US2015368171A1PendingUtilityA1

Process for producing polyols

52
Assignee: EASTMAN CHEM COPriority: Jan 31, 2013Filed: Jan 17, 2014Published: Dec 24, 2015
Est. expiryJan 31, 2033(~6.6 yrs left)· nominal 20-yr term from priority
Inventors:Kenneth Wayne Hampton, Jr.Eugenen H. BrownThomas K. BrownAmy K. ParisKevin S. HoweThomas Allen Puckette
C07C 29/141C07C 45/45C07C 45/75
52
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Claims

Abstract

A process for producing polyols (such as neopentyl glycol) is disclosed which comprises reacting formaldehyde and another aldehyde in the presence of a trialkylamine catalyst and a base promoter to form an Aldol condensation reaction product. The base promoter improves removal of nitrogen containing salts prior to hydrogenation of the hydroxy aldehyde to produce the polyol. The improved process also reduces trialkylamine catalyst usage, improves trialkylamine catalyst recovery, and reduces nitrogen-containing salts prior to hydrogenation.

Claims

exact text as granted — not AI-modified
1 . A process for producing a polyol comprising:
 contacting formaldehyde and another aldehyde in the presence of an amine catalyst and a base promoter under Aldol condensation conditions to produce hydroxy aldehyde; and   hydrogenating the hydroxy aldehyde to form a polyol.   
     
     
         2 . The process according to  claim 1 , further comprising purifying said hydroxy aldehyde prior to hydrogenation and recovering said amine catalyst. 
     
     
         3 . The process according to  claim 1 , wherein the polyol comprises propylene glycol, ethylene glycol, dipropylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, triethanolamine, or glycerol. 
     
     
         4 . The process according to  claim 1 , wherein the hydroxy aldehyde comprises 3-hydroxypropanal, dimethylolethanal, trimethylolethanal (pentaerythrital), 3-hydroxybutanal (acetaldol), 3-hydroxy-2-ethylhexanal (butyl aldol), 3-hydroxy-2-methylpentanal (propyl aldol), 2-methylolpropanal, 2,2-dimethylolpropanal, 3-hydroxy-2-methylbutanal, 3-hydroxypentanal, 2-methylolbutanal, 2,2-dimethylolbutanal, or hydroxypivaldehyde. 
     
     
         5 . The process according to  claim 1 , wherein said another aldehyde comprises formaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde (isovaleraldehyde), 2,2-dimethylpropionaldehyde (pivalinaldehyde), caproaldehyde, 2-methylvaleraldehyde, 3-methylvaleraldehyde, 4-methylvaleraldehyde, 2-ethylbutyraldehyde, 2,2-dimethylbutyraldehyde, 3,3-dimethylbutyraldehyde, caprylic aldehyde, capric aldehyde, or glutaraldehyde. 
     
     
         6 . The process according to  claim 1 , wherein the amine catalyst is triethylamine, tri-n-propylamine, tri-n-butylamine, trimethlyamine, or mixtures thereof. 
     
     
         7 . The process according to  claim 1 , wherein the base promoter comprises a carbonate, a hydrogen carbonate, or a hydroxide, or mixtures thereof of an alkali metal or alkaline earth metal. 
     
     
         8 . The process according to  claim 7 , wherein the base promoter is Na 2 CO 3 , K 2 CO 3 , CaCO 3 , NaHCO 3 , KHCO 3 , NaOH, KOH, Ca(OH) 2 , or combinations thereof. 
     
     
         9 . A process for producing neopentyl glycol comprising:
 contacting formaldehyde and isobutyraldehyde in the presence of an amine catalyst and a base promoter under Aldol condensation conditions to produce hydroxypivaldehyde; and   hydrogenating the hydroxypivaldehyde to form neopentyl glycol.   
     
     
         10 . The process according to  claim 9 , further comprising purifying said hydroxypivaldehyde prior to hydrogenation and recovering said catalyst. 
     
