WO2009140787A1

WO2009140787A1 - Process for production of glycolic acid

Info

Publication number: WO2009140787A1
Application number: PCT/CN2008/000970
Authority: WO
Inventors: Ying Sun; Hua Wang; Zhongmin Liu; Martin Philip Atkins
Original assignee: Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences; Bp P.L.C.
Priority date: 2008-05-20
Filing date: 2008-05-20
Publication date: 2009-11-26
Also published as: PL2294045T3

Abstract

A process for producing glycolic acid from carbon monoxide and formaldehyde, optionally in a solvent, using a catalyst comprising an acidic polyoxometalate compound insoluble in formaldehyde, glycolic acid and the optional solvent, wherein the insoluble acidic polyoxometalate compound has a surface area of greater than 5 m2/g and/or has a Hammett acidity value (H0) of less than -13.6.

Description

PROCESS FOR PRODUCTION OF GLYCOLIC ACID

This invention relates to the production of glycolic acid, more specifically to the production of glycolic acid by carbonylation of formaldehyde. Ethylene glycol is a high volume and widely used chemical product, one of its main uses being in the production of polyester plastics and fibres. It is widely manufactured by the hydration of ethylene oxide, which itself is made by oxidation of ethylene.

An alternative method of producing ethylene glycol that avoids the need for an ethylene derivative, and consequently the need for a steam cracker to produce ethylene, is to use Ci compounds as feedstock. Such processes include the reaction of carbon monoxide with formaldehyde, which results in the formation of glycolic acid, which can then be converted into ethylene glycol through processes such as hydrogenation, optionally after first being converted into a glycolic acid ester.

For example, He et al in Catalysis Today, 51 (1999), 127-134, describe the use of heteropolyacids as homogeneous catalysts for the carbonylation of formaldehyde or methyl formate.

US 2,152,852 and US 2,153,064 describe processes in which formaldehyde is contacted with an acidic catalyst and carbon monoxide, preferably with water, at elevated temperatures and pressures to produce glycolic acid. Inorganic and organic acids are stated to be suitable. In US 2,153,064 pressures of 5 to 1500 atmospheres and temperatures of 50 to 35O⁰C are stated to be suitable.

WO 01/49644 describes a process in which formaldehyde or a derivative thereof is reacted with carbon monoxide in the presence of an acid catalyst and a sulphone solvent, the acid catalyst having a pKa value of below -1. Halogenated sulphonic acids are stated to be preferred, although strongly acidic ion-exchange resins are also stated to be suitable as hetetogeneous catalysts.

There remains a need for an alternative process for producing glycolic acid from Ci reactants.

According to the present invention, there is provided a process for producing glycolic acid comprising contacting carbon monoxide and formaldehyde optionally in the presence of a solvent with a catalyst comprising a solid acid, characterised by the solid acid being an acidic polyoxometalate compound insoluble in formaldehyde, glycolic acid and the optional solvent, and having a surface area of greater than 5 m²/g.

Polyoxometalate compounds comprise polyoxometalate anions, which are formed from a plurality of condensed metal-oxide species. With protons as counter-ions, they exhibit Brønsted acidity. There are a number of known polyoxometalate structures, for example the Wells-Dawson, Anderson and Keggin forms. Examples of acidic polyoxometalate compounds are heteropolyacids, which include silicotungstic acid, H₄SiW₁₂O₄₀, and phosphotungstic acid H₃PW₁₂O₄₀, both of which adopt the Keggin structure. Another example is iodomolybdic acid, HsMo₆IO₂₄, which adopts the Anderson structure. A further example is a different polymorph of phosphotungstic acid which adopts the Wells-Dawson structure, H₆P₂WIgO₆₂. Polyoxometalate structures and examples of compounds with such structures are described, for example, in Catalysis for Fine Chemical Synthesis, Volume 2: Catalysis by Polyoxometalates, edited by I. Kozhevnikov, Springer- Verlag, Berlin, 2003. Such acids are generally highly soluble in water and polar organic solvents, such as alcohols, glycols, carboxylic acids, ketones and aldehydes. They can be supported on insoluble solids to produce heterogeneous catalysts, which can allow a high dispersion of heteropolyacid to be achieved. Typical supports include silica, alumina, aluminosilica, zirconia, ceria, titania, and carbon. However, in liquid phase reaction compositions there is a tendency for the polyoxometalate compounds to dissolve in the reaction mixture which, in the case of the present invention, comprises formaldehyde and glycolic acid, often in the presence of a solvent.

