CA1089876A - Alcohol production - Google Patents
Alcohol productionInfo
- Publication number
- CA1089876A CA1089876A CA286,276A CA286276A CA1089876A CA 1089876 A CA1089876 A CA 1089876A CA 286276 A CA286276 A CA 286276A CA 1089876 A CA1089876 A CA 1089876A
- Authority
- CA
- Canada
- Prior art keywords
- rhodium
- process according
- psig
- hydrogen
- cobalt
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
ALCOHOL PRODUCTION
Ethylene glycol is prepared in one step by contacting carbon monoxide, hydrogen and formaldehyde in the presence of a catalyst comprising rhodium or a rhodium compound.
ALCOHOL PRODUCTION
Ethylene glycol is prepared in one step by contacting carbon monoxide, hydrogen and formaldehyde in the presence of a catalyst comprising rhodium or a rhodium compound.
Description
BAC~(Gl~OUND OF THE INVENTION
2 ~he procsss of this invention is used to prepare
3 ethylene glycol. ~ore particularly, the process prepa-es
4 ethylene glycol in on~ step from carbon ~ono~ide, hydrogen and S for~aldehyde under ~oderate reaction condit.ons using a catalyst 6 co~prising rhodium or a rhodiu~ compound.
7 Ethylene glycol is an i~portant industrial alcohol 8 kno~n pri~arily for its use as an organic solvent and non-9 volatile antifreeze or coolant. It is currently produced by a variety of ~ethods. On a commsrcial scale ~ost ethyleDa glycol 11 is produced by hydrolysis of ethylene oxide with dilute sulfuric 12 acid, or ~ith wa~er, at high temFerature.
14 ~CH2)zO + HzO ~ HOCH2CH20H
In yet another process ethylene glycol is produced by 16 the high temperature, bigh pressure reaction of carbon ~onorid~
17 and hydrogen. For eYa~ple, Ger~an Patent 2,426,~95 describes a 18 process for producing sthylene glycol and ~ethanol by the netal-19 carbonyl-ca~alyzed reaction of hydrogen and carbon ~onoside at high Fressures and tecperatures.
21 20,000 psi 22 3C0 ~ 5H2 ~ HOC~2CH20H ~ CH30H
24 U.S. Patsnt 2,451,333 granted October 12, 1948 and Gsroan Patent ~75,802 illustrate the conventio~al t~o-step 26 hydrofor~ylation and reduction of for~aldehyde. According to the 27 disclosures, hydrofor~ylation of for~aldehyde using a cobalt 28 catalyst yields a ~ixture of acetals and acetaldehyde, ~hich can 29 be reduced to ethylene glycol and ethylene glycol ethers. ~en the reaction is carried out in an alcohcl solve~, the ~a~or 31 product is the glycol ether.
10~9876 1 The prior art has relied upon harsh reaction condition 2 or ~ultiple step processes to prepare ethylsne glycol.
3 Accordingly, a one-step process ~hich can be conducted under 4 ~oderate conditions is desirable.
SUMMARY OF THE IN~ENTION
6 It has no~ been discovered that ethylene glycol can be 7 produced by contacting for~aldehyde, carbon mono~ide and hydrogen 8 in the pres~nce of an alcohol solvent and a catalyst co~prising a 9 rhodiu~ co~pound at a temperature af f ro~ aDou~ 100C to about 200C and a pressure of from about 1000 psi to about 10,000 psi.
11 Ethylene glycol is readily separatea from the reaction product 12 ~i~ture.
13 DETAIL13D DESCRIPTION OF $HE INVENTION
14 The process of this in~ention provides a ons-step process for preparing ethylene glycol under noderate reaction 16 conditions. The process is based upon the finding that carbon 17 ~onoside, for~aldehyde and hydrogen can be co~bined under 18 oderate reaction conditions to produce ethylene glycol using a 19 catalyst co~prising a rhodium co~pound. ~y-products include ~ethanol and glycol ethers.
21 Carbon ~onoxide, hydrogen and formaldehyde are read~ly 22 available from numerous co~ercial sources. The nolar ratios of 23 these reactants ~h~ch are suitable for use in the process of this 24 in~ention ~ll vary depending upo~ the reaction conditions.
However, for general guidance, accepta~le ~olar ratios of 26 for~aldehyde to carbon nonoYide to hydrogen range fron about 27 1:20:1 to about 1:1:20, ~ithin this range, ratios of fro~ about 28 1:20:1 to about 1:1:10 have been found to provide a preferred 29 process.
In practice, the carbon ~onoYide and hydrogen reactants 31 ~ay be pro~ided as a synthesis g~s strea~ ~hich is passed either 32 co-currently or counter-currently to the for~aldehyde reactant.