     
         11 . The process according to  claim 9 , wherein the amine catalyst is triethylamine, tri-n-propylamine, tri-n-butylamine, trimethlyamine, or mixtures thereof. 
     
     
         12 . The process according to  claim 9 , wherein the base promoter comprises a carbonate, a hydrogen carbonate, or a hydroxide, or mixtures thereof of an alkali metal or alkaline earth metal. 
     
     
         13 . The process according to  claim 12 , wherein the base promoter is Na 2 CO 3 , K 2 CO 3 , CaCO 3 , NaHCO 3 , KHCO 3 , NaOH, KOH, Ca(OH) 2 , or combinations thereof. 
     
     
         14 . A process for producing a hydroxy aldehyde comprising:
 contacting formaldehyde and another aldehyde in the presence of an amine catalyst and a base promoter under Aldol condensation conditions to produce hydroxy aldehyde.   
     
     
         15 . The process according to  claim 14 , further comprising purifying said hydroxy aldehyde and recovering said catalyst. 
     
     
         16 . The process according to  claim 14 , wherein the hydroxy aldehyde comprises 3-hydroxypropanal, dimethylolethanal, trimethylolethanal (pentaerythrital), 3-hydroxybutanal (acetaldol), 3-hydroxy-2-ethylhexanal (butyl aldol), 3-hydroxy-2-methylpentanal (propyl aldol), 2-methylolpropanal, 2,2-dimethylolpropanal, 3-hydroxy-2-methylbutanal, 3-hydroxypentanal, 2-methylolbutanal, 2,2-dimethylolbutanal, or hydroxypivaldehyde. 
     
     
         17 . The process according to  claim 14 , wherein said another aldehyde comprises formaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde (isovaleraldehyde), 2,2-dimethylpropionaldehyde (pivalinaldehyde), caproaldehyde, 2-methylvaleraldehyde, 3-methylvaleraldehyde, 4-methylvaleraldehyde, 2-ethylbutyraldehyde, 2,2-dimethylbutyraldehyde, 3,3-dimethylbutyraldehyde, caprylic aldehyde, capric aldehyde, or glutaraldehyde. 
     
     
         18 . The process according to  claim 14 , wherein the amine catalyst is triethylamine, tri-n-propylamine, tri-n-butylamine, trimethlyamine, or mixtures thereof. 
     
     
         19 . The process according to  claim 14 , wherein the base promoter comprises a carbonate, a hydrogen carbonate, or a hydroxide, or mixtures thereof of an alkali metal or alkaline earth metal. 
     
     
         20 . The process according to  claim 19 , wherein the base promoter is Na 2 CO 3 , K 2 CO 3 , CaCO 3 , NaHCO 3 , KHCO 3 , NaOH, KOH, Ca(OH) 2 , or combinations thereof. 
     
     
         21 . The process according to  claim 1 , wherein the contacting of formaldehyde and another aldehyde is carried out in an Aldol reactor, wherein the base promoter is added to the Aldol reactor. 
     
     
         22 . The process according to  claim 1 , wherein the contacting of formaldehyde and another aldehyde is carried out in an Aldol reactor, wherein the base promoter is added to the formaldehyde upstream of the Aldol reactor. 
     
     
         23 . The process according to  claim 1 , wherein the contacting of formaldehyde and another aldehyde causes the formation one or more amine salts. 
     
     
         24 . The process according to  claim 23 , wherein the base promoter is present in an amount sufficient to achieve dissociation of the amine salts. 
     
     
         25 . The process according to  claim 23 , wherein the base promoter is present in an amount that is less than 10 weight percent excess compared to the weight percent of the amine salts. 
     
     
         26 . The process according to  claim 1 , wherein the contacting of formaldehyde and another aldehyde is carried out in an Aldol reactor, wherein the base promoter is present in the Aldol reactor in an amount of about 500 ppm to about 3000 ppm by weight. 
     
     
         27 . The process according to  claim 1 , wherein the contacting of formaldehyde and another aldehyde is carried out in a homogeneous reaction mixture. 
     
