CA1051037A - Process for the production of butanediol - Google Patents

Abstract

APPLICATION FOR LETTERS PATENT
FOR
A PROCESS FOR THE PRODUCTION OF BUTANEDIOL

Abstract of the Disclosure A process for the production of butanediol which com-prises reacting propylene, oxygen and acid in the presence of a catalyst to produce a carboxylate which is hydroformylated to a mixture of aldehydes which aldehydes are hydrogenated to produce diol esters which are de-esterified to butanediols.

Description

ll 8C~l-190~ ' ~LV~

'lhis invention relates to a process for the produstion of butanediol which comprises: (a) reacting propylenel oxygen and a lower alkanoic acid in the presence of cataIyst comprising : ¦¦a Group VIII noble metal, or its sal~s,or its oxides,or mixtures 5 il thereof at an elevated temperature to produce the corresponding carboxylate; (b) hydroformylating the carboxylate under hydro- :
:, , .~ I formylating conditions to produce aLdehydes; (c) hydrogenating the aldehydes under hydrogenating conditions to produce diol esters; ~d) de-esterifying the diol esters under de-esterifica-I,tion conditions to produce butanediols and an:acid; and (e) ; `
isolating the acid from the butanediols in a form suitable for use in (a), ~:,"~

, ` Background o~ the l ention , But ediol has been prepared by a number of diLferent 15: ¦Imethods. U.S. Patent 3,060,244, for example, discloses preparing $~
jbu~anediol by reacting 1,3-butadiene with diborane in the presence . , . I of a saturated aIiphatic ether. U,S. Patent 2,686,817 describes the production of butanedlol ~om tetrahydro~uran~ Also, : U.S. Patents 2,912,471;and 2,928,884 disclose the preparation of ` :

1 1,4-dichlorobutene to~whic~ sodium hydroxide may be added to ~orm butenediol which, in turn, is hydrogenated to form butanediol.

¦ British Patent~1,230,276 discloses a process for preparing 1,4-I butanediol from ~Y'-butryolactone. From an article by White et aL.

l¦entitled "~atalytic Reduction of Ozonides.~ I. Synthesis of i: '- ` ' ` - ' ' ~ .

105'103~7 acH-Iso7 ,~lcohols ~r~m ~'ilefins" in Tetralledron Letters, No. 39, T3P- 3S87-.~ , ;, 3589, i.t is known that a butanediol may b~ prepared from an ~¦olefin by reacting the olefin with ozone and an alcohol to form ? an ozonide with a subsequent two-stage cataLytic hydrogenation to Iyield butanediol. U.S. Patents 2,300,598; 2,712,560; 2,768,215;

2,953,604 and 3,2949849 disclose preparing 1,4 butynediol from ¦ acetylene. Subsequent hydrogenation of the 1,4 butynediol yields I
the butanediol. However, all of these methods involve starting ~ :
, ~ materials which are costly or, in the case of acetylene, involve .`~ lO ila danger o~ explosions.

,; This invention relates to a novel process for preparing butanediol from oxygen, propylene and an acid, preferably acetic ¦acid The instant process proceeds by way of several steps, i.e.,, preparing the carboxylate, hydrofor~ylation, hydrogenation, llde-esterification and recycling the acid The general step o~
prep~ring the unsa~urated ester by contacting an olefin with a IlGro~ip VIII catalyst in a reaction medium comprising a carboxylic j ~ `
¦ acid is illustrated by U.S. Patents 3,190,912; 3,275,680 and ~ 3,670~014 and South African Patent 701,007, ~or example The i 20 j!reaction of olefinic compounds with carbon monQxide and hydrogen , j, .. . .
:~' i,at elevated temperatures and pressure in the presence of certain ~catalyst to produce aldehydes is illustrated by U.S. Patents 2,497,303 and 2~564,104 Also, U.S. Patents 2,437,600 and ?

2,500,913 illustrate that the aldehyde product can be converted I,to an alcohol I ?
? 3 ?

` 11 ' I

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i 8CH-14~7 ~ ~ S~ ~ 3'7 ; 1l Description of the Invention I -It has been discovered that butanediol may be prepared ' from inexpensive startin~ materials as compared with the prior ;~ art methods, i.e., propylene, carbon monoxide, hydrogen and oxygen :5 11 and without the detonation hazards of acetylene. Acetic acid, in this process, merely acts as a mediatin~ a~ent and is not consumed ~ " : -F` :` 1i in the overall reaction.
' 11 i .;
¦ Another objec~ of ~he inst~nt invention is to provide a novel process for preparing butanediol from inexpensive starting L0 1, materials, i.e., propyleneg carbon monoxide, hydro~en and oxygen by way of several intermediate steps.
~'' ' I` ' ~ .,.
Preferably, the present invention concerns a process for ~ I ; .
'I the production of butanediol which comprises: (a) reactin~
propylene, oxygen and acetic acid in the presence of a catalyst ~15~ l~comprising a Group VIII noble metal or its salt or its oxides or ~, l,mixtures thereof at anelevated temperature to yield allyl acetate;
(b3 hydroformylatin~ the allyl acetate under hydro~ormylatin~
, ~ . I! i conditions to produce a mixture of isomerLc acetoxybutyraldehydes;
(c) hydro~ena~ing the mixture o~ isomeric acetoxyb~tyraldehydes ~ 20 1~ under hydro~ena~ing conditions to produce a mlxture comprising , -}~ the acetate esters of the corresponding butanediols; (d) de-esterifying the mixture of the acetate esters of the butanedials nder de-esterification condi~ions to produce the butanediols and ~' .: ! . ' .,. , , i .'j,'~ . I . , .
!i .. . .. ~ ~
. ~i.... . .

