Purification Of Bio Based Acrylic Acid To Crude And Glacial Acrylic Acid

Abstract

Processes for the purification of bio-based acrylic acid to crude and glacial acrylic acid are provided. The bio-based acrylic acid is produced from hydroxypropionic acid, hydroxypropionic acid derivatives, or mixtures thereof. The purification includes some or all of the following processes: extraction, drying, distillation, and melt crystallization. The produced glacial or crude acrylic acid contains hydroxypropionic, hydroxypropionic acid derivatives, or mixtures thereof as an impurity.

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         6 . A glacial acrylic acid composition produced by the steps comprising:
 a. Providing an aqueous solution of acrylic acid comprising: 1) acrylic acid; and 2) lactic acid, lactic acid derivatives, or mixtures thereof, and wherein said aqueous solution of acrylic acid is essentially free of maleic anhydride, furfural, and formic acid;   b. Extracting said aqueous solution of acrylic acid, with a solvent to produce an extract;   c. Drying said extract to produce a dried extract;   d. Distilling said dried extract to produce distilled acrylic acid composition;   e. Cooling said distilled acrylic acid composition to a temperature from about −21° C. to about 14° C. to produce crystals of acrylic acid;   f. Partially melting said crystals of acrylic acid to produce a liquid/solid mixture;   g. Decanting said liquid/solid mixture to produce a purified acrylic acid solid composition;   h. Fully melting said purified acrylic acid solid composition to produce a purified acrylic acid liquid composition; and   i. Determining the acrylic acid purity of said purified acrylic acid liquid composition, and if the purity is less than about 98 wt % acrylic acid, repeating said cooling, partially melting, decanting, and fully melting steps on the purified acrylic acid liquid composition until a purity of about 98 wt % acrylic acid is achieved and said glacial acrylic acid composition is produced.   
     
     
         7 . The composition of  claim 6 , wherein the aqueous solution of acrylic acid comprises from about 4 wt % to about 80 wt % acrylic acid. 
     
     
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         9 . The composition of  claim 6 , wherein the aqueous solution of acrylic acid comprises from about 0.001 wt % to about 50 wt % lactic acid, lactic acid derivatives, or mixtures thereof. 
     
     
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         11 . The composition of  claim 6 , wherein said solvent is selected from the group consisting of ethyl acetate, isobutyl acetate, methyl acetate, toluene, dimethyl phthalate, hexane, pentane, diphenyl ether, ethyl hexanoic acid, N-methylpyrrolidone, C6 to C10 paraffin fractions, and mixtures thereof. 
     
     
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         14 . The composition of  claim 6 , wherein said drying is performed by sorption. 
     
     
         15 . The composition of  claim 14 , wherein said sorption is performed on a solid powder selected from the group consisting of magnesium sulfate, sodium sulfate, calcium sulfate, molecular sieves, metal hydrides, reactive metals, and mixtures thereof. 
     
     
         16 . A glacial acrylic acid composition produced by the steps comprising:
 a. Providing an aqueous solution of acrylic acid comprising: 1) acrylic acid; and 2) lactic acid, lactic acid derivatives, or mixtures thereof, and wherein said aqueous solution of acrylic acid is essentially free of maleic anhydride, furfural, and formic acid;   b. Extracting said aqueous solution of acrylic acid with a solvent to produce an extract;   c. Drying said extract to produce a dried extract;   d. Distilling said dried extract to produce a distilled acrylic acid composition; and   e. Determining the acrylic acid purity of said distilled acrylic acid composition, and if the purity is less than about 98 wt % acrylic acid, repeating said distilling step on the purified acrylic acid composition until a purity of about 98 wt % acrylic acid is achieved and said glacial acrylic acid composition is produced.   
     
     
         17 . The composition of  claim 16 , wherein the aqueous solution of acrylic acid comprises from about 4 wt % to about 80 wt % acrylic acid. 
     
