CN111051274A - 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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- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
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- 150000003839 salts Chemical class 0.000 description 9
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- 230000007062 hydrolysis Effects 0.000 description 3
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
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- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
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- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
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- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
- B01J8/0257—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical annular shaped bed
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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在反应器中接触,其中所述催化剂的平均直径为至少200微米,其中反应器出口处的氧浓度为0.5至7.5mol%,且其中所述反应器包含隔板,在所述隔板的第一侧上具有催化剂床,且具有沿第一方向通过所述催化剂床的流和在所述隔板的第二侧上沿相反方向的流。
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。
已知在连续搅拌槽反应器中的氧化酯化反应中使用具有贵金属的非均相催化剂的方法,参见例如美国专利第6,228,800号。但是,需要一种可提供改进的性能的方法。
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含有包含载体和贵金属的非均相催化剂的催化剂床在反应器中接触,其中所述催化剂的平均直径为至少200微米,其中反应器出口处的氧浓度为0.5至7.5mol%,且其中所述反应器包含隔板,在所述隔板的第一侧上具有催化剂床,且具有沿第一方向通过所述催化剂床的流和在所述隔板的第二侧上沿相反方向的流。
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,二氧化钛或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%、优选地催化剂体积的外部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,催化剂粒子的平均直径为至少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5mm,优选地不超过4mm,优选地不超过3mm。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,通过在载体的存在下从金属盐的水溶液中沉淀贵金属产生催化剂。在一个优选实施例中,通过初始润湿技术产生催化剂,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。
在本发明的方法中,用于生产甲基丙烯酸甲酯(MMA)的方法包含在含有催化剂床的氧化酯化反应器(OER)中用甲醇和氧气处理甲基丙烯醛。催化剂床包含催化剂粒子且位于OER内,使得液体流可通过催化剂床并在催化剂床周围发生。优选地,催化剂床仅占据反应器直径的一部分,使得反应物在催化剂床周围并通过催化剂床循环。OER进一步包含有包含甲基丙烯醛、甲醇和MMA的液相和包含氧气的气相。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)。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至14MPa);优选地不超过2000kPa,优选地不超过1500kPa。优选地,催化剂床在管式连续反应器或连续搅拌槽反应器中,优选为含有用于控制反应器温度的热交换元件,如盘管或散热片的反应器。
催化剂床中的催化剂粒子通常通过固体壁和通过筛子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。优选地,反应器包含烟囱,其为具有内部和外部的竖直固体隔板(即,其垂直于高度的截面为连续的闭合曲线),允许液体在烟囱的一侧(例如内部或外部)向上流动且在另一侧向下流动。在优选实施例中,催化剂床呈位于烟囱与反应器壁之间的基本上圆柱形的壳体的形状。烟囱可为圆柱形壳体(具有圆柱形孔的圆柱体)、矩形壳体或更复杂的形状,例如通过在端部向外(朝向反应器壁)扩口而从圆柱形壳体衍生的形状,或具有圆筒形壳体的外表面或内表面但在另一表面上逐渐变窄以产生可变厚度的形状;优选地,垂直于高度的烟囱的截面由两个或更多个同心圆组成。优选地,烟囱在反应器中居中。优选地,烟囱相对于反应器壁是静止的。优选地,烟囱的长度为反应器的长度的30至90%,优选地40至80%。优选地,烟囱的最大截面直径为反应器的直径的40至90%,优选地至少45%,优选地至少50%,优选地不超过85%,优选地不超过80%。在反应器为连续搅拌槽反应器(CSTR)的优选实施例中,烟囱的高度为反应器的高度的30至80%;优选地至少40%,优选地不超过75%,优选地不超过70%。在CSTR中,优选地,催化剂床的高度为烟囱的高度的30至90%,优选地至少40%,优选地不超过80%。优选地,催化剂床的侧面与烟囱接触。优选地,CSTR被配置成具有烟囱与反应器壁之间的催化剂床,其中液体在烟囱内部向下流动且通过催化剂床向上流动。优选地,气态反应物和惰性气体(氧气、氮气、二氧化碳)通过催化剂床向上上升。
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在催化剂上方和/或下方的惰性材料。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,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、盐和水的介质中水解。MDA可在来自甲醇回收蒸馏塔的塔底物料流中水解;所述物料流包含MMA、MDA、甲基丙烯酸、盐和水。在另一实施例中,MDA在从甲醇回收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。
优选地,反应器出口处的氧浓度为至少1mol%,优选地至少2mol%,优选地至少3mol%;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,通过催化剂床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20mm/s,优选地不超过15mm/s。
可将碱添加至反应器,以此方式减少可能由迈克尔反应产生的加合物的形成,并延长催化剂寿命。在本发明的一个优选实施例中,未直接或通过外部混合槽将碱添加至反应器。
实例
实例#1
CSTR的配置是通过以高再循环率操作的再循环管式反应器以实验方式估计,其在理论上与具有相同再循环比的CSTR相同。进行了一个操作,其中将20重量%甲基丙烯醛、200ppm抑制剂和其余的甲醇馈入至3/8”(9.5mm)不锈钢管式反应器,所述反应器含有短的碳化硅前段,接着为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。也将在氮气中含有8%氧气的气体馈入至反应器中。反应器在60℃和160psig(1200kPa)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。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。产物MMA是源自甲基丙烯醛反应物的产物中的MMA%。
进料 | 再循环 | 气体 | 气体类型 | 产物MMA | 转化率 | STY | MIB |
(g/hr) | (g/hr) | (sccm) | (wt%) | (%) | (m/Kg cat.hr) | (ppm) | |
20 | 180 | 380 | 8%O<sub>2</sub> | 97.8 | 63 | 3.2 | 480 |
Claims (10)
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,其中所述催化剂的平均直径为至少200微米,其中反应器出口处的氧浓度为0.5至7.5mol%且其中所述反应器包含隔板,在所述隔板的第一侧上具有催化剂床,且具有沿第一方向通过所述催化剂床的流和在所述隔板的第二侧上沿相反方向的流。
2.根据权利要求1所述的方法,其中所述催化剂床呈位于所述隔板与反应器壁之间的圆柱形壳体的形状。
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,其中所述催化剂床的温度为40至120℃。
5.根据权利要求4所述的方法,其中所述反应器为连续搅拌槽反应器且所述隔板的高度为所述反应器的高度的30至90%。
6.根据权利要求5所述的方法,其中所述连续搅拌槽反应器被配置成具有在所述隔板内部向下流动且通过所述催化剂床向上流动的液体。
7.根据权利要求6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。
8.根据权利要求7所述的方法,其中所述贵金属选自由金和钯组成的群组。
9.根据权利要求8所述的方法,其中所述载体选自由二氧化钛或γ-、δ-或θ-氧化铝组成的群组。
10.根据权利要求9所述的方法,其中至少95重量%的所述贵金属在催化剂体积的外部50%中。
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