CN115260035A - 一种丙酸丙酯的合成方法 - Google Patents
一种丙酸丙酯的合成方法 Download PDFInfo
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- 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 49
- 238000001308 synthesis method Methods 0.000 title abstract description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000011949 solid catalyst Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 15
- 150000002739 metals Chemical group 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 230000002194 synthesizing effect Effects 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 239000012263 liquid product Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 36
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 36
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 18
- 235000019260 propionic acid Nutrition 0.000 description 18
- 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 18
- 239000003054 catalyst Substances 0.000 description 15
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007806 chemical reaction intermediate Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 3
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- PZAGQUOSOTUKEC-UHFFFAOYSA-N acetic acid;sulfuric acid Chemical compound CC(O)=O.OS(O)(=O)=O PZAGQUOSOTUKEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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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
- 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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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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Abstract
本发明公开一种丙酸丙酯的合成方法:包括(1)以丙醇作为原料并将其加热成为丙醇气体;(2)将所述丙醇气体连续流过一个内部填充有混合金属氧化物固体催化剂的固定床反应器,进行气固催化反应;所述的混合金属氧化物固体催化剂其组成为MOx,其中M代表金属元素,且M选自铜以及其余金属,所述的其余金属选自锌、锆、铈、钴、铝中几种金属的组合,X为满足所述混合金属氧化物固体催化剂中各元素化合价的氧原子总数;(3)催化反应后冷却,精馏,得到丙酸丙酯。本发明的合成方法为丙酸丙酯一步合成工艺,其工艺简单,适宜连续化大规模生产;本发明的合成方法中所采用的混合金属氧化物固体催化剂不含贵金属和对环境有害的元素。