     
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         19 . The composition of  claim 16 , wherein the aqueous solution of acrylic acid comprises from about 0.001 wt % to about 50 wt % lactic acid, lactic acid derivatives, or mixtures thereof. 
     
     
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         21 . The composition of  claim 16 , wherein said solvent is selected from the group consisting of ethyl acetate, isobutyl acetate, methyl acetate, toluene, dimethyl phthalate, hexane, pentane, diphenyl ether, ethyl hexanoic acid, N-methylpyrrolidone, C6 to C10 paraffin fractions, and mixtures thereof. 
     
     
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         23 . The composition of  claim 16 , wherein said drying is performed by distillation. 
     
     
         24 . The composition of  claim 16 , wherein said drying is performed by sorption. 
     
     
         25 . The composition of  claim 24 , wherein said sorption is performed on a solid powder selected from the group consisting of magnesium sulfate, sodium sulfate, calcium sulfate, molecular sieves, metal hydrides, reactive metals, and mixtures thereof. 
     
     
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         49 . A glacial acrylic acid composition wherein a portion of the remaining impurities in said glacial acrylic acid composition is propanoic acid; wherein said glacial acrylic acid composition has a bio-based content greater than about 3%; and wherein said glacial acrylic acid composition is produced by the steps comprising:
 a. Providing an aqueous solution comprising lactic acid, lactic acid derivatives, or mixtures thereof, wherein said lactic acid is in monomeric form in said aqueous solution of lactic acid, lactic acid derivatives, or mixtures thereof;   b. Combining said aqueous solution of lactic acid, lactic acid derivatives, or mixtures thereof, with an inert gas to form an aqueous solution/gas blend;   c. Evaporating said aqueous solution/gas blend to produce a gaseous mixture; and   d. Dehydrating said gaseous mixture by contacting said mixture with a dehydration catalyst under a pressure of at least about 80 psig to provide an aqueous solution of acrylic acid comprising: 1) acrylic acid; and 2) lactic acid, lactic acid derivatives, or mixtures thereof, and wherein said aqueous solution of acrylic acid is essentially free of maleic anhydride, furfural, and formic acid;   e. Extracting said aqueous solution of acrylic acid, with a solvent to produce an extract;   f. Drying said extract to produce a dried extract;   g. Distilling said dried extract to produce distilled acrylic acid composition;   h. Cooling said distilled acrylic acid composition to a temperature from about −21° C. to about 14° C. to produce crystals of acrylic acid;   i. Partially melting said crystals of acrylic acid to produce a liquid/solid mixture;   j. Decanting said liquid/solid mixture to produce a purified acrylic acid solid composition;   k. Fully melting said purified acrylic acid solid composition to produce a purified acrylic acid liquid composition; and   determining the acrylic acid purity of said purified acrylic acid liquid composition, and if the purity is less than about  98  wt % acrylic acid, repeating said cooling, partially melting, decanting, and fully melting steps on the purified acrylic acid liquid composition until a purity of about  98  wt % acrylic acid is achieved and said glacial acrylic acid composition is produced.   
     
     
         50 . The composition of  claim 49 , wherein said dehydration catalyst comprises:
 a. At least one condensed phosphate anion selected from the group consisting of formulae (I), (II), and (III),
   [P n O 3n+1 ] (n+2)−   (I)
 
   [P n O 3n ] n−   (II)
 
   [P (2m+n) O (5m+3n) ] n−   (III)
 
   
       wherein n is at least 2 and m is at least 1; and
 b. At least two different cations, wherein said catalyst is essentially neutrally charged; and further, wherein the molar ratio of phosphorus to said at least two different cations is between about 0.7 and about 1.7. 
 