     
         28 . The process according to  claim 1 , wherein the another aldehyde is isobutyralaldehyde, the amine catalyst is trimethylamine, and the alkaline additive is NaOH. 
     
     
         29 . The process according to  claim 1 , wherein the contacting of formaldehyde and another aldehyde is carried out at a temperature in the range of from about 20° C., to about 150° C., a pressure in the range from about 5 psig to about 100 psig, and a total reaction time in the range of from about 30 minutes to about 2 hours. 
     
     
         30 . The process according to  claim 1 , wherein the process is a continuous process. 
     
     
         31 . The process according to  claim 14 , wherein the contacting of formaldehyde and another aldehyde is carried out in an Aldol reactor, wherein the base promoter is added to the Aldol reactor or to the formaldehyde upstream of the Aldol reactor. 
     
     
         32 . The process according to  claim 14 , wherein the contacting of formaldehyde and another aldehyde causes the formation one or more amine salts. 
     
     
         33 . The process according to  claim 32 , wherein the base promoter is present in an amount sufficient to achieve dissociation of the amine salts. 
     
     
         34 . The process according to  claim 32 , wherein the base promoter is present in an amount that is less than 10 weight percent excess compared to the weight percent of the amine salts. 
     
     
         35 . The process according to  claim 14 , wherein the contacting of formaldehyde and another aldehyde is carried out in an Aldol reactor, wherein the base promoter is present in the Aldol reactor in an amount of about 500 ppm to about 3000 ppm by weight. 
     
     
         36 . The process according to  claim 14 , wherein the another aldehyde is isobutyralaldehyde, the amine catalyst is trimethylamine, and the alkaline additive is NaOH. 
     
     
         37 . The process according to  claim 14 , wherein the contacting of formaldehyde and another aldehyde is carried out at a temperature in the range of from about 20° C. to about 150° C., a pressure in the range from about 5 psig to about 100 psig, and a total reaction time in the range of from about 30 minutes to about 2 hours. 
     
     
         38 . The process according to  claim 15 , wherein the purifying is by distillation and produces an overhead stream, wherein the contacting of formaldehyde and another aldehyde is carried out in an Aldol reactor, wherein at least a portion of said overhead stream is recycled back to the Aldol reactor, wherein the overhead stream comprises at least a portion of the amine catalyst. 
     
     
         39 . A process comprising:
 conducting an Aldol condensation reaction in an Aldol reactor containing an amine catalyst to thereby produce a reaction mixture comprising a hydroxy aldehyde, wherein one or more amine salts are produced during the Aldol condensation reaction; and   contacting the amine salts with a base to thereby cause dissociation of at least a portion of the amine salts.   
     
     
         40 . The process according to  claim 39 , wherein the base is added to the Aldol reactor. 
     
     
         41 . The process according to  claim 39 , wherein the base is added upstream of the Aldol reactor. 
     
     
         42 . The process according to  claim 39 , wherein the base is added in an amount that is less than 10 weight percent excess compared to the weight percent of the amine salts. 
     
     
         43 . The process according to  claim 39 , wherein the base is added in an amount of about 500 ppm to about 3000 ppm based on the weight of the reaction mixture. 
     
     
         44 . The process according to  claim 39 , wherein the amine catalyst is triethylamine, tri-n-propylamine, tri-n-butylamine, trimethlyamine, or mixtures thereof. 
     
     
         45 . The process according to  claim 39 , wherein the base comprises a carbonate, a hydrogen carbonate, or a hydroxide of an alkali metal or alkaline earth metal. 
     
     
         46 . The process according to  claim 39 , wherein the base is Na 2 CO 3 , K 2 CO 3 , CaCO 3 , NaHCO 3 , KHCO 3 , NaOH, KOH, Ca(OH) 2 , or combinations thereof. 
     
