CA2066452A1 - Process for the production of alkali metal salts of ethercarboxylic acids - Google Patents
Process for the production of alkali metal salts of ethercarboxylic acidsInfo
- Publication number
- CA2066452A1 CA2066452A1 CA002066452A CA2066452A CA2066452A1 CA 2066452 A1 CA2066452 A1 CA 2066452A1 CA 002066452 A CA002066452 A CA 002066452A CA 2066452 A CA2066452 A CA 2066452A CA 2066452 A1 CA2066452 A1 CA 2066452A1
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- Prior art keywords
- ether
- alcohol
- oxygen
- alkali metal
- oxidation
- 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
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Process for the preparation of alkali metal salts of ether-carboxylic acids Abstract A process for the preparation of alkali metal salts of ether-carboxylic acids by oxidation of ether-alcohols in an aqueous phase with oxygen or gases con-taining oxygen at elevated temperatures in the presence of alkali metal hydroxides and noble metal catalysts, in which an aqueous solution, containing an alkali metal hydroxide solution, of the ether-alcohols is brought into contact in a thin layer on a solid carrier or in the form of fine particles with oxygen or the gases containing oxygen as a continuous phase, the concentration of the ether-alcohols in the aqueous phase being in the range from 0.1 to 15% by weight, based on the total weight of the aqueous phase, enables aqueous solutions of the alkali metal salts of the ether-carboxylic acids in high concentrations to be prepared.
Description
r ~
Henkel 30.8.1989 Xommanditgeqellqchaft auf Aktien S p 13481/89 M/MH (#27) Proceqs for the preparation of alkali metal salts of ether-carboxylic acid~
The in~ention relates to a proce~s for the preparation of alkali metal ~alts of ether-carboxylic acidq of the general ~ormula I
R-(OCmH~)n-O-CH2COOM (I) in which R denote~ an alkyl group having 1 to 22 carbon atom~, an aryl group or an aralkyl group, m denotes the number 2 and/or 3, n denote~ a number in the range from 0 to 20 and M denotes an alkali metal from the group formed by lithium, sodium and pota~sium, by oxidation of ether-alcohol~ of the general formula II
R-(OC~H~)n-OcHzcH2oH (II) in which R, m and n are a~ defined abQve, in the aqueous phase with oxygen or gases contalning oxygen at elevated temperatures in the presence of alkali met~l hydroxldes and noble metal catalyst~.
Alkali metal ~alts of ether-carboxylic acids are compounds which have interestinq surface-active proper-ties and are employed in the form of their aqueous olution~, or example in co~met~cs formulation~.
It i~ ~nown that alkali metal salts of ether-c~rboxylic acids of the general formula I can be prepared by catalytic oxidation of the corre-qponding ether-alco-hols of the general formula II, compare EP-~-0,039,111, EP-B-0,018,681, EP-B-0,073,545, US-C-3,342,858, DE-C-2,816,127, DE-A-3, 135,946, DE-A-2,936,123 and DE-A-3,446,561.
-- 2 .~ , However, only dllute solutions of the alXali metal salts of the ether-carb~xylic acids can be prepared by the ~nown catalytic proce~qe~. In particular, if oxygen or a gas containing oxygen i~ passed into a S relatively highly concentrated ~olution of the ether-alcohol~ in water in the presence of the catalyst-~, the viccosity of the reaction mixtur~ increases greatly a~
the conversion increases, pas~es through a maximum at about 30% conversion (about 30~ of sodium salt of the ether-carboxylic acid and about 70% of ether-alcohol) and then drops greatly again aY the conv~r~ion becomeq higher; compare DE-C-2,816,127. The rate of reaction becomes so slow during thi~ procedure, becauYe the ma~
tran~fer i~ impeded by the vi3cosity, that the proce~s i~
uneconomical since the reaction tLme i3 then too long; in the ~xtreme case, th~ reaction here can even qtop com-pletely. Low concentrations of an organic sub~tance (that is to say total weight of ether-alcohol and sodium salt of the ether-carboxylic acid) ar~ therefore used in the known proces~es in order to avoid a high increa~e in tho viscosity. However, thi~ require~ 3ubsequent concentra-tion.
It is indeed possible for the dilute aqueous solution~ of the alXali metal salts of the ether-car-boxylic acid~ obtained after the oxidation to be con-centrated by removing some of the water contained in the -solution~ by distillation or by acidifying the solution~
with ~trong acids, for example with sulfuric acid, liberating the ether-carboxylic acid and precipitating it, isolating the ether-carboxylic acid and preparing concentrated aqueous ~olution~ after renewed conversion into the alkali metal salts. However, these processe~
have the following disadvantagess 1. Aqueous solutions of alkali metal 3alt~ of ether-carboxylic acid3 foam greatly during removal of the water by di~tillation. The profitability of the process i~ moreover greatly reduced by the energy required for removal of water by distillation.
Henkel 30.8.1989 Xommanditgeqellqchaft auf Aktien S p 13481/89 M/MH (#27) Proceqs for the preparation of alkali metal salts of ether-carboxylic acid~
The in~ention relates to a proce~s for the preparation of alkali metal ~alts of ether-carboxylic acidq of the general ~ormula I
R-(OCmH~)n-O-CH2COOM (I) in which R denote~ an alkyl group having 1 to 22 carbon atom~, an aryl group or an aralkyl group, m denotes the number 2 and/or 3, n denote~ a number in the range from 0 to 20 and M denotes an alkali metal from the group formed by lithium, sodium and pota~sium, by oxidation of ether-alcohol~ of the general formula II
R-(OC~H~)n-OcHzcH2oH (II) in which R, m and n are a~ defined abQve, in the aqueous phase with oxygen or gases contalning oxygen at elevated temperatures in the presence of alkali met~l hydroxldes and noble metal catalyst~.
Alkali metal ~alts of ether-carboxylic acids are compounds which have interestinq surface-active proper-ties and are employed in the form of their aqueous olution~, or example in co~met~cs formulation~.
It i~ ~nown that alkali metal salts of ether-c~rboxylic acids of the general formula I can be prepared by catalytic oxidation of the corre-qponding ether-alco-hols of the general formula II, compare EP-~-0,039,111, EP-B-0,018,681, EP-B-0,073,545, US-C-3,342,858, DE-C-2,816,127, DE-A-3, 135,946, DE-A-2,936,123 and DE-A-3,446,561.