!l ', C~-1907 5 ~ 3 ace~ic acid; and (e) isolating ~he ace~ic aci.d from the butane-diols in a fonm suitable for use in ~a).

I I ' In the inst~nt method, allyl acetate is produced by ~: i reacting propylene, oxygen and a lower alkanoic acid, preferably ~ il .
1! acetic acid, in the presence of a catalyst comprising a Group VIII~ ;
noble metal or its salts or its oxides or mixtures thereo~ at an elevated tempera~ure.

Thls process may be illustrated, taking acetic acid as / ~ an example, by ~he following equation~

.~ 10 CH2 ~ CH - C}13 ~ CH3cooH ~ l/2 2 ~~~~
, CH2 - CH-cH2 -C-C~3 + ~12 .

, .~.! , ' jl wherein the yield average of allyl acetate is better than 96% ;
, , 1 . i :~

The oxygen în the instant process may be used in pure elementary form or in admixture with inert gases, for example, in the ~orm of alr. However, i~ is preferred to work with concen-~;; lS 1 trated oxygen : .

.; l . .
.. ,,. , . I . . . .
:.1 The propylene in the instant process may be used in I ?
pure elementary ~orm or in admixture with inert gases, for example, propane.

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,, ~., ~ , _ ___ ___ _ s ¦i 8C,H~1907 5 ~ 3~ 1 ;
The acids which are employed in the instant invention i! are lower alkanoic acids having 1-6 carbon atofms. Preferably, : acetic acid is employed herein.

Any type of acetic acid may be ~m,ployed herein. The f ¦ acetic acid obtained from step (e) may be recycled to step (a) of , ¦¦the instant process.

j~ Water may b~ used in the feed streffam of the instant ¦¦invention. Preferably, water in thef gaseous phase is employed, The acetic acid obtained from step (e) ~s aqueou~and is suitable llfor use in step (a).

. ~ The reaction ter~erature or r-action pressure are not. I critical. However, the preferred working temperature is in theran8e o~from about 100 to about 225C, while the preferred ' ~
, l working pressure is in the range from atmospheric to about 150 psi. ~ .
IlSom,~what higher ~r lower temp,~ratures and pressures may, however be used within the scope of the invention.

,., , I . I .
The catalysts which may be used in preparing the al.Lyl acetate of~this invention are the Group VIII noble metals, or ¦¦their salts or their oxides or ~ixtures thereof. Speci~ic '' ¦ examples of these catalysts include metals such as palladium, i ~ :
ruthenium, rhodium, platinum, osmium~, and iridiu,m as well as I :

-, ' ' 'i ' ; , .
. f i 8CH-1907 05 10 3'~
~ ¦ oxides and salts su~h as palladous propionate, palladous benzoate, i.' , palladous chloride, palladous bromide, palladous oxide~ etc., ~¦ruthenium acetate, etc,, rhodium acetate, etc., platinous ben~oate, ¦p~atinum dichloride, platinum oxide, etc,, iridium chloride, etc.,l jjand the like and mixtures thereof. ~ ;
~ ~ } 11 , ' ~
The preferred catalyst system i~ a mixture of the Group ¦ VIII nvbel metal and its salt. A preferred catalyst is a mixture of palladium and palladous acetate.

The catalyst i& preferably applied ~o a support such as aluminum oxide, carbon such as charcoal, silicas and the like.
1 , ' I
l I A promoter may be added to the catalyst which influences, activity and selectivity. Among the preferred promoters are the transition metals, their salts, gold or copper.
1l!
l¦ ~ The catalyst may be prepared in a number of different ¦ method~. For example, a 6upport such as aluminum oxide is ¦ impregnated with a palladium acetyl acetonate solution in benzene ,I and dried. The aluminum oxide is then impregnated with a solution, ~
,, ,1 , -:
lo~ potassium acetate in water and dried. The catalyst is then ~ ;
.. . , j ,.
treated with propylene. The palladium is reduced ~o the palladium' ¦ metal. The catalyst thus obtained contains palladium metal an~
~potassium acetate in about l:10 parts.

_ . 1 , ,, , ;'' . :
, :., . ,. . . . .... ~ ~ . . ....

`I 8C~-19V7 ~105~
~ il V3rying amount~ of the catalyst can be used within the .
jscope of this invention. Amounts as low as about .1% based on ¦weight of support have been found to be effec~ive.
1 ` I /' ,';
In carrying out the process of this invention, a ' I ~' !Ir~actor tube is charged with the catalyst. A'mlxture of propylene;, oxygen snd acetic acid is passed through the ~ube. Upon leaving ' ;
the resction zone, the allyl acetate phase is separated from,the aqueous phase and is fed in~o the second s~ep of the overall ' ~ ~-jlprocess~ Preerably, the propylene, oxygen-and acetic acid are ~ '~
!lin the~ga~eous phase.

