CN111939915A - 由丙醛一步合成丙酸丙酯用催化剂及其方法 - Google Patents
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- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title claims description 8
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
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- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 150000001299 aldehydes Chemical class 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 18
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- 125000004429 atom Chemical group 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
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- 150000002148 esters Chemical class 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000005234 alkyl aluminium group Chemical group 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 229910014863 CaCl2—MgCl2 Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
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- 208000012839 conversion disease Diseases 0.000 description 1
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- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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Abstract
由丙醛一步合成丙酸丙酯用催化剂,属于化工工艺技术领域,催化剂为固体混合氧化物,组成为MOx,其中金属元素M为Zn,Cu,Zr,La,Ti,Al中的至少两种以上,x为满足催化剂中各元素化合价的氧原子总数;气固反应工艺与设备简单,反应产物与催化剂自动分离,适宜连续化大规模生产,无污染,无废渣排放,基本不生成副产物。
Description
技术领域
本发明涉及一种由丙醛一步合成丙酸丙酯用的催化剂以及方法,属于化工工艺技术领域。
背景技术
丙酸丙酯添加到锂电池中,可以拓宽它使用的温度范围。随着锂电池日益广泛应用,需求不断增加。丙酸丙酯工业生产方法经由乙烯氢甲酰化合成丙醛,丙醛氧化成丙酸,丙醛加氢为丙醇,丙酸与丙醇在硫酸等催化剂下反应生成,需要4个工厂或车间的几个装置才能完成,工艺路线长,生产成本高,而且,醛氧化成酸时不可避免会产生副产物,增加环保压力。因此,有必要开发由丙醛一步合成丙酸丙酯的新方法。
已报道的醛一步合成酯的方法中,有通过双氧水为氧化剂的氧化酯化法,直接从芳香醛得到酯,所用催化剂分别为ZnBr2,CaCl2-MgCl2,杂多酸/MCM-41等。也有用烷基铝催化剂液相催化乙醛合成乙酸乙酯,异丁醛合成异丁酸异丁酯。但还没有发现有文献或专利报道由丙醛一步合成丙酸丙酯的方法。
发明内容
本发明关键是设计使用了一种催化剂,用其完成由丙醛一步合成丙酸丙酯的方法。
适用反应是以丙醛作原料,两个丙醛分子合成一个丙酸丙酯分子:
2CH3CH2CHO = CH3CH2COOCH2CH2CH3 (1)
该反应机理与一般的缩合反应机理与过程(如用烷基铝催化剂液相催化醛合成酯)不同,是在同一个催化剂的不同活性中心上,经由先醛岐化为酸和醇,酸和醇再酯化得到酯的两个连串反应:
2CH3CH2CHO + H2O = CH3CH2COOH + CH3CH2CH2OH (2)
CH3CH2COOH + CH3CH2CH2OH = CH3CH2COOCH2CH2CH3 + H2O (3)
本发明的技术方案为:由丙醛一步合成丙酸丙酯用催化剂,其特征在于催化剂为固体混合氧化物,组成为MOx,其中金属元素M为Zn,Cu,Zr,La,Ti,Al中的至少两种以上,x为满足催化剂中各元素化合价的氧原子总数。催化剂中元素组成不同,催化反应效果会有差异,如表1所示。
进一步地,金属元素M的各原子较好的质量百分配比是:Zn0-50%, Cu 0-40%, Zr0-70%, La 0-10%, Ti 0-20%, Al 10-40%;更优的各原子的质量百分配比是:Zn20-50%,Cu 0-40%, Zr 10-70%, La 0-5%, Ti 0-20%, Al 10-30%。
由丙醛一步合成丙酸丙酯的方法,使用丙醛为原料,预热为气体后,流过一个内装上述固体催化剂的反应器,进行气固相催化反应,一步(指的是只通过一个反应器而不是微观历程步骤数)合成出丙酸丙酯。反应产物从反应器引出后与原料丙醛换热回收热量,再经水冷成为液体,经精馏分离除去未反应的原料,得到产品。
反应器最好用固定床,也可以用流化床或微通道反应器。
