CA1077517A - Process for the preparation of hydroxy-carboxylic acids and derivatives - Google Patents
Process for the preparation of hydroxy-carboxylic acids and derivativesInfo
- Publication number
- CA1077517A CA1077517A CA248,666A CA248666A CA1077517A CA 1077517 A CA1077517 A CA 1077517A CA 248666 A CA248666 A CA 248666A CA 1077517 A CA1077517 A CA 1077517A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- process according
- reaction
- acid
- carbon monoxide
- 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
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (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)
- Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An improvement is disclosed in the known liquid phase acid catalyzed process for preparing hydroxy carboxylic acids and their acyloxy derivatives from aldehydes, carbon monoxide and water, alcohol or carboxylic acid, the improvement relating to the use of a solid insoluble acidic catalyst rather than conventional liquid catalyst with the solid catalyst being mechanically separated from the reaction product.
An improvement is disclosed in the known liquid phase acid catalyzed process for preparing hydroxy carboxylic acids and their acyloxy derivatives from aldehydes, carbon monoxide and water, alcohol or carboxylic acid, the improvement relating to the use of a solid insoluble acidic catalyst rather than conventional liquid catalyst with the solid catalyst being mechanically separated from the reaction product.
Description
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Backgro~md o the Invention Carbon monoxide and aldehydes are known to react under heat and pressure wlth water, alcohols or carboxylic acids in liquid phase acid catalyzed processes to produce hydroxy carboxylic acids, acyloxy derivatives of carboxylic acids and esters of hydroxy carboxylic acids, respectively. - ;
- Illustrative reactions are as follows:
(1) Preparation of lactic acid ; CH3CH-0 + C0 ~ H20 0.1 mole 112S04 cat- ~HOCH2COOH
165 C., 900 ATM ~H
- (See, U.S. Patent 2,265,945 issued to D. J. Loder; patented December 9, 1941).
; (2) Preparation of propionoxy acetic acid CH3CHz~ - OH ~ CH20 ~ C0 02 ~oles H2S4 cat-200C., 850 ATM
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(See,U.S. Patent 2,211,624 issued to D. J. Loder et al;
patented August 13, 1940).
~3) Preparation of`methyl glycolate CH20 ~ CO + CH3 OH 0.05 mole H2S~ cat.
0 215C., 850 ATM
' .
~See, U.S. Patent 2,211,625 issued to D. J. Loder; patented August 13, 1940).
Hydroxy carboxylic acids, for example, glycolic acid will undergo a variety of intermolecular dehydration reactions to form productq such as diglycolic acid or hydroxyacetoxyacetic acid (see, U.S. Patent 2,331,094 issued to D. J. Loder; patented October 5, 1943). Depending on the reaction condi~ions, these types of complex dehydration products may accompany simpler reaction products.
Catalysts heretofore described in the literature to be useful for the liquid phase reaction of aldehyde and carbon monoxide were strongly acidic salts and inorganic acids. In practice, these catalysts were used at low concentration. In the case of forming glycolic acid from the reaction of carbon monoxide, formaldehyde and water, typical industrial practice employed 2 mole percent H2SO~ ~per mole of formaldehyde) at 200C.
and 700 atm. Low catalyst concentrations were preferred since high con-centrations of soluble catalysts would require an additional difficult catalyst removal step.
The Invention This invention concerns the preparation of compounds consisting of hydroxy carboxylic acids or their derivatives represented by the formula:
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Backgro~md o the Invention Carbon monoxide and aldehydes are known to react under heat and pressure wlth water, alcohols or carboxylic acids in liquid phase acid catalyzed processes to produce hydroxy carboxylic acids, acyloxy derivatives of carboxylic acids and esters of hydroxy carboxylic acids, respectively. - ;
- Illustrative reactions are as follows:
(1) Preparation of lactic acid ; CH3CH-0 + C0 ~ H20 0.1 mole 112S04 cat- ~HOCH2COOH
165 C., 900 ATM ~H
- (See, U.S. Patent 2,265,945 issued to D. J. Loder; patented December 9, 1941).
; (2) Preparation of propionoxy acetic acid CH3CHz~ - OH ~ CH20 ~ C0 02 ~oles H2S4 cat-200C., 850 ATM
,'; . .
.
- ' , ~, ~ .
1~77~
(See,U.S. Patent 2,211,624 issued to D. J. Loder et al;
patented August 13, 1940).
~3) Preparation of`methyl glycolate CH20 ~ CO + CH3 OH 0.05 mole H2S~ cat.
0 215C., 850 ATM
' .
~See, U.S. Patent 2,211,625 issued to D. J. Loder; patented August 13, 1940).
Hydroxy carboxylic acids, for example, glycolic acid will undergo a variety of intermolecular dehydration reactions to form productq such as diglycolic acid or hydroxyacetoxyacetic acid (see, U.S. Patent 2,331,094 issued to D. J. Loder; patented October 5, 1943). Depending on the reaction condi~ions, these types of complex dehydration products may accompany simpler reaction products.
