WO2007010299A1 - Process - Google Patents

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Publication number
WO2007010299A1
WO2007010299A1 PCT/GB2006/050181 GB2006050181W WO2007010299A1 WO 2007010299 A1 WO2007010299 A1 WO 2007010299A1 GB 2006050181 W GB2006050181 W GB 2006050181W WO 2007010299 A1 WO2007010299 A1 WO 2007010299A1
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WO
WIPO (PCT)
Prior art keywords
glycerol
process according
hydrogenation
catalyst
hydrogen
Prior art date
Application number
PCT/GB2006/050181
Other languages
French (fr)
Inventor
Michael William Marshall Tuck
Simon Nicholas Tilley
Original Assignee
Davy Process Technology Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2008520964A priority Critical patent/JP5149796B2/en
Priority to ES06744361T priority patent/ES2298101T3/en
Priority to CN2006800006177A priority patent/CN101006036B/en
Priority to AU2006252177A priority patent/AU2006252177B2/en
Priority to KR1020077000311A priority patent/KR101325084B1/en
Priority to BRPI0606159-1A priority patent/BRPI0606159B1/en
Priority to EA200700445A priority patent/EA010314B1/en
Priority to EP06744361A priority patent/EP1836147B1/en
Application filed by Davy Process Technology Ltd filed Critical Davy Process Technology Ltd
Priority to DK06744361.4T priority patent/DK1836147T3/en
Priority to NZ551994A priority patent/NZ551994A/en
Priority to CA2569622A priority patent/CA2569622C/en
Priority to PL06744361T priority patent/PL1836147T3/en
Publication of WO2007010299A1 publication Critical patent/WO2007010299A1/en
Priority to US11/668,884 priority patent/US7355083B2/en

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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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/10—Monohydroxylic acyclic alcohols containing three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols

Definitions

  • the present invention relates to a process for the hydrogenation of 1 ,2,3-propanetriol, also known as glycerol, in the vapour phase. More particularly it relates to the selective hydrogenation of glycerol in the vapour phase whereby alteration of the process conditions enables selection of 1 ,2-propanediol or propanols as the major product.
  • Glycerol is available in large quantities and it is anticipated that the supply of glycerol will increase as it is a by-product of processes which are becoming increasingly attractive since they are based on natural products such as oils and fats as starting materials.
  • oils and fats include palm oil, rape seed oil, beef tallow and the like.
  • glycerol does not have uses to match its availability, it can be converted to 1 ,2- propanediol and 2-propanol which are valuable starting materials which have various applications.
  • Various processes have been proposed for effecting the conversion.
  • US5214219 which is incorporated herein by reference, describes a process in which glycerol is converted to 1 ,2-propanediol and 1 ,2-ethanediol.
  • hydrogenation of the glycerol is carried out in the liquid phase in the presence of a copper/zinc catalyst and at a temperature of about 22O 0 C.
  • An alternative processes for the liquid phase hydrogenation of glycerol is described in US5616817, which is incorporated herein by reference.
  • the process which is directed to the production of 1 ,2-propanediol, requires the glycerol to have a water content of no more than 20% by weight.
  • the hydrogenation is carried out in the presence of a catalyst comprising cobalt, copper, manganese and molybdenum.
  • DE4302464 and DE524101 describe in detail liquid phase processes for the production of 1,2- propanediol form glycerol. Whilst each makes passing reference to the possibility of the production being carried out in the vapour phase, neither document describes how the process can be efficiently and commercially carried out in the vapour phase to obtain high conversion and selectivity.
  • a process for hydrogenation of glycerol in which a feed comprising glycerol is contacted with a stream of a hydrogen-containing gas and subjected to hydrogenation in the vapour phase in the presence of a catalyst at a temperature of from about 160 0 C to about 260 0 C, a pressure of from about 10 to about 30 bar, a hydrogen to glycerol ratio of from 400: 1 to about 600: 1 and a residence time of from about 0.01 to about 2.5 sees.
  • the glycerol is vaporised into a stream of hydrogen-containing gas in a vaporiser before being passed to a hydrogenation reactor. It will be understood that the vaporiser and the hydrogenation reactor may be separate or may be zones located in the same reactor. Where a vaporiser is present, the hydrogen rich vapour stream will generally be passed directly to the hydrogenation reactor.
  • the hydrogen-containing gas stream may be fed to the vaporiser where present or to the hydrogenation reactor at any suitable temperature.
  • the hydrogenation-containing gas may include minor amounts of one or more inert gases which may include nitrogen, carbon oxides, neon, argon and/or low molecular weight hydrocarbons such as methane, ethane, propane, n-butane and Iso-butane. Ethanol and ethyl acetate may also be present.
  • inert gases may include nitrogen, carbon oxides, neon, argon and/or low molecular weight hydrocarbons such as methane, ethane, propane, n-butane and Iso-butane. Ethanol and ethyl acetate may also be present.
  • the glycerol feed may be from any source. It may be pure glycerol or it may contain other components such as other organic compounds, water and/or impurities.
  • the glycerol feed may include one or more of water, alcohols such as methanol, ethanol, propanol, hydroxy propanone, butanols and the like and esters. Involatile components may also be present.
  • Such components may be removed from the reaction by means of a purge which is usually taken form the bottom of the vaporiser.
  • the other components present will largely depend on the source of the glycerol. Since the process of the present invention may be carried out in the presence of such components there is no requirement to purify the glycerol prior to it being used as a feedstock. This offers significant advantages when the process of the present invention is to be coupled to plants in which glycerol is formed as a by-product. The process of the present invention will also be able to operate in the presence of a high salt and/or ash content.
  • any suitable catalyst system may be used.
  • the catalyst will be provided as a fixed bed located in the hydrogenation reactor.
  • Any suitable catalyst may be used.
  • a reduced copper catalyst may be used. Examples include copper/alumina/manganese, copper chromite, copper silica, copper zinc alumina, copper zinc oxide, raney copper and the like.
  • Reduced nickel or reduced cobalt containing catalysts may also be used.
  • Precious metal catalysts such as those containing ruthenium, palladium, platinum, rhodium and/or iridium may be used. These may be supported on, for example, carbon, alumina and silica.
  • the process may be carried out at any suitable reaction conditions within the ranges of the present invention.
  • Preferred temperatures are from about 200 0 C to about 24O 0 C. Temperatures of from about 205 0 C to about 220 0 C are particularly suitable. Pressures in the range of from about 17 bar to about 23 bar preferred with a pressure of 20 bar being particularly suitable. A residence time of from about 0.3 to about 1.5 sees may be used with a residence time of about 0.5 sees being particularly suitable.
  • the ratio of hydrogen to glycerol In the hydrogenation reactor feed is a function of temperature and the operating pressure. Preferred hydrogen to glycerol ratio is in the range of form about about 450:1 to about 550:1. A ratio of about 500:1 is most preferred.
  • the process of the present invention offers excellent conversion. Conversions in excess of 95%, 98% and even in excess of 99% have been noted. However, in the event of incomplete conversion, separation of product from glycerol is readily achieved and unreacted glycerol may be recycled. By-products which may be formed, such as 1 -hydroxy propanone, may ⁇ be recycled for further reaction to the desired product.
  • Water will be produced in the reaction and at least a portion of the water produced may be recycled. Thus, other than at start up it is not generally necessary to add water to the glycerol to protect the catalyst which has been a feature of liquid phase reactions.
  • the present invention relates to the selective hydrogenation of glycerol.
  • the invention selectively forms 1 ,2-propanediol and in an alternative arrangement the invention selectively forms propanols.
  • reaction temperatures of less than about 210 0 C favour the formation of the 1,2- propanediol while those of about 210 0 C and above favour the formation of propanols.
  • Examples 1 to 6 A 0.75" reactor was charged with 75 g (5OmIs) of catalyst DRD 9289 A, a copper based catalyst from Davy Process Technology Ltd, and reduced by conventional means. A feed of glycerol and methanol was fed to a heated vessel with the hydrogen at the reaction pressure and complete vapourisation of the feed mixture. The resultant gaseous stream was then passed to the reactor and contacted with the catalyst. Products removed from the reactor were condensed at 10 0 C and were analysed on a Hewlett Packard HP3560 GC equipped with a micro TCD detector. The conditions for the various examples are set out in Table 1 and the results are set out in Table 2. Table 1

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for hydrogenation of glycerol in which a feed comprising glycerol is contacted with a stream of a hydrogen-containing gas and subjected to hydrogenation in the vapour phase in the presence of a catalyst at a temperature of from about 160°C to about 260°C, a pressure of from about 10 to about 30 bar. a hydrogen to glycerol ratio of from 400: 1 to about 600: 1 and a residence time of from about 0.01 to about 2.5 hr-