It has been found that by proceeding ,by the method for preparing allyl acetate outlined above, the c~t'alyst lS not;' diminished~in effectiveness even after 1000 hours of operatlon. ~, Step (b) of the instant process for preparing butanediol 15 ¦l comprlses hydroformylating ~he al,lyl acetate under hydroformy-,,;!~ ¦ lating conditions to produce a mixture of isomeric acetoxybutyr-aldehydes while step (c) of this process comprises hydrogenating " ~
~ ¦the mixture of isomeric acetoxybutyraIdehydes under hydrogenating r ~ 1 conditions'to produce a mixture comprising the acetàte esters of ~ -~

20 !¦ the corresponding butanediols~

~ Preferably, step (b) comprises reacting allyl aceeate , ;~
b'`~ with~carbon monoxide and hydrogen at an elevated temperature and i , . ~ .. .. .. . . . . .. . . . . .. . . .

! 8CH-1907 0 S ~ 3f7 I pressure in the presence o~ a hydroformylation catalyst to~produce i a mixture of isomeric acetoxybutyraldehydes. T~ mixture of q il isomeric acetoxybu~yraldehydes is then hydrogena~ed in step (c) ' ~ ~
¦ under hydro~enating conditions to prod~ce a mixture comprising l ~-' 5 ¦ the acetate esters of the corresponding butanediols. j ~
~I ! I ~
The hydroformylation ~atalysts which may be employed ~¦ include carbonyls of Group VIII metals, iron, cobalt, nickel, ru~henium, rhodium, palladium, osmium, iridium, platinum or mixtures thereof as well as these carbonyls mixed with Group VIII
o ~ ¦! metals may be used. The cobalt catalyst comprises complex cobalt The complexed cobalt may be cobalt in complex combination with carbon monoxide. A preferred cobalt catalyst in compLex combina-¦ tion with carbon monoxide is dLcobalt octacarbonyl. The rhodium catalys~ comprises complexed rhodium. The complexed rhodium may Ibe in complex combination with carbon monoxlde. Pre~erred rhodium catalysts are rhodium tris(triphenylphosphine) carbonyl hydride and rhodium bis(triphenylphosphine) dlcarbonyl chloride. ~ ;~

The active form of the cobalt catalyst is a cob lt ~ carbonyl hydride which resul~s from cLeavage o~ the dicobale oc~a~
,~ 1 20 11l carbonyl. This cleavage takes place in situ` under the hydrogen ;~;
5,~ pressure used~m the reaction.

,. i ,,, , .

9_ ' r (: 11 , 8CH-l901 The hydroformylation may be carried out at temperatures and pressures which are well known ~o those skilled i.n the art. ' , ¦Preferably pressures of from about lO00 to about S000 psi and I i temperatures in the range of from about llO to abo~t 160C. are ' 5 ,'employed. Somewhat higher or lower.temperatures and pressures may, however, be employed within the scope of this invention. ', ., , 11 , ' It has been found that the hydroformylation of aLlyl j1acetate is considerably faster than for simple olefins. An amount of catalyst as low as 0.1% based on the weight of cobalt relative ' ~' lO l¦to allyl aceta~e is su~ficient to adequately promote the rcaction.
Amounts of from 0.1% to about 2.~% have been employed effectively.~

The hydrogenation catalyst which may be employed lncludes ! the hydrogenation catalysts generà1ly, sjuch as nicke1~ cobalt, ~
iron, copper, ruthenium, molybdenum, platinum, palladium and the ~1 -15 ~ !like and mixtures or compounds ther~of. The metals or mixtures thereof may be used with an inert support such as silica or the like,~ for example. Preferred catalysts include nickel, platinum, cobalt,!palladium, molybdenum sulide and copper,chromite.

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The hydrogenation may be carried out at temperatures and ' l 20 ~pressures which are well known to those skilled in the art.
,¦Preferably, pressures of rom, about 500 to sbout 3000 psi and ~temperatures in the range of from about 7 5 to abou~ 200C . are '"'' ' : .~ , , .,, il ' ,~

-~ 8CH-1907 ~ ~
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~S~()37 ~ ~ -employed. Somewhat higher or lower temperatures and pressures may, however, be employed within the scope of this invention.
`
The cobalt hydroformylation catalyst can be recovered in three general forms: (1) as cobalt metal~ (2) as cobaltous `
ion, or (3) as active catalyst. In the first two cases, the . - ,-~, cobaLt carbonyl in the reactor product is decomposed by heat and/
,. ~ . .
` or aqueous acids. Thermal decobalting to cobalt metal can be accomplished by releasing the carbon monoxide pressure from the ~ hot liquid. However, to facilitate the separation of the resulting`~
- lO solids from the crude product, steam or hot water is often used.
:~ .; . .
l~ In that manner, a cobalt-free organic phase can be decanted from ;
,., . :
;` the aqueous slurry. Because organic acids are formed in the ~ ;
hydroformylation step as by-products, steam decobalting is a com~ination of thermal and acid decobalting. The resulting solids ;~
are mixtures of cobalt metal, cobalt~oxides, and cobalt salts. `
; The use of aqueous acids for decobalting is usually carried out `~ ;;
at eIevated temperatures. This technique requires good mixing to ~
ensure contact bet~een the two liquid phases to transfer the cohalt from the organic to the aqueous phase. ~ater-soluble organic acids such as formic, acetic, or propionic may be used;
inorganic acids such as sulfuric or phosphoric are also effective.
~, The co~alt salts obtained from organic acid decobalting are some-~J
times recycled directly back to the oxo reactor. When inorganic ~;
;~ acids are used, the salts are converted to the hydroxide or ... ....
", .. , :~