Catalysts heretofore described in the literature to be useful for the liquid phase reaction of aldehyde and carbon monoxide were strongly acidic salts and inorganic acids. In practice, these catalysts were used at low concentration. In the case of forming glycolic acid from the reaction of carbon monoxide, formaldehyde and water, typical industrial practice employed 2 mole percent H2SO~ ~per mole of formaldehyde) at 200C.
and 700 atm. Low catalyst concentrations were preferred since high con-centrations of soluble catalysts would require an additional difficult catalyst removal step.
The Invention This invention concerns the preparation of compounds consisting of hydroxy carboxylic acids or their derivatives represented by the formula:
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Rl _ ~ - CH - R
or intermolecular dehydration products of said compounds, where R is alkyl,jal,ky~lene or hydrogen, R is hydroxy or alkoxy, R is hydroxy or acyloxy, provided at least one of Rl or R2 is hydroxyl by reacting a mixture of carbon monoxide and aliphatic aldehyde together with water or carboxylic acid or alkanol in a liquid reaction media at temperatures above 25C. and superatmospheric pressures using as c~alyst solid insoluble particulate acidic material having hydrogen ion-exchange capacity in excess of 0.1 milliequivalents per gram; and subsequently mechanically separating reaction media from the catalyst.
The radical "R" is determined by the aliphatic aldehyde selected for reaction. For example, when formaldehyde is used, R is hydrogen and when acetaldehyde is used, R is methyl.
The radical R is determined by the use of water or an alkyl alcohol as a reactant. For example, when water is used R is hydroxy, when ethanol is used R is ethoxy; and when isopropanol is used R i9 isopropoxy.
The radical R is determined by the selection of aliphatic organic acid reactant. For example, when no acid is used, R is hydroxy and when acetic acid is used R is acetoxy.
In particular, this invention is an improved process for the formation of a-hydroxy alkanoic acids, ~-acyloxy derivatives of alkanoic acids, and alkyl esters of ~-hydroxy alkanoic acids, using a solid insoluble particulate acidic catalyst in a liquid phase heterogeneous catalyzed reaction process.
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Rl _ ~ - CH - R
or intermolecular dehydration products of said compounds, where R is alkyl,jal,ky~lene or hydrogen, R is hydroxy or alkoxy, R is hydroxy or acyloxy, provided at least one of Rl or R2 is hydroxyl by reacting a mixture of carbon monoxide and aliphatic aldehyde together with water or carboxylic acid or alkanol in a liquid reaction media at temperatures above 25C. and superatmospheric pressures using as c~alyst solid insoluble particulate acidic material having hydrogen ion-exchange capacity in excess of 0.1 milliequivalents per gram; and subsequently mechanically separating reaction media from the catalyst.
The radical "R" is determined by the aliphatic aldehyde selected for reaction. For example, when formaldehyde is used, R is hydrogen and when acetaldehyde is used, R is methyl.
The radical R is determined by the use of water or an alkyl alcohol as a reactant. For example, when water is used R is hydroxy, when ethanol is used R is ethoxy; and when isopropanol is used R i9 isopropoxy.
The radical R is determined by the selection of aliphatic organic acid reactant. For example, when no acid is used, R is hydroxy and when acetic acid is used R is acetoxy.
In particular, this invention is an improved process for the formation of a-hydroxy alkanoic acids, ~-acyloxy derivatives of alkanoic acids, and alkyl esters of ~-hydroxy alkanoic acids, using a solid insoluble particulate acidic catalyst in a liquid phase heterogeneous catalyzed reaction process.
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The improved process of this invention permits the effective use of lower reaction temperatures, times and pressures than the prior art liquid phase acid catalyzed processes for the formation of hydroxy carboxylic acids and derivatives.
The improved process of this invention permits higher acidity levels catalyzing the reaction and simultaneously reduces corrosion due to soluble strong acids.
The improved process of this invention permits a simple mechanical separation of catalyst and reaction media which promotes rapid retrieval of reaction product, omission of a catalyst removal step and ease of operation.
Detailed Description of the Invention The Catalyst The liquid phase reaction of carbon monoxide and aldehyde is promoted by using as the acid catalyst a solid insoluble particulate acidic catalyst material. The term, "insoluble" as used herein means that the catalyst is substantially insoluble in any combination of re-actants or reaction products under reaction conditions present in the practice o this invention, e.g., that substantially all of the catalyst i9 present in a separate solid phase. The description of the catalyst as "particulate" refers to its si~e being sùch that it is separable from a liquid medium by simple mechanical means. Typical catalyst particle diameters are 2.0 to 0.001 millimeters.
In general, substances capable of forming Le~is or Bronstead type acids are useful catalysts. They are characteri~ed in having their acid function available on a solid surface without releasing acidity into the liquid reaction medium. The acidity required of materials useful ., ~a377s~
as catalysts in the practice of this invention may be measured as hydrogen ion-exchange capacity. Although the catalysts or process of this invention are not based on any theory of ion-exchange, it is useful to define the acidity criteria of acceptable solid catalysts as those which have hydrogen ion-exchange capacity of at least 0.1 milliequivalents per gram.
