CN1498215A - 由乙酰丙酸制备5-甲基丁内酯的方法 - Google Patents
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Abstract
本发明描述了一种由乙酰丙酸制备5-甲基丁内酯的方法,该方法使用任选负载在载体上的金属催化剂,该催化剂既有加氢的功能又有闭环的功能。
Description
技术领域
本发明涉及利用任选负载在载体上的金属催化剂由乙酰丙酸制备5-甲基丁内酯的方法。
背景技术
众所周知,乙酰丙酸是己糖酸解后的一种产物,并且可以从纤维素原料中廉价的获得。因此,它是用来生产许多有用的5碳化合物比如甲基四氢呋喃及其衍生物的一种诱人的起始原料。5-甲基丁内酯(也称为5-戊内酯或γ-戊内酯)如下图所示从乙酰丙酸制得。
USP 5 883 266公开了利用双功能催化剂由乙酰丙酸制备包括5-戊内酯在内的多种产品的方法,该催化剂的第一个功能是加氢,第二个功能是开环。USP 2 786 852公开了使用还原的氧化铜催化剂从乙酰丙酸制备5-戊内酯的方法。USP 4 420 622公开了使用金属催化剂由乙酰丙酸制备5-烷基丁内酯的方法。
发明内容
本发明涉及一种制备5-甲基丁内酯的方法,该方法包括在氢气以及催化量的催化剂的存在下加热乙酰丙酸,其中的催化剂既有加氢的功能又有闭环的功能,该催化剂是金属。这种金属催化剂任选负载在催化剂载体上。优选催化剂载体选自碳、二氧化硅和三氧化二铝。更优选的催化剂载体成员是碳。最优选的催化剂载体成员是氧化稳定的碳。
本发明的金属催化剂可以选自元素周期表中的VII族(第8-10族)元素;优选选自铱、钯、铂、铼、铑、钌及其组合。更优选金属催化剂是钌;最优选负载在氧化稳定碳上的钌。
本发明的方法优选在约100℃~约200℃的温度下进行;更优选在约140-160℃的温度下进行。本发明方法还优选在约0.5-约10.0MPa的压力下进行;更可取的情形是在约4.0-约6.0MPa的压力下进行。本发明方法也优选在液相中进行。
本发明的催化剂可任选用至少一种助催化剂促进,优选所述助催化剂是金属。更可取的是,助催化剂选自元素周期表中VII族(第8-10族)和IB族(第11族)的元素,更优选金,银和铜。
发明详述
本发明涉及在金属催化剂存在下由乙酰丙酸制备5-甲基丁内酯也就是5-戊内酯或γ-戊内酯的方法。
本发明的催化剂包括一种或多种选自元素周期表中VIII族(第8族-10族)的金属,更优选选自铱、钯、铂、铼、铑和钌。金属催化剂可任选负载在催化剂载体上。可用现有技术中的任何方法将金属沉积在载体上。优选的是,催化剂含约1%-约10%重量负载在载体上的金属,更优选约5%的重量。
催化剂任选包括一种或多种助催化剂。较好的情形是该助催化剂也是一金属,相对金属催化剂而言,助催化剂的含量不超过50%重量。更可取的情形是助催化剂是元素周期表中VIII或IB族(11族)的金属。
每种金属独自具有加氢的功能和闭环的功能;也就是反应一步进行,产生极少的或不产生戊基醇比如戊二醇之类的物质。
催化剂载体可以是包括但不限于金属氧化物例如二氧化硅、三氧化铝、和二氧化钛以及碳的任何惰性固态物质。优选表面积大于200m2/gm的碳。催化剂载体可以是粉末、颗粒、小球或类似形状的形式。
“氧化稳定的碳”在这里定义为在空气中受热时其重量基本上不变的碳。这类碳在WO97/30932中有更进一步的描述。特别是,当碳在空气中于125℃下受热30分钟,接着在200℃下受热30分钟,接着在300℃下受热30分钟,接着在350℃下受热45分钟,接着在400℃下受热45分钟,接着在450℃下受热45分钟,最后在500℃下受热30分钟的情况下,本发明使用的碳失重不超过20%。用来评价在空气中碳样受热效应的这种时间和温度条件的次序在这里被定义为“WVC温度试验”。可用热重分析法(TGA)来进行“WVC温度试验”。经历“WVC温度试验”后失重约20%或更少的碳被认为是高度氧化稳定的。从以下任一途经获得的碳都可用于本发明的方法中:木头、泥炭、煤、椰子壳、骨头、褐煤、石油残渣和糖。可用于本发明的、可商业获得的碳包括以下列商标出售的碳:Bameby & SutcliffeTM,DarcoTM,NucharTM,Columbia JXNTM,Columbia LCKTM,Calgon PCBTM,Calgon BPLTM,WestvacoTM,NoritTM和Barnaby Cheny NBTM。
该方法最好在约50℃-约250℃下进行,优选在约100℃-约200℃,更优选在约140℃-约160℃下进行。该方法在约5-约100个大气压(0.5MPa-10MPa)下进行,优选在约40-约60个大气压(4.0MPa-6.0MPa)下进行。该方法在纯氢气氛围或氢气和惰性气体的混合物气氛下进行。
该方法优选在液相中进行。溶剂的选择并不重要,前提是溶剂对催化剂、反应物或产品无害。较好的溶剂是二噁烷或5-戊内酯,较好的反应器装置是喷淋床和泥浆。
