CA1133522A - Process for hydrolyzing alkylene oxides to alkylene glycols - Google Patents

Process for hydrolyzing alkylene oxides to alkylene glycols

Info

Publication number
CA1133522A
CA1133522A CA328,573A CA328573A CA1133522A CA 1133522 A CA1133522 A CA 1133522A CA 328573 A CA328573 A CA 328573A CA 1133522 A CA1133522 A CA 1133522A
Authority
CA
Canada
Prior art keywords
alkylene
carbonate
glycol
catalyst
reaction
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
Application number
CA328,573A
Other languages
French (fr)
Inventor
Glenn A. Taylor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Union Carbide Corp
Original Assignee
Union Carbide Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Union Carbide Corp filed Critical Union Carbide Corp
Application granted granted Critical
Publication of CA1133522A publication Critical patent/CA1133522A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
    • C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
    • 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
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
    • 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

Abstract

12,204 A PROCESS FOR HYDROLYZING ALKYLENE
OXIDES TO ALKYLENE GLYCOLS

ABSTRACT OF THE DISCLOSURE

There is described herein a process for hydrolyzing alkylene oxides to alkylene glycols in the presence of CO2, and a particular non-halogen containing catalyst. The reaction is effected under a carbon dioxide pressure of less than about 350 psig and a reaction temperature between about 85°C and 400°C.
The reaction is preferably effected in the presence of an organic solvent.

S P E C I F I C A T I O N

Description

12,204 This invention relates to a process for the manuracture o,~ al~ylene glyco~s, such as ethylene glycol and propylene glycol, by the hydrolysis of the correspond-ing all.~ylene oxide, such as ethylene oxide and propylene oxide. More particularly, this invention involves the catalytic hydrolysis of such a:Ll~ylene oxides in the presence of C2 via a glycol ester intermediate to the corresponding alXylene glycols. The hydrolysis is preferably carried out in the presence of an organic solvent.

The prior art states that alkylene oxides can be hydrolyzed to produce the corresponding alkylene glycols. For e~ample, German patent No. 2,141,470 reacts ethylene o~ide in aqueous streams in the presence of salts of carboxylic acid and C2 pressures in excess of about 438 psig and up to 730 psig and temperatures in the range of 160 to 200~C to give selectivity to monoethylene glycol in the range of 74 to 99 weight percent. The German patent describes that nigh CO2 pressures are more ravorable towards producing higher quality monoethylene glycol product and these pressures are between 30 and ~Q atmospheres (43~ to 730 psig) at temperatures in the range of 150 to 300C.
German patent ~o. 2,3;9,497 hydrolyzes ethylene o~ide to monoethylene glycol and concentrates the C02 in the aqueous stream. The reaction is carried out with C02 pressures in excess of 400 psig and with dilute solutions of ethylen~ o~ide.
:
. ~ ~ ~

. ,, ~.

~1~3$:~
12,204-C
U. S. Patent No. 376~9,343 to Levin et al describes the hydrolysis of ethylene oxide in the presence o:E carbon dioxide to yield ethylene glycol. Levin et al speculates that hydrolyzing ethylene oxide in the presence of water and carbon dioxide forms, in somle instances, a transitory ethylene carbonate intermediate which is hydrolyzed to ethylene glycol. According to this patent, basic compounds such as carbonates, bicarbonates or hydroxides of alkali metals are utilized for the purpose of diminishing "the fo~mation of dialkylene glycols and accelerate the re-action", see column 2, lines 26-30, of U. S. Patent 3,629,343. In the practice of that process, such basic compounds are employed in combination with halo salts of tetraalkylammonium compounds. The examples in this patent illustrate the basic compounds as including sodium bi-carbonate, potassium bicarbonate, sodium carbonate, and sodium hydroxide. In the examples of this patent, the maximum yield of noalkylene glycol was 95.5 percent, based on initial alkylene oxide concentration.
The subject matter of this patent has been care-fully reviewed by the Stanford Research Institute, in the private report entitled "Ethylene Glycols, Glycol Ethers and Ethanolamines," Process Economic Program, Report No.
70 (1970). In Report No. 70, a careful consideration was given to British Patent No. 338,026, published in 1970. The author of the report notes the postulation of the reactions `
which take place in the process of the aforementioned British Patent, which is, the reaction of ethylene oxide 3 ;