     
     
         51 . The composition of  claim 50 , wherein said catalyst is prepared by a method comprising mixing and heating at least two different phosphorus containing compounds, wherein each said compound is described by one of the formulae (IV) to (XXV), or any of the hydrated forms of said formulae:
   M I   y (H 3−y PO 4 )   (IV)
     M II   y (H 3−y PO 4 ) 2    (V)
     M III   y (H 3−y PO 4 ) 3    (VI)
     M IV   y (H 3−y PO 4 ) 4    (VII)
     (NH 4 ) y (H 3−y PO 4 )   (VIII)
     M II   a (OH) b (PO 4 ) c    (IX)
     M III   d (OH) e (PO 4 ) c    (X)
     M II M I PO 4    (XI)
     M III M I   3 (PO 4 ) 2    (XII)
     M IV   2 M I (PO 4 ) 3    (XIII)
     M I   z H 4−z P 2 O 7    (XIV)
     M II   v H (4−2v) P 2 O 7    (XV)
     M IV P 2 O 7    (XVI)
     (NH 4 ) z H 4−z P 2 O 7    (XVII)
     M III M I P 2 O 7    (XVIII)
     M I H w (PO 3 ) (1+w)    (XIX)
     M II H w (PO 3 ) (2+w)    (XX)
     M III H 2 (PO 3 ) (3+w)    (XXI)
     M IV H 2 (PO 3 ) (4+w)    (XXII)
     M II   g M I   h (PO 3 ) i    (XXIII)
     M III   j M I   k (PO 3 ) I    (XXIV)
     P 2 O 5    (XXV)
   wherein M I  is a monovalent cation; wherein M II  is a divalent cation; wherein M III  is a trivalent cation; wherein M IV  is a tetravalent cation; wherein y is 0, 1, 2, or 3; wherein z is 0, 1, 2, 3, or 4; wherein v is 0, 1, or 2; wherein w is 0 or any positive integer; and wherein a, b, c, d, e, f, g, h, i, j, k, and 1 are any positive integers, such that the equations: 2a=b+3c, 3d=e+3f, i=2g+h, and l=3j+k are satisfied.   
     
     
         52 . The composition of  claim 51  , wherein said method of preparation of said catalyst further comprises mixing an inert support with said phosphorus containing compounds either before, during, or after said mixing and heating of the phosphorus containing compounds, wherein said inert support comprises silicates, aluminates, carbons, metal oxides, and mixtures thereof. 
     
     
         53 . The composition of  claim 50 , wherein said catalyst is prepared by a method comprising mixing and heating:
 (a) at least one phosphorus containing compound, wherein each said compound is described by one of the formulae (IV) to (XXV), or any of the hydrated forms of said formulae:
   M I   y (H 3—y PO 4 )   (IV)
 
   M II   y (H 3−y PO 4 ) 2    (V)
 
   M III   y (H 3−y PO 4 ) 3    (VI)
 
   M IV   y (H 3−y PO 4 ) 4    (VII)
 
   (NH 4 ) y (H 3−y PO 4 )   (VII)
 
   M II   a (OH) b (PO 4 ) c    (IX)
 
   M III   d (OH) c (PO 4 ) f    (X)
 
   M II M I PO 4    (XI)
 
   M III M I   3 (PO 4 ) 2    (XII)
 
   M IV   2 M I (PO 4 ) 3    (XIII)
 
   M 1   z H 4−z P 2 O 7    (XIV)
 
   M II   v H (4−2v) P 2 O 7    (XV)
 
   M IV P 2 O 7    (XVI)
 
   (NH 4 ) z H 4−z P 2 O 7    (XVII)
 
   M III M I P 2 O 7    (XVIII)
 
   M I H w (PO 3 ) (1+w)    (XIX)
 
   M II H w (PO 3 ) (2+w)    (XX)
 
   M III H 2 (PO 3 ) (3+w)    (XXI)
 
   M IV H 2 (PO 3 ) (4+w)    (XXII)
 
   M II   g M I   h (PO 3 ) i    (XXIII)
 
   M III   j M I   k (PO 3 ) I    (XXIV)
 