1()~9876 1 In a preferred continuous e~bodi~ent a synthesis gas -~treau 2 couprising carbon aono~iae and hydrogen is passed counter-3 currently to a for~aldeh~de strea- in cascade fashio~ so that the 4 carbon uonoxide is re~cted out of the up~ard flowing ~trear Rhodium is the catalyst for this process It uay be 6 used in either the ele~ental rhodiu- etal or as a rhodiu~-7 containing co~pound. Rhodiuu es~sts in five oxidation states 8 ranging fro~ the zero state to tbe tetraEositive state. Of the 9 positive oxidation states erhibited, the tripositive st~te is the ~ost stable. Accordingly, the tripositi~e rhodiu- co~pounds are 11 pref~rred. The o~des, hallaes and ~ulfates are exa-plos of 12 suitable rhodlu- trlpo~itlve co-pou~ds. The halo ana cyano 13 co~pound~ aDa the a~ine co~pleres are also acceptable sources of 14 rhoaiu-Rhodlu~(III) oside, Rh203 is an especially preferred 16 rhodium co~pound. It 18 formed ~hen po~dered rhodiun etal is 17 heat~d in air ~bove 600C. Slo~ addition of al~ali to solutions 18 of tripositive rhodiu~ results in the precipitation of the ~ello~
19 hydrate Rh203-5H20, ~hich i8 also a preferred rhodiun source.
Anionic coDpleses of tripo~iti~e rhodiua ~lth all t~e 21 haloqen~ are acceptable. Tho~e ~ith fluorine, chlorine, and 22 bro~ine being particularly preferr6d. The anhydrous rhoalu-23 trihalides are repre~o~tative halo co-pounds. Th~y are obtainea 24 by appropriate dir~ct union of the ele~ents. The iodide can also be prepared by precipitation fro~ agueous solutioD. Tbe 26 trifluoride is 8 dark red substance, practically ~nert to ~ater, 27 acids and bases. The trichloride, as prepared by direct union, 28 t s also red and is insoluble in ~ater and acids. Evaporation of 29 a solution of r~odiuJ~III) oxide hydrate in hydrochloric acid yields RhCl3-4H20. Re~oval of the vater of crystallization at 31 180C in a hydrogen chloride at~osphere gives an anhyarous ..
1 trichloride which is water-solu~le; heating of this latter 2 ~aterial to higher te~peratures con~erts it ~o the ~ater-3 ~nsoluble for~
4 The rhodium sulfate hydrates are pr~ferred sulfates.
Th~ best kno~n are Rh2(SO~)3-14H2O and Rh2(SO~)3-6H2O The 6 for~çr is a yello~ ~aterial obtained by dissolving the oxide 7 hydrate in cold dilute sulfuric acid and crystallizing by 8 evaporation in vacuo at 0; the red heYahydrate is prepared by 9 evaporating a~ agueous solution o~ the 14-hydrate to dryness at 100C. Pro- aqueous solutions of the 14-hydrate all the sulfate 11 i5 i~ediately precipitated by addition of barium ion.
12 Cationic auine co~plexes of rhodiu~(III) aro also 13 sultable sources of rhoaiu~. Representative co~pound types 14 include, aDong oth~rs, ~Rh(NH3)~]XJ, ~h~NH3)3~X3, tRh (~3) ~ (H2O)]X3~ and [Rh~NHJ)sF ]X2 (R=nonovalent acid radical 16 or OH- group) wherein X is a suitable anion, for esa~ple halide.
17 In a preferred embodi~ent, the catalyst also co~prises 18 a cobalt carbon~l. The ter~ "cobalt carbonyl" is used in the 19 conventional se~se to include cobalt co-pleses vith carbon ~onox$ds. Suitable carbonyls ~ay be either pure carbonyls 21 ~herein carbon ~onoxide for~s a ~table co~pl~Y ~ith the lo~est 22 oxidation state of cobalt, or cobalt car~onyls bound to an 23 add~tional ~oiety ~uch as a halide or hydride. ~hus, carbon 24 ~onoxide acts as either a ~onodentate liga~d or a divalent bridging group. Suitable cobalt carbonyls can be ~oDon~ric, 26 di-eric, or pol~eric.
27 In general, cobalt carbonyls suitable for us~ as 2~ catalysts in the process of this invention are of the foraula 29 Co ~CO) D (X) 1-_ 1 ~herein X is an anionic ligand bcund to the cobalt ion, n is l to 2 6, ~ is 0 to 6, and n~m is 3 to 6. The coordination number of 3 the cobalt ion is rspreseDted by n~, and the valence or 4 o~idation state of the cobalt Doiety is represented by ~. This for~ula depicts only the e~pirical composition ~h~ch may also 6 exist in di~eric or polyneric form. Cobalt octacarbonyl is an -7 especially preferred catalyst. Ihe cobalt carbonyl coupound can 8 be for~ed in advance and introduced into the reaction zone, or, 9 it ay be for~ed in situ fro~ a suita~le precursor. For exa~ple, coC03 has been found tc be a precursor for cobal~ carbonyls under 11 the conditions of this process.
12 Effecti~e catalyst concentrations will ~ary depending 13 upon the reaction conditions e~ployed. In ge~eral, the process 14 can be carried out in the presence of a catalyt~cally effecti~e amount of a catalyst co-prising rhodium. Ths rëaction starts 16 readily at catalyst concentrations of only 0.3 ~elqht %, although 17 e~en s~all quantities are effecti~e. Ihe ~asi~u~ concentrat~on 1~ ~ay go as high as 10 weight %. Ho~ever, in practice, econouic 19 con~iderations will lirit the concentration as no appreciable ad~antages are gained by concentrations above about 5 ~eight %.
21 Typical catalyst concentrations ~ill range from about 0.1 to 22 about S ~eight S, preferably fron about 0.3 to about 3 ~elght S.
