优选地不超过1500kPa。优选地，催化剂床在包含液态和气态反应物的轴向流的管式连续反应器中；优选地，管式反应器具有圆形横截面。优选地，催化剂床进一步包含氧气。
OER通常产生MMA，连同甲基丙烯酸和未反应的甲醇。优选地，以1:10至100:1，优选地1:2至20:1，优选地1:1至10:1的甲醇:甲基丙烯醛摩尔比将甲醇和甲基丙烯醛馈入至含有催化剂床的反应器中。优选地，催化剂床进一步包含位于催化剂下方和/或上方的惰性材料。优选的惰性材料包括例如氧化铝、粘土、玻璃、碳化硅和石英。优选地，惰性材料的平均直径等于或大于催化剂的平均直径。优选地，将反应产物馈入至甲醇回收蒸馏塔，其提供富含甲醇和甲基丙烯醛的塔顶物料流；优选地，此物料流被再循环返回OER。来自甲醇回收蒸馏塔的塔底物料流包含MMA、MDA、甲基丙烯酸、盐和水。在本发明的一个实施例中，MDA在包含MMA、MDA、甲基丙烯酸和水的介质中水解。在另一实施例中，MDA在从甲醇回收蒸馏塔的塔底物料流分离的有机相中水解。可能有必要向有机相中加水，以确保有足够的水用于MDA水解；这些量可容易地由有机相的组成确定。MDA水解反应器的产物是相分离的，且有机相穿过一个或多个蒸馏塔以产生MMA产物以及轻质和/或重质副产物。在另一实施例中，水解可在蒸馏塔本身内进行。
一个优选实施例为在再循环回路中具有冷却能力的再循环反应器。另一优选实施例为一系列反应器，在反应器之间具有冷却和混合能力。
优选地，反应器出口的氧浓度为至少1.4mol％，优选地至少1.6mol％，优选地至少1.8mol％，优选地至少2.0mol％，优选地至少2.2mol％；优选地不超过7mol％，优选地不超过6.5mol％，优选地不超过6mol％，优选地不超过5.5mol％。优选地，通过反应器的液体的表观速度为1至50mm/s，优选地至少2mm/s，优选地至少3mm/s，优选地至少4mm/s，优选地至少5mm/s；优选地不超过40mm/s，优选地不超过25mm/s。
在本发明的一个优选实施例中，反应器出口处的pH为至少3，优选地至少3.5，优选地至少4，优选地至少4.5，优选地至少5；优选地不超过7.2，优选地不超过7，优选地不超过6.8，优选地不超过6.7，优选地不超过6.6，优选地不超过6.5。优选地，不将碱添加至反应器或进入反应器的液流中。优选地，反应器不连接至引入碱的外部混合槽。反应器中的pH可能在入口附近更高，可能高于7，且朝向出口稳步下降。
用于氧化酯化的固定床反应器的一个优选实施例为滴流床反应器，其含有催化剂的固定床且使气体和液体进料均沿向下的方向穿过反应器。在滴流中，气相是连续的液相。因此，在固定床上方的反应器顶部的区域将充满氮气、氧气和挥发性液体组分在其各自的蒸气压下的气相混合物。在典型的操作温度和压力(50-90℃和60-300psig)下，如果气体进料是空气，则此蒸气混合物在易燃包壳内。因此，仅需要点火源即可启动爆燃，这可能导致主安全壳的损失且损害附近的物理基础设施和人员。为了解决工艺安全性考虑，操作滴流床反应器同时避免易燃的顶部空间气氛的方法是用含足够低的氧气摩尔分数的气体进料进行操作，以确保蒸气顶部空间中的氧浓度低于极限氧浓度(LOC)。
有关的燃料混合物、温度和压力需要了解LOC。由于LOC随着温度和压力的升高而降低，且考虑到甲醇给出的LOC低于其它两种重要燃料(甲基丙烯醛和甲基丙烯酸甲酯)，因此保守的设计选择一进料氧氮比，其确保具有低于在最高预期操作温度和压力下的LOC的组成。例如，对于在最高100℃和275psig下操作的反应器，氮气中的进料氧浓度不应超过7.4mol％。
实例
以下提供了排气口O2浓度和pH的影响的实例。
实例1
进行了一系列操作，其中将20重量％甲基丙烯醛、200ppm抑制剂和其余的甲醇馈入至含有短的碳化硅前段的3/8"(9.5mm)不锈钢管式反应器，接着馈入10g催化剂。催化剂由NORPRO 1mm直径高表面积氧化铝球形载体上的1.5wt％Au组成。在所有情况下，也将在氮气中含有8％氧气的气体馈入至反应器，除非另外指示(**)，在此情况下，将空气馈入至反应器。反应器在60℃和160psig(1205kPa)下操作。将反应器的产物送至液体-蒸气分离器，且将蒸气送至具有液体回流的冷凝器。在一些情况下，将来自此分离器的一部分产物流再循环至反应器入口，且与进入反应器的进料合并。结果描述于下表中。以100％MMA产物计，MIB以ppm报告。在所有运行中，由甲基丙烯醛形成的产物中的MMA％均超过95重量％。
表1.反应器出口处的摩尔％氧气和pH对MIB形成的影响*
*液体速度(Liq.Vel.)是表观速度且平均氧分压(Avg.PO2)是以kPa绝对值计。平均分压是入口和出口氧分压的算术平均值。
**在此情况下使用空气代替8％O2。
Claims (9)
1. 一种从甲基丙烯醛和甲醇制备甲基丙烯酸甲酯的方法；所述方法包含使包含甲基丙烯醛、甲醇和氧气的混合物与包含载体和贵金属的非均相催化剂在反应器中接触，其中所述贵金属是金，包括催化剂的反应混合物含有小于500ppm的非贵金属的重金属，所述催化剂的平均直径至少为300微米，其中反应器出口处的氧浓度为1至7.5 mol%且其中反应器出口处的pH为不超过7.5；
其中所述反应器是固定床反应器；
不将碱添加至反应器或进入反应器的液流中。
2. 根据权利要求1所述的方法，其中所述反应器为轴向流反应器，其具有0.5至20 mm/s的液相表观速度和大于50 kPa的平均氧分压。
3.根据权利要求2所述的方法，其中所述催化剂的平均直径为400微米至10毫米。