- 12,204 ~133S;;~Z

T.vith carbon dio~id- to for~ e;hylene carbonat2 and the hydrolysis of the ethylene carbonate to form monoethylene glycol. ~ccording to the patenl, these reactions are erfected si~ultaneously. However, in a continuous oper-ation employing multiple reac~ors, the first reactor involves the utilization of a carDonation catalyst and carbon dioxide and the second reactor, in series with the rirst, employs hydrolysis using various bases. Report ~o. 70 attempts to characterize 2 continuous process from tne data whic'n is contained ln the aforementionèd Britisn Patent. In characterizing a continuous process, the report points out that the water to o~ide feed ratios were 1.04 to L and 1.06 to 1 in the two e~amples demonstrating a con-tinuous process~ In the second reactor, in which the base, water and carbon dioxide were provided, the temperature was 200C and the pressure in the whole system was 25 to 30 atmospheres~ that is, 367.~ pounds per square inch to 4'.1 pounds per s~,uare inch, respectively.

According to the author of the report, it is -~
believed that muc~ of the critical materials of construct-ion will have to be e~pensive Monel clad construction.
In charact2rizing the continuous process that the authors have discussed in the report, there is an assumption that 90~/, or the catalyst can be recycled T~hich is regarded as econo~ically important. In defining catalyst recycle, the following is stated:

.. - . .

12,204 ~3L3;3 SZ2 "The system ,~or catalyst recycle, based on crystallization from the cooled, heavy ends, wit~ recycle of a thickened catalyst slurry, is quite uncertain, re~uiring data on solubi-lity relationships and other factors, which are not available."
Thus, the process as describe~ in Levin et al and characterized in the Stanford Research Institute Report is a continuous process which utilizes pressures in eæcess of 367 pounds per square inch. Additionally, said process uses halo salts of tetralkylammonium compounds along with the basic catalysts so that halide is present in an aqueous syste~. The halide creates corrosion proble~s and thus necessitates the use of eactors made out of costly specialized materials to prevent corrosion. Figure 5.1 of the report schematically illustrates equip~ent and process desisn for making "ethylene glycols by carbonation process."
Presence of halides in the column bottoms illustrated in Figure 5.1 would result in hi~her concentrations of heavy residual material. In addition, as the report points out, catalyst recycle would be very difficult.
Literature reports by N.N. Lebedev et al entitled '~inetics and Selectivity In Ethylene Oxide Hydrolysis T.~hen Catalyzed By Salts ofCarboxylic Acids," translated from ~inetika i Kataliz, Vol. 17, No. 4, pp. 888-892, July-.~ugust, 1976 (hereina~ter Report I) and N.N. Lebedev et al, "Selectivity or ~-Oxide Hydrolysis Catalyzed by Carbonates,"
translated from Kinetika i Kataliz, Vol. 1, No. 3, pp. 583- `-588, ~lay-June, 1976, (hereinafter Repor~ II) describe studies , : ..

L2 ~0~
11335~ ' T.~herein glycol esters are produced _rom ethylene oxide and a ubsequently hydrolyzed to the glycol.
In Re?ort I it is sho~n that when ethylene oxide is hydrolyzed in aqueous solutions of carboxylic acid salts, ethylene glycol is ~ormed in quantitative yield. Poly-glycols are or~ed only in parallel alkaline and non-catalytic hydrolysis reactions. Report I then concludes that due to the marked contribution from alkaline hydroly-sis (formed from reaction (II), page 775) when carbonate and oxalate ~also acetate and formate) ions are used as catalysts, the greatest yield of monoglycol (monoethylene glycol) occurs when bicarbonate ions are used as catalysts.
Report II describes t~e selectivity of ~ -o~ide hydrolysis catalyzed by carbonates. Specifically, ethyl-ene oxide is hydrolyzed to ethylene glycol with and without catalyst and with and without C02 at pressures of 0 to 146 ~ ;
?sig, Report IT states on page ;12:

"~t high bicarbonate and glycidol concentrations the steady alkali concentration reaches values at which alkaline hydrolysis is fast and leads to an increase in the yield of polyglycerols. '~ydrolysis under the pressure of carbon dioxide pro~o~es the reverse conversion of alkali to bicarbonate and heightens the glycerol yield, the calculated values of the latter coinciding under these conditions ~ith the experimental values (Fig, 3, Table 3). .
Propylane and ethylena glycol carbonates are hydrolyzed far more ra?idly. For this reason, even at high reagent concentrations the steady alkali concentration is low and carbon dioxide has no affect on the distribution of the products of these reactions."
~lso, neither o ;he processes as described in Reports I
and II utilize an organic solvent.

::

... . ~

~335~Z ~2,204 Tne process or this lnvention is directed to the manufacture of alkylene g~ycols, such as ethylene and propylene glycol, by t~e ~ydrolysis of the corresponding alkylene oæide, such as ethylene or proplyler~e oæide,in the presence o~ C02 at a t-mperature between about 85 and 400C and pressure of less than about 350 psig, in the presence of selected catalysts. Preferably t'ne reaction is affected in an organic solvent.

It has been discovered that the process of the present invention is very selective toward the formation o~ monoethylene glycol. ~dditionally, the process of the present invention does not require the use of a halide ion containing compound,which halide ion necessitates ~'ne use of special equipment to prevent corrosion caused by the halide ion. The process Ot this invention does not suffer from any problem in catalyst recycle and it can be carried out in conventional metal equipment, suc'n as stain-less steel. Moreover, the process of the present invention takes place under conditions of temperatures and pressures e~isting in commercial operations which means that the present process can be used with equipment which is avail-able in existing co~mercial racilities. This is quite important since little if any investment in new equipment would be required~ ~oreover, it has been ~ound that the initial concentràtlon of alkylene oxide 'nas no effect on the product distribution so that concentrated alkylene .. . . . . . .

1~33S22 12,204-C

oxide solutions may be treated according to the process of the present invention. Furthermore~ the process of the present invention may be utilized to treat the major waste streams emanating from a process in which ethylene oxide is carbonated and subsequently hydrolyzed to mono-ethylene glycol as set forth in United States Patent No.
4,117,250.
Another advantage of the present invention is that the hydrolysis can be utilized using waste water obtained 10 from industrial reactions, such as, the scrubber waters in ~;
ethylene oxide production, thereby providing an ecological advantage through the operation of the process.
In the practice of this invention, an alkylene oxide is reacted with C02 and particular catalysts to form, in situ, a cyclic or acyclic carbonate intermediate. This intermediate is hydrolyzed, using only a small excess of water, to form the alkylene glycol and regenerate C02.
C2 can function in the reaction as a selective catalyst (it supplies a kinetically preferred reaction path by means of a carbonate intermediate which hydrolyzes to give the desired product) and also C02 can eliminate free hydroxide ions in solution, which hydroxide ions cause loss of selectivity to monoethylene glyco'. The process of the present invention is preferably carried out in the presence of an organic solvent. The organic solvent helps control the hydroxide ions and C02 in the liquid phase ~ . ~
- .

12 . 204-C

which allows the use of more active catalysts, such as potassium carbona~e, lower C02 reaction pressures, and lower operating temperatures, while producing higher monoethylene glycol yields.
The catalysts which can be used in the present invention are basic compounds suitable for producing a glycol ester intermediate and include the alkali and alkaline earth metal salts of carbonates, bicarbonates, hydroxides, and phosphates. These catalysts include potassium hydroxide, potassium acetate, potassium phosphate, potassium oxalate, and the like.
The catalysts which may be used in the process of this invention include compounds which contain one to three nitrogen atoms, which ~hen incorporated into protic medium ~nder carbon dioxide pressure produce the carbonate salt, including a double salt. These catalysts include guanidine carbonate, ENH2C(=NH)NH2]H] CO3;

substituted guanidine carbonate ~NR2C (=NH) NR2 ] H] 2CO3 wherein R is ,.ndependently an alkyl radical of 1 to 5 carbon atoms or aryl radical of 6 or 7 carbon atoms; ammonium uranyl carbonate, j~ `
.. ..