Polyoxometalate acids can be partially neutralised by other cations, for example ammonium, alkali-metal and alkaline-earth metal cations, some of which are insoluble in formaldehyde carbonylation reaction compositions. It has now been found that a particular class of insoluble acidic polyoxometalate salts are unexpectedly particularly active for the formaldehyde carbonylation reaction, in that their catalytic activity is not related to the number of protons associated with each polyoxometalate unit, but is instead related to the surface area of the insoluble acidic polyoxometalate compounds. In particular, compounds that have a surface area of greater than 5 m²/g, preferably greater than 10 m²/g, more preferably greater than 50 m²/g, for example greater than 100 m²/g, show surprisingly high activity. It has also been found that the activity of the insoluble acidic polyoxometalate compounds appears to be related to the acid strength of the protons, as opposed to the number of protons. In particular, insoluble polyoxometalate acid compounds having Hammett acidity values (Ho) of less than -12.8 exhibit surprisingly enhanced catalytic activity. Preferably, the H₀ value of the insoluble polyoxometate acid is less than -13.5, more preferably less than -14.0.

In one embodiment of the invention, the solid insoluble polyoxometalate acid is a caesium salt of phosphotungstic acid represented by the formula Cs_xH_3-xPW₁₂θ₄₀ where 2 < x < 3. The value of x is less than 3, as otherwise the phosphotungstic acid is completely neutralised. Where x is greater than 2, then the surface area is greater than 5 m²/g. Where x is 2.5, the catalyst is particularly active, and the surface area is in excess of 100 m²/g.

Other examples of insoluble polyoxometalate acids include potassium, barium and lead salts of the Keggin forms of phosphotungstic acid and silicotunstic acid, for example K_2.5Ho_.5PW₁₂C>₄o and (NH₄)_ZsHo₅PWi₂O_4O, which have surface areas of about 122 m²g^"! and 161 m²g^"' respectively.

The solid insoluble polyoxometalate acid can optionally be supported. This enables high dispersions of the polyoxometalate acid to be achieved, which can increase the catalyst turnover number, while its insoluble nature renders it resistant to leaching from the support. Typical supports include silica, alumina, aluminosilica, zirconia, ceria, titania, and carbon. Optionally, the support can have an ordered porous structure, as found in zeolites for example, such as those with the faujasite (FAU) structure exemplified by zeolite Y or dealuminated analogues such as USY (ultra-stable Y). Optionally, the support can comprise a mesoporous structure, such as found in the silicas or aluminosilicas SBA- 15, MCM-41 or MCM-48. Mesoporous solids are typically defined as those which comprise pores with diameters of 20 A or more. An advantage associated with mesoporous supports is that they tend to have a high surface area, which allows a high degree of dispersion and/or loading of polyoxometalate, while the large pores associated with the structure ensure the high surface area is accessible to large reagents and catalysts with low restriction to diffusion for reagents and products, and also reduced potential for pore blocking.

Caesium salts of phosphotungstic acid can be made by adding a caesium salt, for example a halide, nitrate sulphate or hydroxide salt, to a solution of phosphotungstic acid. The caesium salts are typically insoluble in water or other polar solvents, for example alcohols, and hence can be readily separated by techniques such as filtration or centrifugation. The quantity of caesium salt required will depend on the desired value of x. In the case of x = 2.5, for example, the synthesis is conducted so that 2.5 moles of caesium are added for each mole ofphosphotungstic acid present in the solution. The phosphotungstic acid is preferably in the Keggin-form, i.e. with a heteropolyanion formula Of [PW₁₂O₄₀]^3".

