CA1105059A - Process for preparing polyols from a cyclic acetal - Google Patents
Process for preparing polyols from a cyclic acetalInfo
- Publication number
- CA1105059A CA1105059A CA293,719A CA293719A CA1105059A CA 1105059 A CA1105059 A CA 1105059A CA 293719 A CA293719 A CA 293719A CA 1105059 A CA1105059 A CA 1105059A
- Authority
- CA
- Canada
- Prior art keywords
- methyl
- nickel
- dioxane
- granular
- butanediol
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT
Process for the simultaneous hydrolysis and hydrogenation of a cyclic acetal comprising conducting the hydrolysis at a pH of from 4.0 to 5.5 in the presence of an aqueous acid solution and a hydrogenation catalyst optionally containing rhenium to prepare 1,4-butanediol and byproduct diols.
Process for the simultaneous hydrolysis and hydrogenation of a cyclic acetal comprising conducting the hydrolysis at a pH of from 4.0 to 5.5 in the presence of an aqueous acid solution and a hydrogenation catalyst optionally containing rhenium to prepare 1,4-butanediol and byproduct diols.
Description
BACKGROUND OF TEIE INVE:NTION
.
1. Field of the Invention This invention relates to a process for the simultaneous catalytic hydrolysis and hydrogenation of cyclic acetals. More specifically, this invention relates to a process for the simultaneous catalytic hydrolysis and hydrogenation of cyclic acstals carried out at a pH of at least 4Ø
.
1. Field of the Invention This invention relates to a process for the simultaneous catalytic hydrolysis and hydrogenation of cyclic acetals. More specifically, this invention relates to a process for the simultaneous catalytic hydrolysis and hydrogenation of cyclic acstals carried out at a pH of at least 4Ø
2. Prior Art The preparation of diols from cyclic acetals is known. However, the methods used have experienced unsatis-factory catalyst life, especially where the hydrogenation catalyst is not a no~le metal and where the hydrolysis and hydrogenation are conducted simultaneously. U.S. .
Patent 2,8B8l492 discloses the simultaneous hydrolysis and hydrogenation o certain hydroxy aldehydes in the pxesence of an aqueous acidic medium and a hydrogenation catalyst. However, in such cases when a base metal hydro-genation catalyst i5 used the catalyst life is unsatisfactor-ily low. U.S. Patent 2~618,663 discloses the simultaneous hydrolysis and reduction o polyether alkano.l acetals to the corresponding polye.ther alcohols by carrying out said simultaneous hydrolysis and reduction in an aqueous solu-tion conta:ining catalytic quant.ities o hydrolyzable metal salts of mineral and organic acids with Raney nickel cata-.
lyst and hydrogen at a pH of 4.5 to S.S to minimize corrosion of the equipment. :U.S. Patent 3,886,21g discloses a process for the preparation of saturated aliphatic al~ohols by the hydrogenation of saturated or unsaturated aldehydes and/or ketones in the presence of catalysts supported on silica ..
gel having a surface pH o~ 6 to 10. U.S. Patent 3,492,314 discloses the hydrogenation of succinic anhydrida in the presence of a reduced nickel-rhenium catalyst to improve the catalyst life. However, there is still a need to further improve the performance of catalysts in hydrogenation/
hydrolysis reactions.
SUMMARY OF THE INVENTION
Now it has been found that the catalyst life in hydrolysis and hydroganation reactions of cyclic acetals to 1,4~butanediol is extanded by conducting said reactions at a pH of at least 4Ø
In accordance with the invention, a process has been found for the simultaneous catalytic hydrolysis and hydrogenation of a cyclic acetal of the general ormula 4 ~ O
- C-M~ and mixtures thereof /~ ~ - O~
R6 l R3 .
wherein M is an alkyl group of 1 ko 20 carbon atoms, X is C~O or CH~OH and Rl, R2, R3~ R4~ R5 and R6 m y or different hydroge~ or alkyl groups of 1 to 20 carbon atoms which comprises hydroly2ing and hydrogenating said cyclic acetal in the presance of both an aqueous acid solu-tion and a base metal hydrogenation catalyst at a pH of 4.0 ~or more until a product o 1/4-butanediol is produced with byproduc~ diols. :
Some spacific exampIes of cyclic acetals which may be hydrolyzed and hydrogenated in accordance wi~h ~his ~n invention include ~'~
Patent 2,8B8l492 discloses the simultaneous hydrolysis and hydrogenation o certain hydroxy aldehydes in the pxesence of an aqueous acidic medium and a hydrogenation catalyst. However, in such cases when a base metal hydro-genation catalyst i5 used the catalyst life is unsatisfactor-ily low. U.S. Patent 2~618,663 discloses the simultaneous hydrolysis and reduction o polyether alkano.l acetals to the corresponding polye.ther alcohols by carrying out said simultaneous hydrolysis and reduction in an aqueous solu-tion conta:ining catalytic quant.ities o hydrolyzable metal salts of mineral and organic acids with Raney nickel cata-.
lyst and hydrogen at a pH of 4.5 to S.S to minimize corrosion of the equipment. :U.S. Patent 3,886,21g discloses a process for the preparation of saturated aliphatic al~ohols by the hydrogenation of saturated or unsaturated aldehydes and/or ketones in the presence of catalysts supported on silica ..
gel having a surface pH o~ 6 to 10. U.S. Patent 3,492,314 discloses the hydrogenation of succinic anhydrida in the presence of a reduced nickel-rhenium catalyst to improve the catalyst life. However, there is still a need to further improve the performance of catalysts in hydrogenation/
hydrolysis reactions.
SUMMARY OF THE INVENTION
Now it has been found that the catalyst life in hydrolysis and hydroganation reactions of cyclic acetals to 1,4~butanediol is extanded by conducting said reactions at a pH of at least 4Ø
In accordance with the invention, a process has been found for the simultaneous catalytic hydrolysis and hydrogenation of a cyclic acetal of the general ormula 4 ~ O
- C-M~ and mixtures thereof /~ ~ - O~
R6 l R3 .
wherein M is an alkyl group of 1 ko 20 carbon atoms, X is C~O or CH~OH and Rl, R2, R3~ R4~ R5 and R6 m y or different hydroge~ or alkyl groups of 1 to 20 carbon atoms which comprises hydroly2ing and hydrogenating said cyclic acetal in the presance of both an aqueous acid solu-tion and a base metal hydrogenation catalyst at a pH of 4.0 ~or more until a product o 1/4-butanediol is produced with byproduc~ diols. :
Some spacific exampIes of cyclic acetals which may be hydrolyzed and hydrogenated in accordance wi~h ~his ~n invention include ~'~
3 - ~
~ .. . . . . . . .. .. .