Ion-Exchange_Resins Strong acid type cation-exchange resins in hydrogen form are use-ful catalysts in the practice of this invention. It is especially pre-ferred to use ion-exchange resins having a hydrogen-ion exchange capacity of over one milliequivalent of hydrogen per gram. Illustrative resins are those strong acid types having sulfonic acid functionality. The strong acid moiety may be pendant to a variety of polymeric backbones such as styrene-divinylbenzene or tetrafluoroethylene. The choice of polymeric backbone will depend on a variety of factors such as cost, temperature resis-tance, etc.
Inorganic Acidic Substances Natural and synthetic products such as acid-treated clays and zeo-lites have acidic properties useful in the process of this i~vention. A
great variety of clay minerals have cation-exchange capacity. Suitable classes of clay minerals are kaolinite, halloysite, smectite, illite, vermiculite, chlorite, sepiolite, attapulgite, and polygorskite (Encyclopedia Brltannica, ~ol. 4, page 700, 15th Edition; H.H. Benton, Publ., Chicago, Ill.j. The degree of cation-exchange capacity varies with the type of clay, particle size, and degree of crystallinity. Especially useful are the acid ' .~
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~L~7751~7 catalysts derived from montmorillonite and natural and synthetic mordenites. In some instances the activity of inorganic acid catalysts is increased by a calcination step.
The Reactants Carbon Monoxide The reactants may be solids, liquids or gases. It is necessary that all reactants be dissolved or dispersed in the reaction media to , assure mutual contact with each other and the catalyst.
~, Carbon monoxide may be supplied as a pure gas or as a component of a commercial product such as producer gas.
Aldehyde ~i Aldehydes useful in the preparation of hydroxy carboxylic acids li and their derivatives are aliphatic aldehydes of 1 to 20 carbon atoms ;1` which are dissolved or dispersed in the reaction media. Illustrative .~ , aldehydes are formaldehyde, acetaldehyde, isobutyraldehyde and stearic aldahyde. Where formaldehyde is the desired reactant, it may be introduced in pure form, in aqueous solution, or produced in situ from reagents such as paraformaldehyde or trioxane.
Additional Reactants Aliphatic carboxylic acids preferably containing 1 to 20 carbon atoms may be reacted with carbon monoxide and aldehyde to form a-acyloxy carboxylic acids. Illustrative of organic acids which may be introduced into the reaction media are, acetic acid, isobutyric acid, decanoic acid and stearic acid.
Glycolic acid and the condensed (self-esterified) products of glycolic acid (having an average degree of polymerization of less than three) may be reacted with formaldehyde and carbon monoxide to yield higher con-densed glycolic acids. Additional water mAy be introduced in the reaction mixture to reduce the extent of condensat$on in the glycolic acid product.
_ ~, _ ~775 7 Water may be added as a reactant to form ~-hydroxy carboxylic ;~
acids. It has been found that large proportions of water in the re-action mixture result in reduced conversion at the lower pressures or temperatures used in the process of this Invention. In some instances it is more desirable to obtain hydroxy acids by a hydrolysis of an acyloxy derivative of the corresponding hydroxy carboxylic acid.
; Alcohols, preferably alkanols, containing 1 to 20 carbon atoms may be reacted with carbon monoxide and aldehyde to form the corresponding alkyl esters of ~-hydroxy acids. Illustrative alcohols include methanol, ethanol, isopropanol, cetyl alcohol, ethylene glycol, and glycerol.
The Reaction Media The reaction of carbon monoxide and aldehyde i5 conveniently performed in any liquid media which will permit contact of the reactants.
The reaction media may be provided by inert diluents such as hydrocarbons (hexane, decane and xylene~, however, it is preferred practice to use a liquid reactant or reaction product as the reaction media. Illustrative examples of useful reaction media are acetic acid, glycolic acid and condensed (self-esterified) polyesters of glycolic acid having an average degree of polymerization of less than three.
Reaction Conditions The process must be carried out above ambient temperatures to initiate reaction. Temperatures above 25C. are generally suitable with temperatures of 100C. to 250C. being particularly preferred. The maximum operating temperature will vary depending on the specific solid insoluble catalyst. For example, strong acid ion-exchange resins with a styrene-divinylbenzene backbone have acceptable thermal stability only up to about 150C. Reduced corrosion is also an inducement to the selection of lower operating temperatures.
_ ~ _ 10775~
Reactor pressure may vary over wide limits, for example, from I.03 x 10 to 1600 x 10 Pa. Pressures in the range of 10 x 105 to 350 x 10 Pa. are generally suitable with pressures of 10 x 105 to 210 x 105 Pa., being particularly preferred. Reaction vessel pressuri7ation is rost conveniently accomplished by introductlon of excess carbon monoxide;
however, other gases inert to the reaction such as nitrogen and argon may be used.
