WO2008089899A1 - Verfahren zur herstellung von 1,2-propandiol durch hydrogenolyse von glycerin - Google Patents
Verfahren zur herstellung von 1,2-propandiol durch hydrogenolyse von glycerin Download PDFInfo
- Publication number
- WO2008089899A1 WO2008089899A1 PCT/EP2008/000255 EP2008000255W WO2008089899A1 WO 2008089899 A1 WO2008089899 A1 WO 2008089899A1 EP 2008000255 W EP2008000255 W EP 2008000255W WO 2008089899 A1 WO2008089899 A1 WO 2008089899A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glycerol
- propanediol
- weight
- catalyst
- reaction
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/02—Pitching yeast
Definitions
- the present invention relates to a process for the preparation of 1,2-propanediol from glycerol.
- 1, 2-Propanediol is currently produced industrially from propylene oxide by water addition and used in a variety of applications, such. as a component of brake and hydraulic fluids, lubricants and antifreeze, in cosmetics, in the food industry and as a solvent for fats, oils, resins and dyes.
- Propylene oxide and thus also 1, 2-propanediol is currently produced entirely from fossil fuels.
- glycerol Due to the constant demand for the use of renewable raw materials and the rising crude and falling glycerol prices, there is a great need to use glycerol, which is a by-product in large quantities in biodiesel production, as a starting material for suitable chemical reactions on a large industrial scale.
- DE-A-44 42 124 describes the catalytic hydrogenation of glycerol with a water content of up to 20 wt .-% to propylene glycol in a yield of 92%, as by-products n-propanol and lower alcohols are obtained.
- Complete conversion of glycerine is achieved through the use of a mixed catalyst of the metals cobalt, copper, manganese and molybdenum.
- the reaction conditions are in a pressure and temperature range of 100 to 700 bar and 180 to 270 0 C.
- Preferred hydrogenation conditions are 200 to 325 bar and 200 to 25O 0 C.
- the disadvantage is that at lower pressures, the reaction of glycerol is incomplete, and increasingly form lower alcohols at higher pressures.
- US 4,642,394 describes a process for the catalytic hydrogenation of glycerol with a catalyst consisting of tungsten and a group VIII metal.
- the Reaction conditions range from 100 psi to 15,000 psi and 75 to 250 ° C. Preferred process conditions are 100 to 200 ° C and 200 to 10,000 psi.
- the reaction is carried out under basic conditions by the use of amines or amides as solvent. It is also possible to use metal hydroxides, metal carbonates or quaternary ammonium salts.
- the solvent is added in a concentration of 5 to 100 ml per gram of glycerol. Carbon monoxide is used to stabilize and activate the catalyst.
- EP-AO 523 015 describes the hydrogenation of glycerol over Cu / Zn catalysts, but using very dilute aqueous solutions (about 30% by weight of glycerol content) which are further diluted by the water of reaction formed. To obtain 1, 2-propanediol therefore a large amount of water must be distilled off from the product, which means a lot of energy and does not make the process economical. Furthermore, the process at relatively high pressures of preferably 100, - bar and high temperatures 230150-270 0 C. The conversion of glycerol is in the range of 8 to 100% at a selectivity to propylene glycol of 80 to 98%, as by-products of alcohols and ethylene glycol are formed.
- DE-A-43 02 464 describes a process in which glycerol is hydrogenated in a continuous mode over a fixed bed CuO / ZnO catalyst.
- a complete hydrogenation of glycerol is achieved at 200 0 C, as by-products low-level alcohols and relatively large amounts (5.4 wt .-%) of unknown substances are formed.
- Another disadvantage is the very high reaction pressure of 250 bar. At lower pressures (50-150 bar) and higher temperatures (240 ° C.), increasingly unknown substances (25-34% by weight) are formed, the selectivity to 1,2-propanediol dropping to 22-31% by weight ,
- 1, 2-propanediol can be prepared by hydrogenation of substantially pure glycerol on a manganese-containing copper oxide / zinc oxide catalyst in high yield and high selectivity.
- a selectivity to 1,2-propanediol of 97-98% is achieved with complete conversion of glycerol, as by-products only monoethylene glycol (about 1 - 2%) and in small amounts of n-propanol and methanol are detectable.
- the invention relates to a process for the preparation of 1, 2-propanediol by reacting glycerol, which has a purity of at least 95 wt .-%, with hydrogen at a hydrogen pressure of 20 to 100 bar and a temperature of 180 to 240 0 C. in the presence of a catalyst comprising 20 to 60% by weight of copper oxide, 30 to 70% by weight of zinc oxide and 1 to 10% by weight of manganese oxide in an autoclave.