(cl-c~o) ~ CH ( C -C 2 0 ) CHO
C ~ CH-CH2-CH2--CHO ~`' O
H3C { \CH-CH2-CEI2-CHO
~3 \ CH-CH2 -CH ~-CHO
~CH3) 2 {~c~c~2-cH2-cHO
CHO
Co/
__o\ C~HO
E~3C~ ~CH-CH-CH3 ~ \Cti-C3-C!13 CHO
t~H3 ) ;~ {0~CH~ C~3 ~: ~
and the corresponding alcohol (where -CHO i~ replaced with . .
~ OEI). ~ ", In the proce~ of this inventloxl, ~ny catalytic amount of any o~ he metal or metal compound catalysts o~ :
the type well known and customa~ ly re:f erred to in the art as ba~e me tal hydrogenation cataly~ts can be u~ed, The base metQl hydrogerlatlon cataly:t may be a me1ial, ~ mix~
ture of metals or a compound of a metal wherein the metals ( 8 ox~dizes rapidly and the hydrox~de o~ t}le metal ~s~ 13 ~ol-uble in water. Representatiue example~ o~ ~uch ba~e mei;al hydrogenation catalys~s include nlckel, conventional Raney n~ ckelg conventiona:L Raney nickel promo~ed with molybdenum, conventional Raney nickel promotet3 with chromium~ granula~
foramlnou~ nic~el, granular ~or~aminou~ nickel ~ctiv~ted with molybdenum~ chromium, cob~lt or chromium an~ molybdenum, What i~ meant by conYentional R~ney n~ ckel i~ an alloy of nickel and alumlnum ~rherein the aluminum is 50 to 70% by weight and wherein es~entially all of the aluminum that can be removed by normal mean~ i8 removed, What i~ meant by granular foraminous nickel ~ ~ a ~ree-~anding granula~ alloy o:~ the RaE~ey nickel type wlth 50 to 70~ ~y weight aluminum which has from 10 to 50~b o~
the aluminum removed from l;he alloy, What i~ meant by convention~l Raney nickel act-vated wi th either molyb~enum or chromLum i9 ~n alloy o:f nickel, a~.uminum and chromium or moly~denum whereln 1 to loq6 by weight ~ 9 chromium or molybd~num, 50 to 70% by weight : :
i~ aluminum and 49 to 20% by weight i8 nickeï and whereln e~entlall~ al'l o~ the aluminum that c~n be removed by nor-mal mean~ i~ rernoved.
What, is meant by granular :f ~raminouB nickel 5- :
... ..
.
f~
acti~ated with.either molybden~m or chromium is a free-standing alloy of the Raney nickel type with 50 to 70% by weight aluminum, 4~ to 20% by ~eight nickel and 1 to 10% chromium or molybdenum which has from 10 to 50% of the aluminum removed from the alloy.
The aluminum is generally removed from the alloy with an aquec,us alkali-metal hydroxide solution unti`l the ~es~red amount of 31uminum is leached ~rom the alloy. The alkali metal hydraxide solution will generally contain a~out Q.l to 5% by weight of alkali metal hydroxide. When more than about 50% of the aluminum is removed, the mechani.cal strength of the nickel-aluminum catalyst particles is reduced such that they are no longer suitable for use in a f;xed ~ed. Representa-tive examples of metal compounds within the scope of this i.nvention include copper chromite~ The preferred base ~ metal hydrogenation catalysts are selected from the ~ group consisting of nickel, granular foraminous nickel, conventional Raney nickelj conventional Raney nickel promoted with either chromium or molybdenum and granular foraminous nickel promoted with.either chromium or molybdenum. Most preferred are granular :Eorami.nous nickel, conventional Raney nickel, granular foraminous nickel promoted with molybdenum or chromium and conven-tional Raney nickel promoted with molyhdenum or chromium.
Th.e chromium nickel and molybdenum nickel mixtures or alloys are available commercially from ` ~
Davison Chemical, a division of W. R Grace and Co~pany. ~ -Chromium promoted nickel and moly~denum promoted nickel are the most active of the hydrogenation catalysts men-tioned herein.
In the process of th.e present in~ention, it was ~ ~, - 6 - .
5~
~ .~
found that in the stream being hydrogenated a more active catalyst wi.ll increase the conversion of the cyclic acetal to 1,4-butanediol. It was ~ound that catalysts which are less active do not promote sufficiently high conversion and result in the prepara~ion of more undesirable byproducts.
The chromium promoted nickel and more especially the molybdenum-promoted ni.ckel result in rapid hydrogenation and low undeslrable byproducts. In the hydrogenation/hydrolysis reaction of this invention, i-t is essential in order to attain low undesirable byproducts that the hydrogenation be conducted as fast a.~ possible to avoid competing reactions of the aldehyde formed by hydroly~is. The presence of said aldehydes will promote the formation of undesirable by-products. For example, molybdenum nickel catalyst in the process of the present invention results in less undesir-able byproducts than Raney nickel because of its superior hydrogenation activity.
The following equations describe the formation believed to contribute to undesirable byproducts that are ~0 minimized with active hydrogenation catalysts:
... .
r ,c C~ C c~ 2--~ { + ~C-C-C-C~
O OH
A . B
1N2 li2~l { C_C_C_C~ 2~ ~ ~ HO-C-C C_C=O
/ ~ OH
C ' . . .
~IH2 , - OH
_ ~ ~ Ho-C~C-C-C-OH
OH
The aldehyde group~ in A, B and C undexgo reactions producing undesirable byproducts unless these aldehyde groups aré hydrogenated rapidly to alcohol yroups.
Hydrogenation reactions generally do not require any high degree of hydrogenation to prevent undesirable byproduct formation.
The base metal hydxogenation catalyst may be em-ployed in a fin~ly divided form or slurry without a support and dispersed in and throughout the reaction mixture, or it may be employed in a granu1ar ~orm with aluminum as a support or in a more massLve state, either in essentially the pure state or supported upon or aarried by an inert or ,: ; catalytically ~activ~ supporting or carr.ier material, such as pumica, kieselguhr, diatomaceous earth, clay, alumina , charcoal, carbon, or the like, and the reaction mixture contacted therewith as by flowing the mixture over or through a b~d of the catalyst or according to other methods that are known in the art.
In the process of this invention rhenium or a rhenium compound may optionally be used as a component of the base metal hydrogenation catalyst for the purpose of further extending the life of said catalyst. The rhenium modified base hydrogenation catalysts of this invention may be prepared by adding a solution of Re2O7 in water to~ e.g., nickel on alumina. The nickel on alumina absorbs the rhenium and the xesulting catalyst is placed in a reactor and treated with H2 at a temperature and pressure and or a time that will reduce and insolubilize the Re2O7, e.g., at 1 atmosphere and 180C for 2 hours.