     
         47 . The process according to  claim 39 , wherein the hydroxy aldehyde comprises 3-hydroxypropanal, dimethylolethanal, trimethylolethanal (pentaerythrital), 3-hydroxybutanal (acetaldol), 3-hydroxy-2-ethylhexanal (butyl aldol), 3-hydroxy-2-methylpentanal (propyl aldol), 2-methylolpropanal, 2,2-dimethylolpropanal, 3-hydroxy-2-methylbutanal, 3-hydroxypentanal, 2-methylolbutanal, 2,2-dimethylolbutanal, or hydroxypivaldehyde. 
     
     
         48 . The process according to  claim 39 , wherein the amine catalyst is trimethylamine, the base is NaOH, and the hydroxy aldehyde is hydroxypivaldehyde. 
     
     
         49 . The process according to  claim 39 , wherein the Aldol condensation reaction includes contacting formaldehyde and another aldehyde with the amine catalyst. 
     
     
         50 . The process according to  claim 49 , wherein the another aldehyde comprises formaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde (isovaleraldehyde), 2,2-dimethylpropionaldehyde (pivalinaldehyde), caproaldehyde, 2-methylvaleraldehyde, 3-methylvaleraldehyde, 4-methylvaleraldehyde, 2-ethylbutyraldehyde, 2,2-dimethylbutyraldehyde, 3,3-dimethylbutyraldehyde, caprylic aldehyde, capric aldehyde, or glutaraldehyde. 
     
     
         51 . The process according to  claim 49 , wherein the another aldehyde is isobutyralaldehyde. 
     
     
         52 . The process according to  claim 39 , further comprising purifying at least a portion of the reaction mixture in a purification zone to thereby produce a purified product comprising at least a portion of the hydroxy aldehyde. 
     
     
         53 . The process according to  claim 52 , further comprising hydrogenating the purified product to form a polyol. 
     
     
         54 . The process according to  claim 53 , wherein the polyol is neopentyl glycol. 
     
     
         55 . The process according to  claim 53 , wherein the amine catalyst is trimethylamine, the base is NaOH, and the hydroxy aldehyde is hydroxypivaldehyde, and the polyol is neopentyl glycol. 
     
     
         56 . The process according to  claim 52 , wherein the purifying is by distillation and produces an overhead stream, wherein at least a portion of said overhead stream is recycled back to the Aldol reactor, wherein the overhead stream comprises at least a portion of the amine catalyst. 
     
     
         57 . The process according to  claim 52 , further comprising measuring the sodium and nitrogen content of the purified product, further comprising controlling the amount of the base contacted with the amine salt based on the measured sodium and nitrogen content of the purified product. 
     
     
         58 . The process according to  claim 39 , wherein the Aldol condensation reaction is carried out at a temperature in the range of from about 20° C. to about 150° C., a pressure in the range from about 5 psig to about 100 psig, and a total reaction time in the range of from about 30 minutes to about 2 hours. 
     
     
         59 . The process according to  claim 39 , wherein the reaction mixture is homogeneous. 
     
     
         60 . The process according to  claim 39 , wherein the process is continuous. 
     
     
         61 . The process according to  claim 39 , wherein the Aldol condensation reaction includes contacting formaldehyde and another aldehyde with the amine catalyst, wherein the Aldol condensation reaction is carried out at a temperature in the range of from about 20° C. to about 150° C., a pressure in the range from about 5 psig to about 100 psig, and a total reaction time in the range of from about 30 minutes to about 2 hours, further comprising purifying at least a portion of the reaction mixture in a purification zone to thereby produce a purified product comprising at least a portion of the hydroxy aldehyde, further comprising hydrogenating the purified product to form a polyol, wherein the hydroxy aldehyde is hydroxypivaldehyde and the polyol is neopentyl glycol. 
     
     
         62 . The process according to  claim 61 , wherein the amine catalyst is triethylamine, tri-n-propylamine, tri-n-butylamine, trimethlyamine, or mixtures thereof, wherein the base comprises a carbonate, a hydrogen carbonate, or a hydroxide of an alkali metal or alkaline earth metal. 
     
     
         63 . The process according to  claim 61 , wherein the amine catalyst is trimethylamine and the base is NaOH.

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