- the catalyst used in the process according to the invention is preferably free of carrier material and preferably contains 40-45% by weight of copper oxide, preferably 50-55% by weight of zinc oxide and preferably 2% to 5% by weight of manganese oxide.
- copper oxide, zinc oxide and manganese oxide add up to 100% by weight.
- the hydrogenation of glycerol is in the process of this invention at hydrogen pressures of preferably 50 - 80 bar, and temperatures of preferably 200 - 22O 0 C performed.
- the hydrogenation of glycerol of high purity of 99% by weight and higher is preferred. If crude glycerol from the transesterification of fats and oils is used in the process according to the invention, this should expediently be concentrated by distillation and freed from catalyst poisons such as the sulfuric acid often used as transesterification catalyst.
- the inventive method has the advantage that a complete hydrogenation of the glycerol is achieved, wherein the desired reaction product 1, 2-propanediol is formed in high selectivity of up to 98 wt .-%.
- By-products are only monoethylene glycol and detectable in small amounts of n-propanol and methanol, which can be easily removed by distillation with the water of reaction. If required, the product mixture obtained can either be used directly for chemical applications or converted into pure 1,2-propanediol (> 99.5% by weight) by further purification by distillation.
- Example 1 Process for the preparation of 1,2-propanediol by hydrogenolysis of glycerol on a CuO / ZnO / MnO 2 catalyst
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Mycology (AREA)
- Food Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/523,880 US7868212B2 (en) | 2007-01-22 | 2008-01-15 | Method for preparing 1,2-propanediol by hydrogenolysis of glycerol |
EP08701112A EP2111386A1 (de) | 2007-01-22 | 2008-01-15 | Verfahren zur herstellung von 1,2-propandiol durch hydrogenolyse von glycerin |
BRPI0806717-1A BRPI0806717A2 (pt) | 2007-01-22 | 2008-01-15 | método para a preparação de 1,2 propandiol através da hidrogenólise de glicerina |
JP2009545866A JP2010516642A (ja) | 2007-01-22 | 2008-01-15 | グリセリンの水素化分解による1,2−プロパンジオールの製造方法 |
CA002676055A CA2676055A1 (en) | 2007-01-22 | 2008-01-15 | Method for preparing 1,2-propanediol by hydrogenolysis of glycerol |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007003188.4 | 2007-01-22 | ||
DE102007003188A DE102007003188B3 (de) | 2007-01-22 | 2007-01-22 | Verfahren zur Herstellung von 1,2-Propandiol durch Hydrogenolyse von Glycerin |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008089899A1 true WO2008089899A1 (de) | 2008-07-31 |
Family
ID=39204857
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2008/000255 WO2008089899A1 (de) | 2007-01-22 | 2008-01-15 | Verfahren zur herstellung von 1,2-propandiol durch hydrogenolyse von glycerin |
Country Status (8)
Country | Link |
---|---|
US (1) | US7868212B2 (de) |
EP (1) | EP2111386A1 (de) |
JP (1) | JP2010516642A (de) |
CN (1) | CN101568510A (de) |
CA (1) | CA2676055A1 (de) |
DE (1) | DE102007003188B3 (de) |
RU (1) | RU2436761C2 (de) |
WO (1) | WO2008089899A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009027502A3 (de) * | 2007-08-31 | 2009-04-30 | Basf Se | Verfahren zur herstellung von 1,2-propandiol durch niederdruck-hydrierung von glycerin |
WO2011009936A3 (en) * | 2009-07-24 | 2011-07-28 | Basf Se | Process for the preparation of 1,2-propanediol from glycerol |
US8252962B2 (en) | 2007-08-31 | 2012-08-28 | Basf Se | Method for producing 1,2-propandiol by hydrogenating glycerine in a two-step reactor cascade |
US8293951B2 (en) | 2007-08-31 | 2012-10-23 | Basf Se | Method for producing 1,2-propandiol by hydrogenation in at least three successive reactors |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5350059B2 (ja) * | 2008-04-22 | 2013-11-27 | 三井化学株式会社 | プロピレングリコールの製造方法 |