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;~3 ;

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, 8CH-1907 !¦ ~051V3~7 ` 11 1 carbonate for recycle or for converslon into the pre~erred fo~n of cobalt. I
', The strongly acidic properties of cobalt hydrocarbonyl ~are taken advantage of in two methods used to recycle active j,~talyst to the reactor. In one case, aqueous solutions of ¦Icobaltous ions are used to remove ~he cobalt carbonyl from the ! organic phase by orma~ion of the cobalt salt, Co(Co(C0)4)2. Thisj ~alt has a very high solubility in wa~er and allows the r~cycle of, ~concentrated catalyst, part of which is in the carbonyl form. In I
¦¦the secoind ca~e, the organic liquid i9 decobalted with an a~ueous I -¦alkali at high pressures and temperatures to form the alkaLi-metal, salt of cobalt hydrocarbonyl. The volatile cobalt hydrocarbonyl , !¦ is regenerated by.contac~ing the aqueous s~olution ~i~h dilute mineral acid in the presence of a conSinuous flow of gas such as , 15 ll nitrogen or synthesis gas. The hydrocarbonyl is then transferred~ , ;
to the liquid olein eed by contacting in an absorption tower.
This prscess has found w.ide ~cceptance throughout the world.

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~ In view o~ the water miscibility o~ the aldel~ydes of l I the instant invention, a preerred method o~ decobalting comprises I .
,.
I 20 ! eXp~sin~ a heated hydro~ormyla.tion produGt soluti.on to air. The .
i 2C~iC acid which i8 presen~ rom de~ompos.ition of an aldehyde by-p~oduct is sufficient to cause the precipltation of cobaltous acetate whlch~is i~ola~ed and recycled. .The cobaltous- ace~ate can lZ

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r~ :
8CH-1~07 105~L03~ ~
be converted to dicobalt octacarhonyl in a separate reaction ~ith.
carbon monoxide and hydrogen at elevated temperature and pressure or can be converted to active catalyst in situ~ ~ :
It has been discovered that the following mixture of ::
aldehydes is in evidence whén the product is examined a~ter hydroformylation of the allyl acetate: . ~?

O
H-c-cH2cH2cH2oAc 4-acetoxybutyraldehyde :; -about 7 parts `1:

~, H-C~CH CH20Ac 2-methyl-3-acetoxypropionaldehyde : , i about 1~5 parts ~ ~
., ; ., i 11 1 c j H-C-CH CH2CH3 2-acetoxybutyraldehyde ;~ about l.S parts Upon the subsequent hydrogenation of the mixture of -~
these aldehydes, the follo~ing acetate esters of butanediol are in evidence~
} -.;. : .
OCH2CH2C~2CH20AC 4-acetoxybutanol about 7 parts : :
CH

3 . ~.:;.
~ H0 CH2CHCH20Ac 2-methyl-3-acetoxybutanol ;1 about 1.5 parts :1 : .'. :. ' .' ,:
'i', '' ~, '.

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:j - 13 -,i : .- , :', ~ ,.

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~ ¦1 8C!1-19~7 L
Il lOS~03~ , li OAc 'I I .
IIO CH2CHC~12CH3 2-acetoxybutanol abou~ 1.5 parts Il .
The reaction may be carried out in the presence of a solvent. Any solvent which is inert or does not interfere with the reaction under the conditions employed may be used. Preferred ,Isolvents are inert organic solvents, particularly aromatic or !aliphatie hydrocarbons.
.', I
-' 1¦ The ratios of hydrogen ~o carbon monoxide of the ,Isynthesis gas (carbon ~onoxide and hydrogen) charged may vary idely wi~hin the scope of this invention. Suitable ratios of . ;, . . .
Ihydrogen to carbon monoxide comprise those withln ~he ratio of from about 1:3 to about 10:1. Preerred ratios of hydrogen to .;
,carbon monoxide are from about 1:1 to about 2:1. Higher or lower -~

ratios, however, are within the scope of this invention.

l, Step (d) of the overall process comprises de-esterifying !j the mixture of the acetate es~ers of the butanediols under de-l,e6terification conditions to produce the butanediols and acetic ; I'iacid. The de-esterification takes place by any of the well known . .
~methods in the art as by hydrolysis or alcoholysis J for example, Hydrolysis and alcoholysis may take place in the presence of a , 1 !l . . . j .
~ 20 ~,catalyst such as An acid, base, or acidic or basic ion-e~change .. .. . ..
, ~ 14-'' li ' I :' . .
. . . . . .... .
. . . . . .... . ~ :. :