4.根据权利要求3所述的方法，其中所述催化剂包含于温度为40至120℃的催化剂床中。
5.根据权利要求4所述的方法，其中所述反应器中的pH为3至7.2。
6. 根据权利要求5所述的方法，其中反应器出口处的氧浓度为1.6至6 mol%。
7.根据权利要求6所述的方法，其中所述载体选自由以下组成的组：γ-、δ-或θ-氧化铝、二氧化硅、氧化镁、二氧化钛、氧化锆、氧化铪、氧化钒、氧化铌、氧化钽、二氧化铈、氧化钇、氧化镧和其组合。
8.根据权利要求7所述的方法，其中甲醇和甲基丙烯醛分别以1:1至10:1的摩尔比馈入至含有所述催化剂床的反应器中。
9.根据权利要求8所述的方法，其中至少90重量%的所述贵金属在催化剂体积的外部70%中。
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| EP2886529A1 (en) * | 2013-12-20 | 2015-06-24 | Evonik Industries AG | Process for producing methyl methacrylate |
| WO2016113106A1 (de) | 2015-01-16 | 2016-07-21 | Evonik Röhm Gmbh | Gold basierten katalysator für die oxidative veresterung von aldehyden zu carbonsäureestern |
| EP3170558A1 (de) | 2015-11-19 | 2017-05-24 | Evonik Röhm GmbH | Gold-basierten katalysator für die oxidative veresterung von aldehyden zu carbonsäureestern |
| EP3235560A1 (de) * | 2016-04-22 | 2017-10-25 | Evonik Röhm GmbH | Verfahren zur durchführung einer heterogen-katalysierten reaktion |
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- 2018-09-12 JP JP2020514283A patent/JP7268007B2/ja active Active
- 2018-09-12 MX MX2020002600A patent/MX2020002600A/es unknown
- 2018-09-12 BR BR112020004818-6A patent/BR112020004818B1/pt active IP Right Grant
- 2018-09-12 KR KR1020207009564A patent/KR102666708B1/ko active IP Right Grant
- 2018-09-12 WO PCT/US2018/050598 patent/WO2019060192A1/en unknown
- 2018-09-12 EP EP18779184.3A patent/EP3684752A1/en active Pending
- 2018-09-12 CA CA3075083A patent/CA3075083A1/en active Pending
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- 2018-09-12 CN CN201880057877.0A patent/CN111417617B/zh active Active
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| JPH10114708A (ja) * | 1996-10-07 | 1998-05-06 | Asahi Chem Ind Co Ltd | カルボン酸エステルの連続的製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112020004818B1 (pt) | 2023-04-11 |
| CN111417617A (zh) | 2020-07-14 |
| JP7268007B2 (ja) | 2023-05-02 |
| WO2019060192A1 (en) | 2019-03-28 |
| EP3684752A1 (en) | 2020-07-29 |
| BR112020004818A2 (pt) | 2020-09-24 |
| US10865179B2 (en) | 2020-12-15 |
| CA3075083A1 (en) | 2019-03-28 |
| KR20200051692A (ko) | 2020-05-13 |
| MX2020002600A (es) | 2020-07-20 |
| SG11202002227SA (en) | 2020-04-29 |
| US20200216381A1 (en) | 2020-07-09 |
| JP2020534262A (ja) | 2020-11-26 |
| KR102666708B1 (ko) | 2024-05-17 |
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