The hydrogenation and hydrolysis o this invention is carried out at an elevated temperature under supera~mo-spheric hydrogen pressure and in the presence of an aqueous m2dium as well as in the presence of an acid hydrolysis catalyst and the base metal h~drogenation catalyst.
Generally, the amount of water present is that amount that is sufficient for the hydrolysis/hydrogenation step; that is, a molar ratio of water to acetal of 1:1 to 100:1, preferably 1:1 to 10:1. The hydrogen pressure is generally from 500 to 10,000 psi~, preferably 1,000 to 5,000 p5.ig.
The temperature is generally 125 to 200C, preferably 125 to 175C.
The hydrolysis portion of the process of the ; present invention requires an acid catalyst. In view of ~ 30 the requirement that water ~e presen~ for the hydrolysis, g3~i~
the acid is generally present as an aqueous acid. The aqueous acid for the hydrolysis reaction may be selected from a wide variety of acid-reacting materials and can be used for imparting the required acidi~y to said aqueous reaction medium. Acids and acid-reacting salts have both been successfully used. Mineral acids such as sulfuric, phosphoric and the like acids or such acid-acting salts as sodium ~isulate, monosodium orthophosphate, aluminum sulfate an~ the like may be used in the process of the present invention. Water-soluble organic caxboxylic acids are also acidifying agents for use in the process of this invention. Particularly useful are the lower atty acids o 1 to 4 carbon atoms, especially acetic, propionic, isobutyric and normal butyric acids but polycarboxyli~
acids such as succinic, malonic, and adipic acids are suitable. These organic acids are useful in amounts of about 5 to lOQ~ by weight of the water used in the reaction.
However, a normality of ~rom about 0.005 to about 1 is preferred. Insoluble acid ion exchange resins may also be used in the process of the present invention.
In the preparation of the cyalic acetals of the aforesaid general formula there is normally suf~i-cient acid present wi~h the cyclic acetal to not require the addition of acid beyond that present thereby. Thus normally in order to maintain the pH within the in~ention, it is necessary to add caustic~ Any caustic solution may be usedO ~owever, because of availability and convenience sodium hydroxide and potassium hydroxide are preferred.
The pH of the reaction mixture for the simulta~
neous hydrolysis/hydrog nation of this invention may be . .. . . : . . . . . . :
maintained above 4.0 by merely the addition of caustic in view of the presence of acids with the cyclic aldehydes of this invention. At pH values below 4.0 the base metal hydrogenation catalyst life is surprisingly short as compared to values at 4~0 and above. Generally the upper pH limit in the process of the present invention for main-taining improved catalyst life is not critical. At pH
values up to 6.9 an acceptable hydrogenation rate may be obtained. The upper limit on pH should be chosen to achieve a hydrolysis rate such that the reaction is completed in an acceptable len~th of time. Thus, while the pH ranye may be generally from 4.0 to 6.9, the preferred pH range is 4.0 to 5.5. Most preferably the pH is 4.0 to 4.5~
In the process of the present invention the yiald of 2-methyl-1,3-propanediol (MPD~ was found to be extremely sensitive to pH. Th~ yield o MPD as a byproduct can be substantially improved or maximized without a loss in yield of 1,4-butanediol by controlling the pH in the pro ess of ~ ~ .
the present invention in the preerred range of 4.0 to 5.5, most preferably 4.0 to 4.5.
A mixture within the scope o this invention, 2(2'-propanal)-4-methyl-1,3-dioxane and 2(3'-propanall-4-methyl-1,3-dioxane, is simultaneously hydrogenated and hydrolyzed in the presence of a nickel catalyst promoted with rhenium and aqueous sulfuric acid to yield 1,4-butanediol and 2-methyl 1,3-propanediol. The contxol of the pH of the reaction mixture at from 4uO to 5.5 greatly extends the life o the catalyst over that where he p~ of the reaction mix-ture is below 4.0 and also, without a yield loss of 1,4-butanediol, produces increased yields of 2 methyl-1,3-propanediol.
:-.. . . .............. . . .
. . . . . . . .
Another mixture within the scope of this inven-tion, 2(2'-propanol)-4-methyl-1~3-dioxane and 2(3'-propanol)-
~ .. . . . . . . .. .. .
(cl-c~o) ~ CH ( C -C 2 0 ) CHO
C ~ CH-CH2-CH2--CHO ~`' O
H3C { \CH-CH2-CEI2-CHO
~3 \ CH-CH2 -CH ~-CHO
~CH3) 2 {~c~c~2-cH2-cHO
CHO
Co/
__o\ C~HO
E~3C~ ~CH-CH-CH3 ~ \Cti-C3-C!13 CHO
t~H3 ) ;~ {0~CH~ C~3 ~: ~
and the corresponding alcohol (where -CHO i~ replaced with . .
~ OEI). ~ ", In the proce~ of this inventloxl, ~ny catalytic amount of any o~ he metal or metal compound catalysts o~ :
the type well known and customa~ ly re:f erred to in the art as ba~e me tal hydrogenation cataly~ts can be u~ed, The base metQl hydrogerlatlon cataly:t may be a me1ial, ~ mix~
ture of metals or a compound of a metal wherein the metals ( 8 ox~dizes rapidly and the hydrox~de o~ t}le metal ~s~ 13 ~ol-uble in water. Representatiue example~ o~ ~uch ba~e mei;al hydrogenation catalys~s include nlckel, conventional Raney n~ ckelg conventiona:L Raney nickel promo~ed with molybdenum, conventional Raney nickel promotet3 with chromium~ granula~
foramlnou~ nic~el, granular ~or~aminou~ nickel ~ctiv~ted with molybdenum~ chromium, cob~lt or chromium an~ molybdenum, What i~ meant by conYentional R~ney n~ ckel i~ an alloy of nickel and alumlnum ~rherein the aluminum is 50 to 70% by weight and wherein es~entially all of the aluminum that can be removed by normal mean~ i8 removed, What i~ meant by granular foraminous nickel ~ ~ a ~ree-~anding granula~ alloy o:~ the RaE~ey nickel type wlth 50 to 70~ ~y weight aluminum which has from 10 to 50~b o~
the aluminum removed from l;he alloy, What i~ meant by convention~l Raney nickel act-vated wi th either molyb~enum or chromLum i9 ~n alloy o:f nickel, a~.uminum and chromium or moly~denum whereln 1 to loq6 by weight ~ 9 chromium or molybd~num, 50 to 70% by weight : :
i~ aluminum and 49 to 20% by weight i8 nickeï and whereln e~entlall~ al'l o~ the aluminum that c~n be removed by nor-mal mean~ i~ rernoved.
What, is meant by granular :f ~raminouB nickel 5- :
... ..
.
f~
acti~ated with.either molybden~m or chromium is a free-standing alloy of the Raney nickel type with 50 to 70% by weight aluminum, 4~ to 20% by ~eight nickel and 1 to 10% chromium or molybdenum which has from 10 to 50% of the aluminum removed from the alloy.