-- 2 .~ , However, only dllute solutions of the alXali metal salts of the ether-carb~xylic acids can be prepared by the ~nown catalytic proce~qe~. In particular, if oxygen or a gas containing oxygen i~ passed into a S relatively highly concentrated ~olution of the ether-alcohol~ in water in the presence of the catalyst-~, the viccosity of the reaction mixtur~ increases greatly a~
the conversion increases, pas~es through a maximum at about 30% conversion (about 30~ of sodium salt of the ether-carboxylic acid and about 70% of ether-alcohol) and then drops greatly again aY the conv~r~ion becomeq higher; compare DE-C-2,816,127. The rate of reaction becomes so slow during thi~ procedure, becauYe the ma~
tran~fer i~ impeded by the vi3cosity, that the proce~s i~
uneconomical since the reaction tLme i3 then too long; in the ~xtreme case, th~ reaction here can even qtop com-pletely. Low concentrations of an organic sub~tance (that is to say total weight of ether-alcohol and sodium salt of the ether-carboxylic acid) ar~ therefore used in the known proces~es in order to avoid a high increa~e in tho viscosity. However, thi~ require~ 3ubsequent concentra-tion.
It is indeed possible for the dilute aqueous solution~ of the alXali metal salts of the ether-car-boxylic acid~ obtained after the oxidation to be con-centrated by removing some of the water contained in the -solution~ by distillation or by acidifying the solution~
with ~trong acids, for example with sulfuric acid, liberating the ether-carboxylic acid and precipitating it, isolating the ether-carboxylic acid and preparing concentrated aqueous ~olution~ after renewed conversion into the alkali metal salts. However, these processe~
have the following disadvantagess 1. Aqueous solutions of alkali metal 3alt~ of ether-carboxylic acid3 foam greatly during removal of the water by di~tillation. The profitability of the process i~ moreover greatly reduced by the energy required for removal of water by distillation.
2. During precipitation of the ether-carboxylic acids ~3 with acids, the aqu~ous phase which remains i polluted by a hiqh salt load, residual ether-car-boxylic acids and unreacted ether-alcohol; it~
disposal i~ uneconomical. Renewed conver~ion of the ether-carboxylic acids into their alkali metal salt~
also leads to an additional increase in the co~ts of the reaction product.
An additional hindrance occurs in particular if air i~ used a~ the oxidizing agent. In thi3 case, the oxidation procedure is made difficult by the foam formed a~ a result of the surface-active properties of th~
starting substances and end products. The foam i~sue~
'rom the reactor with the waste gas and must be recycled from there back into the reactor after its destruction.
The rate of foam formation is always high if air i5 r~ dispersed in the solution, as i8 the case, for example, ~ I in ~ reactor~ or bubble column rsactors. In I ~ btirrcd ]cottl~ reactors in particular, the reaction solution can be converted into a foam-like state by the stirring action, so that mass tran~fer of the oxygen i9 prevented and the reaction is inhibited; compare DE-C-2,816,127.
The invention relates to a proces~ for the preparation of alkali metals salts of ether-carboxylic acids of the abovemsntioned type, in which the above-men~ioned di~advantages in respect of the increa~e in vi~c08ity and the foaming of the reaction mixture are avoided and highly concentrated aqueou~ solutions of alkali metal ~alts of the ether-carboxyllc acid~, for exampl~ having a concentration of 20 to 50% by weight, ba~ed on tha total weight of the solution, can be obtained.
According to the inventlon, thiJ ob~ect is achieved by bringing an aqueous solution, containing an alkali metal hydroxide ~olution, of the ether-alcohol~ in a thin layer on a solid support or in the form of fine particlss or droplet~ into con~act with oxygen or tha gase~ containing oxygen as the continuous phase, the concentration of the ether-alcohols in the aqueou~ phase - 4 ~
bein~ in the range from at lea~t 0.1, in particular from 0.5 to 15% by weight, ba~ed on the total weight of the aqueous phase. Below the stated range the rate of reac-tion iq generally too low qo that the concentration should fall below this range only towards the end of the reaction, when the addition of ether-alcohol has ended.
Alkali metal salts of ether-carboxylic acid~ of the general formula (I) in which the group R can be a straight-chain or branched alkyl group having 1 to 22 carbon atomq can be prepared by the process according to the invention; typical examples of such alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and docosyl. The proce~Y according to the invention i~ particularly suitable for the prepara-tion of alkali metal 3alt~ of ether-carboxylic acids in which the radical R i~ derived from Clz-ClO-fatty alcohol~, or indu3trial mixtures thereof, obtainable from animal and/or vegetable fats and oils. The group R c~n also be an aryl radical, for example a phenyl group, or an aralkyl radical, for example a phenylalkylene group having 1 to 3 carbon atom~ in the alkylene radical.
If n > 0, the compound of the general formula II
i8 an addition product of ethylene oxide or ethylene oxide and propylene oxide on alcohols of the formula ROH, it being po~ible, in the case of the ethylene oxida/pro-~ylane oxide adducts of the formul~ II, for the propylene-glycol radical~ to be in random or block di~tribution in the alkoxylate ch~in, but a terminal ethyleneglycol radical always being present. Addition products of ethylene oxide on alcohols of the formula II are pre-ferred in the context of the invention, 80 that m ~ 2 i9 a preferred mean~ng for the compounds of the formulae I
and II.
The increa~e in visco~ity which occurs at higher concentrations of ether-alcohols i~ avoided if, according to the invention, ~he reaction i~ started with only ~ low ether-alcohol concentration at the beginning and ether-alcohol i3 metered into the reactlon ~olution - S _ foJ ~ t~ 2 continuou~ly or in portions a~ the reaction pregres~e~
further, and in particular at a rate such that the con-centration of the ether-alcohol~ in the reaction mixture does not exceed the value of 15~ by weight.
S The abovementioned problem of foaming i avoided or con~iderably reduced by the reaction solution being present in the form of thin layers on a solid ~upport or in the form of fine particles in a contlnuou~ phase of oxygen or gases containing oxygen.
According to an advantageous embodiment of the process according to the invention, the oxidation i~
carried out at a tempsrature in tha range from 40 to 130C, in particular 60 to 85-C. The rate of reaction is too low below the stated range. Although the reaction can al~o be carried out above the 3tated range, this gives only an in~ignificant increase in the rate of reaction.
According to another advantageou~ embodlment of the procesq according to the invention, the oxidation i~
carr~ed out under an oxygen partial pre~sure of 0.1 to 5 bar. With oxygen-containing gase~ in particular, foaming is suppre~sed more and more as the system pres-sure increases and the effective gas throughput thus decreases. The rate of reaction furthermore increa~es under certain circumstance~ as the oxygen partial pre~-~ure increase~.