Description

VAPOUR-PHASE HYDROGENATION OF GLYCEROL
The present invention relates to a process for the hydrogenation of 1 ,2,3-propanetriol, also known as glycerol, in the vapour phase. More particularly it relates to the selective hydrogenation of glycerol in the vapour phase whereby alteration of the process conditions enables selection of 1 ,2-propanediol or propanols as the major product.
Glycerol is available in large quantities and it is anticipated that the supply of glycerol will increase as it is a by-product of processes which are becoming increasingly attractive since they are based on natural products such as oils and fats as starting materials. Examples of oils and fats include palm oil, rape seed oil, beef tallow and the like.
However, whilst glycerol is available in large quantities its present uses are limited in volume. It is therefore desirable to provide processes which enable the glycerol to be converted to useful materials. It will therefore be understood coupling downstream processes which use glycerol as a feedstock to processes which have glycerol as a by-product offers economic advantages. Thus processes to which a glycerol reactor could be coupled include bio-diesel units and fat splitters such as feed units to natural detergent plants and the like.
Although glycerol does not have uses to match its availability, it can be converted to 1 ,2- propanediol and 2-propanol which are valuable starting materials which have various applications. Various processes have been proposed for effecting the conversion.
In US 5426249, which is incorporated herein by reference, there is described a process in which a gaseous stream of glycerol is dehydrated to acrolein. The acrolein is then condensed and hydrated to 3-hydroxypropionaldehyde which is then subjected to hydrogenation in the liquid phase. This multi-step process enables 1,2- and 1,3 -propanediol to be obtained simultaneously.
US5214219, which is incorporated herein by reference, describes a process in which glycerol is converted to 1 ,2-propanediol and 1 ,2-ethanediol. In this process hydrogenation of the glycerol is carried out in the liquid phase in the presence of a copper/zinc catalyst and at a temperature of about 22O0C. An alternative processes for the liquid phase hydrogenation of glycerol is described in US5616817, which is incorporated herein by reference. The process, which is directed to the production of 1 ,2-propanediol, requires the glycerol to have a water content of no more than 20% by weight. The hydrogenation is carried out in the presence of a catalyst comprising cobalt, copper, manganese and molybdenum.
Chaminand el al. Green Chem. 6, (2004) 359-361 describes a process in which the glycerol is hydrogenated in the liquid phase using a supported metal catalyst. At the process conditions of 18O0C and 85 bar the reaction rate is slow with only 20% conversion being achieved after 168 hours.
An alternative process is described in Desari et al Catalysis A281, (2005) 225-231 in which a copper/chrome catalyst is used for the liquid phase hydrogenation of glycerol. However, conversion was low with conversion rates of less than 30% being noted. It is suggested that this is due to the catalyst becoming deactivated and reactivation of the catalyst between tests was required.
DE4302464 and DE524101 describe in detail liquid phase processes for the production of 1,2- propanediol form glycerol. Whilst each makes passing reference to the possibility of the production being carried out in the vapour phase, neither document describes how the process can be efficiently and commercially carried out in the vapour phase to obtain high conversion and selectivity.
Whilst the processes described above offer means for obtaining desirable products from glycerol, they suffer from various disadvantages and drawbacks in terms of conversion, rate and/or economics and it is therefore desirable to provide alternative, and preferably improved, processes.
It has now been discovered that glycerol can be efficiently converted to the desired products by means of a hydrogenation reaction carried out in the vapour phase.
Thus according to one aspect of the present invention there is provided a process for hydrogenation of glycerol in which a feed comprising glycerol is contacted with a stream of a hydrogen-containing gas and subjected to hydrogenation in the vapour phase in the presence of a catalyst at a temperature of from about 1600C to about 2600C, a pressure of from about 10 to about 30 bar, a hydrogen to glycerol ratio of from 400: 1 to about 600: 1 and a residence time of from about 0.01 to about 2.5 sees.
It is surprising that it has been possible to carry out the hydrogenation reaction in the vapour phase since it has generally been believed that this was not possible due to the high boiling point of the glycerol. The requirement to use high temperatures would be anticipated to cause the glycerol to coke leading to operating problems. The high operating temperatures would also be expected to adversely affect the catalyst.
However, it has now been found that using the conditions of a temperature of from about 16O0C to about 26O0C, a pressure of from about 10 to about 30 bar, a hydrogen to glycerol ratio of from about 400: 1 to about 600: 1 and a residence time of from about 0.01 to about 2.5 sees enables the expected problems to be obviated. Carrying out the hydrogenation in the vapour phase offers various advantages over prior art liquid phase processes. In general, the residence time in the hydrogenation reactor is less. This is advantageous since short residence times lead to the formation of fewer by-products. The present invention also makes it possible to operate at lower pressures whilst maintaining high overall selectivities to the desired products.