Supported catalysts can be prepared by first impregnating the support with a soluble source of caesium, for example by evaporating to dryness a suspension of the support in a solution of a soluble caesium salt. The anions of the soluble caesium salt are preferably readily removable from the support, for example by being easily decomposed to volatile products or being easily removed through processes such as heating or calcination. Thus, salts such as hydroxide, nitrate or carbonate salts are preferred. In one embodiment, the support is calcined in air after impregnation with the soluble caesium salt to remove the anion. After impregnation with soluble caesium salt and optional further treatment such as calcination, the support can be contacted with a phosphotungstic acid solution. Typically, the solutions used in impregnating the caesium salt and phosphotungstic acid are aqueous, but organic solvents such as an alcohol, for example ethanol, n-propanol, iso-propanol or n-butanol, can also be used. The resulting catalyst is a solid, which can be separated by techniques such as filtration or centrifugation. Insoluble salts of other polyoxometalate acids can be produced in an analogous way.

When the catalyst is supported on a support, it is resistant to leaching, and even in the presence of solvent it can be reused several times without substantial sign of deactivation. This is in contrast to catalysts formed from soluble polyoxometalates, which tend to leach and hence deactivate with repeated use.

In the process of the present invention, the catalyst is contacted with carbon monoxide and formaldehyde, optionally in the presence of a solvent. The reaction temperature is typically in the range of from 50 to 400⁰C, for example in the range of from 100 to 25O⁰C. Pressures are typically in the range of from 1 to 1000 bara (0.1 to 100 MPa), such as in the range of from 1 to 200 bara (0.1 to 20 MPa).

The process can be a liquid-phase process, in which the reaction composition comprises a solvent. In one embodiment, the solvent is a sulphone, for example 2,3,4,5- tetrahydrothiophene- 1 , 1 -dioxide, often known as sulfolane. Water can optionally be present, either as the solvent or mixed with one or more other solvents.

Liquid phase processes can be conducted in a continuous flow configuration, which in one embodiment involves feeding the components of the reaction composition, i.e. carbon monoxide, formaldehyde and optional solvent, either pre-mixed or separately, to a reactor comprising a fixed bed of catalyst, to produce a product composition which is continuously withdrawn from the reactor. Alternatively, the reaction can be conducted batch-wise, in which in one embodiment involves suspending and stirring a suspension of the catalyst in a liquid reaction composition comprising solvent and formaldehyde, with carbon monoxide being fed into the reactor under pressure. The resulting product composition can then be periodically removed from the reactor. Typically, any catalyst being removed from the reactor with the product stream is separated and fed back to the reactor to minimise catalyst loss.

The product composition comprises glycolic acid. The product composition can be treated to recover solvent and unreacted reactants, for example formaldehyde and carbon monoxide. This can be achieved by a variety of means. For example, formaldehyde and carbon monoxide can be recovered by flash separation and/or distillation.

Glycolic acid can be separated from the product composition by precipitation, for example by treatment with a salt such as a calcium salt, which converts the glycolic acid to an insoluble form which can then be separated by filtration, centrifugation or decantation. In another embodiment, the glycolic acid is treated with an alcohol, for example methanol or ethanol, to produce a glycolic acid ester which can be separated by distillation.

In one embodiment of the invention, the glycolic acid is converted to ethylene glycol. This is typically achieved by hydrogenation of the glycolic acid, or a process stream comprising glycolic acid. In a further embodiment, the glycolic acid is first converted to an ester, for example a methyl or ethyl ester by reaction with methanol or ethanol respectively, which can then be hydrogenated to recover the alcohol and produce ethylene glycol (often also referred to as mono-ethylene glycol or MEG). The hydrogenation is typically carried out catalytically, using a conventional hydrogenation catalyst for example palladium, platinum, rhodium, ruthenium, cobalt or nickel on a support such as carbon, silica or alumina. Other catalysts include mixed oxides of copper and one or more of magnesium, manganese, nickel, iron, cobalt, chromium, calcium, barium, strontium, potassium, caesium, zinc, cadmium and silver. Hydrogenation of glycolic acid or glycolic acid ester is described in US 2,285,448.