According to another advantageouff embodiment of th~ invention, tha oxidation i~ carried out with air.
This is another con~iderable advantage over the processes known from the prior art, in which oxygen i~ in general used in order to prevent th~ nitrogen content of air a~
the oxidizing agent promoting undesirable foaming, and in order to carry out the reaction without a waste ~as.
Useful catalysts for use in tha proces~ according to the invention are the nobla metal catalysts known from the abovementioned prior art, in particular those ba~ed on pl~tinum or palladium. P~lladium catalysts, for example palladium-un-charcoal, have proved to be par-ticularly suitable for the process according to the invention. The cataly3~ i~ preferably introduced into the ; ~
- ' , " ' .
- 6 ~ r~d procQs~ in the form of a ~u~pen~ion in thQ aqueou~
solution of the ether-alcohol~. However, it i3 al~o poc~ible for the cataly~t to be located on a solid support material, over which the aqueous solution of the S ether-alcohols ic passed. Pos ible support material~ for thi~ purpose are, for example, active charcoal, graphite, kieselguhr, ~ilica g~l, spinel-~, aluminum oxid~ or ceramic materials. The catalyst-q can furthermore also contain combination3 of a plurality of noble metals instead of one noble metal, for example mixtures of Pd and Pt, and moreovar 3uitable activator~, such as lead, bismuth or cadmium, in the form of their metal-R or their compounds, including combination~ thereof. Suitable cataly~t~ are described in the abovementioned litera~ure and in US-B-4,607,121.
According to another advantageous embodiment of the proce~s according to the invention, the cataly3t i8 employed in the form of a suspension in a concentration of 0.2 to 3% by weight, based on the total weight of the suspen~ion containing the ether-alcohols and water.
The process according to the invention is in general carried out at pH valua~ of at lea~t 8. Par-ticularly adv~ntageous pH value~ are at least 9, in particular in the range from 9 to 11. Surprisingly, it has been found that, in contrast to the doctrine of US-C-4,607,121, in spite of these h~gh pH value~ neither ~d1s~olving of the catalyst nor oxidative chain degrada-tion or by-product formation occurs when air i~ u~ed a~
the oxidizing agent; the end product of the process accordinq to the invention i~ Pd-free and the cataly~t can be reused after waYhing with hot water and treatment with hydrogen.
According to another advantageous embodiment of the in~ention, the oxidation of the ether-alcohol~ is carried out in a reactor in which the oxygen or the ga~es containing oxygen and the aqueou~ phase containing the ether-alcohol, alkali metal hydroxide ~olution and if appropriate the catalyst are introduced at the top of the reactor, the reaction mixture containing ether-carboxylic , ' i I ~ er~ ~_ acid salt~, unreacted ether-alcohol and if appropriate the cataly~t i9 removed at the bottom part of ths re~ctor and the reaction mixture i~ recycled to the upper part of the reactor for renewed oxidation of a~ yet unreacted ether-alcohol. It iR preferable here for alkali metal hydroxide ~olution, for maintaining the pH of at least 9, in particular 9 to 11, and ether-alcohol, for maintaining the ether-alcohol concentration of at least 0.1, in particular 0.5 to 15% by weight in the reaction mixture, 10 to be added continuou~ly to the reaction mixture removed at the lower part of the reactor before recycling to the upper part.
According to another advantageou embodLment of the invention, packed column~ of the usual con~truction, 15 such a~ are described, for example, in Ullmann, Enzyklopadie der technischen Chemie, 4th edition, volume c~ r 3, pages 390 to 392 (1973), Verlag Chemie, WeinheLm, a3 beunte-r curron~ packed cOlumn8~ are used for carrying out the proce~.
The packingR to be employed in the packed cOlumn8 advantageou~ly have a high intermediate volume 80 that the gas speed and the rate of foaming does not become too high. Typical examples of ~uitable packing~ are known from Ullmanns Enzyklop~die dsr technischen Chemie, 4th 25 edition, volume 2, page 529 (1972) and 5th edition, volume B3, pages 4-82 to 4-83 (1988); the use of Pall rings, Novalox saddle~, Berl saddle~, Intralox ~addles and Interpack bodies is particularly preferred. Ordered packing~ such as are described in volume 2 of the 4th 30 edition of the abovementioned encyclopedia, page~ 533 -534, for example of the Sulzer packing type, can further-more al~o be employed. Finally, it is al80 possible to employ bulX cataly~t~ or catalyst fixed beds in~tead of ~ulk packing. Ordered cataly~t packing~, for example in 35 honeycomb form, can al~o be employed.
According to another advantageous embodiment of the invention, the reaction mixture removed at the lower end of the column i~ recycled, after the pH and the ether-alcohel concentration ha~ been ad~usted, to the .. ~
, .
:.
- 8 - ~ J
upper part of the column for renewed reaction until a concentratlon of the ether-carboxylic acid ~alt of 20 to 50~ by weight, ba~ed on the total weight of the solution, i~ reached and the ether-alcohol metered in ha3 reacted.
5The invention is illustrated in more detail below with the aid of the drawing and a preferred exemplary embodiment. The drawing show~ a ~chematic representation of an installation for carrying out the proce~ according ~o the invention.
10The in~tallation compri~e~ a packed column 1 which is provided at it~ upper end with a feedlin* for oxygen or gases containing oxy~en, in particular air. A
line 3 ~erves to feed in the water~ether-alcohol mixture, containing the ~uspended catalyst if appropriate. A line 154 is located at the lower end of the packed column for removal of the oxidized reaction mixtura; the reaction mixture can be recycled to the top of the packed column via a circulating pump 5, a valve 6, which i8 open during the reaction and clo~ed only during the filtrat$on 20di~cussed below, and a heat exchanger 7 and via line 3.
Aqueous -~odium hydroxide solution 18 fed in via line 8 and a metering pump 9, and the ether-alcohol to be oxidized i9 fed in via line 10 and a metering pump 11.
The waste air flowing out of the packed column 1 is 25removed laterally via line 12 and passed to a waste gas heater 13. In this, the foam formed, for example during -incorrect operation of the installation, and entrained with the wa~te air can be destroyed and recycled to the reactor as a liquid via line 14. The waste air which has 30been freed from the foam i~ fed via line 15 to a cooler 16 and i~ removed from the sy~tem via a valve 17 and line 18; any entrained droplet~ of liquid or condensate obtained are likewise recycled to the reactor via a line 19. The aqueou~ su~pension containing the end product is 35removed via a line 20 and a valve 21 and fed to a filter unit 22 where the aqueous solution of the process pro-ducts and the su~pended cataly~t are sep~rated, these each being removed via lina~ 23 and 24 respectively. The catalyst i~ introduced at a point not 3hown in line 4.