3~7 ~resin, ~or example. A preferred method for de-esteri~ying the mixture of the acetate esters of ~he butanediols to butanedi.ols l¦is by hydrolyzing these acetate esters in the presence of water j! and alkali. Butanediols and the corresponding acetates are pro-'Iduced. The butanediols may be isolated from ~he salts by extrac-tion with isobutanol, or ~xample. Preferred alkali ar~ the ~ ~
~alkali metal and alkaline earth metal hydroxides. The alkali ~ :
acetate ~io produced is acidified to produce the acetic acid. The Ipreferred acidifying agents are the inorganic acids, Many methodsl ~ ~
10 j! for isol~ting the acetic acid are well known such as distillation, ~ :
¦jfor example, The acetic acid so produced is in a `~orm suitable for use as a starting ma~erial in the preparation o allyl acetate, ;i il As stated, the pre~erred method o~ de-esterifying the ' :
mixture of the acetate esters o butanediols is by hydrolysi.s in , .
5 ll the presence o water and alkali. The butanediols produced com- , i prise in admixture ~he fo.llowing compounds~
I l! HO(GH~ H 194-butanediol ¦¦about 7 parts HOCH2CHCH20H 2-methyl-1,3-propanediol ; ~.
¦I CH3 I~about 1,5 parts I, j, OH
"~1OCH2CHC~2CH3 L,2-butanediol about i.5 parts - :

I! -lS-..

, ~S~L~3~
Il The desired product l,4-butanediol can be separated rom lithe isomeric by-products in greater than 99% purity by distillatia~

~¦ The overall process for preparing butanediol as des-cribed may be carried out semi-continuously, I ' :: ~
5 1 A preferred process for the production of butanediol comprises: (a) reacting propylene, oxygen and a~etic acid in the !¦presence of a catalys~ comprising a mixture of palladiu~t metal and.
i i~s salt at a temperature o from about lO0 to about 225C. and I
i a pressure of from atmospheric to about lS0 psi to produce allyl ll acetate; (b) hydrofo~mylatintg the allyl acetate with carbon jlmonoxide and hydrogen at a temperature o~ from about 110 to about 1~ I L60C. and a pressure of from about 1000 to about 5000 psi in the Il llpresence of a catalyst consisting essentially of cobalt in;complex com~ination with carbon monoxide to produce a mixture of isomeric I ;

l, acetoxybutyrald~hydes~; (c) hydrogenating ~he mixture of isomeric ! acetoxybutyraldehydes in the presence of a catalyst con~isting o~ ~`

I¦cobalt on an inert support at a temperature o~ from about 75 to : I¦ about 200C, and a pr~ssure of from 500 to about 3000 psi to I

Il produce a mixture~comprising the acetate esters of the correspond~

: 20 Il ing butanediols; (d) de-esterifying the mix~ure of the acetate `.

¦¦ es~er~ of the butanediols so produced in the presence,of water and ~:

. i an alkali metal hydroxide or an alka~earth metal hydroxide to ' : : I yield butanediols and the corresponding alkaLi metal acetate or i ~, 11, . . i . .~
16- , ~

' li ' ' ' ` -' i "

I, 8CH-1907 S~03t7 , !
I la ~al~ earth metal ac~tate; (e) a~idifying the acetate so ; 1 :, , Ijproduced with an inorganic acid to produce acetic acid which is iiisolated in a form suitable for use in (a).
Il . I :
t Description of the Preferred_Embodiments I The following examples are se~ forth to illustrate more ~clearly the principle and practice of this invention to those skilled in the art. Unless otherwise specified, where parts or percents are mentioned, they are parts or percents by weight.

Example 1 ~ A miniplant is constructed and operated for the produc- , , tion of butanediol from propylene via the disclosed cyclic process. :
!~ An 8 ft. x 1 in. diameter stainless steel tube is charged with one iter ~1000 grams) of catalyst composed of alumina impregnated ~ ith 0.;3~b palladium and 3% potassium acetate. The ~eactor temper~
1 15 lla~ure is maintained at 180C (circulating oil jacket) while a ¦mlx~ure per hour o 2000 grams of propylene, 600 grams of acetic acid, 170 grams of oxy~en and 900 grams o water, all in the ¦¦gaseous phase, is passed through. The output per hour is a j .I' ..
mlxture of about 960 grams of allyl ace~ate and 1050 grams of 20 ¦¦ water~ in addition to 18 grams of C0z and the excess propyLene ~¦and oxygen, ~hich are recycled. The allyL acetate phase, which contains about 0.1% acetic acid, is separated and used directly in the second stage of the process.