下面用实施例进一步说明本发明。
材料和方法
本文使用了下列缩写及其定义:
LA 乙酰丙酸
5-MGBL 5-甲基-γ-丁内酯
所用的催化剂载体列表如下。根据“WVC温度试验”用热重分析法(TGA)测试了氧化稳定的碳催化剂载体的重量稳定性。
载体
失重
材料来源
Sibunit碳 1.6% Boreskov Inst.Of
catalysis,
Novosibirsk,
Russia
Silica grade 55 没有 W.R.Grace & Co.,
Columbia,MD
Calsicat碳 14.9% Englehard Corp.,E.
Windor,CT
Calgon PCB碳 49% Nalco Chemical Co.,
Naperville,IL
Al2O3 没有 Harshaw Chemical
Co.,Cleveland,OH
实施例
以初期湿润法(incipient wetness)用金属盐浸渍催化剂载体制备催化剂。所用前体是:NiCl2·6H2O(Alfa Aesar,Ward Hill,MA),Re2O7(Alfa),PdCl2(Alfa),RuCl3·xH2O(Aldrich,Milwaukee,WI),H2PtCl6(Johnson Matthey,Ward Hill,MA),用RhCl3·xH2O的5%Rh(Alfa),Re2O7(Alfa),和IrCl3·3H2O(Johnson Matthey)。在氢气中于400℃干燥和还原样品2小时。在2mL压力容器中放置原料以及1mL由50%的乙酰丙酸/二噁烷溶液和如表中列出量的催化剂组成的溶液进行反应。容器填充氢气并在215℃加热2小时,在实施例1-22中,压力为800psi(5.5MPa),而在实施例23-32中,压力为700psi(4.8MPa)。然后冷却、排空,产物以甲氧乙基醚作为内标进行GC-MS分析。如下表1显示结果,列中“LA Con”是指LA转化量,通过用乙酰丙酸的起始量减去乙酰丙酸的剩余量(起始LA量-剩余LA量)测得。
表1
实例 | H2(psi) | 催化剂 | 5-MGBLSel(%) | LACon(%) | 原料(mg) | 催化剂(mg) |
1 | 700 | 5%Ir/Al2O3 | 70.3 | 36.3 | 974.5 | 103.2 |
2 | 700 | 5%Ir/Calgon C | 96.7 | 31.4 | 979.3 | 103.8 |
3 | 700 | 5%Ir/Calsicat C | 98.1 | 40.4 | 972.8 | 98 |
4 | 800 | 5%Ir/Calsicat C | 98.5 | 98.7 | 986.4 | 100.9 |
5 | 800 | 5%Ir/Calsicat C | 95.4 | 99.4 | 990.1 | 101 |
6 | 700 | 5%Ir/Sibunit C | 95.1 | 40.8 | 984.8 | 106.1 |
7 | 800 | 5%Ir/Sibunit C | 97.0 | 67.3 | 998.2 | 99.8 |
8 | 800 | 5%Ir/Sibunit C | 96.9 | 63.5 | 989.9 | 100.7 |
9 | 700 | 5%Ir/SiO2 | 85.7 | 19.9 | 986.3 | 101.7 |
10 | 800 | 5%Pd/Calgon C | 89.0 | 15.7 | 967.5 | 99.1 |
11 | 800 | 5%Pd/Calsicat C | 92.4 | 32.1 | 982 | 100.4 |
12 | 800 | 5%Pd/Calsicat C | 96.8 | 69.4 | 976.6 | 98.6 |
13 | 800 | 5%Pd/Calsicat C | 91.5 | 66.8 | 991.8 | 99.7 |
14 | 800 | 5%Pd/Sibunit C | 82.2 | 16.3 | 981.3 | 102.3 |
15 | 800 | 5%Pd/SiO2 | 67.0 | 17.7 | 1028.5 | 99 |
16 | 800 | 5%Pt/Calgon C | 72.1 | 25.3 | 1017.8 | 105.8 |
17 | 700 | 5%Pt/Calsicat C | 82.5 | 15.6 | 940.7 | 99.7 |
18 | 800 | 5%Pt/Sibunit C | 81.8 | 18.4 | 958.1 | 97.7 |
19 | 800 | 5%Pt/SiO2 | 71.9 | 19.0 | 981.9 | 97.2 |
20 | 700 | 5%Re/Calgon C | 83.2 | 7.8 | 970 | 97.6 |
21 | 700 | 5%Re/Calsicat C | 82.3 | 8.9 | 961 | 97.9 |