: ' ~
: : , The in~tallation ~hown in Figure 1 i4 oper~ted a~
follows:
In the packed reactor flu~hed with nitrogen, the su~pen~ion of the pulverulent noble metal catalyst in water is recycled from the bottom of the reactor to its top by mean~ of the circulating pump S. When the solution ha~ been heated to th~ reaction temperatur~ by the heat exchanger 7 in the ~olvent circulation, a small amoun~ of ether-alcohol and sodium hydroxide solution is metered in the form of an aqueou-q solution into the circulating su~pension by mean~ of the metering pump~ 9, 10. The nitrogen is then di~placed by oxygen or a gas containing oxygen and immediately after the desired pressure has been reached, the gas throughput required for the oxida-tion and the metering in of sodium hydroxide solution andalcohol via the metering pumps 9 and 11 are ad~uqted.
During the reaction, which i8 detectable by an oxygen uptake, alcohol and aqueou~ sod~um hydroxide solution ars metsred in continuously. The metering rate 20 i3 ad~usted or varied and m~tched to the rate of reaction 80 that a ~mall amount of ether-alcohol which ha~ not yst reacted and therefore a low viscosity i8 en~ured in the solution throughout the entirs course of the reaction.
When the required amount~ of ether-alcohol and ~odium hydroxide solution have been metered in, the metering i9 stopped; the reaction i~ then continusd until ~t~e oxyqen uptake decrease~ ~ignificantly.
When thQ reaction h~ ended, the gaJ feed i~
interruptsd and the catalyst i~ ~eparated off from the ~olution by filtration.
Example 1.
A cu~tomary packed column of internal diameter 50 mm and haight of the packing of lO00 ~m was used for thi~ exemplary smbodiment; the column wa~ charged with packing of the typ~ Interpack 15/40.
The feed material wa~ a commercially availabls fatty alcohol ethoxylate (addition product o~ about 4 mol of ethylens oxlde on an indu~trial fatty alcohol of chain - ~ .
length Cl2-Cl~, molecular weight: 369). A palladium cata-ly~t containing 5~ of palladium-on-charcoal (Degus~a), which had been reduced with hydrogen before u e in the form of an aqueou~ suspen~ion, wa3 used a~ the catalyst.
The installation wa~ initially charged with a suspension of, based on the dry ~ub~tance, 35 g of cataly~t in 2400 g of demineralized water. To start the reaction, 30 g of ether-alcohol (about 1.2% by weight) and 3.3 g of NaOH (a~ 25~ strength sodium hydroxide solution) were metered into the in~allation. The par-ticular content of free ether-alcohol wa~ determined mathematically from the amount of oxygen taken up by the reaction solution by the period up to each point in time of the reaction and the amount of ether-alcohol metered in by thsn.
In dstail, the proce~s parameterq were as fol-low~s Sy~tem pressures 1.9 bar ab~olute Suspension temperatures 75-C
Air throughput (reactor outlet)s 30 Nl/hour Solution circulations 170 l/hour Metering rate o ether-alcohol~ about 140 g/hour ~0.379 gmol) Metering rate of NaOH (calculated a~ 100S strength NaOH~s 15.2 g/hour ~O.379 gmol/hour) Total amount of ether-alcohol metered in~ 720 g ~1.95 gmol) Total amount of NaOH metered ln (a~ 100% ~trength NaOH)s 78.0 g (l.g5 gmol) Average or maximum content of ether-alcohol which ha~ not yet reacteds 3 and 4~ by weight re~pectively Duration of the reactions 6.3 hour~
Conversion (determined mathemxtically from the 2 uptake and the NaOH con~umption~: about 97%.
When the reaction has ended and the catalyst has been removed by filtration, an approximately 23% ~trenqth solution of the sot~um salt of the ether-carboxylic acid formed, ba~ed on the total weight of the solution, was obtained with a pale yellow color. N~R analy~is of the - -proces~ product ~howed an average degree of ethoxylation which wa~ lower than that of the ether-alcohol by one unit. ~tomic spectroscopy analysis of the filtrate on palladium -~howed a content of < 1 ppm.
The experiment was performed seven timeq using the ~ame catalyst without los~es in activity being detectable. Before each use, the catalyst wa~ washed with hot water, ~uspended in water and reduced with H2 at room temperature.
Example 2.
An addition product of on average 5 mol of ethyleneoxide on 1 mol of the indu~trial fatty alcohol described in Example 1, of chain length C~2-Cl~, wa~
oxidized by a proce~s analogou~ to that of Example 1.
After a reaction time of 6.7 hour~, a 23.5% strength ~olution of the ~odium ~alt of the corre~ponding ether-carboxylic acid wa~ obtained in a conversion of about 97%, calculated from the oxygan consumption. An addition product of on average 9 mol of ethylene oxide on 1 mol of an indu~trial fatty alcohol of chain length C~2-C1~ wa~
oxidized in the same manner. After a reaction time of 6.2 hours, a 19.5~ strength solution of the ~odium salt o the corre~ponding ether-carboxylic acid was obtained at a conver~ion, calculated from the oxygen consumption, of about 105%.
- In deviation from the procedure of the exemplary embodiment explained above, it i~ also possLble to use star~ing concentrations other than 1.2~ by weight of ether-alcohol. Thus, for example, the reaction can also be started without initial addition of ether-alcohol, that i8 to ~y the ether-alcohol i~ metered in only at the ~tart of the introduction of air. However, thi procedurQ can lead to a premature discontinuation of the reaction and mu~t therefore be regarded a~ unstable.
Higher initial concentrations, for example of 7S by weight of ether-alcohol, are al~o possibla, but offer no ad~antages in re~pect of the dur~t~on of the reaction in the case of the ether-alcohol employed in the pre~ent 3 .i J
exemplary embodiment.
I t has proved advantageou~ for an adequato rate of reaction to choo~e the NaOH metering so that at each point in tLme the acid formed up until that point ha~
been bonded completely; at this equivalence point, the ~olution ha~ a pH of about 9. However, a ~ignificantly higher rate of reaction i~ obtained if the total amount of NaOH metered in at each point in time i~ equivalent to the to~al amount of ether-alcohol metered in, that is to say at pH value~ of more than 9, for example of 10 to 11.