:

12,~0~
11335:~2 ~ )2C03 U02C03 ~H20] wher2in x is an integer defining the water of h~dration and is generally 2; am~onium carbonate, (~H4)2C03; substituted a.~monium carbonate, (R NH4_n)~C03 T~herein ~ is as previously defined and n is an int~ger or 1 to '.
The catalyst may be added as t~e salt or it may be rormed in situ.
The amount of cataltst which is provided with the initi21 eed o} reactants may range between about 0.10 to about 15.0 w2isht percent, based on the total weight of initial reactants. Preferably, the amount of t~e catalyst is about 0 S to about 10.0 weight percent, and most pref2rably, the greatest catalytic effect, for t~e amount or^ catalyst employed, is achieved when the catalys~ amount ranGes between O.S and about 5 0 w2ight percent, based on the to~al weight of initial raact2nts. In characterizing the catalyst concentration, it has been characterized in terms of its salt. ~`
The temperature which is n_cessary to hydrol~tze the al7.~ylene oxide can be as low as 85 and one might con-te~plate that the maximum temperatura is about '00C. How-2ver, it ~s pre~erred that a minimum temperatur2 o~ 100C
be employed and that the maYimum temperature be 7~ept below 300C. In the most prarerred operation or the reaction, it is desired that the temperature be bet~.~een about 120C and about 130C.

- . . , -. ,, . . . . ; . ~ , . ~

1~33S2~ 12,204 The pressure at l~hich the reaction is carried out should be less than about 350 psig. The preferred operating pressure is between about 100 and about 300 psig, and the most preferred operating pressure is between about 150 and about 275 psig~
The organic solvent which is used in the practice of the present invention has the following characteristics:
high C02 absorbtivity; high ethylene oxide absorbtivity;
inert towards ethylene oxide; totally miscible with the reaction medium; and it should be a solvent which is easily separated from the product. Any liquid at the reaction temperature,which is miscible with the alkylene oxide and the glycol product can be, to the extent that it continues to be miscible in the syste~, a solvent provided that it is not reactive with either the alkylene oxide reactant, the glycol produced or the catalyst employed. These solvents include ketones, esters, or ethers,such as acetone, alkylene carbonate and dioxane. It is desirable that the alkylene carbonate employed would produce an alkylene glycol the same as the product glycol being produced.
The solvent is added in amounts of from about 5.0 to 60 weight percent,based on the weight of total feed.
Preferably, the solvent is added in amounts of from about 10 to 40 weight percent.
The initial mole ratio of water to alkylene oxide which is employed in the hydrolysis reaction, that is, the amount of water which is combined with the alkylene oxide 11 ~`

;. . :- .. .

1133522 12,20~

in the reaction zone in order to effect hydrolysis, should be at least one mole of water per mole of alkylene oxide, However, fro~ a practical standpoint, in order to achieve the ~ind of performance characterized for the process of this invention, one should employ at least about 1,0 mole of water and at most about 20 moles of water for each mole of alkylene oxide. The preferred ratio is about 2.0 to 11 and most preferred 4 to 10. The mole ratios of water to alkylene oxide will of course vary when organic solvent is used in the reaction. -The process of this invention may be carried out as a batch reaction or as a continuous process. The batch reactions may be carried out in pressure resistant vessels ~suita~ly constructed to withstand the pressures of this reaction.
The process, as stated, may be employed in a conventional autoclave or can be effected in a glassware type of equipment when operated at moderate pressures, It may also be employed in a plug-flow reactor utilizing con-ventional procedures to effect the process continuously.
Solvent may be recycled and catalyst may be recovered. The process is very advantageously employed by concentrating the catalyst over a vacuum evaporator and recycling it to the reaction.
The reaction may be carried out for very short periods of time in terms of fractions of a second and if desired may be carried out over reaction periods amounting , . . . . .