Catalyst Concentration In general, the rate of reaction increases with increasing catalyst concentration. Since the catalysts of this invention are easily mechanically separated from the reaction media, it is advantageous to employ the solid catalyats (with associated hydrogen ion content) at much higher levels than prior art practice to achieve short reaction times, lower temperatures or lower pressures. Although the catalyst may be present in amounts as low as to provide a minimum of 0.01 mole of hydrogen-ion per mole of aldehyde, it~is advantageous to use much greater proportions of catalyst, approaching or exceeding one mole of hydrogen-ion (contained as solid catalyst) per mole of aldehyde reactant. In the operation of a continuous proces~ the maximum allowable catalyst concentration would be limited only by the weight of catalyst which may be packed into the volume of the reaction zone while preserving effective contact of reactants and practical flow ra~es.
Reactant Proportions The process of forming hydroxy carboxylic acids and derivatives is not critical with respect to the relative proportions of reactants.
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It may be performed with a stoichiometric proportion of ingredients or any combination of ingredients may be used in excess.
Process Operation Reactants and catalyst may be introduced separately or in any sequence or combination to the reactor. In addition, one or more reactants may be introduced at different locations in the reaction zone.
For example, in a continuously operated process containing a catalyst bed the addition of aldehyde may be staged throughout the reaction zone.
The process may be operated on a batch or continuous basis. The solid insoluble particulate acidic catalyst is contacted with the reactants in a liquid phase. In some cases, such as the preparation of ~lycolic acid or acetoxyacetic acid, i~ may be desirable to recirculate a portion of the reaction media to the reactor to act as a liquid reaction media for the next synthesis.
The catalyst may be introduced to the reaction zone before or during the synthesis. The catalyst should be dispersed throughout the reaction media to effectively assist contact of reactants and catalyst.
When operating the process on a continuous basis, fresh catalyst may be introduced and used catalyst simultaneously witlldrawn from the reaction zone. The wlthdrawn catàlyst may be recharged and reused if desired.
The catalyst may be introduced as small particles which are conveniently slurried or suspended in the agitated reaction mixture. Alternatively, the catalyst may assume the form of a fixed bed or fluidi~ed bed through which reactants are continuou~ly circulated.
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The reaction media is preferably agitated to assist contact of the reactants in solution with the carbon monoxide. If desired, agitation may be provided by lntroductlon of carbon monoxide into the reaction media.
At the conclusion of the reaction ~or continuously in a con- -tinuous reaction scheme), the reaction media-containing product may be separated from the catalyst. The separation may be effected by a variety o~ mechanical techniques such as decantation, filtration, floatation or centrifugation. If desired, a combination of meahanical and non-mechanical separation systems may be used. For example, the major portion of the reaction media may be decanted from the catalyst and the remaining portion then distilled to remove ~he volatile components.
The following Examples further illustrate the practice of this invention:
EXAMPLE I
This example illustrates the preparation of acetoxyacetic acid using a variety of solid insoluble acidic catalysts.
A 300 milliliter, type 316 stainless steel, magnetically stirred autoclave was used as the reaction vessel. Paraformaldehyde was used as the source of formaldehyde. The autoclave was charged with 15 grams of paraformaldehyde (equivalent to 0.5 mole CH20), 120 grams (2 moles) acetic acid and acid catalyst (as indicated in Table 1 below). The auto-clave was pressurized with carbon monoxide to an initial pressure in-dicated in the Table, sealed, and heated in an oil bath to reaction temperature. At the conclusion of the reaction period, as determined by the absence of pressure change with time, the autoclave was cooled to room temperature and the catalyst separated from the re~ction product by filtration.
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~77Sl'7 , The acetoxyacetic acid reaction product was hydrolyzed to glycolic ~ acid for purposes of analysis. The percent convers:ion was calculated as :: moles of glycolic acid x 100. Clycolic acid was determined by oxidation with moles CH20 charged an excess of hot ceric sulfate, after any unreacted formaldehyde has be~n removed, thèn a back titration with ferrous sulfate using ferroin indicator.
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EXAMPLE II
This example illustrates the reduced corrosion which results from the practice of the process of this invention.
A 300 milliliter type 316 stainless steel, magnetically stirred ,, ! j, l ~' autoclave was charged with 15 grams, (0.5 mole of CH20) of para~ormaldehyde, 2 moles of acetic acid and catalyst (see, Table below). The autoclave was pressurized with carbon noxide to 2250 p.s.i.g. (15.5 x 106 Pa.) and heated to the indicated temperature in an oil bath. At the conclusion of the reactlon the autoclave was cooled and the reaction product analyzed.
TABLE 2 ' Corrosion Analysis for the Use of Different Catalysts in the Reaction of Carbon Monoxide, Formaldehyde and ~ `
; , Acetic Acid (0.5 Moles CH 0, 2 Moles Acetic Acid) , Max. Reaction Catalyst Reactign Time, Reaction Mixture Percent -Catalyst Moles of ~1+ Temp. C. Min.Ni ppmFe ppm Conversion 2S~40.10 151 30 75 235 100 ~ AMberlyst 0.05 152 ` 30 $ 2 100 -~ XN-1011 The use of solid acidic catalysts results in reduced corrosion of the reaction vessel for the same degree of conversion of reactan~s into, acetoxy acetic acid.