The source of carbon monoxide reactant can be a pure source of carbon monoxide, optionally comprising small quantities of impurities such as one or more of light alkanes, carbon dioxide or hydrogen. Alternatively, the carbon monoxide source can be a component of a gaseous mixture, for example syngas which is a mixture of hydrogen and carbon monoxide.

Formaldehyde reactant can be generated in situ within the reactor. For example, in one embodiment of the invention, paraformaldehyde is used as a reactant. Paraformaldehyde is a polymer of formaldehyde, which reverts to monomelic formaldehyde in the presence of polar molecules, such as water or alcohol solvents.

There now follow non-limiting examples of how the process of the present invention can be practiced. The examples are illustrated by the following Figures in which;

Figure 1 is a graph showing the yields of glycolic acid produced with supported and unsupported CS_xH_3-XPW₁₂O₄₀ catalysts.

Figure 2 is a graph showing the yields of glycolic acid produced and the Hammett acidity value of Cs_xH_3-xPW₁₂0₄o catalysts.

Figure 3 is a series of X-Ray Diffraction patterns comparing the crystal structures of the different caesium salts of phosphotungstic acid. Figure 4 is a series of X-Ray Diffraction patterns comparing the crystal structures of the supported and unsupported caesium salts of phosphotungstic acid.

Example 1 Cs₂.₅Ho_.5PWi₂0₄o was prepared by adding 2OmL of 0.1 M Cs₂CO₃ at a rate of lmL/min to 20 mL of a 0.08M solution of phosphotungstic acid hydrate, resulting in the appearance of a white precipitate. The mixture was left to stand overnight at room temperature. The resulting white powder was isolated by slow evaporation at 4O⁰C to produce a glass-like solid, which was ground to a powder before use in the catalytic experiments. Comparative Example 2

Cs₂HPW₁₂O₄₀ was prepared in the same way as Example 1, except that 12.7mL of 0.1M Cs₂CO₃ and 15.9mL of 0.08M phosphotungstic acid hydrate were used.

Comparative Example 3

CsH₂PW₁₂O₄₀ was prepared in the same way as Example 1, except that 12mL of 0.1M Cs₂CO₃ and 3OmL of 0.08M phosphotungstic acid hydrate were used.

Comparative Example 4 Cs₀.₅H_{2 5}PW₁₂θ4o was prepared in the same way as Example 1, except that 6mL of

0.1M Cs₂CO₃ and 3OmL of 0.08M phosphotungstic acid hydrate were used.

Comparative Example 5

Cs₃PW₁₂O_4O was prepared in the same way as Example 1, except that 27mL of 0.1 M Cs₂CO₃ and 22.5mL of 0.08M phosphotungstic acid hydrate were used.

Example 6

Cs_2.5Ho_.5PWi₂0₄₀ was supported on the mesoporous silica SBA- 15 by suspending 3g of SBA- 15 in 3OmL of an aqueous 0.09M Cs₂CO₃ solution, and stirring the mixture overnight at room temperature. The suspension was then dried overnight at HO⁰C. The resulting solid was then calcined in air at 55O⁰C for 4 hours.

The solid was then impregnated with polyoxometalate using the incipient wetness technique, in this case by adding a solution of 0.072 mmol phosphotungstic acid dissolved in 15mL 1-butanol, and stirring overnight at room temperature. The mixture was then dried at HO⁰C for 12 hours, and calcined in air at 55O⁰C for 4 hours. The surface area of this Cs_2.5H_0.5PWi₂0₄o/SBA-15 material was 621 m²g^"'-

Comparative Example 7

Cs₂HPW₁₂O₄₀ / SBA- 15 was prepared using the same procedure as Example 6, except that 0.09 mmol phosphotungstic acid was dissolved in the 15mL 1-butanol. Comparative Example 8

CsH₂PW₁₂O_4O/ SBA- 15 was prepared using the same procedure as Example 6, except that 0.18 mmol phosphotungstic acid was dissolved in the 15mL 1-butanol.

Comparative Example 9

Cso.₅H_2.5P Wi₂O₄₀ / SBA- 15 was prepared using the same procedure as Example 6, except that 0.36 mmol phosphotungstic acid was dissolved in the 15mL 1-butanol.