! ~
~ 17~
1 ~ j ,, . I ' , ' , , ' ' 1' '~
: : ~' ' ~ ' 8CH~19~7 A 2 li~er stlrred autoclave heated ~t 125~ is pressuri~
~Iwith 3000 psi of 2:1 hydrogen/carbon monoxide and charged with a ¦¦mixture oE 400 grams of the allyl acetate~ 8.0 ~rams of dicobalt ¦¦octacarbonyl and 400 ml. of benæene. An exQthermic reaction and 1! gas uptake ensues. After 15 minute~ at 125-145qC, the product i~
¦¦mixture is pumped from the autoclave~ cooled and vented. It is ~then decobalte~ by heating at ll~C for 10 minutes in a closed , ' ¦vessel, the addition of acetic ~cid being unnecessary because of ¦lits pres~nce as a decomposition product. (The cobaltous acetate j ,~
,Iso formed is,~iltered of~ and transformed to dicobalt octacarbonyl~
by subjection to hydrogen/carbon monoxide at elevated temperature jand pressure [160C,3000 psl]). The benzene solution is concen-¦~trated and the produrts are flash distilled, affording 474 grams ll(91% yield) of oxo aldehydes containing minor,amounts of 15 libutanediol aceta~e compounds. VPC analysis in,dicates the presence ~ ;
of 4-acetoxybutyraldehyde, 3-acetoxy-2-me~hylpropionaldehyde and ~ 2-acetoxybutyraldehyde in 7:1.5:1.5 ratio.

I ¦ The aldehyde mixture is combined in a stirred autoclave with 50 grams of a 13% cobalt on silica ca~alyst, subjected to ,'~
2Q, ~13000 psi of hydrogen, and heate~ for,30 minutes at 75-125C. 1 , !j` Reduction to the monoacetates is complete, in essentially quanti~
I ¦ tative yield. The hydrogenation catalyst is removed by filtration, ``
VPC analysis of the product shows it to be co~posed of 4- `, l acetoxybutanol, 3-acetoxy-2-methylpropanol and 2-acetoxybutanol, ~l all of which are essentially undisproportionated.
!1 ll ~

_ ,.,. , ~ . :

Il 8C~-1907 ~:
!~ ~.051~37 i ~:-!1 The monoacetate mixtures derived from 5 such hydro-jlformylation~hydrogenation sequences are combined and hydrolyzed ¦!with 5 liters of 5 N NaOH. After 1 hour at re~ux (llO~), the mixtur~ is cooled and neutrallzed (to pH 10) with H2SO4, then ll extracted with isobutanol. Distillati~n of the extract af~ords~
1532 grams of mixed diols (85% yield in the conversion from allyl acetate) 9 bp 70-~/lmm~ VPC analysis indicates the presence of ~
j 1,4~bu~anediol, 2-methyl-1,3-propanediol and 1,2-bu~anediol in ~ -:
7:1.5:1.5 r~tio. These diols are separable by distillation.
I . ' . .~
1 The aqueous phase and distillation residue are combined ' :
¦and scidiied to pH 3. Distilla~ion afor~s the acetic acid ~5/O ~
. ¦Irecovery) in a form suitable ~or use (about 40%j in the propylene I :
i l¦to allyl acetate eonversion. :~

The process as described is operated semi-continuousLy 15 I,~ provide butanediol a~ about 2 pounds per hour~ ;
~,` ' 1i ' " . ' I ,'' .
Ii Example 2 l ' . j ' A mixture o~ 100 grams o~ allyl acetate (obtained as in Example 1), 4.0 grams of dicobal~ octacarbonyl and 200 ml. of ~, : I
b~zene is subjec~ed to 3000 psi of 2;1 hydrogen/carbon monoxide and heatcd to 125C, At that point, rapid gas uptake begins. After ~`
lS mlnutes a~ 125-14SC,the mixture is cooled and decobalted (10 ' ~
ml. o~ acetic acid is added and the mlxture is heated at 8C~ for ' ~ :
30 minutes to precipitate the cobaltous acetate). The benzene 9~
;

. ., ' . . .
, .. .. . .

il 8CH-1907 1 ~
~05~37 solution is eoncetltrated and the oxo aldehydes are flash distilled.
IlVPC analysis indicates the presence of ~-acetoxybutyraldehyde, ¦ 3-acetoxy-2-methylpropionaldehyde and 2 acetoxybutyraldehyde in ¦¦7.2:1.5:1.3 ratio.

!I The aldehyde mixture is subjected to 1000 psi of hydro-.¦ gen over 10 grams of 5% platinum on carbon catalyst and heated to Il125Co Reduction to the monoacetate derivatives is complete in ¦¦1 hour~ in essentially quantitative yield. VPC analysis of the products shows the presence of 4-acetoxybutanol, 3-acetoxy-2 ! methylpropanol and 2-acetoxybutanol, all of which are essentially ' tl undisproportionated~ ~
.~ j, . . .
'; 'I ' ¦ The hydrogenation catalyst is removed by filtration and i ~ ,the products are subjected dirèctly to hydrolysis with 300 ml. of ~ !5 ~ NaOH as in the above Example. Isolated by~isobutanol '~ 15 ' extracti~n and distillation are 81.0 grams (90%~yield in the ! : .
iconversion from allyl acetate3 of the mixed diols, 1,4-butanediol,l ;2-methyl-1,3-propanediol and 1,2-butanediol, in 7 2:1.4:1 4 ratio.