Any suitable process is used for the hydrogenation reaction. In one arrangement, the glycerol is vaporised into a stream of hydrogen-containing gas in a vaporiser before being passed to a hydrogenation reactor. It will be understood that the vaporiser and the hydrogenation reactor may be separate or may be zones located in the same reactor. Where a vaporiser is present, the hydrogen rich vapour stream will generally be passed directly to the hydrogenation reactor.
The hydrogen-containing gas stream may be fed to the vaporiser where present or to the hydrogenation reactor at any suitable temperature.
The hydrogenation-containing gas may include minor amounts of one or more inert gases which may include nitrogen, carbon oxides, neon, argon and/or low molecular weight hydrocarbons such as methane, ethane, propane, n-butane and Iso-butane. Ethanol and ethyl acetate may also be present.
The glycerol feed may be from any source. It may be pure glycerol or it may contain other components such as other organic compounds, water and/or impurities. For example, the glycerol feed may include one or more of water, alcohols such as methanol, ethanol, propanol, hydroxy propanone, butanols and the like and esters. Involatile components may also be present.
Where such components are present, they may be removed from the reaction by means of a purge which is usually taken form the bottom of the vaporiser. The other components present will largely depend on the source of the glycerol. Since the process of the present invention may be carried out in the presence of such components there is no requirement to purify the glycerol prior to it being used as a feedstock. This offers significant advantages when the process of the present invention is to be coupled to plants in which glycerol is formed as a by-product. The process of the present invention will also be able to operate in the presence of a high salt and/or ash content.
Any suitable catalyst system may be used. In a preferred arrangement, the catalyst will be provided as a fixed bed located in the hydrogenation reactor. Any suitable catalyst may be used. In one arrangement, a reduced copper catalyst may be used. Examples include copper/alumina/manganese, copper chromite, copper silica, copper zinc alumina, copper zinc oxide, raney copper and the like. Reduced nickel or reduced cobalt containing catalysts may also be used. Precious metal catalysts such as those containing ruthenium, palladium, platinum, rhodium and/or iridium may be used. These may be supported on, for example, carbon, alumina and silica.
The process may be carried out at any suitable reaction conditions within the ranges of the present invention. Preferred temperatures are from about 2000C to about 24O0C. Temperatures of from about 2050C to about 2200C are particularly suitable. Pressures in the range of from about 17 bar to about 23 bar preferred with a pressure of 20 bar being particularly suitable. A residence time of from about 0.3 to about 1.5 sees may be used with a residence time of about 0.5 sees being particularly suitable. The ratio of hydrogen to glycerol In the hydrogenation reactor feed is a function of temperature and the operating pressure. Preferred hydrogen to glycerol ratio is in the range of form about about 450:1 to about 550:1. A ratio of about 500:1 is most preferred.
Surprisingly the process of the present invention offers excellent conversion. Conversions in excess of 95%, 98% and even in excess of 99% have been noted. However, in the event of incomplete conversion, separation of product from glycerol is readily achieved and unreacted glycerol may be recycled. By-products which may be formed, such as 1 -hydroxy propanone, may¬ be recycled for further reaction to the desired product.
Water will be produced in the reaction and at least a portion of the water produced may be recycled. Thus, other than at start up it is not generally necessary to add water to the glycerol to protect the catalyst which has been a feature of liquid phase reactions.
In a most preferred embodiment, the present invention relates to the selective hydrogenation of glycerol. In one arrangement, the invention selectively forms 1 ,2-propanediol and in an alternative arrangement the invention selectively forms propanols.
In general reaction temperatures of less than about 2100C favour the formation of the 1,2- propanediol while those of about 2100C and above favour the formation of propanols.
The present invention will now be described with reference to the following examples.
Examples 1 to 6 A 0.75" reactor was charged with 75 g (5OmIs) of catalyst DRD 9289 A, a copper based catalyst from Davy Process Technology Ltd, and reduced by conventional means. A feed of glycerol and methanol was fed to a heated vessel with the hydrogen at the reaction pressure and complete vapourisation of the feed mixture. The resultant gaseous stream was then passed to the reactor and contacted with the catalyst. Products removed from the reactor were condensed at 100C and were analysed on a Hewlett Packard HP3560 GC equipped with a micro TCD detector. The conditions for the various examples are set out in Table 1 and the results are set out in Table 2. Table 1
Figure imgf000007_0001
Table 2
Figure imgf000008_0001