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It is to be understood that althou~h the invention has been ' ~, d,escrib~d wi~h specific references and speclfic details of embodiments ~`. , ' .
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thereof, it is not to be so limited since changes and alterations : therein may be made which are within the full intended scope of this invention as defined by the appended claims.
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The improved process of this invention permits the effective use of lower reaction temperatures, times and pressures than the prior art liquid phase acid catalyzed processes for the formation of hydroxy carboxylic acids and derivatives.
The improved process of this invention permits higher acidity levels catalyzing the reaction and simultaneously reduces corrosion due to soluble strong acids.
The improved process of this invention permits a simple mechanical separation of catalyst and reaction media which promotes rapid retrieval of reaction product, omission of a catalyst removal step and ease of operation.
Detailed Description of the Invention The Catalyst The liquid phase reaction of carbon monoxide and aldehyde is promoted by using as the acid catalyst a solid insoluble particulate acidic catalyst material. The term, "insoluble" as used herein means that the catalyst is substantially insoluble in any combination of re-actants or reaction products under reaction conditions present in the practice o this invention, e.g., that substantially all of the catalyst i9 present in a separate solid phase. The description of the catalyst as "particulate" refers to its si~e being sùch that it is separable from a liquid medium by simple mechanical means. Typical catalyst particle diameters are 2.0 to 0.001 millimeters.
In general, substances capable of forming Le~is or Bronstead type acids are useful catalysts. They are characteri~ed in having their acid function available on a solid surface without releasing acidity into the liquid reaction medium. The acidity required of materials useful ., ~a377s~
as catalysts in the practice of this invention may be measured as hydrogen ion-exchange capacity. Although the catalysts or process of this invention are not based on any theory of ion-exchange, it is useful to define the acidity criteria of acceptable solid catalysts as those which have hydrogen ion-exchange capacity of at least 0.1 milliequivalents per gram.
Ion-Exchange_Resins Strong acid type cation-exchange resins in hydrogen form are use-ful catalysts in the practice of this invention. It is especially pre-ferred to use ion-exchange resins having a hydrogen-ion exchange capacity of over one milliequivalent of hydrogen per gram. Illustrative resins are those strong acid types having sulfonic acid functionality. The strong acid moiety may be pendant to a variety of polymeric backbones such as styrene-divinylbenzene or tetrafluoroethylene. The choice of polymeric backbone will depend on a variety of factors such as cost, temperature resis-tance, etc.
Inorganic Acidic Substances Natural and synthetic products such as acid-treated clays and zeo-lites have acidic properties useful in the process of this i~vention. A
great variety of clay minerals have cation-exchange capacity. Suitable classes of clay minerals are kaolinite, halloysite, smectite, illite, vermiculite, chlorite, sepiolite, attapulgite, and polygorskite (Encyclopedia Brltannica, ~ol. 4, page 700, 15th Edition; H.H. Benton, Publ., Chicago, Ill.j. The degree of cation-exchange capacity varies with the type of clay, particle size, and degree of crystallinity. Especially useful are the acid ' .~
...
.
~ ` , .
~L~7751~7 catalysts derived from montmorillonite and natural and synthetic mordenites. In some instances the activity of inorganic acid catalysts is increased by a calcination step.
The Reactants Carbon Monoxide The reactants may be solids, liquids or gases. It is necessary that all reactants be dissolved or dispersed in the reaction media to , assure mutual contact with each other and the catalyst.
~, Carbon monoxide may be supplied as a pure gas or as a component of a commercial product such as producer gas.
Aldehyde ~i Aldehydes useful in the preparation of hydroxy carboxylic acids li and their derivatives are aliphatic aldehydes of 1 to 20 carbon atoms ;1` which are dissolved or dispersed in the reaction media. Illustrative .~ , aldehydes are formaldehyde, acetaldehyde, isobutyraldehyde and stearic aldahyde. Where formaldehyde is the desired reactant, it may be introduced in pure form, in aqueous solution, or produced in situ from reagents such as paraformaldehyde or trioxane.
Additional Reactants Aliphatic carboxylic acids preferably containing 1 to 20 carbon atoms may be reacted with carbon monoxide and aldehyde to form a-acyloxy carboxylic acids. Illustrative of organic acids which may be introduced into the reaction media are, acetic acid, isobutyric acid, decanoic acid and stearic acid.
Glycolic acid and the condensed (self-esterified) products of glycolic acid (having an average degree of polymerization of less than three) may be reacted with formaldehyde and carbon monoxide to yield higher con-densed glycolic acids. Additional water mAy be introduced in the reaction mixture to reduce the extent of condensat$on in the glycolic acid product.
_ ~, _ ~775 7 Water may be added as a reactant to form ~-hydroxy carboxylic ;~
acids. It has been found that large proportions of water in the re-action mixture result in reduced conversion at the lower pressures or temperatures used in the process of this Invention. In some instances it is more desirable to obtain hydroxy acids by a hydrolysis of an acyloxy derivative of the corresponding hydroxy carboxylic acid.