本发明的反应形式为原料连续通入反应器的连续流动型,进料重量空速为0.2-5h-1,反应温度200-350℃,反应压力0.1-4 MPa。工艺参数中,原料丙醛的流量以重量空速表示(原料重量流量Kg/催化剂重量Kg•小时,简记作h-1),范围为0.2-5 h-1。该重量空速物理意义为单位时间内单位重量催化剂上流过的原料重量,因此也称为催化剂负荷。反应温度范围200-350℃,反应压力0.1-4 MPa。因为是减分子反应,加压对化学平衡有利,也可提高处理量。根据实际操作的温度和压力,可计算出原料在催化剂上的停留时间,约几秒到十几秒钟。更优化的进料重量空速为0.2-1 h-1,反应温度265-300℃,反应压力1.5-4 MPa。
由反应历程可知,原料中的水仅参加了反应,反应后并不消耗,考虑到醛的岐化反应是速度控制步骤,需要水的参与,醛与水互溶性差,醛中含水量低,因此有必要加入一些水,这对提高反应速度有利,但水太多会副产酸。丙醛原料中可加入占醛重量0-10%的水。相比于烷基铝催化剂液相催化醛合成酯,由于烷基铝催化剂容易水解而失活,醛不宜含水。
在原料中加入适量丙醇是有利的。一是因为醛合成酯是一个中等强度的放热反应,加入醇后,其脱氢为醛是一个吸热反应,可使总反应放热量减少,反应更平稳又容易控制。二是醇可与酸反应,减少产物中酸含量。三是醇脱氢为醛时放出的氢气,可使反应压力平稳和容易控制。丙醛原料中可加入占醛重量0-30%的丙醇。
本发明的方法具有以下突出优点:
1)气固反应工艺与设备简单,反应产物与催化剂自动分离,适宜连续化大规模生产。
2)环境友好(无污染,无废渣排放),原子经济性强(基本不生成副产物)。
3)催化剂不含贵金属和对环境有害元素,制备方法简单。
4)反应是中等强度放热反应,可副产水蒸气,部分满足分离所需要的热能。
具体实施方式
实施例1-6,设计由丙醛一步合成丙酸丙酯用催化剂,催化剂为固体混合氧化物,组成为MOx,其中金属元素M为Zn,Cu,Zr,La,Ti,Al中的至少两种以上,x为满足催化剂中各元素化合价的氧原子总数。催化剂中的金属组成(质量比)见表一。
将4g 固体催化剂放在尺寸为Φ20×3×300 mm的不锈钢单管反应器的中部,两头填充惰性的粗石英砂固定位置。反应器的温度由温控仪控制。催化剂用H2/N2混合气程序升温活化。升温到反应温度后,由计量泵泵入丙醛(工业品本身含水量0.3%左右,不作处理)。丙醛经预热器预热到265℃左右,进入反应器。气体反应产物流出后,直接进入水冷器,冷却为液体,分离后得酯产品。色谱分析出副产物主要为丙酸。丙酸分离后可以加入适量丙醇再作为原料使用。由于小试进料量少,省去了原料与产物之间换热。
反应条件为:原料液体重量空速1 h-1,反应温度265℃,反应压力1.5 MPa。
转化率与选择性均指丙醛的单程转化结果,定义为:
转化率= 已转化丙醛量 / 进入反应器丙醛原料量×100%
选择性= 生成的丙酸丙酯质量数 / 进入反应器丙醛原料质量数×100%
各催化剂反应的转化率和选择性见表一。
表一
实施例7-14
将固体催化剂放在固定床反应器的反应管内。反应开始前,先用H2/N2混合气进行升温活化,催化剂床层温度升高到反应温度后,用泵泵入原料醛,与反应产物换热及加热到反应温度后,成为气体,从反应器上部进入反应器进行气固催化反应,反应产物从反应器底部流出,经与原料换热及水冷后,成为液体。经精馏除去未反应的原料醛后,得到产品酯。对列管反应器,反应温度由流经管间的导热油控制,对单管反应器,可用电加热或空冷控温,以进行等温反应。反应压力由水冷器中的产物出口阀门控制。其工艺条件参数与各反应转化率和选择性见表二。
表二
实施例15-26,参考实施例1和实施例3,催化剂床层温度升高到反应温度后,用泵泵入的原料醛中加入少量水或丙醇。添加成份及反应转化率和选择性见表三。
表三
Claims (10)
1.由丙醛一步合成丙酸丙酯用催化剂,其特征在于催化剂为固体混合氧化物,组成为MOx,其中金属元素M为Zn,Cu,Zr,La,Ti,Al中的至少两种以上,x为满足催化剂中各元素化合价的氧原子总数。
2.根据权利要求1所述的由丙醛一步合成丙酸丙酯用催化剂,其特征在于金属元素M的各原子的质量百分配比是:Zn0-50%, Cu 0-40%, Zr 0-70%, La 0-10%, Ti 0-20%, Al10-40%。
3.根据权利要求2所述的由丙醛一步合成丙酸丙酯用催化剂,其特征在于金属元素M的各原子的质量百分配比是:Zn20-50%, Cu 0-40%, Zr 10-70%, La 0-5%, Ti 0-20%, Al10-30%。
4.由丙醛一步合成丙酸丙酯的方法,其特征在于使用丙醛为原料,预热为气体后,流过一个内装权利要求1-3之一的固体催化剂的反应器,进行气固相催化反应,一步合成出丙酸丙酯。
5.根据权利要求4所述的由丙醛一步合成丙酸丙酯的方法,其特征在于反应产物从反应器引出后与原料丙醛换热回收热量,再经水冷成为液体,经精馏分离除去未反应的原料,得到产品。
6.根据权利要求4所述的由丙醛一步合成丙酸丙酯的方法,其特征在于反应器为固定床或流化床或微通道反应器。
7.根据权利要求4所述的由丙醛一步合成丙酸丙酯的方法,其特征在于反应形式为原料连续通入反应器的连续流动型,进料重量空速为0.2-5 h-1,反应温度200-350℃,反应压力0.1-4 MPa。
8.根据权利要求7所述的由丙醛一步合成丙酸丙酯的方法,其特征在于进料重量空速为0.2-1 h-1,反应温度265-300℃,反应压力1.5-4 MPa。
9.根据权利要求4所述的由丙醛一步合成丙酸丙酯的方法,其特征在于丙醛原料中加入占醛重量0-10%的水。
10.根据权利要求4所述的由丙醛一步合成丙酸丙酯的方法,其特征在于丙醛原料中加入占醛重量0-30%的丙醇。
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