   P 2 O 5    (XXV)
 
   wherein M I  is a monovalent cation; wherein M II  is a divalent cation; wherein M III  is a trivalent cation; wherein M IV  is a tetravalent cation; wherein y is 0, 1, 2, or 3; wherein z is 0, 1, 2, 3, or 4; wherein v is 0, 1, or 2; wherein w is 0 or any positive integer; and wherein a, b, c, d, e, f, g, h, i, j, k, and 1 are any positive integers, such that the equations: 2a=b+3c, 3d=e+3f, i=2g+h, and l=3j+k are satisfied; and   (b) at least one non-phosphorus containing compound selected from the group consisting of nitrate salts, carbonate salts, acetate salts, metal oxides, chloride salts, sulfate salts, and metal hydroxides, wherein each said compound is described by one of the formulae (XXVI) to (XL), or any of the hydrated forms of said formulae.
   M I NO 3    (XXVI)
 
   M II (NO 3 ) 2    (XXVII)
 
   M III (NO 3 ) 3    (XXVIII)
 
   M I   2 CO 3    (XXIX)
 
   M II CO 3    (XXX)
 
   M III   2 (CO 3 ) 3    (XXXI)
 
   (CH 3 COO)M I    (XXXII)
 
   (CH 3 COO) 2 M II    (XXXIII)
 
   (CH 3 COO) 3 M III    (XXXIV)
 
   (CH 3 COO) 4 M IV    (XXXV)
 
   M I   2 O   (XXXVI)
 
   M II O   (XXXVII)
 
   M III   2 O 3    (XXXVIII)
 
   M IV O 2    (XXXIX)
 
   M I Cl   (XXXX)
 
   M II Cl 2    (XXXXI)
 
   M III Cl 3    (XXXXII)
 
   M IV Cl 4    (XXXXIII)
 
   M I   2 SO 4    (XXXXIV)
 
   M II SO 4    (XXXXV)
 
   M III   2 (SO 4 ) 3    (XXXXVI)
 
   M IV (SO 4 ) 2    (XXXXVII)
 
   M I OH   (XXXVIII)
 
   M II (OH) 2    (XXXIX)
 
   M III (OH) 3    (XL).
 
   
     
     
         54 . The composition of  claim 53 , wherein said method of preparation of said catalyst further comprises mixing an inert support with said phosphorus containing compounds either before, during, or after said mixing and heating of the phosphorus containing compounds, wherein said inert support comprises silicates, aluminates, carbons, metal oxides, and mixtures thereof. 
     
     
         55 . The composition of  claim 51 , wherein said phosphorus containing compounds comprise Ba 2 P 2 O 7  and (KPO 3 ) n . 
     
     
         56 . The composition of  claim 53 , wherein said phosphorus containing compound comprises K 2 HPO 4  and H 3 PO 4 , and wherein said non-phosphorous containing compound comprises Ba(NO 3 ) 2 . 
     
     
         57 . A glacial acrylic acid composition wherein a portion of the remaining impurities in said glacial acrylic acid composition is propanoic acid; wherein said glacial acrylic acid composition has a bio-based content greater than about 3%; and
 wherein said glacial acrylic acid composition is produced by the steps comprising:   a. Providing an aqueous solution comprising lactic acid, lactic acid derivatives, or mixtures thereof, wherein said lactic acid is in monomeric form in said aqueous solution of lactic acid, lactic acid derivatives, or mixtures thereof;   b. Combining said aqueous solution of lactic acid, lactic acid derivatives, or mixtures thereof, with an inert gas to form an aqueous solution/gas blend;   c. Evaporating said aqueous solution/gas blend to produce a gaseous mixture; and   d. Dehydrating said gaseous mixture by contacting said mixture with a dehydration catalyst under a pressure of at least about 80 psig to provide an aqueous solution of acrylic acid comprising: 1) acrylic acid; and 2) lactic acid, lactic acid derivatives, or mixtures thereof, and wherein said aqueous solution of acrylic acid is essentially free of maleic anhydride, furfural, and formic acid;   e. Extracting said aqueous solution of acrylic acid with a solvent to produce an extract;   f. Drying said extract to produce a dried extract;   g. Distilling said dried extract to produce a distilled acrylic acid composition; and   h. Determining the acrylic acid purity of said distilled acrylic acid composition, and if the purity is less than about 98 wt % acrylic acid, repeating said distilling step on the purified acrylic acid composition until a purity of about 98 wt % acrylic acid is achieved and said glacial acrylic acid composition is produced.   
     