; Alcohols, preferably alkanols, containing 1 to 20 carbon atoms may be reacted with carbon monoxide and aldehyde to form the corresponding alkyl esters of ~-hydroxy acids. Illustrative alcohols include methanol, ethanol, isopropanol, cetyl alcohol, ethylene glycol, and glycerol.
The Reaction Media The reaction of carbon monoxide and aldehyde i5 conveniently performed in any liquid media which will permit contact of the reactants.
The reaction media may be provided by inert diluents such as hydrocarbons (hexane, decane and xylene~, however, it is preferred practice to use a liquid reactant or reaction product as the reaction media. Illustrative examples of useful reaction media are acetic acid, glycolic acid and condensed (self-esterified) polyesters of glycolic acid having an average degree of polymerization of less than three.
Reaction Conditions The process must be carried out above ambient temperatures to initiate reaction. Temperatures above 25C. are generally suitable with temperatures of 100C. to 250C. being particularly preferred. The maximum operating temperature will vary depending on the specific solid insoluble catalyst. For example, strong acid ion-exchange resins with a styrene-divinylbenzene backbone have acceptable thermal stability only up to about 150C. Reduced corrosion is also an inducement to the selection of lower operating temperatures.
_ ~ _ 10775~
Reactor pressure may vary over wide limits, for example, from I.03 x 10 to 1600 x 10 Pa. Pressures in the range of 10 x 105 to 350 x 10 Pa. are generally suitable with pressures of 10 x 105 to 210 x 105 Pa., being particularly preferred. Reaction vessel pressuri7ation is rost conveniently accomplished by introductlon of excess carbon monoxide;
however, other gases inert to the reaction such as nitrogen and argon may be used.
Catalyst Concentration In general, the rate of reaction increases with increasing catalyst concentration. Since the catalysts of this invention are easily mechanically separated from the reaction media, it is advantageous to employ the solid catalyats (with associated hydrogen ion content) at much higher levels than prior art practice to achieve short reaction times, lower temperatures or lower pressures. Although the catalyst may be present in amounts as low as to provide a minimum of 0.01 mole of hydrogen-ion per mole of aldehyde, it~is advantageous to use much greater proportions of catalyst, approaching or exceeding one mole of hydrogen-ion (contained as solid catalyst) per mole of aldehyde reactant. In the operation of a continuous proces~ the maximum allowable catalyst concentration would be limited only by the weight of catalyst which may be packed into the volume of the reaction zone while preserving effective contact of reactants and practical flow ra~es.
Reactant Proportions The process of forming hydroxy carboxylic acids and derivatives is not critical with respect to the relative proportions of reactants.
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It may be performed with a stoichiometric proportion of ingredients or any combination of ingredients may be used in excess.
Process Operation Reactants and catalyst may be introduced separately or in any sequence or combination to the reactor. In addition, one or more reactants may be introduced at different locations in the reaction zone.
For example, in a continuously operated process containing a catalyst bed the addition of aldehyde may be staged throughout the reaction zone.
The process may be operated on a batch or continuous basis. The solid insoluble particulate acidic catalyst is contacted with the reactants in a liquid phase. In some cases, such as the preparation of ~lycolic acid or acetoxyacetic acid, i~ may be desirable to recirculate a portion of the reaction media to the reactor to act as a liquid reaction media for the next synthesis.
The catalyst may be introduced to the reaction zone before or during the synthesis. The catalyst should be dispersed throughout the reaction media to effectively assist contact of reactants and catalyst.
When operating the process on a continuous basis, fresh catalyst may be introduced and used catalyst simultaneously witlldrawn from the reaction zone. The wlthdrawn catàlyst may be recharged and reused if desired.
The catalyst may be introduced as small particles which are conveniently slurried or suspended in the agitated reaction mixture. Alternatively, the catalyst may assume the form of a fixed bed or fluidi~ed bed through which reactants are continuou~ly circulated.
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The reaction media is preferably agitated to assist contact of the reactants in solution with the carbon monoxide. If desired, agitation may be provided by lntroductlon of carbon monoxide into the reaction media.
At the conclusion of the reaction ~or continuously in a con- -tinuous reaction scheme), the reaction media-containing product may be separated from the catalyst. The separation may be effected by a variety o~ mechanical techniques such as decantation, filtration, floatation or centrifugation. If desired, a combination of meahanical and non-mechanical separation systems may be used. For example, the major portion of the reaction media may be decanted from the catalyst and the remaining portion then distilled to remove ~he volatile components.
The following Examples further illustrate the practice of this invention:
EXAMPLE I
This example illustrates the preparation of acetoxyacetic acid using a variety of solid insoluble acidic catalysts.
A 300 milliliter, type 316 stainless steel, magnetically stirred autoclave was used as the reaction vessel. Paraformaldehyde was used as the source of formaldehyde. The autoclave was charged with 15 grams of paraformaldehyde (equivalent to 0.5 mole CH20), 120 grams (2 moles) acetic acid and acid catalyst (as indicated in Table 1 below). The auto-clave was pressurized with carbon monoxide to an initial pressure in-dicated in the Table, sealed, and heated in an oil bath to reaction temperature. At the conclusion of the reaction period, as determined by the absence of pressure change with time, the autoclave was cooled to room temperature and the catalyst separated from the re~ction product by filtration.