The aluminum is generally removed from the alloy with an aquec,us alkali-metal hydroxide solution unti`l the ~es~red amount of 31uminum is leached ~rom the alloy. The alkali metal hydraxide solution will generally contain a~out Q.l to 5% by weight of alkali metal hydroxide. When more than about 50% of the aluminum is removed, the mechani.cal strength of the nickel-aluminum catalyst particles is reduced such that they are no longer suitable for use in a f;xed ~ed. Representa-tive examples of metal compounds within the scope of this i.nvention include copper chromite~ The preferred base ~ metal hydrogenation catalysts are selected from the ~ group consisting of nickel, granular foraminous nickel, conventional Raney nickelj conventional Raney nickel promoted with either chromium or molybdenum and granular foraminous nickel promoted with.either chromium or molybdenum. Most preferred are granular :Eorami.nous nickel, conventional Raney nickel, granular foraminous nickel promoted with molybdenum or chromium and conven-tional Raney nickel promoted with molyhdenum or chromium.
Th.e chromium nickel and molybdenum nickel mixtures or alloys are available commercially from ` ~
Davison Chemical, a division of W. R Grace and Co~pany. ~ -Chromium promoted nickel and moly~denum promoted nickel are the most active of the hydrogenation catalysts men-tioned herein.
In the process of th.e present in~ention, it was ~ ~, - 6 - .
5~
~ .~
found that in the stream being hydrogenated a more active catalyst wi.ll increase the conversion of the cyclic acetal to 1,4-butanediol. It was ~ound that catalysts which are less active do not promote sufficiently high conversion and result in the prepara~ion of more undesirable byproducts.
The chromium promoted nickel and more especially the molybdenum-promoted ni.ckel result in rapid hydrogenation and low undeslrable byproducts. In the hydrogenation/hydrolysis reaction of this invention, i-t is essential in order to attain low undesirable byproducts that the hydrogenation be conducted as fast a.~ possible to avoid competing reactions of the aldehyde formed by hydroly~is. The presence of said aldehydes will promote the formation of undesirable by-products. For example, molybdenum nickel catalyst in the process of the present invention results in less undesir-able byproducts than Raney nickel because of its superior hydrogenation activity.
The following equations describe the formation believed to contribute to undesirable byproducts that are ~0 minimized with active hydrogenation catalysts:
... .
r ,c C~ C c~ 2--~ { + ~C-C-C-C~
O OH
A . B
1N2 li2~l { C_C_C_C~ 2~ ~ ~ HO-C-C C_C=O
/ ~ OH
C ' . . .
~IH2 , - OH
_ ~ ~ Ho-C~C-C-C-OH
OH
The aldehyde group~ in A, B and C undexgo reactions producing undesirable byproducts unless these aldehyde groups aré hydrogenated rapidly to alcohol yroups.
Hydrogenation reactions generally do not require any high degree of hydrogenation to prevent undesirable byproduct formation.
The base metal hydxogenation catalyst may be em-ployed in a fin~ly divided form or slurry without a support and dispersed in and throughout the reaction mixture, or it may be employed in a granu1ar ~orm with aluminum as a support or in a more massLve state, either in essentially the pure state or supported upon or aarried by an inert or ,: ; catalytically ~activ~ supporting or carr.ier material, such as pumica, kieselguhr, diatomaceous earth, clay, alumina , charcoal, carbon, or the like, and the reaction mixture contacted therewith as by flowing the mixture over or through a b~d of the catalyst or according to other methods that are known in the art.
In the process of this invention rhenium or a rhenium compound may optionally be used as a component of the base metal hydrogenation catalyst for the purpose of further extending the life of said catalyst. The rhenium modified base hydrogenation catalysts of this invention may be prepared by adding a solution of Re2O7 in water to~ e.g., nickel on alumina. The nickel on alumina absorbs the rhenium and the xesulting catalyst is placed in a reactor and treated with H2 at a temperature and pressure and or a time that will reduce and insolubilize the Re2O7, e.g., at 1 atmosphere and 180C for 2 hours.
The hydrogenation and hydrolysis o this invention is carried out at an elevated temperature under supera~mo-spheric hydrogen pressure and in the presence of an aqueous m2dium as well as in the presence of an acid hydrolysis catalyst and the base metal h~drogenation catalyst.
Generally, the amount of water present is that amount that is sufficient for the hydrolysis/hydrogenation step; that is, a molar ratio of water to acetal of 1:1 to 100:1, preferably 1:1 to 10:1. The hydrogen pressure is generally from 500 to 10,000 psi~, preferably 1,000 to 5,000 p5.ig.
The temperature is generally 125 to 200C, preferably 125 to 175C.
The hydrolysis portion of the process of the ; present invention requires an acid catalyst. In view of ~ 30 the requirement that water ~e presen~ for the hydrolysis, g3~i~
the acid is generally present as an aqueous acid. The aqueous acid for the hydrolysis reaction may be selected from a wide variety of acid-reacting materials and can be used for imparting the required acidi~y to said aqueous reaction medium. Acids and acid-reacting salts have both been successfully used. Mineral acids such as sulfuric, phosphoric and the like acids or such acid-acting salts as sodium ~isulate, monosodium orthophosphate, aluminum sulfate an~ the like may be used in the process of the present invention. Water-soluble organic caxboxylic acids are also acidifying agents for use in the process of this invention. Particularly useful are the lower atty acids o 1 to 4 carbon atoms, especially acetic, propionic, isobutyric and normal butyric acids but polycarboxyli~
acids such as succinic, malonic, and adipic acids are suitable. These organic acids are useful in amounts of about 5 to lOQ~ by weight of the water used in the reaction.
However, a normality of ~rom about 0.005 to about 1 is preferred. Insoluble acid ion exchange resins may also be used in the process of the present invention.
In the preparation of the cyalic acetals of the aforesaid general formula there is normally suf~i-cient acid present wi~h the cyclic acetal to not require the addition of acid beyond that present thereby. Thus normally in order to maintain the pH within the in~ention, it is necessary to add caustic~ Any caustic solution may be usedO ~owever, because of availability and convenience sodium hydroxide and potassium hydroxide are preferred.