No oxidative chain degradation on tAe ethoxylate groupa and no dissolving of the catalyst were to be found even at the~e higher pH values.
Finally, it is also possible for the entire amount of NaOH to be initially introduced from the beginning; however, thi~ ia not an advantage in reapect of the duration of the reaction compared with the reac-t;.on procedure de~cribed above in the exemplary embodi-ment.
disposal i~ uneconomical. Renewed conver~ion of the ether-carboxylic acids into their alkali metal salt~
also leads to an additional increase in the co~ts of the reaction product.
An additional hindrance occurs in particular if air i~ used a~ the oxidizing agent. In thi3 case, the oxidation procedure is made difficult by the foam formed a~ a result of the surface-active properties of th~
starting substances and end products. The foam i~sue~
'rom the reactor with the waste gas and must be recycled from there back into the reactor after its destruction.
The rate of foam formation is always high if air i5 r~ dispersed in the solution, as i8 the case, for example, ~ I in ~ reactor~ or bubble column rsactors. In I ~ btirrcd ]cottl~ reactors in particular, the reaction solution can be converted into a foam-like state by the stirring action, so that mass tran~fer of the oxygen i9 prevented and the reaction is inhibited; compare DE-C-2,816,127.
The invention relates to a proces~ for the preparation of alkali metals salts of ether-carboxylic acids of the abovemsntioned type, in which the above-men~ioned di~advantages in respect of the increa~e in vi~c08ity and the foaming of the reaction mixture are avoided and highly concentrated aqueou~ solutions of alkali metal ~alts of the ether-carboxyllc acid~, for exampl~ having a concentration of 20 to 50% by weight, ba~ed on tha total weight of the solution, can be obtained.
According to the inventlon, thiJ ob~ect is achieved by bringing an aqueous solution, containing an alkali metal hydroxide ~olution, of the ether-alcohol~ in a thin layer on a solid support or in the form of fine particlss or droplet~ into con~act with oxygen or tha gase~ containing oxygen as the continuous phase, the concentration of the ether-alcohols in the aqueou~ phase - 4 ~
bein~ in the range from at lea~t 0.1, in particular from 0.5 to 15% by weight, ba~ed on the total weight of the aqueous phase. Below the stated range the rate of reac-tion iq generally too low qo that the concentration should fall below this range only towards the end of the reaction, when the addition of ether-alcohol has ended.
Alkali metal salts of ether-carboxylic acid~ of the general formula (I) in which the group R can be a straight-chain or branched alkyl group having 1 to 22 carbon atomq can be prepared by the process according to the invention; typical examples of such alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and docosyl. The proce~Y according to the invention i~ particularly suitable for the prepara-tion of alkali metal 3alt~ of ether-carboxylic acids in which the radical R i~ derived from Clz-ClO-fatty alcohol~, or indu3trial mixtures thereof, obtainable from animal and/or vegetable fats and oils. The group R c~n also be an aryl radical, for example a phenyl group, or an aralkyl radical, for example a phenylalkylene group having 1 to 3 carbon atom~ in the alkylene radical.
If n > 0, the compound of the general formula II
i8 an addition product of ethylene oxide or ethylene oxide and propylene oxide on alcohols of the formula ROH, it being po~ible, in the case of the ethylene oxida/pro-~ylane oxide adducts of the formul~ II, for the propylene-glycol radical~ to be in random or block di~tribution in the alkoxylate ch~in, but a terminal ethyleneglycol radical always being present. Addition products of ethylene oxide on alcohols of the formula II are pre-ferred in the context of the invention, 80 that m ~ 2 i9 a preferred mean~ng for the compounds of the formulae I
and II.
The increa~e in visco~ity which occurs at higher concentrations of ether-alcohols i~ avoided if, according to the invention, ~he reaction i~ started with only ~ low ether-alcohol concentration at the beginning and ether-alcohol i3 metered into the reactlon ~olution - S _ foJ ~ t~ 2 continuou~ly or in portions a~ the reaction pregres~e~
further, and in particular at a rate such that the con-centration of the ether-alcohol~ in the reaction mixture does not exceed the value of 15~ by weight.
S The abovementioned problem of foaming i avoided or con~iderably reduced by the reaction solution being present in the form of thin layers on a solid ~upport or in the form of fine particles in a contlnuou~ phase of oxygen or gases containing oxygen.
According to an advantageous embodiment of the process according to the invention, the oxidation i~
carried out at a tempsrature in tha range from 40 to 130C, in particular 60 to 85-C. The rate of reaction is too low below the stated range. Although the reaction can al~o be carried out above the 3tated range, this gives only an in~ignificant increase in the rate of reaction.
According to another advantageou~ embodlment of the procesq according to the invention, the oxidation i~
carr~ed out under an oxygen partial pre~sure of 0.1 to 5 bar. With oxygen-containing gase~ in particular, foaming is suppre~sed more and more as the system pres-sure increases and the effective gas throughput thus decreases. The rate of reaction furthermore increa~es under certain circumstance~ as the oxygen partial pre~-~ure increase~.
According to another advantageouff embodiment of th~ invention, tha oxidation i~ carried out with air.
This is another con~iderable advantage over the processes known from the prior art, in which oxygen i~ in general used in order to prevent th~ nitrogen content of air a~
the oxidizing agent promoting undesirable foaming, and in order to carry out the reaction without a waste ~as.
Useful catalysts for use in tha proces~ according to the invention are the nobla metal catalysts known from the abovementioned prior art, in particular those ba~ed on pl~tinum or palladium. P~lladium catalysts, for example palladium-un-charcoal, have proved to be par-ticularly suitable for the process according to the invention. The cataly3~ i~ preferably introduced into the ; ~
- ' , " ' .
- 6 ~ r~d procQs~ in the form of a ~u~pen~ion in thQ aqueou~
solution of the ether-alcohol~. However, it i3 al~o poc~ible for the cataly~t to be located on a solid support material, over which the aqueous solution of the S ether-alcohols ic passed. Pos ible support material~ for thi~ purpose are, for example, active charcoal, graphite, kieselguhr, ~ilica g~l, spinel-~, aluminum oxid~ or ceramic materials. The catalyst-q can furthermore also contain combination3 of a plurality of noble metals instead of one noble metal, for example mixtures of Pd and Pt, and moreovar 3uitable activator~, such as lead, bismuth or cadmium, in the form of their metal-R or their compounds, including combination~ thereof. Suitable cataly~t~ are described in the abovementioned litera~ure and in US-B-4,607,121.