!I Example 3 i, I~ . :
'` /1 , , Allyl acetate (100 grams) prepared as in Example 1 is 1¦ subjécted to the hydroformylation reaction at 15GC and 3000 psi . . .
of 2:1 hydrogen/carbon monoxide with catalyst generated in situ ~
rom 4.8 grams of cobaltous acetate tetrahydrate. The products ; ~ -ij ' ' ~ 20- ~
`' ~1 .

Ij 8C~-1907 ~ .
5~1~3~

(isolated as in the above cases) are the 4-acetoxybu~yraldehyde~
3-acetoxy-2-methylpropionaldehyde and 2-acetoxybutyraldPhyde ln :
7.5~ 1.4 ratio. : ~

I Hydrogenation of the aldehyde mixture over copper ~ . ..
5 ~lchromite (10% by weight) at 3000 psi and ~2g~ af~ords-the mono~
. ~lacetates as in the above cases, the reaction being complete within ~:-.`. ¦ll hour. Hydrolysis, extraction and distillation as in the above I :
¦IExamples affords 73.1.grams (81% yield from allyl ace~ate) of ~mixed diols, l,4-butanediol, 2-methyl-1,3-propanediol and ~ 0 1¦1 7 2-butanediol in 7.5:L.0 1.5 ratio.

!: . il . . ~ .

A mixture o~ 40 4 grams of aLlyl acetate, 0.74 grams of rhodium tris(triphenylphosphine) c-rbonyl hydrlde ~RhH(CO).(PPh3)3], ~ and 200 ml. of benzene is subjected to 300 psi each o~ carbon ,~ 15 Ilmonoxi~de and hydrogen, then heated at 25-lOOC for 24 hours. .The j products are distiLled and analyze~ by VPC. Produc~d are 20 5 grams ~39V~o yield) o~ 4-acetoxybutyraldehyde, as well as 9.3 grams . ¦ (38~/o) Of acetic acld. In contrast to the resùlts in the above Examples, no o~her aldehyde acetates are detected.
., ; Example 5 : ~ A mixture of 20.0 grams of allyI acetate, 0.25 grams of , rhodium bis(triphenylphosphine)dicarbonyl~chloride . ., , . . , , , I

8C~-19~7 3'7 I ', , I lRhCl(C0)2~PPh3)2J, 0.035 grams of triethylamine, and 60 ml. of ben2ene are subjected to 1000 psi o~ 1:1 hydrogen/carbon ~onoxide ¦and heated at 75-100C for 1 hour. Gas is replenished ~o maintain !~the pressure at 1000-1200 psi.

ll Direct quantitative VPC analysis of the products , :~
llindicates the presence of 13.1 grams of 4-acetoxybutyraldehyde :~
; ji~50% yield), 0.2 grams of 3-acetoxy-2-methylpropionaldehyde (1%), and 0.2 grams of 2-ace~oxybutyraldehyde (1%). Also detected are ll1.7 grams oE acetic acid (l4%? and an approximately corresponding , ~.
~lamount of methacrolein.

It should, of course, be apparent to those slcilled in ~the art ~hat changes may be made in the particular embodiments t~f the invention described which are within the full intended ~¦scope of the invention as defined by the appended claims.

1' . ,.

I! :

l. t~

jj - I
'~ 11 ; - '' ' ' .':

~ 22 .` , ' , j ... ,, . : . .. . .. . .

Claims (35)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the production of butanediol which comprises:
(a) reacting propylene, oxygen and a lower alkanoic acid in the presence of a catalyst comprising a Group VIII noble metal, or its salts, or its oxides, or mixtures thereof at an elevated temperature to produce the corresponding carboxylates;
(b) hydroformylating the carboxylates under hydro-formylation conditions to produce the corresponding aldehyde;
(c) hydrogenating the aldehyde under hydrogenating conditions to produce the esters of the corresponding butanediols;
(d) de-esterifying the esters of the diols under de-esterification conditions to produce the butanediols and a carboxylic acid;
(e) isolating the acid from the butanediols in a form suitable for use in (a).

2. A process for the production of butanediol which comprises:
(a) reacting propylene, oxygen and acetic acid in the presence of a catalyst comprising a Group VIII noble metal, or its salts, or its oxides, or mixtures thereof at an elevated temperature to produce allyl acetate;
(b) hydroformylating the allyl acetate under hydro-formylating conditions to produce a mixture of isomeric acetoxy-butyraldehydes;

(c) hydrogenating the mixture of isomeric acetoxybutyraldehydes under hydrogenating conditions to produce a mixture comprising the acetate esters of the corresponding butanediols;
(d) de-esterifying the mixture of the acetate esters of the butanediols so produced under de-esterification conditions to produce the corresponding butanediols;
(e) isolating the acetic acid from the butanediols in a firm suitable for use in (a).

3. The process of claim 2 wherein the Group VIII
noble metal salts are selected from the group consisting of the Group VIII noble metal acetates, benzoates, propionates, halides and mixtures thereof.

4. The process of claim 2 wherein the catalyst in (a) is a mixture of a Group VIII noble metal and its salt.

5. The process of claim 4 wherein the mixture of the Group VIII noble metal and its salt is a mixture of palladium and palladous acetate.