22 | 700 | 5%Re/Sibunit C | 76.4 | 11.1 | 957 | 102.2 |
23 | 800 | 5%Rh/Al2O3 | 81.0 | 52.8 | 962.3 | 103.3 |
24 | 800 | 5%Rh/Calgon C | 96.1 | 62.1 | 989.9 | 105.2 |
25 | 700 | 5%Rh/Calsicat C | 97.6 | 30.7 | 934.8 | 100.4 |
26 | 800 | 5%Rh/Calsicat C | 96.0 | 99.9 | 990.6 | 100.9 |
27 | 800 | 5%Rh/Calsicat C | 96.1 | 100.0 | 986.1 | 98.3 |
28 | 800 | 5%Rh/Sibunit C | 82.1 | 54.8 | 982 | 102.7 |
实例 | H2(psi) | 催化剂 | 5-MGBLSel(%) | LACon(%) | 原料(mg) | 催化剂(mg) |
29 | 800 | 5%Rh/Sibunit C | 97.3 | 97.6 | 993 | 102.2 |
30 | 800 | 5%Rh/Sibunit C | 97.5 | 96.4 | 990.1 | 100.8 |
31 | 800 | 5%Rh/SiO2 | 83.9 | 43.3 | 993.2 | 97.4 |
32 | 800 | 5%Ru/Al2O3 | 64.7 | 42.3 | 999.9 | 96.8 |
33 | 800 | 5%Ru/Calgon C | 88.5 | 57.5 | 1010 | 103.2 |
34 | 800 | 5%Ru/Calgon C | 73.2 | 32.6 | 974.6 | 10.5 |
35 | 800 | 5%Ru/Calgon C | 67.6 | 59.9 | 975.1 | 10.7 |
36 | 800 | 5%Ru/Calsicat C | 92.2 | 81.0 | 987.6 | 97.8 |
37 | 800 | 5%Ru/Calsicat C | 73.5 | 50.0 | 1002 | 10 |
38 | 800 | 5%Ru/Calsicat C | 76.0 | 65.1 | 980.7 | 10.2 |
39 | 800 | 5%Ru/Calsicat C | 97.0 | 100.0 | 985.2 | 100.9 |
40 | 800 | 5%Ru/Calsicat C | 94.2 | 100.0 | 996.5 | 97.8 |
41 | 800 | 5%Ru/Sibunit C | 97.4 | 52.0 | 990.1 | 105.2 |
42 | 800 | 5%Ru/Sibunit C | 81.5 | 31.5 | 975.7 | 10.2 |
43 | 800 | 5%Ru/Sibunit C | 80.9 | 47.9 | 974.7 | 10.8 |
44 | 800 | 5%Ru/Sibunit C | 97.7 | 97.3 | 980.4 | 100 |
45 | 800 | 5%Ru/Sibunit C | 98.5 | 98.3 | 988.6 | 100.1 |
46 | 800 | 5%Ru/SiO2 | 81.6 | 37.1 | 1010.9 | 99.3 |
Claims (16)
1.一种制备5-甲基丁内酯的方法,该方法包括在氢气以及催化量的金属催化剂存在下加热乙酰丙酸,所说的金属催化剂既具加氢的功能又具闭环的功能。
2.权利要求1中所述的方法,其中的金属催化剂负载在催化剂载体上。
3.权利要求2中所述的方法,其中的催化剂载体选自碳、SiO2和Al2O3。
4.权利要求3中所述的方法,其中的碳是氧化稳定的。
5.权利要求1中所述的方法,其中的金属催化剂选自元素周期表中的VIII族元素。
6.权利要求1中所述的方法,其中的金属催化剂选自铂、铼、钌、铹、铱、钯及其组合。
7.权利要求6中所述的方法,其中的金属催化剂是钌。
8.权利要求7中所述的方法,其中的碳是氧化稳定的。
9.权利要求1中所述的方法,其中所说的方法在约100℃~约200℃的温度下进行。
10.权利要求1中所述的方法,其中所说的方法在约140℃~约160℃的温度下进行。
11.权利要求1中所述的方法,其中所说的方法在约0.5MPa~约10.0MPa的压力下进行。
12.权利要求1中所述的方法,其中所说的方法在约4.0MPa~约6.0MPa的压力下进行。
13.权利要求1中所述的方法,其中所说的方法在液相中进行。
14.权利要求1中所述的方法,其中的金属催化剂任选用至少一种助催化剂促进。
15.权利要求14中所述的方法,其中的助催化剂是金属。