     
         58 . The composition of  claim 57 , wherein said dehydration catalyst comprises:
 a. At least one condensed phosphate anion selected from the group consisting of formulae (I), (II), and (III),
   [P n O 3n+1 ] (n+2)−   (I)
 
   [P n O 3n ] n−   (II)
 
   [P (2m+n) O (5m+3n) ] n−   (III)
 
   
       wherein n is at least 2 and m is at least 1; and
 b. At least two different cations, 
 
       wherein said catalyst is essentially neutrally charged; and further, wherein the molar ratio of phosphorus to said at least two different cations is between about 0.7 and about 1.7. 
     
     
         59 . The composition of  claim 58 , wherein said catalyst is prepared by a method comprising mixing and heating at least two different phosphorus containing compounds, wherein each said compound is described by one of the formulae (IV) to (XXV), or any of the hydrated forms of said formulae:
   M I   y (H 3−y PO 4 )   (IV)
     M II   y (H 3−y PO 4 ) 2    (V)
     M III   y (H 3−y PO 4 ) 3    (VI)
     M IV   y (H 3−y PO 4 ) 4    (VII)
     (NH 4 ) y (H 3−y PO 4 )   (VIII)
     M II   a (OH) b (PO 4 ) c    (IX)
     M III   d (OH) e (PO 4 ) c    (X)
     M II M I PO 4    (XI)
     M III M I   3 (PO 4 ) 2    (XII)
     M IV   2 M I (PO 4 ) 3    (XIII)
     M I   z H 4−z P 2 O 7    (XIV)
     M II   v H (4−2v) P 2 O 7    (XV)
     M IV P 2 O 7    (XVI)
     (NH 4 ) z H 4−z P 2 O 7    (XVII)
     M III M I P 2 O 7    (XVIII)
     M I H w (PO 3 ) (1+w)    (XIX)
     M II H w (PO 3 ) (2+w)    (XX)
     M III H 2 (PO 3 ) (3+w)    (XXI)
     M IV H 2 (PO 3 ) (4+w)    (XXII)
     M II   g M I   h (PO 3 ) i    (XXIII)
     M III   j M I   k (PO 3 ) I    (XXIV)
     P 2 O 5    (XXV)
   wherein M I  is a monovalent cation; wherein M II  is a divalent cation; wherein M III  is a trivalent cation; wherein M IV  is a tetravalent cation; wherein y is 0, 1, 2, or 3; wherein z is 0, 1, 2, 3, or 4; wherein v is 0, 1, or 2; wherein w is 0 or any positive integer; and wherein a, b, c, d, e, f, g, h, i, j, k, and 1 are any positive integers, such that the equations: 2a=b+3c, 3d=e+3f, i=2g+h, and l=3j+k are satisfied.   
     
     
         60 . The composition of  claim 59 , wherein said method of preparation of said catalyst further comprises mixing an inert support with said phosphorus containing compounds either before, during, or after said mixing and heating of the phosphorus containing compounds, wherein said inert support comprises silicates, aluminates, carbons, metal oxides, and mixtures thereof. 
     