: - :
~77Sl'7 , The acetoxyacetic acid reaction product was hydrolyzed to glycolic ~ acid for purposes of analysis. The percent convers:ion was calculated as :: moles of glycolic acid x 100. Clycolic acid was determined by oxidation with moles CH20 charged an excess of hot ceric sulfate, after any unreacted formaldehyde has be~n removed, thèn a back titration with ferrous sulfate using ferroin indicator.
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EXAMPLE II
This example illustrates the reduced corrosion which results from the practice of the process of this invention.
A 300 milliliter type 316 stainless steel, magnetically stirred ,, ! j, l ~' autoclave was charged with 15 grams, (0.5 mole of CH20) of para~ormaldehyde, 2 moles of acetic acid and catalyst (see, Table below). The autoclave was pressurized with carbon noxide to 2250 p.s.i.g. (15.5 x 106 Pa.) and heated to the indicated temperature in an oil bath. At the conclusion of the reactlon the autoclave was cooled and the reaction product analyzed.
TABLE 2 ' Corrosion Analysis for the Use of Different Catalysts in the Reaction of Carbon Monoxide, Formaldehyde and ~ `
; , Acetic Acid (0.5 Moles CH 0, 2 Moles Acetic Acid) , Max. Reaction Catalyst Reactign Time, Reaction Mixture Percent -Catalyst Moles of ~1+ Temp. C. Min.Ni ppmFe ppm Conversion 2S~40.10 151 30 75 235 100 ~ AMberlyst 0.05 152 ` 30 $ 2 100 -~ XN-1011 The use of solid acidic catalysts results in reduced corrosion of the reaction vessel for the same degree of conversion of reactan~s into, acetoxy acetic acid.
J
It is to be understood that althou~h the invention has been ' ~, d,escrib~d wi~h specific references and speclfic details of embodiments ~`. , ' .
:`
3~775:~
thereof, it is not to be so limited since changes and alterations : therein may be made which are within the full intended scope of this invention as defined by the appended claims.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of hydroxy carboxylic acids or their derivatives represented by the formula:
or intermolecular dehydration products of said compounds, where:
R is hydrogen or lower alkyl, R1 is hydroxy or lower alkoxy, R2 is hydroxy or lower alkanoyloxy, provided at least one of R1 or R2 is hydroxyl by reacting a mixture comprising carbon monoxide and an aldehyde of the formula RCHO in a liquid reaction medium of the formulae R1H or R2H wherein R, R1 and R2 are as defined, by the improvement which comprises conducting the reaction above 25°C and at superatmospheric pressure in the presence of solid insoluble particulate acidic catalyst having hydrogen ion-exchange capacity in excess of 0.1 milliequivalents per gram; and mechanically spearating reaction medium from the catalyst.
or intermolecular dehydration products of said compounds, where:
R is hydrogen or lower alkyl, R1 is hydroxy or lower alkoxy, R2 is hydroxy or lower alkanoyloxy, provided at least one of R1 or R2 is hydroxyl by reacting a mixture comprising carbon monoxide and an aldehyde of the formula RCHO in a liquid reaction medium of the formulae R1H or R2H wherein R, R1 and R2 are as defined, by the improvement which comprises conducting the reaction above 25°C and at superatmospheric pressure in the presence of solid insoluble particulate acidic catalyst having hydrogen ion-exchange capacity in excess of 0.1 milliequivalents per gram; and mechanically spearating reaction medium from the catalyst.
2. A process according to Claim 1 for preparing acetoxy acetic acid wherein the reactants comprise carbon monoxide, formaldehyde and acetic acid.
3. A process according to Claim 1 for preparing glycolic acid wherein the reactants comprise carbon monoxide, formaldehyde and water.
4. A process according to Claim 1 for preparing condensed glycolic acids wherein the reactants comprise carbon monoxide, foramldehyde and condensed polyesters of glycolic acid having a degree of polymerization of less than three.
5. A process according to Claim 1 wherein the reaction is conducted at a temperature between 100°C and 250°C.
6. A process according to Claim 1 wherein the reaction pressure is between about 10 x 105 to 350 x 105 pascals.
7. A process according to Claim 1 wherein the acidic catalyst is an ion-exchange resin having sulfonic acid func-tionality in hydrogen form with an exchange capacity of over one milliequivalent of hydrogen per gram.