According to another advantageous embodiment of the proce~s according to the invention, the cataly3t i8 employed in the form of a suspension in a concentration of 0.2 to 3% by weight, based on the total weight of the suspen~ion containing the ether-alcohols and water.
The process according to the invention is in general carried out at pH valua~ of at lea~t 8. Par-ticularly adv~ntageous pH value~ are at least 9, in particular in the range from 9 to 11. Surprisingly, it has been found that, in contrast to the doctrine of US-C-4,607,121, in spite of these h~gh pH value~ neither ~d1s~olving of the catalyst nor oxidative chain degrada-tion or by-product formation occurs when air i~ u~ed a~
the oxidizing agent; the end product of the process accordinq to the invention i~ Pd-free and the cataly~t can be reused after waYhing with hot water and treatment with hydrogen.
According to another advantageous embodiment of the in~ention, the oxidation of the ether-alcohol~ is carried out in a reactor in which the oxygen or the ga~es containing oxygen and the aqueou~ phase containing the ether-alcohol, alkali metal hydroxide ~olution and if appropriate the catalyst are introduced at the top of the reactor, the reaction mixture containing ether-carboxylic , ' i I ~ er~ ~_ acid salt~, unreacted ether-alcohol and if appropriate the cataly~t i9 removed at the bottom part of ths re~ctor and the reaction mixture i~ recycled to the upper part of the reactor for renewed oxidation of a~ yet unreacted ether-alcohol. It iR preferable here for alkali metal hydroxide ~olution, for maintaining the pH of at least 9, in particular 9 to 11, and ether-alcohol, for maintaining the ether-alcohol concentration of at least 0.1, in particular 0.5 to 15% by weight in the reaction mixture, 10 to be added continuou~ly to the reaction mixture removed at the lower part of the reactor before recycling to the upper part.
According to another advantageou embodLment of the invention, packed column~ of the usual con~truction, 15 such a~ are described, for example, in Ullmann, Enzyklopadie der technischen Chemie, 4th edition, volume c~ r 3, pages 390 to 392 (1973), Verlag Chemie, WeinheLm, a3 beunte-r curron~ packed cOlumn8~ are used for carrying out the proce~.
The packingR to be employed in the packed cOlumn8 advantageou~ly have a high intermediate volume 80 that the gas speed and the rate of foaming does not become too high. Typical examples of ~uitable packing~ are known from Ullmanns Enzyklop~die dsr technischen Chemie, 4th 25 edition, volume 2, page 529 (1972) and 5th edition, volume B3, pages 4-82 to 4-83 (1988); the use of Pall rings, Novalox saddle~, Berl saddle~, Intralox ~addles and Interpack bodies is particularly preferred. Ordered packing~ such as are described in volume 2 of the 4th 30 edition of the abovementioned encyclopedia, page~ 533 -534, for example of the Sulzer packing type, can further-more al~o be employed. Finally, it is al80 possible to employ bulX cataly~t~ or catalyst fixed beds in~tead of ~ulk packing. Ordered cataly~t packing~, for example in 35 honeycomb form, can al~o be employed.
According to another advantageous embodiment of the invention, the reaction mixture removed at the lower end of the column i~ recycled, after the pH and the ether-alcohel concentration ha~ been ad~usted, to the .. ~
, .
:.
- 8 - ~ J
upper part of the column for renewed reaction until a concentratlon of the ether-carboxylic acid ~alt of 20 to 50~ by weight, ba~ed on the total weight of the solution, i~ reached and the ether-alcohol metered in ha3 reacted.
5The invention is illustrated in more detail below with the aid of the drawing and a preferred exemplary embodiment. The drawing show~ a ~chematic representation of an installation for carrying out the proce~ according ~o the invention.
10The in~tallation compri~e~ a packed column 1 which is provided at it~ upper end with a feedlin* for oxygen or gases containing oxy~en, in particular air. A
line 3 ~erves to feed in the water~ether-alcohol mixture, containing the ~uspended catalyst if appropriate. A line 154 is located at the lower end of the packed column for removal of the oxidized reaction mixtura; the reaction mixture can be recycled to the top of the packed column via a circulating pump 5, a valve 6, which i8 open during the reaction and clo~ed only during the filtrat$on 20di~cussed below, and a heat exchanger 7 and via line 3.
Aqueous -~odium hydroxide solution 18 fed in via line 8 and a metering pump 9, and the ether-alcohol to be oxidized i9 fed in via line 10 and a metering pump 11.
The waste air flowing out of the packed column 1 is 25removed laterally via line 12 and passed to a waste gas heater 13. In this, the foam formed, for example during -incorrect operation of the installation, and entrained with the wa~te air can be destroyed and recycled to the reactor as a liquid via line 14. The waste air which has 30been freed from the foam i~ fed via line 15 to a cooler 16 and i~ removed from the sy~tem via a valve 17 and line 18; any entrained droplet~ of liquid or condensate obtained are likewise recycled to the reactor via a line 19. The aqueou~ su~pension containing the end product is 35removed via a line 20 and a valve 21 and fed to a filter unit 22 where the aqueous solution of the process pro-ducts and the su~pended cataly~t are sep~rated, these each being removed via lina~ 23 and 24 respectively. The catalyst i~ introduced at a point not 3hown in line 4.
: ' ~
: : , The in~tallation ~hown in Figure 1 i4 oper~ted a~
follows:
In the packed reactor flu~hed with nitrogen, the su~pen~ion of the pulverulent noble metal catalyst in water is recycled from the bottom of the reactor to its top by mean~ of the circulating pump S. When the solution ha~ been heated to th~ reaction temperatur~ by the heat exchanger 7 in the ~olvent circulation, a small amoun~ of ether-alcohol and sodium hydroxide solution is metered in the form of an aqueou-q solution into the circulating su~pension by mean~ of the metering pump~ 9, 10. The nitrogen is then di~placed by oxygen or a gas containing oxygen and immediately after the desired pressure has been reached, the gas throughput required for the oxida-tion and the metering in of sodium hydroxide solution andalcohol via the metering pumps 9 and 11 are ad~uqted.
During the reaction, which i8 detectable by an oxygen uptake, alcohol and aqueou~ sod~um hydroxide solution ars metsred in continuously. The metering rate 20 i3 ad~usted or varied and m~tched to the rate of reaction 80 that a ~mall amount of ether-alcohol which ha~ not yst reacted and therefore a low viscosity i8 en~ured in the solution throughout the entirs course of the reaction.
When the required amount~ of ether-alcohol and ~odium hydroxide solution have been metered in, the metering i9 stopped; the reaction i~ then continusd until ~t~e oxyqen uptake decrease~ ~ignificantly.