~335Z2 12,204 to hours, if desiredO These conditions of reaction are governed by the amounts of solvent and catalyst employed, the pressure and teTnperature employed, and like considera-tions.
The following examples depict various modes in the practice of this invention including those modes which are considered to be best for the practice of this invention.
It is not intended that this invention shall be limited by the examples.

~33S22 12,204-C

Examples 1 to 28 The reactor system was a 300 cc, 316 stainless steel, Parr bomb filled with provisions for batchwise charging of reactants, a gas charge tube, thermocouple, stirrer, electric heating mantel &nd cooling coil.
During operation, the reactor was charged with --a mixture of distilled water (mole/1), catalyst (molell), and solvent (mole/l) and heated to reaction temperature.
When the desired reaction temperature (C shown in the Table) was reached, either carbon dioxide or nitrogen was sparged into the reactor. The reactor was brought to 100 psig below the desired operating pressure. At this point ethylene oxide (mole/l) was charged to the reactor. The system was brought to operating pressure (psig shown in the Table) and allowed to react for a period of one hour.
Upon completion of the run, the reactor contents were discharged and weighed. The quantity of liquid pro~
duct was used to estimate the overall reactor mass balance.
The liquid product was analyzed for water (weight percent by the Karl Fisher method) and monoethylene glycol, di-ethylene glycol and triethylene glycol (weight percent by vpc) to determine conversions and efficiency. The vpc employed used a 10 ft by 1/8 inch stainless steel column packed with Tenax - GC (Tradename).
The following Table lists the catalyst, the ' atmosphere (C0~ or nitrogen), reaction pressure ' (P, psig), reaction temperature (T, C), and the moles per 12,204 113352~

liter of ethylene oxide (E0), water, catalyst and solvent used. The weight percent of monoethylene glycol (~EG), diethylene glycol (DEG) and triethylene glycol (TEG) produced,are set forth in the Table.
The reaction was carried out to at least 94 percent and in most cases greater than 98 percent conversions of ethylene oxide to glycols as shown in the Table. The differences in percent conversions was due to differences in rates of reaction for the~
respective catalyst and reaction parameters for that particular experiment.

.
`o~ `o~ v ~; o ~ v v :
_ ~ o ~ ~ ~ ~ ~ o o '` 3 ~ 00 ~ ~ O ~O I~ --I ~ t` ~ 1-- 0 0 U~

C~ ' CO~
O~ _ I I I I I :
~_ . ~, ~_ 5` ~ ~'') ~ ~ r~ ~ ~ N U~
~J o ~ ~ ~ O r~
C)5' OOOOOOOO OOOOO -`:
0 O ~ g ~ 0 ~

,~
~1 , ~. ". u~ ~ ~ 0 ~ o -- C~l N ~ `i ~ N ~i ~ N N N ~ N t~l _ OOOOOOOOOOO
e ~ ,5 ~ ~ ~ ~ O O O O O ~`
'" ' _ ~ ~ ~n o u~ æ ~ ~
_ N N 7 N N N N N N N N N ~I N N ;~

O . ' ~';, S N ~ N N ~I N ~ l N N N N N N
o Z o Z 8 c~ c, 8 ~, ;, 8 8 z z o ~ ~
~ . `.

.. V Y . ' , ~ 8 8 `
_ . . . 8 8 ~ 8 8 ;, ~
~1 -- -- N N N N N N y ~~ y ;~ C~

C
X _ N r~ `t ~1 ~ 1~ ~:1C~ O --I N ~1 ~

~- ' - 1~335Z2 r--I r--i r--i r--i r--I r~ r~l r--I r--I O O 3 O
:,~ o O O O O O O O O
O O O O O O O O
V V V V ~v `V
~ ~ O ~ ~ ~ ~ ~ u r l ~ ¦ I~ ~ ~ O a~ c~ r~~
a 3 '~ a~ a a C