Claims

1. A process for hydrogenation of glycerol in which a feed comprising glycerol is contacted with a stream of a hydrogen-containing gas and subjected to hydrogenation in the vapour phase in the presence of a catalyst at a temperature of from about 1600C to about 2600C5 a pressure of from about 10 to about 30 bar, a hydrogen to glycerol ratio of from 400: 1 to about 600: 1 and a residence time of from about 0.01 to about 2.5 hr"1.
2. A process according to Claim 1 wherein the glycerol feed is vaporised into a stream of hydrogen-containing gas in a vaporiser before being passed to a hydrogenation reactor.
3. A process according to Claim 1 or Claim 2 wherein the catalyst is provided as a fixed bed located in the hydrogenation reactor.
4. A process according to any one of Claims 1 to 3 wherein the catalyst is a reduced copper catalyst.
5. A process according to any one of Claims 1 to 4 wherein the reaction temperature is from about 2000C to about 2400C.
6. A process according to any one of Claims 1 to 5 wherein the reaction temperature is from about 205°C to about 2200C.
7. A process according to any one of Claims 1 to 6 wherein the reaction pressure is from about 17 bar to about 23 bar.
8. A process according to any one of Claims 1 to 7 wherein the reaction pressure is from about 20 bar.
9. A process according to any one of Claims 1 to 8 wherein the residence time is from about 0.3 sees to about 1.5 sees.
10. A process according to any one of Claims 1 to 8 wherein the residue time is about 0.5 sees.
11. A process according to any one of Claims 1 to 10 wherein the hydrogen to glycerol ratio is from about 450:1 to about 550:1.
12. A process according to any one of Claims 1 to 11 wherein the hydrogen to glycerol ratio is from about 500: 1.
13. A process according to any one of Claims 1 to 12 wherein the process is selective for the formation of 1,2-propanediol.
14. A process according to Claim 13 wherein the temperature is less than about 210°C
15. A process according to any one of Claims 1 to 12 wherein the process is selective for the formation of propanols.
16. A process according to Claim 15 wherein the temperature is about 2100C or more.
PCT/GB2006/050181 2005-07-15 2006-06-30 Process WO2007010299A1 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
EA200700445A EA010314B1 (en) 2005-07-15 2006-06-30 A process for hydrogenation of glycerol
CN2006800006177A CN101006036B (en) 2005-07-15 2006-06-30 Vapour-phase hydrogenation of glycerol
AU2006252177A AU2006252177B2 (en) 2005-07-15 2006-06-30 Vapour phase hydrogenation of glycerol
KR1020077000311A KR101325084B1 (en) 2005-07-15 2006-06-30 Vapour phase hydrogenation of glycerol
BRPI0606159-1A BRPI0606159B1 (en) 2005-07-15 2006-06-30 Vapor glycerol hydrogenation
JP2008520964A JP5149796B2 (en) 2005-07-15 2006-06-30 process
EP06744361A EP1836147B1 (en) 2005-07-15 2006-06-30 Vapour phase hydrogenation of glycerol
ES06744361T ES2298101T3 (en) 2005-07-15 2006-06-30 Hydrogenation of glycerol in vapor phase
DK06744361.4T DK1836147T3 (en) 2005-07-15 2006-06-30 VAPOR PHASE HYDROGENATION OF GLYCEROL
NZ551994A NZ551994A (en) 2005-07-15 2006-06-30 Vapour-phase hydrogenation of glycerol
CA2569622A CA2569622C (en) 2005-07-15 2006-06-30 Vapour-phase hydrogenation of glycerol
PL06744361T PL1836147T3 (en) 2005-07-15 2006-06-30 Vapour phase hydrogenation of glycerol
US11/668,884 US7355083B2 (en) 2005-07-15 2007-01-30 Process

Applications Claiming Priority (2)

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GBGB0514593.3A GB0514593D0 (en) 2005-07-15 2005-07-15 Process
GB0514593.3 2005-07-15

Related Child Applications (1)

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US (1) US7355083B2 (en)
EP (1) EP1836147B1 (en)
JP (1) JP5149796B2 (en)
KR (1) KR101325084B1 (en)
CN (1) CN101006036B (en)
AR (1) AR058013A1 (en)
AU (1) AU2006252177B2 (en)
BR (1) BRPI0606159B1 (en)
CA (1) CA2569622C (en)
DK (1) DK1836147T3 (en)
EA (1) EA010314B1 (en)
ES (1) ES2298101T3 (en)
GB (1) GB0514593D0 (en)
MY (1) MY142306A (en)
NZ (1) NZ551994A (en)
PL (1) PL1836147T3 (en)
TW (1) TWI394740B (en)
WO (1) WO2007010299A1 (en)
ZA (1) ZA200700897B (en)