Comparative Example 10 Cs₃PWi₂0₄o/ SBA- 15 was prepared using the same procedure as Example 6, except that 0.06 mmol phosphotungstic acid was dissolved in the 15mL 1-butanol.

Example 11

Cs_{2 S}Ho _SPW₁₂O_4O supported on zeolite USY (a dealuminated form of zeolite Y) was prepared in an analogous way to the catalyst of Example 6, except that the SBA- 15 was replaced with USY.

Comparative Example 12

H₃PWi₂O_4O supported on zeolite USY was prepared by the same method as Example 11, except that the support was not pre-loaded with caesium carbonate.

Before use, catalysts were dried in a glass tube reactor at 300⁰C under vacuum for 6 hours. They were then allowed to cool and were held in dry nitrogen until required. Catalysts were tested in a batch reaction, in which 0.2g paraformaldehyde, 25g (2OmL) sulfolane, 0.12g water and Ig catalyst was added to a 10OmL stainless steel autoclave fitted with a Teflon™ liner. The autoclave was purged with CO three times, before finally being filled with CO to a pressure of 4.0 MPa (40 bara) and heated slowly to reaction temperature of 12O⁰C. Reaction was continued for 4 hours. The pressure in the autoclave at the reaction temperature is estimated as 5.4 MPa (54 bara). The resulting suspension was filtered to remove catalyst, and the reaction product filtrate was treated with 2g methanol at 7O⁰C for 2 hours to convert any glycolic acid to the corresponding methyl ester before the filtrate was analysed by gas chromatography (GC). This is required, as glycolic acid can decompose under GC conditions.

Table 1 lists the surface areas of different caesium salts of phosphotungstic acid, and compares this with catalytic activity.

Table 1 : Surface areas and activities of Cs_xH_3-xPWi₂O₄₀.

X Example Surface Area Acid Strength Glycolic Acid Yield

(m²/g) (Ho) (%)

0.5 4^a 4 -12.7 25.6

1 5 -12.7 36.5

2 2^a 5 -11.35 40

2.5 1 133 -14.52 73.5

3 5^a 152 -8.2 1.2 ^a Comparative Example

In the Figures, labels 1 to 12 correspond to Examples and Comparative Examples 1 to 12.

Figure 1 shows plots of the yield of methyl glycolate in the presence Of Cs_xH_3- _xPWi₂θ₄₀ at various x values, 20, and also methyl glycolate yields for the corresponding compounds supported on the silica SBA- 15, 21. The results demonstrate that activity of the catalysts follows the same trend when caesium salts of phosphptungstic acid (Cs_xH_3- _xPWi₂0₄o) are supported, in this case on a mesoporous silica SBA-15. Supporting the catalyst on a support improves dispersion of the active catalyst, which can improve the catalytic activity per polyoxometalate unit. Figure 1 additionally highlights the sharp increase in activity where x is between 2 and 3. Figure 2 shows the glycolic acid yield, 20, and the Hammett Acidity value (Ho), 22, as a function of x (i.e. caesium content) for the unsupported caesium salts of phosphotunstic acid (Cs_xH₃._xPWi₂O₄₀). Phosphotungstic acid is identified as 13 These results also highlight the sharp increase in activity where x is between 2 and 3, which also correlates with a sharp decrease in the Hammett Acidity value. Figures 3 and 4 show the X-ray diffraction (XRD) patterns of phosphotungstic acid, 13, some caesium salts of phosphotungstic acid, 1-5, and an SBA-15-supported caesium salt, 6. It can be seen that the overall structure for the materials is generally the same, except that the peaks are broader when caesium is present, indicating lower long-range order, and are also shifted to higher 2Θ values, indicating that the unit cell dimensions contract in the presence of caesium. The crystal structure of the supported polyoxometalate does not appear to change when supported on the silica SBA-15.

In Figure 4, the x=0.5 salt appears to be a mixture of two phases, one corresponding to phosphotungstic acid (i.e. x = 0), and one corresponding to the other caesium salts with higher x values. There is also some evidence of such a mixture in the x=l salt, but to a much lesser extent, the predominant phase being associated with the structure of the salts with higher x values.