23 ~here 'he catalyst also co~prises a cobalt carbonyl, the relati~o 24 ~eight proportion of cobalt car~onyl to rhodiu~ ls not critlcal, but ~ill typically raDge fron abcut 1:10 to about tO~
~; 26 The tenperature of reaction is relativel~ nild.
j~ 27 Te~peratures as lo~ as 100C are acceptable. In general, the 28 process is carr$ed out at te~peratures fror about 130C to a~out 29 200C. ~igher temperatures do not significantly iapro~ the reaction rate, ~hile lo~er tsmperatures appreciably decrease the 31 reaction rate.
~08987~
1 The reaction is carried out under ~oderate pressure 2 In ge~eral, the overall pressure will nct greatly esceed the 3 partial pressure of carbon ~onoside and hydrogen ~hich are by far 4 the ~ore ~olatile of the reactants Pressures froe about 1000 psig to about 10,000 psig are suitable At lo~er pressures, the 6 rats of r~action is relatively slov, ~hile at higher pressures, 7 no appreciable advantage is o~tained Preferred pressures range 8 fro- about 1000 psig to about 5000 psig At higher tenperaturQs 9 the cobalt carbonyl ~ay lose sta~ility conseguentl~ reducing the yield of glycol and glycol ethers In order to direct the 11 reaction to~ard increasing yields, higher partial pressures of 12 carbon uonoxide and hydrogen are employ~d.
13 The residence ti~e required for the reaction to reach 14 co~pletion ~ay range fro- a fe~ ~inutes to sever~l hours, depending upon the concentration of reactant and reaction 16 conaitions. In general, a residence ti-e of frou about 1 hr to 17 about 5 hrs ~ill be nece~sary to reach coopletion under preferred 18 reaction conditions. In practice it ~ay be advantageous to 19 continuously recover product there~y driving the reaction to~ard production of glycol and ether. Coupletion is defined as th~
21 point at ~hich the anount of for~aldehyde converted to prod~ct as 22 a fuDction of ti~e does not appreciably increase 23 The process ~ay be carried out in the presence of a 24 801~ent. Esa~ples of organic liguids suitable for use as solvents incluae ethers such as tetrah~drofuran, diethyl ether 26 and the li~e; and alkanols such as etha~ol, oethanol, 2-27 ethylhesanol and the li~e.
t~ 28 The follo~ing Esa~ples further illustrate practice of t 29 the process of this iDvent~on. Ihe E~aoples are represen*ati~e and are not i~te~ded to li-it the inve~tion. Those fa-iliar ~ith 31 the art vill readily perceive ~odifications of t~e process in 32 vie~ of the Esanples 108987~
1 EXA~ELES
2 E~a~Ple I
3 A 300 cc Autoclave Engineers MagnedriYe Autoclave Yas 4 charged vith 16 g of paraformaldehyde, 50 g of ~ethanol, 2 g of cobalt car~onyl [ C2 (CO) ~ ] and 0.1 g of N-(carboYy-ethyl)-N~-(2-6 hydroYyethyl)-N,Nl-ethylenediglycine. The reaction ~as run at 7 180C for 2.5 hours using 67~ H2~33% C0 at 2800 psig. Vapor 8 chro-atographic analysis ~ith an internal standard sho~ed the 9 proauct to contain 6.3 g total of 2-~etho~yethanol and ethylene glycol. This a~ounts to a 16~ yield based on the charged 11 for-aldehyde.
12 gxauDle II ~ -13 The autocla~e used in Bsa~ple I ~as ch~rged ~lth 16 g 14 of parafor~aldehyde, 50 9 of ethanol and 0.2 g of ah2oJ-5H~o.
The reaction ~a~ run ~ith 67~ H2~33~ C0 at 3300 ps~g and 150C
16 for 2 hours. The product contained 2. e g (8.8~ yield) of ~7 ethylene glycol.
18 _~auPle III
19 ~he autocla~e used in Exa~ple I ~as chargea ~ith 16 g of parafor~aldehyde, 50 g of ethanol, 0.2 g of cobalt carbonyl 21 and 0.5 g of Rh203-5H20. The reaction ~as run ~ith 67S ~2~33S C0 - 22 at 3103 p8ig and 150C for 5 hours. The product containea 4.1 g 23 of ethyleno glycol and 9.7 g of 2-ethoYyethanol for ~ co-blned 24 yiel~ of 35~ on tbe charged for-~ldehyae.
~x~4Ple IV
26 T~e autocla~e used in E~a-ple I ~as charged ~ith 16 g 27 of parafor~aldehyde, 50 g of eth~nol, 1 g of cob~lt carbon~l and Z8 0.2 g of Rh203-5H20~ The reaction ~as run ~ith 67X H2/33~ C0 at 29 2700 psig and 13~C for 3 hours. The product containea 1.8 g of ethylene glycol (5.7X yi-ld) and 4.7 g of 2-etho~yethanol (10.2%
31 ~eld).
:
~01~9876 E~auLle V
2 The autoclave used in Esa~ple I ~as charged ~th 50 g 3 of oethylal, 0.2 g of cobalt car~onyl and 0.2 g of Rh2O3-5H20.
4 The reaction ~as run ~ith 67~ H2~33~ C0 at 3000 psig and 150C
for 3 hours. The product ~ontained 14 ~ total of 2-~etho~y-6 ethanol ana ethylene glycol. This corresponds to a 30% yield 7 based on charged ~ethylal.