Description
技术领域
本发明涉及化工合成领域,具体涉及一种丙酸丙酯的合成方法。
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,增加了环保压力。开发丙醇一步合成丙酸丙酯的新方法,可以简化工艺,降低成本。
《精细化工》期刊1995年10月刊报道,在酯化催化剂(H2SO4)作用下,丙醇在Pb-PbO2阳极上电解,可直接合成丙酸丙酯,但这种方法不适用于工业生产。
《精细石油化工进展》期刊2001年第七期登载了题为“丙醇铝催化丙醛一步合成丙酸丙酯”的文章,用丙醇和铝粉直接合成了丙醇铝,确定了合成丙醇铝的工艺条件为:2%AlCl3,0.1%碘,n(铝):n(丙醇)=1:6,反应温度90℃。在该工艺条件下,反应仅需50min,丙醇铝收率可达98%。以合成出的丙醇铝为催化剂,无水氯化锌为助催化剂,用丙醛一步合成了丙酸丙酯,收率可达92%,选择性可达93%。该方法是均相催化反应,缺点是反应后催化剂分离困难。
《新疆大学学报(自然科学版)》2003年12期报道,通过铬酸氧化丙醇制酯法,研究在硫酸-乙酸体系中乙酸丙酯及其形成机理和相关影响因素。除此以外,没有发现有丙醇一步合成丙酸丙酯的文章和专利报道。
发明内容
本发明的目的在于克服传统方法的不足,提供一种工艺与设备简单且适宜连续化大规模生产的丙酸丙酯的合成方法;本发明所提供的方法单以丙醇作为原料一步合成了丙酸丙酯。
本发明是通过如下技术方案实现的:
一种丙酸丙酯的合成方法,其特征在于,包括如下步骤:
(1)以丙醇作为原料并将其加热成为丙醇气体;
(2)将所述丙醇气体连续流过一个内部填充有混合金属氧化物固体催化剂的固定床反应器,进行气固催化反应;所述的混合金属氧化物固体催化剂其组成为MOx,其中M代表金属元素,且M选自铜以及其余金属,所述的其余金属选自锌、锆、铈、钴、铝中几种金属的组合,X为满足所述混合金属氧化物固体催化剂中各元素化合价的氧原子总数;所述的混合金属氧化物固体催化剂中各金属原子的重量百分比为Cu:10-40wt%;Co:0-20wt%;Zn:5-30wt%;Zr:5-30wt%;Ce:0-10wt%;Al:15-50wt%;即所述的混合金属氧化物固体催化剂中混合金属为铜和其余金属的组合物;
(3)催化反应后冷却,精馏,得到丙酸丙酯。
具体的,本发明的丙酸丙酯合成过程是使用丙醇为原料,连续流过一个内装混合金属氧化物固体催化剂的固定床反应器,进行气固催化反应,一步合成出丙酸丙酯并副产氢气。产物与催化剂自动分离,适合于自动化连续化大生产。本发明的反应机理如下:首先本发明的工艺是以丙醇作为原料,将两个丙醇分子合成一个丙酸丙酯分子,并释放出两分子氢气;本发明的合成方法,其总反应过程如下:
2CH3CH2CH2OH=CH3CH2COOCH2CH2CH3+2H2;
该反应机理是在同一个催化剂的不同活性中心上,经由丙醇脱氢为丙醛,丙醛岐化为丙酸和丙醇,丙酸和丙醇再酯化得到丙酸丙酯的三个连串反应,从宏观角度看,属于一步合成;具体的,在丙酸和丙醇的酯化反应过程中丙酸脱去羟基(-OH),丙醇脱去氢,生成丙酸丙酯;该反应的具体反应过程分为如下三步:
第一步由丙醇脱氢生成丙醛和氢气,其反应过程如下所示:
CH3CH2CH2OH=CH3CH2CHO+H2↑ (1);
第二步由丙醛歧化生成丙酸和丙醇,其反应过程如下所示:
2CH3CH2CHO+H2O=CH3CH2COOH+CH3CH2CH2OH (2);
第三步再由丙酸和丙醇酯化生成丙酸丙酯,其反应过程如下所示:
CH3CH2COOH+CH3CH2CH2OH=CH3CH2COOCH2CH2CH3+H2O (3)。
进一步地,步骤(2)中所述丙醇气体的流量以重量空速表示,其重量空速为0.5-3h-1。本发明的反应形式为连续流动型,反应过程中原料丙醇预热形成丙醇气体后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);该重量空速物理意义为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。
进一步地,所述丙醇气体的流量以重量空速表示,其重量空速为1-2.5h-1。
进一步地,步骤(2)中所述气固催化反应的温度为230-320℃,反应压力为0.5-3MPa。