C~ l~ ~ 0 0 I--C
~ ~ C~ r~ ~ r~
c~ ~1 r~l r_ O r--i r~l r--~ r--I O C
~ ~J O O O O 0 OC

a~
r--l ~ a ) c~ r--5 ~ r ~ ~ ~ r r~ ~ O

~3Q ~ r~ r~
-O~ O U~ U~ O ~0~, 0 U') o O O O ~~ o ~ In O

o Z~ o~ C~ o O 0~ 0~ 0 O O O

,,1 o u~ ~ O
,Q ~ Z Z Z
~ ~ h 3 h o c~ C~ æ æ z 7 r~ r--l r--~ O r ;

~ ~3352Z

~, 1 ~
.
, ~ o~ o C3 ~ c~l ~ ~ c~

,~ a ? o o ~ C~
U~ _ cq ~, ~ ~o u~ o a 'Dl ~ O
~ CO o o X

~1 ~

~ o o -- o ~
c; ~ ~o o ~ o o ~r _ 00 0 ~ 0 4 ~ C~
O o O o d C~
11 a~
O
Z~
~X C~ _ ~ ¢
kl _~

Claims (17)

12,204-C

WHAT IS CLAIMED IS:
1. A process for producing alkylene glycol which comprises hydrolyzing alkylene oxide with water in the presence of carbon dioxide at a carbon dioxide pressure of less than 350 psig and a temperature between about 85°C
and 400°C and a non-halogen containing catalyst suitable for producing a glycol ester intermediate and selected from alkali or alkaline earth metal carbonate, bicarbonate hydroxide, or phosphate, or guanidine carbonate.
2. A process as in claim 1 wherein the pressure is between about 100 and 300 psig.
3. A process as in claim 2 wherein the pressure is between about 150 and 275 psig.
4. A process as in claim 1 wherein the temperature is between about 100°C and 300°C.
5. A process as in claim 4 wherein the temperature is between 120°C and 180°C.
6. A process as in claim l wherein the catalyst is potassium carbonate.
7. A process as in claim l wherein the catalyst is potassium phosphate.
8. A process as in claim l wherein the catalyst is potassium acetate.
9. A process as in claim 1 wherein the catalyst is quanidine carbonate.

12,204-C
10. A process as in claim 1 which is effected in the presence of an organic solvent.
11. A process as in claim 10 wherein the organic solvent is selected from ketones, esters or ethers.
12. A process as in claim 11 wherein the solvent is acetone.
13. A process as in claim 11 wherein the solvent is alkylene carbonate.
14. A process as in claim 13 wherein the alkylene carbonate is ethylene carbonate or propylene carbonate.
15. A process as in claim 11 wherein the solvent is dioxane.
16. A process as in claim 1 wherein the alkylene oxide and alkylene glycol are ethylene oxide and ethylene glycol, respectively.
17. A process as in claim 1 wherein the alkylene oxide and alkylene glycol are propylene oxide and propylene glycol, respectively.
CA328,573A 1978-06-20 1979-05-29 Process for hydrolyzing alkylene oxides to alkylene glycols Expired CA1133522A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US91732878A 1978-06-20 1978-06-20
US917,328 1978-06-20

Publications (1)

Publication Number Publication Date
CA1133522A true CA1133522A (en) 1982-10-12

Family

ID=25438636

Family Applications (1)

Application Number Title Priority Date Filing Date
CA328,573A Expired CA1133522A (en) 1978-06-20 1979-05-29 Process for hydrolyzing alkylene oxides to alkylene glycols

Country Status (8)