6. The process of claim 2 wherein said catalyst in (a) is supported on a support selected from the group consisting of aluminum oxide, silica and carbon.

7. The process of claim 2 wherein (a) is carried out at a pressure of from atmospheric to about 150 psi.

8. The process of claim 2 wherein (a) is carried out at a temperature of from about 100 to about 225°C.

9. The process of claim 2 wherein the propylene, oxygen and acetic acid are reacted in the presence of water.

10. The process of claim 2 wherein the propylene, oxygen and acetic acid are reacted in the gaseous state.

11. The process of claim 2 wherein the hydroformulation comprises reacting allyl acetate with carbon monoxide and hydrogen at an elevated temperature and pressure in the presence of a hydroformylation catalyst to produce a mixture of isomeric acetoxybutyraldehydes.

12. The process of claim 11 wherein the hydroformyla-tion catalyst comprises complexed cobalt.

13. The process of claim 12 wherein the complexed cobalt catalyst comprises cobalt in complex combination with carbon monoxide.

14. The process of claim 12 wherein the cobalt in complex combination with carbon monoxide is dicobalt octacarbonyl.

15. The process of claim 11 wherein the hydroformyla-tion catalyst comprises complexed rhodium.

16. The process of claim 15 wherein the complexed rhodium catalyst comprises rhodium in complex combination with carbon monoxide.

17. The process of claim 16 wherein the rhodium in complex combination with carbon monoxide is selected from the group consisting of rhodium tris(triphenylphosphine) carbonyl hydride and rhodium bis(triphenylphosphine) dicarbonyl chloride.

18. The process of claim 11 wherein the hydroformylation is carried out at a temperature of from about 110° to about 160°C.

19, The process of claim 11 wherein the hydroformyla-tion is carried out at a pressure of from about 1000 to about 5000 psi.

20. The process of claim 11 wherein the hydroformyla-tion is carried out in an inert organic solvent.

21. The process of claim 20 wherein the inert organic solvent is an aromatic or aliphatic hydrocarbon.

22. The process of claim 11 wherein the isomeric mixture of acetoxybutyraldehydes comprises in admixture 4-acetoxy-butyraldehyde, 2-methyl-3-acetoxypropionaldehyde and 2-acetoxy-butyraldehyde.

23. The process of claim 2 wherein the hydrogenation comprises hydrogenating the mixture of isomeric acetoxybutyr-aldehydes in the presence of a hydrogenation catalyst at an elevated temperature and pressure to produce butanediol acetates

24. The process of claim 23 wherein the hydrogenation catalyst is selected from the group consisting of platinum, cobalt, palladium, molybdenum sulfide and copper chromite.

25. The process of claim 24 wherein the platinum, cobalt and palladium may be on an inert support.

26. The process of claim 22 wherein the hydrogenation is carried out at a temperature of from about 75° to about 200°C.

27. The process of claim 23 wherein the hydrogenation is carried out at a pressure of from about 500 to about 3000 psi.

28. The process of claim 2 wherein the mixture of the acetate esters of the butanediols are de-esterified by hydrolyzing in the presence of water and alkali to produce the butanediols and alkali acetate.

29. The process of claim 28 wherein the alkali is selected from the group consisting of alkali metal and alkaline earth metal hydroxides.

30. The process of claim 2 wherein the alkali acetate is acidified with an inorganic acid to produce acetic acid which is isolated in a form suitable for use in step (a).

31. The process of claim 2 wherein the butanediol comprises in admixture 1,4-butanediol, 2-methyl-1,3-propanediol and 1,2-butanediol.

32. A process for the production of butanediol which comprises:
(a) reacting propylene, oxygen and acetic acid in the presence of a catalyst comprising a mixture of palladium metal, and its salt at a temperature of from about 100 to about 225°C.
and a pressure of from atmospheric to about 150 psi to produce allyl acetate;

(b) hydroformylating the allyl acetate with carbon monoxide and hydrogen at a temperature of from about 110° to about 160°C. and a pressure of from about 1000 to about 5000 psi in the presence of a catalyst consisting essentially of cobalt in complex combination with carbon monoxide to produce a mixture of isomeric acetoxybutyraldehydes;
(c) hydrogenating the mixture of isomeric acetoxy-butyraldehydes in the presence of a.catalyst consisting of cobalt on an inert support at a temperature of from about 75° to about 200°C. and a pressure of from 500 to about 3000 psi to produce a mixture comprising the acetate esters of the corresponding butanediols;
(d) de-esterifying the mixture of the acetate esters of the butanediols so produced in she presence of water and an alkali metal hydroxide or an alkaline earth metal hydroxide to yield butanediols and the corresponding alkali metal acetate or alkaline earth metal acetate;
(e) acidifying the acetate so produced with an inor-ganic acid to produce acetic acid which is isolated m a form suitable for use in (a).

33. The process of claim 32 wherein the catalyst in (a) is a mixture of palladium and palladous acetate.

34. The process of claim 32 wherein the catalyst con-sisting essentially of cobalt in complex combination with carbon monoxide in (b) is dicobalt octacarbonyl.

35. The process of claim 32 wherein the propylene, oxygen and acetic acid are in the gaseous phase.