8 EYa~Ple VI
9 The autoclave used in E~anple I vas charged ~ith S0 g of ~ethylal, 0.2 g of cobalt carbonyl and 0.2 g of Rh203-5HzO.
11 The reaction ~as run ~ith 67% H2~33~ C0 at 2900 psig and 180C
12 for 4.5 hours. The product contained 12.2 ~ total of 2-aethos~-13 ethanol and ethylene gl~col for a yield of 24~.
14 Esaaples I through VI sho~ that the cobalt carbonyl-Rh203-5BtO cat~lyst cc-binat~on gives better yields of ethylene 16 glycol and ethylene glycol ether than RhzO3-5BzO or cobalt 17 carboDyl aloDe us~ng a 67% H2/33~ C0 s~nthesis gas.
18 EsauDle y~I
19 The autoclave used in ~xa-ple I ~as charged ~ith 16 g of parafor~aldehyde, 50 g of ethanol and 1 g of cobalt c~rbonyl.
21 The reaction vas run ~th S0~ H2/50% C0 at 3000 psig ana 180C
22 for 2 hours. The product contained 1 g of ethylene glycol ana 5 23 g of 2-ethoxrethanol for a conbined 14~ y~eld.
24 ~xa~le VIII
The autocla~e used in Esa-ple ~ ~as charged ~tb ~6 g 26 of parafor~aldehyde, 50 g of ethanol and 0.2 g of Rh2O3-5~2O.
27 The reaction ~as run ~ith 50% B2~50% CO a~ 3000-3500 psig and 28 130C for S hours and another 6.5 hour at 3000-3300 psiq and 29 150C. The product contained 2.9 q (9S yield) of ethylene gl~col.
_ g _ - 108g876 1 E~amPle IX
2 The autoclave used in E~ample I was charg~d with 16 g 3 of par~or~aldehyde, 50 g of ethanol, 0.5 g of cobalt carbonyl 4 and 0.2 g of Rh2O3-5H 2- The reaction was run ~ith 50% ~2/5% C
at 3000 psig and 150C for 3 hours. The produc~ contained 1.6 g 6 of ethylene glycol and 4.7 g of 2-etho~yethanol for a co~bined 7 ~ield of 15.1~.
8 ~xa~ole X
9 A 300 cc Autoclave Engineers ~agnedri~e Autoclave vas 10, charged with 16 g of parafor~aldehyde, 50 g of ethanol, and 0.2 g 11 of Rh2O3-5HzO. ~he autocla~e was heated for 2 hours at 150C and 12 at a pres~ure of 3300 psig us~ng 67S Nz/33S CO. Vapor 13 chroDatographic analysis sho~ed the product contained 2.8 g 14 (8.8%) ethylene glycol and 12.14 g of ~ethanol.
tS Exa~P~e XI
16 The autoclave u~ed in Example X ~as charged wlth 16 g 17 of paraforo~ldehyde, 50 g of ethanol and 0.2 g of Rh20~-5~20.
18 The reaction was run ~ith 50~ ~2~5~ CO at 3000-3500 psig and 19 130C for 5 hours and another 6.5 hours at 3000-3300 pstg and 150C. The product contained 2.9 g ~9% yield) of ethylene g~ycol 21 and 2.9 g (18~ yield) of methanol.
7 Ethylene glycol is an i~portant industrial alcohol 8 kno~n pri~arily for its use as an organic solvent and non-9 volatile antifreeze or coolant. It is currently produced by a variety of ~ethods. On a commsrcial scale ~ost ethyleDa glycol 11 is produced by hydrolysis of ethylene oxide with dilute sulfuric 12 acid, or ~ith wa~er, at high temFerature.
14 ~CH2)zO + HzO ~ HOCH2CH20H
In yet another process ethylene glycol is produced by 16 the high temperature, bigh pressure reaction of carbon ~onorid~
17 and hydrogen. For eYa~ple, Ger~an Patent 2,426,~95 describes a 18 process for producing sthylene glycol and ~ethanol by the netal-19 carbonyl-ca~alyzed reaction of hydrogen and carbon ~onoside at high Fressures and tecperatures.
21 20,000 psi 22 3C0 ~ 5H2 ~ HOC~2CH20H ~ CH30H
24 U.S. Patsnt 2,451,333 granted October 12, 1948 and Gsroan Patent ~75,802 illustrate the conventio~al t~o-step 26 hydrofor~ylation and reduction of for~aldehyde. According to the 27 disclosures, hydrofor~ylation of for~aldehyde using a cobalt 28 catalyst yields a ~ixture of acetals and acetaldehyde, ~hich can 29 be reduced to ethylene glycol and ethylene glycol ethers. ~en the reaction is carried out in an alcohcl solve~, the ~a~or 31 product is the glycol ether.
10~9876 1 The prior art has relied upon harsh reaction condition 2 or ~ultiple step processes to prepare ethylsne glycol.