BRPI0902818A2 (pt) * | 2009-03-09 | 2010-11-23 | Petroleo Brasileiro Sa | processo de produção de propilenoglicol a partir de glicerina de biodiesel |
DE102010015006A1 (de) | 2010-04-14 | 2011-11-24 | Tu Darmstadt | Katalysator zur Hydrierung von wässrigen mehrwertigen Alkohollösungen |
CN112794790A (zh) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | 甘油制备1,2-丙二醇的系统和方法 |
CN113042051B (zh) * | 2021-04-01 | 2022-04-26 | 宁波环洋新材料股份有限公司 | 一种碳掺杂铜催化剂及其制备方法与它的用途 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4302464A1 (de) * | 1993-01-29 | 1994-08-04 | Henkel Kgaa | Herstellung von 1,2-Propandiol aus Glycerin |
US5387753A (en) * | 1993-12-02 | 1995-02-07 | Eastman Chemical Company | Process for the preparation of alcohols and diols |
DE4442124A1 (de) * | 1994-11-26 | 1996-05-30 | Basf Ag | Verfahren zur Herstellung von Propandiol-1,2 |
CN101012149A (zh) * | 2007-02-07 | 2007-08-08 | 南京工业大学 | 甘油催化加氢连续制备1,2-丙二醇的方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4642394A (en) * | 1985-07-16 | 1987-02-10 | Celanese Corporation | Production of propanediols |
IT1249955B (it) | 1991-07-10 | 1995-03-30 | Menon S R L | Procedimento di idrogenazione della glicerina |
GB0514593D0 (en) * | 2005-07-15 | 2005-08-24 | Davy Process Techn Ltd | Process |
JP5279513B2 (ja) * | 2006-03-03 | 2013-09-04 | ビーエーエスエフ ソシエタス・ヨーロピア | 1,2−プロパンジオールの製法 |
-
2007
- 2007-01-22 DE DE102007003188A patent/DE102007003188B3/de not_active Expired - Fee Related
-
2008
- 2008-01-15 RU RU2009131730/04A patent/RU2436761C2/ru not_active IP Right Cessation
- 2008-01-15 US US12/523,880 patent/US7868212B2/en not_active Expired - Fee Related
- 2008-01-15 CA CA002676055A patent/CA2676055A1/en not_active Abandoned
- 2008-01-15 CN CNA2008800012783A patent/CN101568510A/zh active Pending
- 2008-01-15 EP EP08701112A patent/EP2111386A1/de not_active Withdrawn
- 2008-01-15 WO PCT/EP2008/000255 patent/WO2008089899A1/de active Application Filing
- 2008-01-15 JP JP2009545866A patent/JP2010516642A/ja not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4302464A1 (de) * | 1993-01-29 | 1994-08-04 | Henkel Kgaa | Herstellung von 1,2-Propandiol aus Glycerin |
US5387753A (en) * | 1993-12-02 | 1995-02-07 | Eastman Chemical Company | Process for the preparation of alcohols and diols |
DE4442124A1 (de) * | 1994-11-26 | 1996-05-30 | Basf Ag | Verfahren zur Herstellung von Propandiol-1,2 |
CN101012149A (zh) * | 2007-02-07 | 2007-08-08 | 南京工业大学 | 甘油催化加氢连续制备1,2-丙二醇的方法 |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 200808, Derwent World Patents Index; Class E17, AN 2008-B16826, XP002474619, CHEN C ET AL.: "Method of continuous preparation of 1, 2-propanediol with catalyst hydrogenation of glycerol" * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009027502A3 (de) * | 2007-08-31 | 2009-04-30 | Basf Se | Verfahren zur herstellung von 1,2-propandiol durch niederdruck-hydrierung von glycerin |
US8252962B2 (en) | 2007-08-31 | 2012-08-28 | Basf Se | Method for producing 1,2-propandiol by hydrogenating glycerine in a two-step reactor cascade |
US8273924B2 (en) | 2007-08-31 | 2012-09-25 | Basf Se | Method for producing 1,2-propandiol by low-pressure hydrogenation of glycerine |
US8293951B2 (en) | 2007-08-31 | 2012-10-23 | Basf Se | Method for producing 1,2-propandiol by hydrogenation in at least three successive reactors |
WO2011009936A3 (en) * | 2009-07-24 | 2011-07-28 | Basf Se | Process for the preparation of 1,2-propanediol from glycerol |
Also Published As
Publication number | Publication date |
---|---|
DE102007003188B3 (de) | 2008-06-05 |
CN101568510A (zh) | 2009-10-28 |
US20100094064A1 (en) | 2010-04-15 |
RU2436761C2 (ru) | 2011-12-20 |
JP2010516642A (ja) | 2010-05-20 |
CA2676055A1 (en) | 2008-07-31 |
EP2111386A1 (de) | 2009-10-28 |
RU2009131730A (ru) | 2011-02-27 |
US7868212B2 (en) | 2011-01-11 |
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