When thQ reaction h~ ended, the gaJ feed i~
interruptsd and the catalyst i~ ~eparated off from the ~olution by filtration.
Example 1.
A cu~tomary packed column of internal diameter 50 mm and haight of the packing of lO00 ~m was used for thi~ exemplary smbodiment; the column wa~ charged with packing of the typ~ Interpack 15/40.
The feed material wa~ a commercially availabls fatty alcohol ethoxylate (addition product o~ about 4 mol of ethylens oxlde on an indu~trial fatty alcohol of chain - ~ .
length Cl2-Cl~, molecular weight: 369). A palladium cata-ly~t containing 5~ of palladium-on-charcoal (Degus~a), which had been reduced with hydrogen before u e in the form of an aqueou~ suspen~ion, wa3 used a~ the catalyst.
The installation wa~ initially charged with a suspension of, based on the dry ~ub~tance, 35 g of cataly~t in 2400 g of demineralized water. To start the reaction, 30 g of ether-alcohol (about 1.2% by weight) and 3.3 g of NaOH (a~ 25~ strength sodium hydroxide solution) were metered into the in~allation. The par-ticular content of free ether-alcohol wa~ determined mathematically from the amount of oxygen taken up by the reaction solution by the period up to each point in time of the reaction and the amount of ether-alcohol metered in by thsn.
In dstail, the proce~s parameterq were as fol-low~s Sy~tem pressures 1.9 bar ab~olute Suspension temperatures 75-C
Air throughput (reactor outlet)s 30 Nl/hour Solution circulations 170 l/hour Metering rate o ether-alcohol~ about 140 g/hour ~0.379 gmol) Metering rate of NaOH (calculated a~ 100S strength NaOH~s 15.2 g/hour ~O.379 gmol/hour) Total amount of ether-alcohol metered in~ 720 g ~1.95 gmol) Total amount of NaOH metered ln (a~ 100% ~trength NaOH)s 78.0 g (l.g5 gmol) Average or maximum content of ether-alcohol which ha~ not yet reacteds 3 and 4~ by weight re~pectively Duration of the reactions 6.3 hour~
Conversion (determined mathemxtically from the 2 uptake and the NaOH con~umption~: about 97%.
When the reaction has ended and the catalyst has been removed by filtration, an approximately 23% ~trenqth solution of the sot~um salt of the ether-carboxylic acid formed, ba~ed on the total weight of the solution, was obtained with a pale yellow color. N~R analy~is of the - -proces~ product ~howed an average degree of ethoxylation which wa~ lower than that of the ether-alcohol by one unit. ~tomic spectroscopy analysis of the filtrate on palladium -~howed a content of < 1 ppm.
The experiment was performed seven timeq using the ~ame catalyst without los~es in activity being detectable. Before each use, the catalyst wa~ washed with hot water, ~uspended in water and reduced with H2 at room temperature.
Example 2.
An addition product of on average 5 mol of ethyleneoxide on 1 mol of the indu~trial fatty alcohol described in Example 1, of chain length C~2-Cl~, wa~
oxidized by a proce~s analogou~ to that of Example 1.
After a reaction time of 6.7 hour~, a 23.5% strength ~olution of the ~odium ~alt of the corre~ponding ether-carboxylic acid wa~ obtained in a conversion of about 97%, calculated from the oxygan consumption. An addition product of on average 9 mol of ethylene oxide on 1 mol of an indu~trial fatty alcohol of chain length C~2-C1~ wa~
oxidized in the same manner. After a reaction time of 6.2 hours, a 19.5~ strength solution of the ~odium salt o the corre~ponding ether-carboxylic acid was obtained at a conver~ion, calculated from the oxygen consumption, of about 105%.
- In deviation from the procedure of the exemplary embodiment explained above, it i~ also possLble to use star~ing concentrations other than 1.2~ by weight of ether-alcohol. Thus, for example, the reaction can also be started without initial addition of ether-alcohol, that i8 to ~y the ether-alcohol i~ metered in only at the ~tart of the introduction of air. However, thi procedurQ can lead to a premature discontinuation of the reaction and mu~t therefore be regarded a~ unstable.
Higher initial concentrations, for example of 7S by weight of ether-alcohol, are al~o possibla, but offer no ad~antages in re~pect of the dur~t~on of the reaction in the case of the ether-alcohol employed in the pre~ent 3 .i J
exemplary embodiment.
I t has proved advantageou~ for an adequato rate of reaction to choo~e the NaOH metering so that at each point in tLme the acid formed up until that point ha~
been bonded completely; at this equivalence point, the ~olution ha~ a pH of about 9. However, a ~ignificantly higher rate of reaction i~ obtained if the total amount of NaOH metered in at each point in time i~ equivalent to the to~al amount of ether-alcohol metered in, that is to say at pH value~ of more than 9, for example of 10 to 11.
No oxidative chain degradation on tAe ethoxylate groupa and no dissolving of the catalyst were to be found even at the~e higher pH values.
Finally, it is also possible for the entire amount of NaOH to be initially introduced from the beginning; however, thi~ ia not an advantage in reapect of the duration of the reaction compared with the reac-t;.on procedure de~cribed above in the exemplary embodi-ment.
Claims (11)
1. Process for the manufacture of alkali salts of an ether-carboxylic acid of the general Formula I
R-(OCmH2m)n-O-CH2COOM (I) in which R stands for an alkyl group having from 1 to 22 C-atoms, an aryl group or an aralkyl group, m stands for a number 2 and/or 3, n stands for a number in the range from 0 to 20 and M stands for an alkali metal from the group formed by lithium, sodium and potassium, by oxidation of ether alcohols of the general Formula II
R-(OCmH2m)n-0-CH2CH2OH (II) in which R, m and n are defined as above, in the aqueous phase with oxygen and/or oxygen containing gases at increased temperatures in the presence of an alkali metal hydroxides and a precious metal catalysts, characterized thereby that an aqueous, alkali lye containing solution of ether alcohols in a thin layer on a solid carrier or in the form of micrometric particles at a pH-value of at least 9 is brought into contact with oxygen and/or oxygen containing gases as a continuous phase, whereby the concentration of the ether alcohols in the aqueous phase is in the range from at least 0.1, in particular from 0.5 to 15 weight-%-related to the total weight of the aqueous phase.