3 Accordingly, a one-step process ~hich can be conducted under 4 ~oderate conditions is desirable.
SUMMARY OF THE IN~ENTION
6 It has no~ been discovered that ethylene glycol can be 7 produced by contacting for~aldehyde, carbon mono~ide and hydrogen 8 in the pres~nce of an alcohol solvent and a catalyst co~prising a 9 rhodiu~ co~pound at a temperature af f ro~ aDou~ 100C to about 200C and a pressure of from about 1000 psi to about 10,000 psi.
11 Ethylene glycol is readily separatea from the reaction product 12 ~i~ture.
13 DETAIL13D DESCRIPTION OF $HE INVENTION
14 The process of this in~ention provides a ons-step process for preparing ethylene glycol under noderate reaction 16 conditions. The process is based upon the finding that carbon 17 ~onoside, for~aldehyde and hydrogen can be co~bined under 18 oderate reaction conditions to produce ethylene glycol using a 19 catalyst co~prising a rhodium co~pound. ~y-products include ~ethanol and glycol ethers.
21 Carbon ~onoxide, hydrogen and formaldehyde are read~ly 22 available from numerous co~ercial sources. The nolar ratios of 23 these reactants ~h~ch are suitable for use in the process of this 24 in~ention ~ll vary depending upo~ the reaction conditions.
However, for general guidance, accepta~le ~olar ratios of 26 for~aldehyde to carbon nonoYide to hydrogen range fron about 27 1:20:1 to about 1:1:20, ~ithin this range, ratios of fro~ about 28 1:20:1 to about 1:1:10 have been found to provide a preferred 29 process.
In practice, the carbon ~onoYide and hydrogen reactants 31 ~ay be pro~ided as a synthesis g~s strea~ ~hich is passed either 32 co-currently or counter-currently to the for~aldehyde reactant.
1()~9876 1 In a preferred continuous e~bodi~ent a synthesis gas -~treau 2 couprising carbon aono~iae and hydrogen is passed counter-3 currently to a for~aldeh~de strea- in cascade fashio~ so that the 4 carbon uonoxide is re~cted out of the up~ard flowing ~trear Rhodium is the catalyst for this process It uay be 6 used in either the ele~ental rhodiu- etal or as a rhodiu~-7 containing co~pound. Rhodiuu es~sts in five oxidation states 8 ranging fro~ the zero state to tbe tetraEositive state. Of the 9 positive oxidation states erhibited, the tripositive st~te is the ~ost stable. Accordingly, the tripositi~e rhodiu- co~pounds are 11 pref~rred. The o~des, hallaes and ~ulfates are exa-plos of 12 suitable rhodlu- trlpo~itlve co-pou~ds. The halo ana cyano 13 co~pound~ aDa the a~ine co~pleres are also acceptable sources of 14 rhoaiu-Rhodlu~(III) oside, Rh203 is an especially preferred 16 rhodium co~pound. It 18 formed ~hen po~dered rhodiun etal is 17 heat~d in air ~bove 600C. Slo~ addition of al~ali to solutions 18 of tripositive rhodiu~ results in the precipitation of the ~ello~
19 hydrate Rh203-5H20, ~hich i8 also a preferred rhodiun source.
Anionic coDpleses of tripo~iti~e rhodiua ~lth all t~e 21 haloqen~ are acceptable. Tho~e ~ith fluorine, chlorine, and 22 bro~ine being particularly preferr6d. The anhydrous rhoalu-23 trihalides are repre~o~tative halo co-pounds. Th~y are obtainea 24 by appropriate dir~ct union of the ele~ents. The iodide can also be prepared by precipitation fro~ agueous solutioD. Tbe 26 trifluoride is 8 dark red substance, practically ~nert to ~ater, 27 acids and bases. The trichloride, as prepared by direct union, 28 t s also red and is insoluble in ~ater and acids. Evaporation of 29 a solution of r~odiuJ~III) oxide hydrate in hydrochloric acid yields RhCl3-4H20. Re~oval of the vater of crystallization at 31 180C in a hydrogen chloride at~osphere gives an anhyarous ..
1 trichloride which is water-solu~le; heating of this latter 2 ~aterial to higher te~peratures con~erts it ~o the ~ater-3 ~nsoluble for~
4 The rhodium sulfate hydrates are pr~ferred sulfates.
Th~ best kno~n are Rh2(SO~)3-14H2O and Rh2(SO~)3-6H2O The 6 for~çr is a yello~ ~aterial obtained by dissolving the oxide 7 hydrate in cold dilute sulfuric acid and crystallizing by 8 evaporation in vacuo at 0; the red heYahydrate is prepared by 9 evaporating a~ agueous solution o~ the 14-hydrate to dryness at 100C. Pro- aqueous solutions of the 14-hydrate all the sulfate 11 i5 i~ediately precipitated by addition of barium ion.
12 Cationic auine co~plexes of rhodiu~(III) aro also 13 sultable sources of rhoaiu~. Representative co~pound types 14 include, aDong oth~rs, ~Rh(NH3)~]XJ, ~h~NH3)3~X3, tRh (~3) ~ (H2O)]X3~ and [Rh~NHJ)sF ]X2 (R=nonovalent acid radical 16 or OH- group) wherein X is a suitable anion, for esa~ple halide.