8. A process according to Claim 1 wherein the acidic catalyst is an acid clay.
9. A process according to Claim 1 wherein the acidic catalyst is a zeolite.
10. A process according to Claim 1 where the catalyst is separated from the major portion of reaction medium by filtra-tion, decantation, or centrifugation.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57069175A | 1975-04-23 | 1975-04-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1077517A true CA1077517A (en) | 1980-05-13 |
Family
ID=24280665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA248,666A Expired CA1077517A (en) | 1975-04-23 | 1976-03-24 | Process for the preparation of hydroxy-carboxylic acids and derivatives |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS51127024A (en) |
| BE (1) | BE841073A (en) |
| CA (1) | CA1077517A (en) |
| DE (1) | DE2617085A1 (en) |
| FR (1) | FR2308612A1 (en) |
| GB (1) | GB1499245A (en) |
| IT (1) | IT1059478B (en) |
| NL (1) | NL7604129A (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5673042A (en) * | 1979-11-20 | 1981-06-17 | Mitsubishi Gas Chem Co Inc | Preparation of glycolic acid |
| DE3133353C2 (en) * | 1981-08-22 | 1985-07-18 | Chemische Werke Hüls AG, 4370 Marl | Process for the production of glycolic acid or its esters |
| JPS60260538A (en) * | 1984-06-07 | 1985-12-23 | Agency Of Ind Science & Technol | Preparation of glycolic acid ester |
| US5900258A (en) * | 1996-02-01 | 1999-05-04 | Zeolitics Inc. | Anti-bacterial compositions |
| US8466328B2 (en) | 2010-08-18 | 2013-06-18 | Eastman Chemical Company | Method for recovery and recycle of ruthenium homogeneous catalysts |
| US9227896B2 (en) | 2010-08-18 | 2016-01-05 | Eastman Chemical Company | Process for the separation and purification of a mixed diol stream |
| US8829248B2 (en) | 2010-08-18 | 2014-09-09 | Eastman Chemical Company | Method for recovery and recycle of ruthenium homogeneous catalysts |
| US8785686B2 (en) | 2010-09-23 | 2014-07-22 | Eastman Chemical Company | Process for recovering and recycling an acid catalyst |
| US8709376B2 (en) | 2010-09-23 | 2014-04-29 | Eastman Chemical Company | Process for recovering and recycling an acid catalyst |
| US8969632B2 (en) | 2012-03-23 | 2015-03-03 | Eastman Chemical Company | Passivation of a homogeneous hydrogenation catalyst for the production of ethylene glycol |
| US8765999B2 (en) | 2012-03-27 | 2014-07-01 | Eastman Chemical Company | Hydrocarboxylation of formaldehyde in the presence of a higher order carboxylic acid and a homogeneous catalyst |
| EP2831040A1 (en) * | 2012-03-27 | 2015-02-04 | Eastman Chemical Company | Process for recovering and recycling an acid catalyst |
| US8829234B2 (en) * | 2012-03-27 | 2014-09-09 | Eastman Chemical Company | Hydrocarboxylation of formaldehyde in the presence of a higher order carboxylic acid and heterogeneous catalyst |
| US8927766B2 (en) | 2012-03-27 | 2015-01-06 | Eastman Chemical Company | Hydrocarboxylation of methylene dipropionate in the presence of a propionic acid and a homogeneous catalyst |
| US8703999B2 (en) * | 2012-03-27 | 2014-04-22 | Eastman Chemical Company | Hydrocarboxylation of methylene dipropionate in the presence of propionic acid and a heterogeneous catalyst |
| US9114328B2 (en) | 2012-05-16 | 2015-08-25 | Eastman Chemical Company | Reactive distillation of a carboxylic acid and a glycol |
| US9040748B2 (en) | 2012-06-08 | 2015-05-26 | Eastman Chemical Company | Hydrocarboxylation of aqueous formaldehyde using a dehydrating recycle stream to decrease water concentration |
| GB201505977D0 (en) | 2015-04-08 | 2015-05-20 | Johnson Matthey Davy Technologies Ltd | Catalyst system and process |
| GB201505981D0 (en) | 2015-04-08 | 2015-05-20 | Johnson Matthey Davy Technologies Ltd | Process |
| GB201615762D0 (en) | 2016-09-16 | 2016-11-02 | Johnson Matthey Davy Technologies Ltd | Process |
-
1976
- 1976-03-24 CA CA248,666A patent/CA1077517A/en not_active Expired
- 1976-04-15 JP JP51043036A patent/JPS51127024A/en active Granted
- 1976-04-17 DE DE19762617085 patent/DE2617085A1/en active Pending
- 1976-04-20 IT IT67944/76A patent/IT1059478B/en active
- 1976-04-20 NL NL7604129A patent/NL7604129A/en not_active Application Discontinuation
- 1976-04-22 GB GB16284/76A patent/GB1499245A/en not_active Expired
- 1976-04-22 FR FR7611941A patent/FR2308612A1/en active Granted
- 1976-04-23 BE BE166419A patent/BE841073A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1499245A (en) | 1978-01-25 |
| FR2308612B1 (en) | 1979-04-20 |
| JPS51127024A (en) | 1976-11-05 |
| BE841073A (en) | 1976-10-25 |
| FR2308612A1 (en) | 1976-11-19 |
| JPS5337332B2 (en) | 1978-10-07 |
| DE2617085A1 (en) | 1976-10-28 |
| IT1059478B (en) | 1982-05-31 |
| NL7604129A (en) | 1976-10-26 |
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