R-(OCmH2m)n-O-CH2COOM (I) in which R stands for an alkyl group having from 1 to 22 C-atoms, an aryl group or an aralkyl group, m stands for a number 2 and/or 3, n stands for a number in the range from 0 to 20 and M stands for an alkali metal from the group formed by lithium, sodium and potassium, by oxidation of ether alcohols of the general Formula II
R-(OCmH2m)n-0-CH2CH2OH (II) in which R, m and n are defined as above, in the aqueous phase with oxygen and/or oxygen containing gases at increased temperatures in the presence of an alkali metal hydroxides and a precious metal catalysts, characterized thereby that an aqueous, alkali lye containing solution of ether alcohols in a thin layer on a solid carrier or in the form of micrometric particles at a pH-value of at least 9 is brought into contact with oxygen and/or oxygen containing gases as a continuous phase, whereby the concentration of the ether alcohols in the aqueous phase is in the range from at least 0.1, in particular from 0.5 to 15 weight-%-related to the total weight of the aqueous phase.
2. The process as claimed in claim 1, wherein the oxidation is carried out at a temperature in the range from 40 to 130°C, in particular 60 to 85°C.
3. The process as claimed in claim 1 or 2, wherein the oxidation is carried out under an oxygen partial pressure in the range from 0.1 to 5, in particular 0.2 to 3 bar.
4. The process as claimed in at least one of claims 1 to 3, wherein the oxidation is carried out with air.
5. The process as claimed in at least one of claims 1 to 4, wherein the catalyst is suspended in the aqueous solution of the ether-alcohol.
6. The process as claimed in at least one of claims 1 to 5, wherein the catalyst is employed in a concentration of 0.2 to 3% by weight, based on the total weight of the suspension containing the ether-alcohol and water.
7. A process according to at least one of the Claims 1 to 6, characterized thereby that the oxidation is carried out at a pH-value of 9 to 11.
8. The process as claimed in at least one of claims 1 to 7, wherein the oxidation is carried out in a reactor in which the oxygen or the gases containing oxygen and the aqueous phase containing the ether-alcohol, alkali metal hydroxide solution and if appropriate the catalyst are introduced at the top of the reactor, the reaction mixture containing the ether-carboxylic acid salt, unreacted ether-alcohol and if appropriate the catalyst is removed at the bottom part of the reactor and the reaction mixture is recycled to the upper part of the reactor for renewed oxidation of the unreacted ether-alcohol.
9. The process as claimed in claim 8, wherein alkali metal hydroxide solution, to maintain the pH of at least 9, in particular 9 to 11, and ether-alcohol, to maintain the ether-alcohol concentration of at least 0.1, in particular 0.5 to 15% by weight, in the reaction mixture are added continuously to the reaction mixture removed at the lower part of the reactor before recycling to the upper part.
10. The process as claimed in claim 8 or 9, wherein a packed column is used.
11. The process as claimed in at least one of claims 8 to 10, wherein the reaction mixture is recycled to the reactor until a concentration of the ether-carbo-xylic acid salt of 20 to 50% by weight, based on the total weight of the solution, is reached and the ether-alcohol metered in has reacted.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3929063A DE3929063A1 (en) | 1989-09-01 | 1989-09-01 | METHOD FOR PRODUCING ALKALINE SALTS OF ETHERCARBONIC ACIDS |
| DEP3929063.8 | 1989-09-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2066452A1 true CA2066452A1 (en) | 1991-03-02 |
Family
ID=6388431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002066452A Abandoned CA2066452A1 (en) | 1989-09-01 | 1990-08-23 | Process for the production of alkali metal salts of ethercarboxylic acids |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0489781A1 (en) |
| JP (1) | JPH05503686A (en) |
| AU (1) | AU6288790A (en) |
| CA (1) | CA2066452A1 (en) |
| DE (1) | DE3929063A1 (en) |
| WO (1) | WO1991003454A1 (en) |
| ZA (1) | ZA906979B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5463114A (en) * | 1994-04-13 | 1995-10-31 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of ether carboxylic acids and salts thereof |
| DE10117222B4 (en) | 2001-04-06 | 2004-12-30 | Goldschmidt Ag | Process for the preparation of glycine derivatives |
| JP5511369B2 (en) | 2009-12-28 | 2014-06-04 | 花王株式会社 | Method for producing carboxylic acid |
| JP5520088B2 (en) * | 2010-03-10 | 2014-06-11 | 花王株式会社 | Method for producing ether carboxylate |
| JP5520089B2 (en) * | 2010-03-10 | 2014-06-11 | 花王株式会社 | Method for producing ether carboxylate |
| JP2013067565A (en) * | 2011-09-20 | 2013-04-18 | Kao Corp | Method of producing carboxylate |
| JP5985965B2 (en) | 2011-12-28 | 2016-09-06 | 花王株式会社 | Process for producing polyoxyalkylene alkyl ether carboxylic acid or salt thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2936123A1 (en) * | 1979-09-07 | 1981-04-02 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING ALKOXY ACETIC ACIDS |
| US4348509A (en) * | 1981-07-06 | 1982-09-07 | Shell Oil Company | Alkoxyalkanoic acid preparation |
| DE3135946A1 (en) * | 1981-09-10 | 1983-03-24 | Bayer Ag, 5090 Leverkusen | Process for preparing alkoxyacetic acids |
| IT1175314B (en) * | 1983-12-28 | 1987-07-01 | Anic Spa | PROCEDURE FOR THE PREPARATION OF ALKALINE METAL SALTS OF POLYETHOXYCARBOXYLIC ACIDS |
| DE3728222A1 (en) * | 1987-08-24 | 1989-03-09 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF ETHERCARBONIC ACIDS |
-
1989
- 1989-09-01 DE DE3929063A patent/DE3929063A1/en not_active Withdrawn
-
1990
- 1990-08-23 JP JP2512142A patent/JPH05503686A/en active Pending
- 1990-08-23 AU AU62887/90A patent/AU6288790A/en not_active Abandoned
- 1990-08-23 WO PCT/EP1990/001402 patent/WO1991003454A1/en not_active Application Discontinuation
- 1990-08-23 CA CA002066452A patent/CA2066452A1/en not_active Abandoned
- 1990-08-23 EP EP90912729A patent/EP0489781A1/en not_active Withdrawn
- 1990-08-31 ZA ZA906979A patent/ZA906979B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3929063A1 (en) | 1991-03-07 |
| ZA906979B (en) | 1991-06-26 |
| WO1991003454A1 (en) | 1991-03-21 |
| EP0489781A1 (en) | 1992-06-17 |
| AU6288790A (en) | 1991-04-08 |
| JPH05503686A (en) | 1993-06-17 |
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