17 In a preferred embodi~ent, the catalyst also co~prises 18 a cobalt carbon~l. The ter~ "cobalt carbonyl" is used in the 19 conventional se~se to include cobalt co-pleses vith carbon ~onox$ds. Suitable carbonyls ~ay be either pure carbonyls 21 ~herein carbon ~onoxide for~s a ~table co~pl~Y ~ith the lo~est 22 oxidation state of cobalt, or cobalt car~onyls bound to an 23 add~tional ~oiety ~uch as a halide or hydride. ~hus, carbon 24 ~onoxide acts as either a ~onodentate liga~d or a divalent bridging group. Suitable cobalt carbonyls can be ~oDon~ric, 26 di-eric, or pol~eric.
27 In general, cobalt carbonyls suitable for us~ as 2~ catalysts in the process of this invention are of the foraula 29 Co ~CO) D (X) 1-_ 1 ~herein X is an anionic ligand bcund to the cobalt ion, n is l to 2 6, ~ is 0 to 6, and n~m is 3 to 6. The coordination number of 3 the cobalt ion is rspreseDted by n~, and the valence or 4 o~idation state of the cobalt Doiety is represented by ~. This for~ula depicts only the e~pirical composition ~h~ch may also 6 exist in di~eric or polyneric form. Cobalt octacarbonyl is an -7 especially preferred catalyst. Ihe cobalt carbonyl coupound can 8 be for~ed in advance and introduced into the reaction zone, or, 9 it ay be for~ed in situ fro~ a suita~le precursor. For exa~ple, coC03 has been found tc be a precursor for cobal~ carbonyls under 11 the conditions of this process.
12 Effecti~e catalyst concentrations will ~ary depending 13 upon the reaction conditions e~ployed. In ge~eral, the process 14 can be carried out in the presence of a catalyt~cally effecti~e amount of a catalyst co-prising rhodium. Ths rëaction starts 16 readily at catalyst concentrations of only 0.3 ~elqht %, although 17 e~en s~all quantities are effecti~e. Ihe ~asi~u~ concentrat~on 1~ ~ay go as high as 10 weight %. Ho~ever, in practice, econouic 19 con~iderations will lirit the concentration as no appreciable ad~antages are gained by concentrations above about 5 ~eight %.
21 Typical catalyst concentrations ~ill range from about 0.1 to 22 about S ~eight S, preferably fron about 0.3 to about 3 ~elght S.
23 ~here 'he catalyst also co~prises a cobalt carbonyl, the relati~o 24 ~eight proportion of cobalt car~onyl to rhodiu~ ls not critlcal, but ~ill typically raDge fron abcut 1:10 to about tO~
~; 26 The tenperature of reaction is relativel~ nild.
j~ 27 Te~peratures as lo~ as 100C are acceptable. In general, the 28 process is carr$ed out at te~peratures fror about 130C to a~out 29 200C. ~igher temperatures do not significantly iapro~ the reaction rate, ~hile lo~er tsmperatures appreciably decrease the 31 reaction rate.
~08987~
1 The reaction is carried out under ~oderate pressure 2 In ge~eral, the overall pressure will nct greatly esceed the 3 partial pressure of carbon ~onoside and hydrogen ~hich are by far 4 the ~ore ~olatile of the reactants Pressures froe about 1000 psig to about 10,000 psig are suitable At lo~er pressures, the 6 rats of r~action is relatively slov, ~hile at higher pressures, 7 no appreciable advantage is o~tained Preferred pressures range 8 fro- about 1000 psig to about 5000 psig At higher tenperaturQs 9 the cobalt carbonyl ~ay lose sta~ility conseguentl~ reducing the yield of glycol and glycol ethers In order to direct the 11 reaction to~ard increasing yields, higher partial pressures of 12 carbon uonoxide and hydrogen are employ~d.
13 The residence ti~e required for the reaction to reach 14 co~pletion ~ay range fro- a fe~ ~inutes to sever~l hours, depending upon the concentration of reactant and reaction 16 conaitions. In general, a residence ti-e of frou about 1 hr to 17 about 5 hrs ~ill be nece~sary to reach coopletion under preferred 18 reaction conditions. In practice it ~ay be advantageous to 19 continuously recover product there~y driving the reaction to~ard production of glycol and ether. Coupletion is defined as th~
21 point at ~hich the anount of for~aldehyde converted to prod~ct as 22 a fuDction of ti~e does not appreciably increase 23 The process ~ay be carried out in the presence of a 24 801~ent. Esa~ples of organic liguids suitable for use as solvents incluae ethers such as tetrah~drofuran, diethyl ether 26 and the li~e; and alkanols such as etha~ol, oethanol, 2-27 ethylhesanol and the li~e.
t~ 28 The follo~ing Esa~ples further illustrate practice of t 29 the process of this iDvent~on. Ihe E~aoples are represen*ati~e and are not i~te~ded to li-it the inve~tion. Those fa-iliar ~ith 31 the art vill readily perceive ~odifications of t~e process in 32 vie~ of the Esanples 108987~
1 EXA~ELES
2 E~a~Ple I
3 A 300 cc Autoclave Engineers MagnedriYe Autoclave Yas 4 charged vith 16 g of paraformaldehyde, 50 g of ~ethanol, 2 g of cobalt car~onyl [ C2 (CO) ~ ] and 0.1 g of N-(carboYy-ethyl)-N~-(2-6 hydroYyethyl)-N,Nl-ethylenediglycine. The reaction ~as run at 7 180C for 2.5 hours using 67~ H2~33% C0 at 2800 psig. Vapor 8 chro-atographic analysis ~ith an internal standard sho~ed the 9 proauct to contain 6.3 g total of 2-~etho~yethanol and ethylene glycol. This a~ounts to a 16~ yield based on the charged 11 for-aldehyde.