Thus, from XRD, there does not appear to be any significant change in long-range crystal structure that could explain the unexpectedly enhanced activity of the x=2.5 salt compared, for example, to salts with x values of lower value, and it is therefore not obvious why the x=2.5 salt has such a comparatively high surface area or such a high H₀ value.

Table 2 compares the activity of Cs₂₅P Wi₂O₄₀ and H₃PW₁₂O₄₀ supported on zeolite USY after a number of re-uses. It is clear from the retention of glycolic acid yield for each use that the caesium salt of phosphotungstic acid retains its activity between each re-use. From Table 3, which shows the extent of polyoxometalate loss from the support between each use, the loss of glycolic acid yield with the supported phosphotungstic acid catalyst correlates with the extent of leaching of phosphotungstic acid from the support.

Table 2: Glycolic acid yields for re-used catalysts.

Glycolic Acid Yield (%)

Catalyst Example 1 2 3 4 5

30% Cs_{2 5}H₀₅PW / USY 11 75.6 74. 8 75.2 73.5 74.1 30% H₃PW₁₂O₄₀ / USY 12^a 79.8 21. 7 8.6 2.7 1.2

¹ Comparative Example Table 3: Cumulative loss of polyoxometalate from the support over repeated catalyst use.

Polyoxometalate Loss (%)^b

Catalyst Example 1 2 3 4 5

30% Cs_{2 5}H₀₅PW / USY 11 0 0.1 0.1 0.2 0.2 30% H₃PW₁₂O₄₀ / USY 12 79.1 85.8 87.0 87.5 87.8 ^a Comparative Example

Claims

Claims:

1. A process for producing glycolic acid comprising contacting carbon monoxide and formaldehyde, optionally in the presence of a solvent, with a catalyst comprising a solid acid, characterised by the solid acid being an acidic polyoxometalate compound insoluble in formaldehyde, glycolic acid and the optional solvent, and having a surface area of greater than 5 m²/g.

2. A process as claimed in claim 1 , in which the surface area is greater than 50 m² g^"1.

3. A process as claimed in claim 1 or claim 2, in which the Hammett acidity value (H₀) of the acidic polyoxometalate compound is less than -12.8.

4. A process for producing glycolic acid comprising contacting carbon monoxide and formaldehyde, optionally in the presence of a solvent, with a catalyst comprising a solid acid, characterised by the solid acid being an acidic polyoxometalate compound insoluble in formaldehyde, glycolic acid and the optional solvent, and having a Hammett acidity value (H₀) of less than -12.8.

5. A process as claimed in claim 4, in which the H₀ value of the acidic polyoxometalate compound is less than -14.0.

6. A process as claimed in claim 4 or claim 5, in which the surface area of the acidic polyoxometalate compound is greater than 5 m²g^"1.

7. A process as claimed in any one of claims 1 to 6, in which the solid acid is a caesium salt of the Keggin form of phosphotungstic acid with a formula OfCs_xH_3-XPW₁₂O_4O, where 2 < x < 3.

8. A process as claimed in claim 7, in which x = 2.5.

9. A process as claimed in any one of claims 1 to 8, in which the solid acid is supported.

10. A process as claimed in any one of claims 1 to 9, in which the process is a liquid phase process, the process being carried out in the presence of a solvent.

11. A process as claimed in claim 10, in which the solvent is a sulphone or a combination of a sulphone and water.

12. A process as claimed in any one of claims 1 to 11, in which the reaction temperature is in the range of from 50 to 400⁰C, and the pressure is in the range of from 1 to 1000 bara (0.1 to 100 MPa).

13. A process as claimed in any one of claims 1 to 12 in which the glycolic acid product is converted into ethylene glycol.

14. A process as claimed in claim 13, in which the glycolic acid product is converted into ethylene glycol through hydrogenation.

15. A process as claimed in claim 14, in which the glycolic acid is first converted to an ester by reaction with an alcohol before being hydrogenated to ethylene glycol.