The pH of the reaction mixture for the simulta~
neous hydrolysis/hydrog nation of this invention may be . .. . . : . . . . . . :
maintained above 4.0 by merely the addition of caustic in view of the presence of acids with the cyclic aldehydes of this invention. At pH values below 4.0 the base metal hydrogenation catalyst life is surprisingly short as compared to values at 4~0 and above. Generally the upper pH limit in the process of the present invention for main-taining improved catalyst life is not critical. At pH
values up to 6.9 an acceptable hydrogenation rate may be obtained. The upper limit on pH should be chosen to achieve a hydrolysis rate such that the reaction is completed in an acceptable len~th of time. Thus, while the pH ranye may be generally from 4.0 to 6.9, the preferred pH range is 4.0 to 5.5. Most preferably the pH is 4.0 to 4.5~
In the process of the present invention the yiald of 2-methyl-1,3-propanediol (MPD~ was found to be extremely sensitive to pH. Th~ yield o MPD as a byproduct can be substantially improved or maximized without a loss in yield of 1,4-butanediol by controlling the pH in the pro ess of ~ ~ .
the present invention in the preerred range of 4.0 to 5.5, most preferably 4.0 to 4.5.
A mixture within the scope o this invention, 2(2'-propanal)-4-methyl-1,3-dioxane and 2(3'-propanall-4-methyl-1,3-dioxane, is simultaneously hydrogenated and hydrolyzed in the presence of a nickel catalyst promoted with rhenium and aqueous sulfuric acid to yield 1,4-butanediol and 2-methyl 1,3-propanediol. The contxol of the pH of the reaction mixture at from 4uO to 5.5 greatly extends the life o the catalyst over that where he p~ of the reaction mix-ture is below 4.0 and also, without a yield loss of 1,4-butanediol, produces increased yields of 2 methyl-1,3-propanediol.
:-.. . . .............. . . .
. . . . . . . .
Another mixture within the scope of this inven-tion, 2(2'-propanol)-4-methyl-1~3-dioxane and 2(3'-propanol)-
4-methyl-],3-dioxane, is likewise simultaneously hydro-genated and hydrolyzed without a yield loss of 1,4-butane-diol, produces increased yields of 2-methyl-1,3-propanediol.
It i5 also within the scope of this invention to u~e mix-tures of 2(2'-propanal)-5-methyl-1,3-dioxane and 2(3'-propanal)-S-methyl-1,3-dioxane and mixtures of 2(2'-propanol)-5-methyl-1,3 dioxane and 2(3'-propanol 5-methyl- ;
1,3-dioxane.
The 1,4-butanediol prepared by the process of this invention may b~ separated from the byproduct diol(s) present therewith if desired. Where the diol is 2-methyl-1,3-propanediol, the separation with 1,4-butanediol is relatively simple due to the difference in boi~ing points.
In any event, the byproduct diol(s~ is separated from the 1,4-~utanediol by conve~tional means.
~.
As can be seen from the aforesaid cyclic acetal general ~o~nula the process o the present invention in-cludes within its scope the step of prehydrogenating kh~
acetal aldehydes in the presence oE a hydrogenation aata-lyst prior to the simultaneous hydrolysis and hydrogenation in Xhe presence of the base metal hydrogenation catalyst and aqueous acid according to the process of the present invention. This prehydrogenation is conducted at normal hydrogenation conditions,except for temperature, in the presence of a base metal hydrogenation catalyst. The pre~
hydrogenation converts the -CHO gxoup to -CH20H before any hyarolysis of the starting compound.
The prehydrogenation, if desired, may be carried out in an aqueous medium in which case the water acts as a :
hea-t sink and a viscosity adjustor although the reaction can also be carried out neat; that is, without the use of water.
If an aqueous medium is used, it is convenient to have enough water present ~or the hydrolysis-hydrogenation stepthat follows.
The prehydrogenation is conducted at a temperature of from ~0 to 125C. Temperatures above 125C will tend to promote simultaneous hydrolysis and hydrogenation.
The pressure for the prehydrogenation is generally from 500 to 10,000 psig, preferably 1,000 to 5,000 psig.
The prehydrogenation results in the preparation of compounds with t'he aforesaid general formula where X is CH2OH.
Thus, the process of the present invention comprlses the simul~
taneous catalytic hydrogenation and hydrolysis at a p~I o~ 4 to
It i5 also within the scope of this invention to u~e mix-tures of 2(2'-propanal)-5-methyl-1,3-dioxane and 2(3'-propanal)-S-methyl-1,3-dioxane and mixtures of 2(2'-propanol)-5-methyl-1,3 dioxane and 2(3'-propanol 5-methyl- ;
1,3-dioxane.
The 1,4-butanediol prepared by the process of this invention may b~ separated from the byproduct diol(s) present therewith if desired. Where the diol is 2-methyl-1,3-propanediol, the separation with 1,4-butanediol is relatively simple due to the difference in boi~ing points.
In any event, the byproduct diol(s~ is separated from the 1,4-~utanediol by conve~tional means.
~.
As can be seen from the aforesaid cyclic acetal general ~o~nula the process o the present invention in-cludes within its scope the step of prehydrogenating kh~
acetal aldehydes in the presence oE a hydrogenation aata-lyst prior to the simultaneous hydrolysis and hydrogenation in Xhe presence of the base metal hydrogenation catalyst and aqueous acid according to the process of the present invention. This prehydrogenation is conducted at normal hydrogenation conditions,except for temperature, in the presence of a base metal hydrogenation catalyst. The pre~
hydrogenation converts the -CHO gxoup to -CH20H before any hyarolysis of the starting compound.
The prehydrogenation, if desired, may be carried out in an aqueous medium in which case the water acts as a :
hea-t sink and a viscosity adjustor although the reaction can also be carried out neat; that is, without the use of water.
If an aqueous medium is used, it is convenient to have enough water present ~or the hydrolysis-hydrogenation stepthat follows.
The prehydrogenation is conducted at a temperature of from ~0 to 125C. Temperatures above 125C will tend to promote simultaneous hydrolysis and hydrogenation.
The pressure for the prehydrogenation is generally from 500 to 10,000 psig, preferably 1,000 to 5,000 psig.
The prehydrogenation results in the preparation of compounds with t'he aforesaid general formula where X is CH2OH.
Thus, the process of the present invention comprlses the simul~
taneous catalytic hydrogenation and hydrolysis at a p~I o~ 4 to
5.5 of compounds of the general formula gi~en above where X is -CHO as well as where X is -C~I2OH.
The process of the present invention is further described by re~erence to specific cyclic acetals. It will be understood, however, that the process of the invention is equally applicable to the cyclic acetals of the general formula given a~ove.
I'he cyclic acetals of the present invention may be prepared by the reaction of an alcohol and/or diol having at least four carbon atoms and a maximum of three carbon atoms separating the diol hydro~y groups with at least a stoichio-metrical]y equivalent quantity of an aldehyde and/or dialdehyde after which hydroformylation produces the cyclic acetals. U.S.
, Patent ~ 024 159 which issued 1977 May 17 discloses the pre- ':
- paration of the cycllc acetals. U.S. ~atents 3,963,754 and 3,963,755 disclose the preparation oE'2(3'-propanal)-5-methyl-l, 3-dio~ane and 2~2'-propanal)-5--methyl-1,3-dioxane. Other ' : , ' ' 1~ .
