CA2213745C - Byproduct stream purification in the preparation of 1,3-propanediol-based polyesters - Google Patents
Byproduct stream purification in the preparation of 1,3-propanediol-based polyesters Download PDFInfo
- Publication number
- CA2213745C CA2213745C CA002213745A CA2213745A CA2213745C CA 2213745 C CA2213745 C CA 2213745C CA 002213745 A CA002213745 A CA 002213745A CA 2213745 A CA2213745 A CA 2213745A CA 2213745 C CA2213745 C CA 2213745C
- Authority
- CA
- Canada
- Prior art keywords
- acrolein
- solution
- aqueous
- byproduct
- propanediol
- 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.)
- Expired - Fee Related
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing a 1,3-propanediol-based polyester which comprises contacting an aqueous stream containing acrolein byproduct with a base for a time effective to reduce the acrolein content of the aqueo us stream. In a specific embodiment, a poly(propylene terephthalate) preparation process comprises the steps of (a) contacting 1,3-propanediol an d terephthalic acid at elevated temperature to produce a reaction product mixture comprising a poly(propylene terephthalate) and an aqueous solution comprising acrolein; (b) removing a major portion of the aqueous solution from said reaction product mixture; (c) adding a sufficient quantity of a base to the aqueous solution to form a basic solution having a pH greater than 7.5 and maintening the basic solutio n for a time effective to lower the acrolein content thereof (d) optionally diluting the basic solution with water, and (e) optionally, biotreating the dilute basic solution. The process of the invention provides a polyester byproduct stream containing reduced levels of acrolein.
Description
BYPRODUCT STREAM PURIFICATION IN THE
PREPARATION OF 1,3-PROPANEDIOL-BASED POLYESTERS
This invention relates to the preparation of polypropylene terephthalate) ("PPT") and related copolyesters. In a specific aspect, the invention relates to the treatment of a byproduct-containing stream in a PPT preparation process.
The preparation of PPT involves the reaction of terephthalic acid and excess 1,3-propanediol (PDO) at about 250 °C under pressure to form an oligomer and water. The water is then distilled from the PPT. The major byproducts of the polymerization reaction, acrolein and allyl alcohol, are contained in solution in ,the distillate.
Although the amount of these byproducts is low, it would be desirable to further reduce the level of byproducts in the aqueous distillate especially for subsequent activated sludge treatment.
It is therefore an object of the invention to provide a process for preparing a 1,3-propanediol-based poly-esters~in which the level of acrolein byproduct in the aqueous stream distilled from the product polyester is reduced. This object is achieved by base treatment of the aqueous byproduct stream, optionally followed by biotreatment thereof.
The present invention therefore provides a process for preparing a 1,3-propanediol-based polyester, comprising contacting an aqueous stream containing acrolein byproduct with a base for a time effective to reduce the acrolein content of the aqueous stream. In a specific embodiment, the invention provides in a process QC~~.~'O.'v:HPA-MCvF_'CHE:\ t)4 ':.2U-- S-97 ' 7F;:~J ~ ~>, -~r) .'377t~141-.
+49 F39 '.>,39944Ei~:# 3 in which at least one dicarboxylic acid and 1,3-propane-diol are contacted at elevated temperature to produce a n aqueous product mixture comprising a 1,3-propanediol-based polyester and an aqueous solution of acrolein , which comprises:
' (a) removing a major portion of said aqueous solution from said aqueous product mixture;
(b) adding to the aqueous solution an amount of a bas e effective to form a basic solution havin a H
g 1G p greater than 7.5; and (c) mai:ltainirg the basic solution for a time effective to reduce the amount of acrolein therein;
(d) optionally, diluting the basic solution with water;
and 1S (e) optionally, biotreating the dilute basic sohition.
The process of the i~l:vention proz~-ides a by rodu t p c stream contair_ing reduced levels of acrolein.
The invention process involves forming a basic aqueous solution of the acrolein byproduct of the 3G condensation pclyrnerization of 1,3-propanediol and at least one dicarboxylic acid to prepare a 1,3-propane- -diol-based polyester. In addition to 1,3-propanediol, the polyester reaction product mixture can contain one or more additional diols such as ethylene glycol, 2S 1,~-bu~.anediol, 1,4-cyclohexane dimethanol and neopentyl glycol. Suitable dicarboxylic acids include for , example, terephthalic acid, isophthalic acid and 2,6-naphthaler~e dicarboxylic acid. The polyester and copolyester condensation products of such diol and diacid 3G monomers are referred to herein as 1,3-propanediol-based polyesters or PDO-based polyesters. "
Water-soluble byproducts are found in the a queous stream distilled from the PDO-based polyester reaction product mixture. The amount of typical byproducts in th e 35 aqueous distillate will generally be within th e range of AMENDED SHED
WO 96!26970 PCT/EP96/00809 about 100 to about 2500 ppm acrolein, 0.1 to 5 weight percent ally! alcohol and 0.1 to 10 weight percent PDO, based on the weight of the distillate.