进一步地,所述气固催化反应的温度为250-300℃,反应压力为1-2MPa。在相同空速的前提下,增加反应压力可以延长原料与催化剂的停留时间,从而提高处理量,但过高的反应压力也对整个反应的平衡不利。因此,在本发明的合成工艺中通过对反应温度和反应压力的优选,进一步提升了丙酸丙酯的合成效率。
进一步地,步骤(2)中所述混合金属氧化物固体催化剂中各金属原子的重量百分比为Cu:15-35wt%;Co:10-20wt%;Zn:10-25wt%;Zr:10-25wt%;Ce:0-10wt%;Al:20-40wt%。
进一步地,步骤(3)催化反应后气体反应产物从所述固定床反应器下部引出,经水冷器冷却为液体产物,然后精馏分离,得到丙酸丙酯产品。
本发明使用的是混合金属氧化物固体催化剂(MOx)填充的固定床反应器,进行气固催化反应;所述混合金属氧化物固体催化剂装在固定床反应器内部,原料丙醇由泵送出,所述的固定床反应器预热到接近反应温度后丙醇汽化成为丙醇气体,丙醇气体从固定床反应器上部进入反应器中进行气固催化反应;反应产物从反应器下部流出,与原料换热回收热量后,经水冷成为液体,经精馏分离除去未反应原料及副产物,得到丙酸丙酯产品。
本发明的有益效果:
(1)本发明提供的丙酸丙酯的合成方法为一步合成工艺,其工艺与设备简单,反应产物与催化剂自动分离,适宜连续化大规模生产;
(2)本发明选用的原料为更为源头的丙醇,其原料来源广泛且成本低,同时本发明所提供的丙酸丙酯合成方法对环境友好,无污染,无废渣排放,原子经济性强;
(3)本发明的合成方法中所采用的混合金属氧化物固体催化剂不含贵金属和对环境有害的元素;本发明的合成工艺中反应副产物氢气为清洁的能源,可供利用。
具体实施方式
下面将结合具体的实施例,对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明的一部分实施例,而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的,决不作为对本发明及其应用或使用的任何限制。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
在选用本发明的这种混合金属氧化物固体催化剂(MOx)进行气固催化合成丙酸丙酯前,先用氢气和氮气(H2/N2)的混合气体对所述混合金属氧化物固体催化剂进行还原,即将所述混合金属氧化物固体催化剂组分中的氧化高钴(Co2O3)、氧化铜(CuO)还原成金属或低价态金属氧化物。
实施例1
一种丙酸丙酯的合成方法,包括如下具体步骤:
(1)将4.0g的混合金属氧化物固体催化剂放在尺寸为Φ20×3×300mm的不锈钢单管反应器的中部,并在反应器的两头填充惰性的粗石英砂固定位置;然后以丙醇作为丙酸丙酯的合成原料,将丙醇通过计量泵泵入反应器中并预热,使丙醇原料成为丙醇气体;所述的混合金属氧化物固体催化剂中各金属的组成为Cu=25wt%,Co=10wt%,Zn=20wt%,Al=15wt%,Zr=20wt%,Ce=10wt%,即该混合金属氧化物固体催化剂为Cu0.25Co0.1Zn0.2Ce0.1Al0.15Zr0.2Ox,X为满足所述混合金属氧化物固体催化剂中各元素化合价的氧原子总数;且在该催化剂使用前先用氢气和氮气(H2/N2)的混合气体对所述混合金属氧化物固体催化剂进行还原;
(2)将丙醇气体连续流过内部填充Cu0.25Co0.1Zn0.2Ce0.1Al0.15Zr0.2Ox混合金属氧化物固体催化剂的反应器,进行气固催化反应;控制反应的温度为250℃,反应压力为1.0MPa,丙醇原料液体重量空速为1h-1;
(3)催化反应后,将气体反应产物从反应器底部引出,直接进入水冷器,冷却为液体,然后精馏除去未反应的丙醇原料、中间产物丙醛与丙酸以及副产物3-戊酮,即可得到丙酸丙酯产品。
经色谱分析得出丙醇转化率为65%,酯选择性为90%,副产物为3-戊酮,还有一些反应中间物丙醛与少量丙酸,丙醛与丙酸分离后可再次用作原料继续合成丙酸丙酯。
实施例2
一种丙酸丙酯的合成方法,包括如下具体步骤:
(1)将4.0g的混合金属氧化物固体催化剂放在尺寸为Φ20×3×300mm的不锈钢单管反应器的中部,并在反应器的两头填充惰性的粗石英砂固定位置;然后以丙醇作为丙酸丙酯的合成原料,将丙醇通过计量泵泵入反应器中并预热,使丙醇原料成为丙醇气体;所述的混合金属氧化物固体催化剂中各金属的组成为Cu=30wt%,Zn=25wt%,Al=20wt%,Zr=25wt%,即该混合金属氧化物固体催化剂为Cu0.35Zn0.25Al0.2Zr0.25Ox,X为满足所述混合金属氧化物固体催化剂中各元素化合价的氧原子总数;且在该催化剂使用前先用氢气和氮气(H2/N2)的混合气体对所述混合金属氧化物固体催化剂进行还原;