!, . .. . ..
cyclic acetals may be prepared according to the disclosure in the aforesaid patents. The starting compounds of this invention of the aforesaid general formula where X is CH2OH
are prepared by the hydrogenation of the cyclic acetals alde-hydes under hydrogenation conditions described herein in the presence of the base metal hydrogenation catalysts of this invention also indicated herein as ~rehydrogenation.
The process of the invention is useful in the pre-paration of 1,4-butanediol which can be converted to tetra-hydrofuran both of which are useful as solvents.
The examples were all conducted with the indicated 4-methyl aldehydes (from the readily available 1,3-butanediol) rather than the 5-methyl aldehydes ~from the less readily availahle MPD). Tests, however, indicate no major differences between the performance of the 4-methyl aldehydes and the 5-methyl aldehydes.
The following examples further illustrate the inven-tion. All percentages are by weight unless otherwise indicated A 100 g sample of nickel catalyst was charged to a 1-1/2" diameter high pressure tubular reactor. rro this was fed 85~ 2(3'-propanal)-4-methyl-1,3-dioxane and 153 2(2'-propanal)-4-methyl-1,3-dioxane and H2O at a 2:1 weight ratio of acetal to water at 270 ml/ hr together with a 5:1 weight ratio oE recycle of reactor product to acetal and water feed. The hydrogenation catalyst bed was maintained at 155C and 2,000 psig H2 pressure.
The catalyst was 50~ Ni on kieselguhr and no ~i .
-5~S~
attempt was made to control pH. The initial pH of the product was 5.0, but after one day th~ pH fell below 4.0 at which time the catalyst activity fell to le~s than half of its original value.
EXA~LE 2 -The procedure of Example 1 was ollowed except that the pH of the reactor mixture was maintained at 5.0 to 5.5 by addi~ion of a small amount of NaOH via the H2O
feed (0.006N NaOH) throughout the reaction. The catalyst survived for eight days before it suddenly lost most of its activity. The yield of 1/4~butanediol remained con-stant for the first eight days at the run at 85%. However, at that point the yield declined rapidly down to 54~ indi-cating a loss in catalyst activity.
The procedure of Example 1 was ollowed except that the catalyst was 1/8 inch diameter pellets of 50% Ni on alumina and no control was exerted over pH. The initial pH of the reactor mixture was 5Ø Over the first four days the pH gradually drifted down to 4.0, but the activity ; remained at its original high value. On the fifth day, the pH fell below 4.0, and the catalyst lost more than half of its oriyinal activity as determined by the loss o yield of 1,4-butanediol and MPD to about 50% of the yield of the first four days.
~ The procedure of Example 1 was followed except ~ ;
that the cataly~t wa~ prepared by adding a solution of 5~0 g Re O in 25 ml ~2 to a fresh 100 g sample of the same Ni on alumina catalyst used in Example 3. The solution was :' ~: :
- 15 ~ ~
completely absorbed by the catalyst. The catalyst was placed in ~he reactor and treated with H2 at 1 atm at 180C for 2 hours to reduce and insolubilize the Re2O7~ Duriny this run the pH was controlled at 4.0 to 5.5 by addition of NaOH
to the water feed (0.0012N NaOH). This run was carried out for 19 days, and there was no siynificant loss of catalyst activity. The effect of p~I on yield of 1,4-butanediol, 2-methyl-1,3-propanediol (MPD), branched and linear hydroxy acetal is summarized in the table that follows:
'. ~ ' .~o oo o o o~ o 0.~ c~
E~,,, a) a~ oo ~ a~
' s~
: ~ ~ 0 ~, o o u~
co ~ ~
~ rl O
~
E~
: ~ l CO ~ Ln Ln C~ Ln In tn N ~ 'I ' ~ 7 m ~ ~ OD C~
O ~D Ln f~
n Ln Ln d~
~ ~ - 17 -- :, , ~ , .. .
:: - . . ' .
Thus, it can be se~n that the yiel.d of MPD de creases with i.ncreasing pH. While the unreacted BHA yield loss can be overcome with further hydrolysis and hydro~
genation to MPD with extended reaction ti~es, this would be disadvantageous.
-The procedure of Example 1 was followed, except the catalyst was 200 g of Raney nickel ~5% aluminum re-moved). During the run the pH was mainta.ined at 4.5 to 5.0 by addition of NaOH with the water feed. The run was carried out for 10 days during which ~ime the yield of 1,4-butanediol was between 85 and 87%, the MPD yield was between 70 to 85%, and the catalyst showed no sign of loss of activity.
The procedure of Example 4 was repeated except that the particle size of the catalyst of Example 3 was decreased to 1/16 inch diameter particles. The run was carried out for 55 days. The acti.vity of the catalyst began to decrease after about 35 days as evidenced by a decrease in BAD and MPD yield. The pH was controlled at 4.0 to 5Ø The yield of BAD for the first 45 days was greater than 95% while the ~PD was 85 to 100% for the first 35 days.
Whlle the invention has been described in consid-erable detaLl in the ~oregoing, it is to be understood that such detail is solely for the purpose of illustration and that variations can be made by those skilled in the art withou~ departing ~rom the spirit and scope of the invention except as sèt forth in the claims.
. . .
' .
.
The process of the present invention is further described by re~erence to specific cyclic acetals. It will be understood, however, that the process of the invention is equally applicable to the cyclic acetals of the general formula given a~ove.
I'he cyclic acetals of the present invention may be prepared by the reaction of an alcohol and/or diol having at least four carbon atoms and a maximum of three carbon atoms separating the diol hydro~y groups with at least a stoichio-metrical]y equivalent quantity of an aldehyde and/or dialdehyde after which hydroformylation produces the cyclic acetals. U.S.
, Patent ~ 024 159 which issued 1977 May 17 discloses the pre- ':
- paration of the cycllc acetals. U.S. ~atents 3,963,754 and 3,963,755 disclose the preparation oE'2(3'-propanal)-5-methyl-l, 3-dio~ane and 2~2'-propanal)-5--methyl-1,3-dioxane. Other ' : , ' ' 1~ .
!, . .. . ..
cyclic acetals may be prepared according to the disclosure in the aforesaid patents. The starting compounds of this invention of the aforesaid general formula where X is CH2OH
are prepared by the hydrogenation of the cyclic acetals alde-hydes under hydrogenation conditions described herein in the presence of the base metal hydrogenation catalysts of this invention also indicated herein as ~rehydrogenation.
The process of the invention is useful in the pre-paration of 1,4-butanediol which can be converted to tetra-hydrofuran both of which are useful as solvents.