12 gxauDle II ~ -13 The autocla~e used in Bsa~ple I ~as ch~rged ~lth 16 g 14 of parafor~aldehyde, 50 9 of ethanol and 0.2 g of ah2oJ-5H~o.
The reaction ~a~ run ~ith 67~ H2~33~ C0 at 3300 ps~g and 150C
16 for 2 hours. The product contained 2. e g (8.8~ yield) of ~7 ethylene glycol.
18 _~auPle III
19 ~he autocla~e used in Exa~ple I ~as chargea ~ith 16 g of parafor~aldehyde, 50 g of ethanol, 0.2 g of cobalt carbonyl 21 and 0.5 g of Rh203-5H20. The reaction ~as run ~ith 67S ~2~33S C0 - 22 at 3103 p8ig and 150C for 5 hours. The product containea 4.1 g 23 of ethyleno glycol and 9.7 g of 2-ethoYyethanol for ~ co-blned 24 yiel~ of 35~ on tbe charged for-~ldehyae.
~x~4Ple IV
26 T~e autocla~e used in E~a-ple I ~as charged ~ith 16 g 27 of parafor~aldehyde, 50 g of eth~nol, 1 g of cob~lt carbon~l and Z8 0.2 g of Rh203-5H20~ The reaction ~as run ~ith 67X H2/33~ C0 at 29 2700 psig and 13~C for 3 hours. The product containea 1.8 g of ethylene glycol (5.7X yi-ld) and 4.7 g of 2-etho~yethanol (10.2%
31 ~eld).
:
~01~9876 E~auLle V
2 The autoclave used in Esa~ple I ~as charged ~th 50 g 3 of oethylal, 0.2 g of cobalt car~onyl and 0.2 g of Rh2O3-5H20.
4 The reaction ~as run ~ith 67~ H2~33~ C0 at 3000 psig and 150C
for 3 hours. The product ~ontained 14 ~ total of 2-~etho~y-6 ethanol ana ethylene glycol. This corresponds to a 30% yield 7 based on charged ~ethylal.
8 EYa~Ple VI
9 The autoclave used in E~anple I vas charged ~ith S0 g of ~ethylal, 0.2 g of cobalt carbonyl and 0.2 g of Rh203-5HzO.
11 The reaction ~as run ~ith 67% H2~33~ C0 at 2900 psig and 180C
12 for 4.5 hours. The product contained 12.2 ~ total of 2-aethos~-13 ethanol and ethylene gl~col for a yield of 24~.
14 Esaaples I through VI sho~ that the cobalt carbonyl-Rh203-5BtO cat~lyst cc-binat~on gives better yields of ethylene 16 glycol and ethylene glycol ether than RhzO3-5BzO or cobalt 17 carboDyl aloDe us~ng a 67% H2/33~ C0 s~nthesis gas.
18 EsauDle y~I
19 The autoclave used in ~xa-ple I ~as charged ~ith 16 g of parafor~aldehyde, 50 g of ethanol and 1 g of cobalt c~rbonyl.
21 The reaction vas run ~th S0~ H2/50% C0 at 3000 psig ana 180C
22 for 2 hours. The product contained 1 g of ethylene glycol ana 5 23 g of 2-ethoxrethanol for a conbined 14~ y~eld.
24 ~xa~le VIII
The autocla~e used in Esa-ple ~ ~as charged ~tb ~6 g 26 of parafor~aldehyde, 50 g of ethanol and 0.2 g of Rh2O3-5~2O.
27 The reaction ~as run ~ith 50% B2~50% CO a~ 3000-3500 psig and 28 130C for S hours and another 6.5 hour at 3000-3300 psiq and 29 150C. The product contained 2.9 q (9S yield) of ethylene gl~col.
_ g _ - 108g876 1 E~amPle IX
2 The autoclave used in E~ample I was charg~d with 16 g 3 of par~or~aldehyde, 50 g of ethanol, 0.5 g of cobalt carbonyl 4 and 0.2 g of Rh2O3-5H 2- The reaction was run ~ith 50% ~2/5% C
at 3000 psig and 150C for 3 hours. The produc~ contained 1.6 g 6 of ethylene glycol and 4.7 g of 2-etho~yethanol for a co~bined 7 ~ield of 15.1~.
8 ~xa~ole X
9 A 300 cc Autoclave Engineers ~agnedri~e Autoclave vas 10, charged with 16 g of parafor~aldehyde, 50 g of ethanol, and 0.2 g 11 of Rh2O3-5HzO. ~he autocla~e was heated for 2 hours at 150C and 12 at a pres~ure of 3300 psig us~ng 67S Nz/33S CO. Vapor 13 chroDatographic analysis sho~ed the product contained 2.8 g 14 (8.8%) ethylene glycol and 12.14 g of ~ethanol.
tS Exa~P~e XI
16 The autoclave u~ed in Example X ~as charged wlth 16 g 17 of paraforo~ldehyde, 50 g of ethanol and 0.2 g of Rh20~-5~20.