(2)将丙醇气体连续流过内部填充有Cu0.3Zn0.25Al0.2Zr0.25Ox混合金属氧化物固体催化剂的反应器,进行气固催化反应;控制反应的温度为265℃,反应压力为1.5MPa,丙醇原料重量空速为1.5h-1;
(3)催化反应后,将气体反应产物从反应器底部引出,直接进入水冷器,冷却为液体,然后精馏除去未反应的丙醇原料、中间产物丙醛与丙酸以及副产物3-戊酮,即可得到丙酸丙酯产品。
经色谱分析得出丙醇转化率为60%,酯选择性为92%,副产物为3-戊酮,还有一些反应中间物丙醛与少量丙酸,丙醛与丙酸分离后可再次用作原料继续合成丙酸丙酯。
实施例3
一种丙酸丙酯的合成方法,包括如下具体步骤:
(1)将4.0g的混合金属氧化物固体催化剂放在尺寸为Φ20×3×300mm的不锈钢单管反应器的中部,并在反应器的两头填充惰性的粗石英砂固定位置;然后以丙醇作为丙酸丙酯的合成原料,将丙醇通过计量泵泵入反应器中并预热,使丙醇原料成为丙醇气体;所述的混合金属氧化物固体催化剂中各金属的组成为Cu=20wt%,Co=20wt%,Zn=20wt%,Al=25wt%,Zr=15wt%,即该混合金属氧化物固体催化剂为Cu0.2Co0.2Zn0.2Al0.25Zr0.15Ox,X为满足所述混合金属氧化物固体催化剂中各元素化合价的氧原子总数;且在该催化剂使用前先用氢气和氮气(H2/N2)的混合气体对所述混合金属氧化物固体催化剂进行还原;
(2)将丙醇气体连续流过内部填充有Cu0.2Co0.2Zn0.2Al0.25Zr0.15Ox混合金属氧化物固体催化剂的反应器,进行气固催化反应;控制反应的温度为300℃,反应压力为2MPa,丙醇原料重量空速为2.5h-1;
(3)催化反应后,将气体反应产物从反应器底部引出,直接进入水冷器,冷却为液体,然后精馏除去未反应的丙醇原料、中间产物丙醛与丙酸以及副产物3-戊酮,即可得到丙酸丙酯产品。
经色谱分析得出丙醇转化率为63%,酯选择性为91%,副产物为3-戊酮,还有一些反应中间物丙醛与少量丙酸,丙醛与丙酸分离后可再次用作原料继续合成丙酸丙酯。
上述为本发明的较佳实施例仅用于解释本发明,并不用于限定本发明。凡由本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之中。
Claims (7)
1.一种丙酸丙酯的合成方法,其特征在于,包括如下步骤:
(1)以丙醇作为原料并将其加热成为丙醇气体;
(2)将所述丙醇气体连续流过一个内部填充有混合金属氧化物固体催化剂的固定床反应器,进行气固催化反应;所述的混合金属氧化物固体催化剂其组成为MOx,其中M代表金属元素,且M选自铜以及其余金属,所述的其余金属选自锌、锆、铈、钴、铝中几种金属的组合,X为满足所述混合金属氧化物固体催化剂中各元素化合价的氧原子总数;所述的混合金属氧化物固体催化剂中各金属原子的重量百分比为Cu:10-40wt%;Co:0-20wt%;Zn:5-30wt%;Zr:5-30wt%;Ce:0-10wt%;Al:15-50wt%;
(3)催化反应后冷却,精馏,得到丙酸丙酯。
2.根据权利要求1所述的一种丙酸丙酯的合成方法,其特征在于,步骤(2)中所述丙醇气体的流量以重量空速表示,其重量空速为0.5-3h-1。
3.根据权利要求2所述的一种丙酸丙酯的合成方法,其特征在于,所述丙醇气体的流量以重量空速表示,其重量空速为1-2.5h-1。
4.根据权利要求1所述的一种丙酸丙酯的合成方法,其特征在于,步骤(2)中所述气固催化反应的温度为230-320℃,反应压力为0.5-3MPa。
5.根据权利要求4所述的一种丙酸丙酯的合成方法,其特征在于,所述气固催化反应的温度为250-300℃,反应压力为1-2MPa。
6.根据权利要求1所述的一种丙酸丙酯的合成方法,其特征在于,步骤(2)中所述混合金属氧化物固体催化剂中各金属原子的重量百分比为Cu:15-35wt%;Co:10-20wt%;Zn:10-25wt%;Zr:10-25wt%;Ce:0-10wt%;Al:20-40wt%。
7.根据权利要求1所述的一种丙酸丙酯的合成方法,其特征在于,步骤(3)催化反应后气体反应产物从所述固定床反应器下部引出,经水冷器冷却为液体产物,然后精馏分离,得到丙酸丙酯产品。
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