     
         61 . The composition of  claim 58 , wherein said catalyst is prepared by a method comprising mixing and heating:
 (a) at least one phosphorus containing compound, wherein each said compound is described by one of the formulae (IV) to (XXV), or any of the hydrated forms of said formulae:
   M I   y (H 3−y PO 4 )   (IV)
 
   M II   y (H 3−y PO 4 ) 2    (V)
 
   M III   y (H 3−y PO 4 ) 3    (VI)
 
   M IV   y (H 3−y PO 4 ) 4    (VII)
 
   (NH 4 ) y (H 3−y PO 4 )   (VII)
 
   M II   a (OH) b (PO 4 ) c    (IX)
 
   M III   d (OH) c (PO 4 ) f    (X)
 
   M II M I PO 4    (XI)
 
   M III M I   3 (PO 4 ) 2    (XII)
 
   M IV   2 M I (PO 4 ) 3    (XIII)
 
   M 1   z H 4−z P 2 O 7    (XIV)
 
   M II   v H (4−2v) P 2 O 7    (XV)
 
   M IV P 2 O 7    (XVI)
 
   (NH 4 ) z H 4−z P 2 O 7    (XVII)
 
   M III M I P 2 O 7    (XVIII)
 
   M I H w (PO 3 ) (1+w)    (XIX)
 
   M II H w (PO 3 ) (2+w)    (XX)
 
   M III H 2 (PO 3 ) (3+w)    (XXI)
 
   M IV H 2 (PO 3 ) (4+w)    (XXII)
 
   M II   g M I   h (PO 3 ) i    (XXIII)
 
   M III   j M I   k (PO 3 ) I    (XXIV)
 
   P 2 O 5    (XXV)
 
   wherein M I  is a monovalent cation; wherein M II  is a divalent cation; wherein M III  is a trivalent cation; wherein M IV  is a tetravalent cation; wherein y is 0, 1, 2, or 3; wherein z is 0, 1, 2, 3, or 4; wherein v is 0, 1, or 2; wherein w is 0 or any positive integer; and wherein a, b, c, d, e, f, g, h, i, j, k, and 1 are any positive integers, such that the equations: 2a=b+3c, 3d=e+3f, i=2g+h, and l=3j+k are satisfied; and   (b) at least one non-phosphorus containing compound selected from the group consisting of nitrate salts, carbonate salts, acetate salts, metal oxides, chloride salts, sulfate salts, and metal hydroxides, wherein each said compound is described by one of the formulae (XXVI) to (XL), or any of the hydrated forms of said formulae.
   M I NO 3    (XXVI)
 
   M II (NO 3 ) 2    (XXVII)
 
   M III (NO 3 ) 3    (XXVIII)
 
   M I   2 CO 3    (XXIX)
 
   M II CO 3    (XXX)
 
   M III   2 (CO 3 ) 3    (XXXI)
 
   (CH 3 COO)M I    (XXXII)
 
   (CH 3 COO) 2 M II    (XXXIII)
 
   (CH 3 COO) 3 M III    (XXXIV)
 
   (CH 3 COO) 4 M IV    (XXXV)
 
   M I   2 O   (XXXVI)
 
   M II O   (XXXVII)
 
   M III   2 O 3    (XXXVIII)
 
   M IV O 2    (XXXIX)
 
   M I Cl   (XXXX)
 
   M II Cl 2    (XXXXI)
 
   M III Cl 3    (XXXXII)
 
   M IV Cl 4    (XXXXIII)
 
   M I   2 SO 4    (XXXXIV)
 
   M II SO 4    (XXXXV)
 
   M III   2 (SO 4 ) 3    (XXXXVI)
 
   M IV (SO 4 ) 2    (XXXXVII)
 
   M I OH   (XXXVIII)
 
   M II (OH) 2    (XXXIX)
 
   M III (OH) 3    (XL).
 
   
     
     
         62 . The composition of  claim 61 , wherein said method of preparation of said catalyst further comprises mixing an inert support with said phosphorus containing compounds either before, during, or after said mixing and heating of the phosphorus containing compounds, wherein said inert support comprises silicates, aluminates, carbons, metal oxides, and mixtures thereof. 
     
     
         63 . The composition of  claim 59 , wherein said phosphorus containing compounds comprise Ba 2 P 2 O 7  and (KPO 3 ) n . 
     
     
         64 . The composition of  claim 61 , wherein said phosphorus containing compound comprises K 2 HPO 4  and H 3 PO 4 , and wherein said non-phosphorous containing compound comprises Ba(NO 3 ) 2 .