16.权利要求15中所述的方法,其中的助催化剂选自元素周期表中的VIII和IB族元素。
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EP (1) | EP1368333A1 (zh) |
JP (1) | JP2005500987A (zh) |
KR (1) | KR20030082984A (zh) |
CN (1) | CN1498215A (zh) |
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FR3008970B1 (fr) * | 2013-07-25 | 2015-08-21 | IFP Energies Nouvelles | Procede de production d'alcools par hydrogenation catalytique d'acide levulinique en une etape |
WO2016056030A1 (en) | 2014-10-08 | 2016-04-14 | Council Of Scientific & Industrial Research | A process for the preparation of gamma-valerolactone by catalytic hydrogenation of levulinic acid using ru-based catalysts |
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EP3381911A4 (en) * | 2015-11-16 | 2019-06-26 | UBE Industries, Ltd. | PROCESS FOR THE PREPARATION OF VALEROLACTONE |
US9878967B2 (en) | 2015-12-23 | 2018-01-30 | Iowa State University Research Foundation, Inc. | Method of converting levulinic acid or a derivative thereof to hydrocarbons and hydrogen, and methods of the production of hydrocarbons and hydrogen |
FI127191B (en) | 2015-12-23 | 2018-01-15 | Neste Oyj | Co-production of levulinic acid and furfural from biomass |
FI127020B (en) | 2015-12-23 | 2017-09-29 | Neste Oyj | Selective process for the conversion of levulinic acid to gamma valerolactone |
CN108014798B (zh) * | 2016-11-04 | 2020-10-30 | 中国石油化工股份有限公司 | 加氢制备2-甲基四氢呋喃的催化剂及其使用方法 |
CN110548505A (zh) * | 2019-08-20 | 2019-12-10 | 青岛科技大学 | 核壳型催化剂及其合成方法、以及其催化乙酰丙酸制备γ-戊内酯的方法 |
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US2368366A (en) * | 1942-08-21 | 1945-01-30 | Monsanto Chemicals | Process for the production of lactones |
US2786852A (en) * | 1953-08-19 | 1957-03-26 | Quaker Oats Co | Process of preparing gammavalerolactone |
GB896949A (en) * | 1957-12-14 | 1962-05-23 | Basf Ag | Improvements in the production of proto-anemonin and its homologues |
NL8103173A (nl) * | 1981-07-02 | 1983-02-01 | Stamicarbon | Werkwijze voor de bereiding van een 5-alkyl-butyrolacton. |
US5883266A (en) * | 1998-01-16 | 1999-03-16 | Battelle Memorial Institute | Hydrogenated 5-carbon compound and method of making |