18 The reaction was run ~ith 50~ ~2~5~ CO at 3000-3500 psig and 19 130C for 5 hours and another 6.5 hours at 3000-3300 pstg and 150C. The product contained 2.9 g ~9% yield) of ethylene g~ycol 21 and 2.9 g (18~ yield) of methanol.
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing ethylene glycol which comprises contacting formaldehyde, carbon monoxide, and hydrogen in the presence of an alcohol solvent and a catalytic amount of a rhodium compound at a temperature of from about 100°C to about 200°C and a pressure of from about 1000 psi to about 10,000 psi.
2. A process according to Claim 1 wherein said rhodium is a tripositive rhodium oxide.
3. A process according to Claim 1 wherein the catalyst concentration is from about 0.1% to about 1%.
4. A process according to Claim 1 wherein the molar ratio of formaldehyde to carbon monoxide to hydrogen is from about 1:20:1 to about 1:1:20.
5. A process according to Claim 1 wherein the temperature is from about 120 & to about 180°C, the pressure is from about 2000 psi to about 5000 psi, and the catalyst comprises a tripositive rhodium oxide.
6. A process for preparing ethylene glycol which comprises contacting formaldehyde, carbon monoxide, and hydrogen in the presence of a catalytic amount of a catalyst comprising a cobalt carbonyl and a rhodium compound at a temperature of from about 100°C to about 200°C and a pressure of from about 1000 psig to about 10,000 psig.
7. A process according to Claim 6 wherein said cobalt carbonyl is cobalt octacarbonyl.
8. A process according to Claim 6 wherein said rhodium is a tripositive rhodium oxide.
9. A process according to Claim 6 wherein the relative weight ratio of the cobalt carbonyl to rhodium is from about 1:10 to about 10:1.
10. A process according to Claim 6 wherein the catalyst concentration is from about 0.1% to about 5%.
11. A process according to Claim 6 wherein the molar ratio of formalde-hyde to carbon monoxide to hydrogen is from about 1:20:1 to about 1:1:20.
12. A process according to Claim 6 wherein the temperature is from about 120°C to about 180°C, the pressure is from about 2000 psig to about 5000 psig, and the catalyst comprises cobalt octacarbonyl and tripositive rhodium oxide.
13. A process for preparing ethylene glycol which comprises: (a) contacting formaldehyde, carbon monoxide, and hydrogen in the presence of an alcohol sovent and a catalytic amount of a rhodium compound; or (b) contacting formaldehyde carbon monoxide, and hydrogen in the presence of a catalytic amount of a catalyst comprising a cobalt carbonyl and a rhodium compound; wherein said contacting is carried out at a temperature of from about 100°C to about 200°C, and at a pressure of from about 1,000 psig to about 10,000 psig.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US73468876A | 1976-10-21 | 1976-10-21 | |
| US734,489 | 1976-10-21 | ||
| US05/734,489 US4079085A (en) | 1976-10-21 | 1976-10-21 | Process for preparing ethylene glycol and ethylene glycol ether |
| US734,688 | 1976-10-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1089876A true CA1089876A (en) | 1980-11-18 |
Family
ID=27112741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA286,276A Expired CA1089876A (en) | 1976-10-21 | 1977-09-07 | Alcohol production |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5353607A (en) |
| CA (1) | CA1089876A (en) |
| DE (1) | DE2746245A1 (en) |
| FR (1) | FR2375172A1 (en) |
| IT (1) | IT1087350B (en) |
| NL (1) | NL7711598A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE45512B1 (en) * | 1976-09-17 | 1982-09-08 | Nat Distillers Chem Corp | Ethylene glycol process |
| DE3532877A1 (en) * | 1985-09-14 | 1987-03-26 | Basf Ag | METHOD FOR PRODUCING ETHYLENE GLYCOL |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB625909A (en) * | 1946-08-14 | 1949-07-06 | Du Pont | Manufacture of polyhydroxy compounds |
| US3833634A (en) * | 1971-12-21 | 1974-09-03 | Union Carbide Corp | Manufacture of polyfunctional compounds |
| IE45512B1 (en) * | 1976-09-17 | 1982-09-08 | Nat Distillers Chem Corp | Ethylene glycol process |
-
1977
- 1977-09-07 CA CA286,276A patent/CA1089876A/en not_active Expired
- 1977-10-14 FR FR7730973A patent/FR2375172A1/en active Granted
- 1977-10-14 DE DE19772746245 patent/DE2746245A1/en not_active Withdrawn
- 1977-10-19 IT IT28773/77A patent/IT1087350B/en active
- 1977-10-20 JP JP12521277A patent/JPS5353607A/en active Pending
- 1977-10-21 NL NL7711598A patent/NL7711598A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2746245A1 (en) | 1978-04-27 |
| IT1087350B (en) | 1985-06-04 |
| FR2375172A1 (en) | 1978-07-21 |
| NL7711598A (en) | 1978-04-25 |
| JPS5353607A (en) | 1978-05-16 |
| FR2375172B1 (en) | 1980-05-16 |
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