The examples were all conducted with the indicated 4-methyl aldehydes (from the readily available 1,3-butanediol) rather than the 5-methyl aldehydes ~from the less readily availahle MPD). Tests, however, indicate no major differences between the performance of the 4-methyl aldehydes and the 5-methyl aldehydes.
The following examples further illustrate the inven-tion. All percentages are by weight unless otherwise indicated A 100 g sample of nickel catalyst was charged to a 1-1/2" diameter high pressure tubular reactor. rro this was fed 85~ 2(3'-propanal)-4-methyl-1,3-dioxane and 153 2(2'-propanal)-4-methyl-1,3-dioxane and H2O at a 2:1 weight ratio of acetal to water at 270 ml/ hr together with a 5:1 weight ratio oE recycle of reactor product to acetal and water feed. The hydrogenation catalyst bed was maintained at 155C and 2,000 psig H2 pressure.
The catalyst was 50~ Ni on kieselguhr and no ~i .
-5~S~
attempt was made to control pH. The initial pH of the product was 5.0, but after one day th~ pH fell below 4.0 at which time the catalyst activity fell to le~s than half of its original value.
EXA~LE 2 -The procedure of Example 1 was ollowed except that the pH of the reactor mixture was maintained at 5.0 to 5.5 by addi~ion of a small amount of NaOH via the H2O
feed (0.006N NaOH) throughout the reaction. The catalyst survived for eight days before it suddenly lost most of its activity. The yield of 1/4~butanediol remained con-stant for the first eight days at the run at 85%. However, at that point the yield declined rapidly down to 54~ indi-cating a loss in catalyst activity.
The procedure of Example 1 was ollowed except that the catalyst was 1/8 inch diameter pellets of 50% Ni on alumina and no control was exerted over pH. The initial pH of the reactor mixture was 5Ø Over the first four days the pH gradually drifted down to 4.0, but the activity ; remained at its original high value. On the fifth day, the pH fell below 4.0, and the catalyst lost more than half of its oriyinal activity as determined by the loss o yield of 1,4-butanediol and MPD to about 50% of the yield of the first four days.
~ The procedure of Example 1 was followed except ~ ;
that the cataly~t wa~ prepared by adding a solution of 5~0 g Re O in 25 ml ~2 to a fresh 100 g sample of the same Ni on alumina catalyst used in Example 3. The solution was :' ~: :
- 15 ~ ~
completely absorbed by the catalyst. The catalyst was placed in ~he reactor and treated with H2 at 1 atm at 180C for 2 hours to reduce and insolubilize the Re2O7~ Duriny this run the pH was controlled at 4.0 to 5.5 by addition of NaOH
to the water feed (0.0012N NaOH). This run was carried out for 19 days, and there was no siynificant loss of catalyst activity. The effect of p~I on yield of 1,4-butanediol, 2-methyl-1,3-propanediol (MPD), branched and linear hydroxy acetal is summarized in the table that follows:
'. ~ ' .~o oo o o o~ o 0.~ c~
E~,,, a) a~ oo ~ a~
' s~
: ~ ~ 0 ~, o o u~
co ~ ~
~ rl O
~
E~
: ~ l CO ~ Ln Ln C~ Ln In tn N ~ 'I ' ~ 7 m ~ ~ OD C~
O ~D Ln f~
n Ln Ln d~
~ ~ - 17 -- :, , ~ , .. .
:: - . . ' .
Thus, it can be se~n that the yiel.d of MPD de creases with i.ncreasing pH. While the unreacted BHA yield loss can be overcome with further hydrolysis and hydro~
genation to MPD with extended reaction ti~es, this would be disadvantageous.
-The procedure of Example 1 was followed, except the catalyst was 200 g of Raney nickel ~5% aluminum re-moved). During the run the pH was mainta.ined at 4.5 to 5.0 by addition of NaOH with the water feed. The run was carried out for 10 days during which ~ime the yield of 1,4-butanediol was between 85 and 87%, the MPD yield was between 70 to 85%, and the catalyst showed no sign of loss of activity.
The procedure of Example 4 was repeated except that the particle size of the catalyst of Example 3 was decreased to 1/16 inch diameter particles. The run was carried out for 55 days. The acti.vity of the catalyst began to decrease after about 35 days as evidenced by a decrease in BAD and MPD yield. The pH was controlled at 4.0 to 5Ø The yield of BAD for the first 45 days was greater than 95% while the ~PD was 85 to 100% for the first 35 days.
Whlle the invention has been described in consid-erable detaLl in the ~oregoing, it is to be understood that such detail is solely for the purpose of illustration and that variations can be made by those skilled in the art withou~ departing ~rom the spirit and scope of the invention except as sèt forth in the claims.
. . .
' .
.
Claims (17)
1. A process for the simultaneous catalytic hydrolysis and hydrogenation of a cyclic acetal of the general formula and mixtures thereof wherein M is an alkyl group of 1 to 20 carbon atoms, X is -CHO or CH2OH and R1, R2, R3, R4, R5, and R6 may be the same or different hydrogen or alkyl groups of 1 to 20 carbon atoms which comprises (a) hydrolyzing and hydrogenating simultaneously said acetal in the presence of an aqueous acid solution and a base metal hydrogenation catalyst and at a temperature of from 125°
to 200°C and a pressure of from 500 to 10,000 psig; and (b) maintaining a pH of from 4.0 to 5.5 until a product comprising a mixture of diols is prepared.
to 200°C and a pressure of from 500 to 10,000 psig; and (b) maintaining a pH of from 4.0 to 5.5 until a product comprising a mixture of diols is prepared.
2. The process of Claim 1 wherein the hydrogena-tion catalyst is treated with rhenium prior to its use in this process.
3. The process of Claim 1 wherein the base metal hydrogenation catalyst is selected from the group consisting of nickel, conventional Raney nickel, conventional Raney nickel promoted with molybdenum, conventional Raney nickel promoted with chromium, granular foraminous nickel, granular foraminous nickel promoted with molybdenum and granular foraminous nickel promoted with chromium.
4. The process of Claim 1 wherein the pH is from 4.0 to 4.5.
5. The process of Claim 4 wherein the cyclic acetal is a mixture of 2(3'-propanal)-5-methyl-1,3-dioxane and 2(2'-propanal)-5-methyl-1,3-dioxane and the product is 1,4-butanediol and 2-methyl-1,3-propanediol.
6. The process of Claim 4 wherein the cyclic acetal is a mixture of 2(3'-propanal)-5-methyl-1,3-dioxane and 2,2'-propanal)-5-methyl-1,3-dioxane and the product is 1,4-butanediol, 2-methyl-1,3-propanediol and 1,3-butanediol.