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2002
- 2002-03-14 KR KR10-2003-7011976A patent/KR20030082984A/ko not_active Application Discontinuation
- 2002-03-14 WO PCT/US2002/007878 patent/WO2002074760A1/en not_active Application Discontinuation
- 2002-03-14 CA CA002437740A patent/CA2437740A1/en not_active Abandoned
- 2002-03-14 BR BR0208248-9A patent/BR0208248A/pt not_active IP Right Cessation
- 2002-03-14 JP JP2002573769A patent/JP2005500987A/ja not_active Withdrawn
- 2002-03-14 CN CNA028067231A patent/CN1498215A/zh active Pending
- 2002-03-14 EP EP02725171A patent/EP1368333A1/en not_active Withdrawn
- 2002-03-15 US US10/099,354 patent/US6617464B2/en not_active Expired - Fee Related
Cited By (11)
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CN101805316A (zh) * | 2010-04-22 | 2010-08-18 | 复旦大学 | 一种用负载型铱催化剂制备γ-戊内酯的方法 |
CN103619826A (zh) * | 2011-06-21 | 2014-03-05 | 帝斯曼知识产权资产管理有限公司 | 用乙酰丙酸生产戊内酯的方法 |
CN103619826B (zh) * | 2011-06-21 | 2015-09-23 | 帝斯曼知识产权资产管理有限公司 | 用乙酰丙酸生产戊内酯的方法 |
CN103827074A (zh) * | 2011-09-23 | 2014-05-28 | 帝斯曼知识产权资产管理有限公司 | 由内酯生产烯酸酯的方法 |
CN103827074B (zh) * | 2011-09-23 | 2016-05-25 | 帝斯曼知识产权资产管理有限公司 | 由内酯生产烯酸酯的方法 |
CN102558108A (zh) * | 2011-12-22 | 2012-07-11 | 南开大学 | 用铱-钳形配体络合物催化剂制备γ-戊内酯的方法 |
CN102558108B (zh) * | 2011-12-22 | 2014-07-16 | 南开大学 | 用铱-钳形配体络合物催化剂制备γ-戊内酯的方法 |
CN102617519A (zh) * | 2012-03-05 | 2012-08-01 | 中国石油大学(华东) | 由乙酰丙酸加氢制备γ-戊内酯的方法 |
CN102617519B (zh) * | 2012-03-05 | 2014-08-13 | 中国石油大学(华东) | 由乙酰丙酸加氢制备γ-戊内酯的方法 |
CN109395723A (zh) * | 2018-12-10 | 2019-03-01 | 郑州师范学院 | 一种乙酰丙酸加氢制γ-戊内酯Ru-Al催化体系及其制备方法和应用 |
CN109395723B (zh) * | 2018-12-10 | 2021-08-31 | 郑州师范学院 | 一种乙酰丙酸加氢制γ-戊内酯Ru-Al催化体系及其制备方法和应用 |
Also Published As
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US20030055270A1 (en) | 2003-03-20 |
CA2437740A1 (en) | 2002-09-26 |
WO2002074760A1 (en) | 2002-09-26 |
US6617464B2 (en) | 2003-09-09 |
KR20030082984A (ko) | 2003-10-23 |
EP1368333A1 (en) | 2003-12-10 |
BR0208248A (pt) | 2004-03-02 |
JP2005500987A (ja) | 2005-01-13 |
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