Country Link
JP (1) JPS552670A (en)
BE (1) BE877082A (en)
CA (1) CA1133522A (en)
DE (1) DE2924680A1 (en)
FR (1) FR2429196A1 (en)
GB (1) GB2023601B (en)
IT (1) IT1121584B (en)
NL (1) NL7904749A (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2931753C2 (en) * 1979-08-04 1984-10-04 Akzo Gmbh, 5600 Wuppertal Process for the preparation of vicinal alkylene glycols
DE3147737A1 (en) * 1981-12-02 1983-06-09 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING CYCLIC 1,2-CIS-DIOLS FROM CYCLIC 1,2-EPOXIES
US4760200A (en) * 1985-12-31 1988-07-26 Union Carbide Corporation Process for the production of alkylene glycols
DE3628674A1 (en) * 1986-08-23 1988-02-25 Degussa CONTINUOUS PROCESS FOR PRODUCING 1,2-DIOLES
GB9005814D0 (en) * 1990-03-15 1990-05-09 Shell Int Research A two-step monoethylene glycol preparation process
US5591874A (en) * 1995-09-29 1997-01-07 Eastman Chemical Company Process for the preparation of 2,5-dihydrofuran compounds
JP4740432B2 (en) * 1999-07-14 2011-08-03 株式会社日本触媒 Purification method of ethylene glycol

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2810768A (en) * 1954-04-19 1957-10-22 Shell Dev Production of glycerine
DE2141470A1 (en) * 1971-08-19 1973-02-22 Erdoelchemie Gmbh Ethylene glycol prodn - with lower by-product formation
JPS4924448A (en) * 1972-06-27 1974-03-04
DE2256907C3 (en) * 1972-11-20 1982-03-18 Henkel KGaA, 4000 Düsseldorf Process for the production of vicinal di- and polyols
IT971363B (en) * 1972-11-30 1974-04-30 Sir Soc Italiana Resine Spa PROCEDURE FOR THE PREPARATION OF ETHYLENE GLYCOL
JPS5611555B2 (en) * 1973-07-16 1981-03-14
IT1034962B (en) * 1975-04-09 1979-10-10 Snam Progetti PROCEDURE FOR THE PREPARATION OF ALKYLENE GLYCOLS

Also Published As

Publication number Publication date
GB2023601B (en) 1982-11-17
DE2924680A1 (en) 1980-01-03
IT7923640A0 (en) 1979-06-14
GB2023601A (en) 1980-01-03
BE877082A (en) 1979-12-19
FR2429196A1 (en) 1980-01-18
IT1121584B (en) 1986-04-02
JPS552670A (en) 1980-01-10
NL7904749A (en) 1979-12-27

Similar Documents

Publication Publication Date Title
Fang et al. Direct synthesis of dimethyl carbonate from carbon dioxide and methanol catalyzed by base
CA1121389A (en) Process for the production of alkylene glycols
KR100609674B1 (en) Method for the continuous production of 1,3-dioxolan-2-ones
CA1133522A (en) Process for hydrolyzing alkylene oxides to alkylene glycols
US4016208A (en) Acid production
US4822921A (en) Method for one-step synthesis of methyl t-butyl ether
CN114105818A (en) Catalyst for catalyzing butyrolactone to obtain succinonitrile and synthesis method
US8969600B2 (en) Method for producing glycidol
US5840994A (en) Process for producing ditrimethylolpropane
US4126752A (en) Homologation of methanol with a carbon monoxide-water mixture
CA1107301A (en) Hydrolysis of alkylene carbonates to alkylene glycols
US4663477A (en) Process for the hydrolysis of dialkyl carbonates
US3956405A (en) Process for manufacturing polyfluoroalkyl propanols
CN1066433C (en) Catalyst recovery method in synthetic process of dimethyl carbonate
GB2113207A (en) Preparation of alkylene carbonates
CN112174801B (en) Method for coproducing glycolic acid and 1,1,1, 2-tetrafluoroethane by one-pot method
US4599467A (en) Production of vicinal alkylene glycols
US4237324A (en) Production of monoglycols from alkylene carbonates
JP2001151711A (en) Method for producing alkylene glycols
CN115784889B (en) Method for preparing methyl ethyl carbonate and diethyl carbonate by taking dimethyl oxalate as raw material
GB2086894A (en) Production of alkylene glycols
US6455459B1 (en) Antimony catalyst compositions
KR101810646B1 (en) A manufacturing method of linear polyglycerol
Dhami Dialkyl Carbonate Synthesis: Recent Scientific And Technological Advancements
JP2003089675A (en) Method for producing dialkyl carbonate

Legal Events

Date Code Title Description
MKEX Expiry