7. The process of Claim 4 wherein the cyclic acetal is a mixture of 2(3'-propanol)-5-methyl-1,3-dioxane and 2(2'-propanol)-5-methyl-1,3-dioxane and the product is 1,4-butanediol and 2-methyl-1,3-propanediol,
8. The process of Claim 1 wherein the base metal hydrogenation catalyst is granular foraminous nickel,
9. The process of Claim 1 wherein the base metal hydrogenation catalyst is conventional Raney nickel.
10. The process of Claim 1 wherein the base metal hydrogenation catalyst is conventional Raney nickel pro-moted with molybdenum or chromium.
11. The process of Claim 1 wherein the base metal hydrogenation catalyst is granular foraminous nickel pro-moted with molybdenum or chromium.
12. The process of Claim 1 wherein X is -CHO.
13. The process of Claim 12 wherein the cyclic acetal is a mixture of 2(3'-propanal)-5-methyl-1,3-dioxane and 2(2'-propanal)-5-methyl-1,3-dioxane and the product is 1,4-butanediol and 2-methyl-1,3-propanediol.
14. The process of Claim 12 wherein the base hydrogenation catalyst is selected from the group con-sisting of nickel, conventional Raney nickel, conventional Raney nickel promoted with molybdenum, conventional Raney nickel promoted with chromium, granular foraminous nickel, granular foraminous nickel promoted with chromium and granular foraminous nickel promoted with molybdenum.
15. The process of Claim 12 wherein the pH is from 4.0 to 4.5.
16. The process of Claim 1 wherein X is -CH2OH.
17. The process of Claim 12 wherein the cyclic acetal is a mixture of 2(3'-propanol)-5-methyl-1,3-dioxane and 2(2'-propanol)-5-methyl-1,3-dioxane and the product is 1,4-butanediol and 2-methyl-1,3-propanediol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75512276A | 1976-12-28 | 1976-12-28 | |
| US755,122 | 1976-12-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1105059A true CA1105059A (en) | 1981-07-14 |
Family
ID=25037816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA293,719A Expired CA1105059A (en) | 1976-12-28 | 1977-12-22 | Process for preparing polyols from a cyclic acetal |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5382712A (en) |
| BE (1) | BE862367A (en) |
| CA (1) | CA1105059A (en) |
| DE (1) | DE2758500A1 (en) |
| FR (1) | FR2376106A1 (en) |
| GB (1) | GB1581379A (en) |
| IT (1) | IT1089990B (en) |
| NL (1) | NL7714433A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4296739B2 (en) * | 2001-03-22 | 2009-07-15 | 昭和電工株式会社 | Catalyst for producing both-end diols, method for producing the catalyst, method for producing both-end diols using the catalyst, and both-end diols obtained by the production method |
| RU2007143051A (en) | 2005-04-21 | 2009-05-27 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL) | HYDRATION CATALYST AND HYDROGENATION METHOD |
| US7381852B2 (en) | 2006-04-13 | 2008-06-03 | Shell Oil Company | Process for hydrogenating an aldehyde |
| US7943792B2 (en) | 2007-04-02 | 2011-05-17 | Inventure Chemical Inc. | Production of biodiesel, cellulosic sugars, and peptides from the simultaneous esterification and alcoholysis/hydrolysis of materials with oil-containing substituents including phospholipids and peptidic content |
| US8212062B2 (en) | 2007-04-02 | 2012-07-03 | Inventure Chemical, Inc. | Production of biodiesel, cellulosic sugars, and peptides from the simultaneous esterification and alcoholysis/hydrolysis of oil-containing materials with cellulosic and peptidic content |
| US7777085B2 (en) | 2008-10-01 | 2010-08-17 | Inventure Chemical, Inc. | Method for conversion of oil-containing algae to 1,3-propanediol |
| DE102011118956A1 (en) * | 2011-11-19 | 2013-05-23 | Oxea Gmbh | A process for recovering di-trimethylolpropane and trimethylolpropane enriched product streams from the sidestreams of trimethylolpropane production |
| US10941092B2 (en) | 2017-06-13 | 2021-03-09 | Basf Se | Hydroformylation process for producing 1,6-hexanediol derivatives |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE626845A (en) * | ||||
| FR1030806A (en) * | 1950-01-19 | 1953-06-17 | British Ind Solvents Ltd | Hydrogenation process |
| US2618663A (en) * | 1951-01-17 | 1952-11-18 | Gen Aniline & Film Corp | Production of polyether alcohols |
| US2888492A (en) * | 1955-08-08 | 1959-05-26 | Shell Dev | Production of polyols |
| US3168579A (en) * | 1960-10-14 | 1965-02-02 | Shell Oil Co | Production of polyols from substituted aldehydes |
| GB966270A (en) * | 1961-09-27 | 1964-08-06 | Shell Int Research | Process for the production of polyols |
| DE2401553C2 (en) * | 1974-01-14 | 1984-05-03 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of 1,4-butanediol |
| US3963755A (en) * | 1974-07-31 | 1976-06-15 | E. I. Du Pont De Nemours And Company | Mixture of 2(2'-propanal)-5-methyl-1,3-dioxane and 2(3'-propanal)-5-methyl-1,3-dioxane |
| US3929915A (en) * | 1974-07-31 | 1975-12-30 | Du Pont | Process for the production of butanediol |
| FR2351935A1 (en) * | 1974-07-31 | 1977-12-16 | Du Pont | PREPARATION OF ACETALS FROM ALDEHYDES AND ALCOHOLS AND / OR DIOLS |
| DE2524039A1 (en) * | 1974-08-02 | 1976-02-19 | Du Pont | PROCESS FOR HYDROLYZING AND HYDRATING ACETALDEHYDE |
| DE2523840A1 (en) * | 1974-08-02 | 1976-02-12 | Du Pont | ONE-STAGE PROCESS FOR HYDROLYZING AND HYDRATING ACETALALDEHYDE |
-
1977
- 1977-12-19 GB GB5274977A patent/GB1581379A/en not_active Expired
- 1977-12-22 CA CA293,719A patent/CA1105059A/en not_active Expired
- 1977-12-27 FR FR7739277A patent/FR2376106A1/en active Granted
- 1977-12-27 NL NL7714433A patent/NL7714433A/en not_active Application Discontinuation
- 1977-12-27 IT IT3130977A patent/IT1089990B/en active
- 1977-12-27 BE BE183886A patent/BE862367A/en not_active IP Right Cessation
- 1977-12-27 JP JP15662177A patent/JPS5382712A/en active Pending
- 1977-12-28 DE DE19772758500 patent/DE2758500A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| IT1089990B (en) | 1985-06-18 |
| FR2376106A1 (en) | 1978-07-28 |
| JPS5382712A (en) | 1978-07-21 |
| FR2376106B1 (en) | 1983-11-18 |
| GB1581379A (en) | 1980-12-10 |
| DE2758500A1 (en) | 1978-06-29 |
| BE862367A (en) | 1978-06-27 |
| NL7714433A (en) | 1978-06-30 |
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