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WO2008012244A1 (en) 2006-07-26 2008-01-31 Davy Process Technology Limited Process for the hydrogenation of glycerol to propyleneglycol
DE102007003188B3 (en) * 2007-01-22 2008-06-05 Clariant International Ltd. Production of 1,2-propanediol for use e.g. in lubricants and antifreeze or as a solvent, involves hydrogenation of pure glycerol at elevated temperature and pressure using a copper-zinc-manganese oxide catalyst
EP1978075A1 (en) * 2007-03-30 2008-10-08 Petroleo Brasileiro S.A. Petrobras Method for recycling and exploitation of the glycerin obtained in the production of biodiesel
WO2008129933A1 (en) * 2007-04-17 2008-10-30 Kao Corporation Process for producing hydrogenolysis products of polyhydric alcohols
KR100870369B1 (en) 2007-08-29 2008-11-25 지에스칼텍스 주식회사 Method of manufacturing catalyst for propanediol, and method of manufacturing propanediol using the same
WO2008144448A1 (en) 2007-05-18 2008-11-27 Primafuel, Inc. Gas phase process for monoalcohol production from glycerol
WO2009027501A2 (en) * 2007-08-31 2009-03-05 Basf Se Method for producing 1,2-propandiol by hydrogenating glycerine in at least three successive reactors
WO2009027500A2 (en) * 2007-08-31 2009-03-05 Basf Se Method for producing 1,2-propandiol by hydrogenating glycerine in a two-step reactor cascade
WO2009027502A3 (en) * 2007-08-31 2009-04-30 Basf Se Method for producing 1,2-propandiol by low-pressure hydrogenation of glycerine
WO2009057584A1 (en) 2007-10-31 2009-05-07 Mitsui Chemicals, Inc. Method for producing propylene glycol
EP2070902A1 (en) 2007-12-13 2009-06-17 Lanzhou Institute of Chemical Physics A method for producing 1, 2-propylene glycol using bio-based glycerol
WO2009074821A1 (en) * 2007-12-12 2009-06-18 Davy Process Technology Limited Process for the production of 1,2-propanediol
JP2009173551A (en) * 2008-01-21 2009-08-06 Kao Corp Method for producing hydrogenolysis product of polyhydric alcohol
WO2009096134A1 (en) * 2008-01-30 2009-08-06 Kao Corporation Method for producing hydrogenolysis product of polyhydric alcohol
US7619119B2 (en) 2006-06-07 2009-11-17 The Procter & Gamble Company Processes for converting glycerol to amino alcohols
US7619118B2 (en) 2006-06-07 2009-11-17 The Procter & Gamble Company Process for the conversion of glycerol to propylene glycol and amino alcohols
DE102008027601A1 (en) 2008-06-10 2009-12-17 Clariant International Limited Process for the preparation of 1,2-propanediol by hydrogenolysis of glycerol
WO2010016462A1 (en) * 2008-08-04 2010-02-11 チッソ株式会社 Methods for producing glycol from glycerin and 1-propanol
US7812200B2 (en) 2006-10-27 2010-10-12 Clariant Finance (Bvi) Limited Process for preparing 1,2-propanediol by hydrogenolysis of glycerol
WO2010074954A3 (en) * 2008-12-23 2010-11-04 Uop Llc Method for converting glycerol to propanol
US7855233B2 (en) 2009-01-23 2010-12-21 Teva Pharmaceutical Industries, Ltd. Citrate salt of Rasagiline
WO2011009936A2 (en) 2009-07-24 2011-01-27 Basf Se Process for the preparation of 1,2-propanediol from glycerol
EP2236486A4 (en) * 2008-01-21 2011-05-18 Kao Corp Method for producing hydrogenolysis product of polyhydric alcohol
WO2011104634A2 (en) 2010-02-24 2011-09-01 Petroleo Brasileiro S.A. Petrobras Production of propylene glycol from glycerol
WO2011128367A1 (en) 2010-04-14 2011-10-20 Technische Universität Darmstadt Catalyst for hydrogenating aqueous multivalent alcohol solutions
CN102924233A (en) * 2012-10-20 2013-02-13 青岛科技大学 Method for preparing propylene glycol by glycerin hydrogenolysis

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