The invention process involves addition of a base to the aqueous byproduct solution. The base is preferably an inorganic base, most preferably selected from alkali and alkaline earth metal hydroxides, including lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, and the corresponding carbonates and bicarbonates. The preferred base, because of its cost and effectiveness, is sodium hydroxide.
The amount of base added to the aqueous byproduct solution is that which is sufficient to impart a pH (at 25 C) of the aqueous solution of greater than 7.5, preferably greater than 8, most preferably greater than 10. For the preferred inorganic bases such as alkali and alkaline earth hydroxides, carbonates and bicarbonates, the amount added will typically be such that the weight ratio of base:acrolein is within the range of 0.01 to 20, preferably 0.1 to 10, most preferably 0.2 to 5. For a typical concentration of acrolein of up to 2500 ppm, the preferred amount of base will be up to 2.5o by weight based on the total weight of the aqueous solution, although higher levels of base can be used if desired for faster reaction and if not detrimental to subsequent biotreatment.
The temperature during the base treatment can affect the rate of disappearance of the acrolein and will generally be within the range of 0 to 50 C, preferably from 10 to 40 C. Temperatures above 50 C, i.e., near or above the boiling point of acrolein, are effective but generally to be avoided since this will increase the evaporation of acrolein. The process is effective at temperatures less than 0 °C, but treatment times may be prolonged.
After the addition of the base, the aqueous stream is held in a vessel such as a tank or pipe for a length of time to allow the acrolein to react with the base. The time will typically be from a few minutes to several days and will depend on the amount of base, the temperature, the initial concentration of acrolein and the final concentration of acrolein desired. Generally, treatment times will fall within the range of 1 to about 100 hours.
After a sufficient treatment time for reduction of the concentration of acrolein in the aqueous solution, the solution may be optionally diluted with additional aqueous fluid such as a second aqueous byproduct stream.
The treated aqueous solution can optionally be passed to a biotreatment process. Biotreatment will generally involve contact with activated sludge in an aeration basin at a temperature within the range of 1 to 40 °C, a dissolved oxygen content within the range of 0.5 to 8 mg/1, and a typical dilution ratio of 10-500:1. It is preferred that treatment with base combined with optional dilution be carried out so as to reduce the concentration of acrolein to less than 3 ppm, most preferably to less than 0.3 ppm, prior to any biotreatment.
Other treatment methods such as reverse osmosis, ultrafiltration and adsorption may be used in combination with the invention process.
The following examples will illustrate the invention.
Example 1 Treatment of PPT Byproduct Solution with NaOH
PPT byproduct solution (76.6427 g) was spiked with 0.1247 g acrolein (97a) to bring the acrolein level to about 1950 ppm by GC analysis. Two samples of this water in screw cap vials were treated with caustic. In one vial, 0.0980 g of 1N sodium hydroxide was added to WO 96/26970 PCTlEP96/00809 10.380 g of the solution. In the other, 0.2341 g of 1N
sodium hydroxide was added to 10.380 g of the solution.
The vials were sealed and allowed to stand at room temperature. The vials were sampled periodically and s 5 analyzed by gas chromatography using clean dioxane as a diluent and tetrahydrofuran as an internal standard. The results are shown in Table 1.
Example 2 Treatment of PPT Byproduct Solution with NaOH
Treatment of samples of PPT byproduct solution containing 1000 ppm acrolein was carried out essentially as in Example 1. Sodium hydroxide was then added to the solution to bring the concentration of NaOH to 1000 ppm.
The initial pH was 12.5. The sample vials were sealed, allowed to stand at room temperature and analyzed periodically for acrolein. Results are shown in Table 1.
Example 3 Treatment of Byproduct Solutions with NaOH
A simulated PPT byproduct mixture was prepared by mixing together 0.4809 g allyl alcohol, 2.6063 g 1,3-propanediol and 0.0484 g acrolein and diluting with distilled water to a final solution of 56.2798 g. Two samples of this solution in screw cap vials were treated with caustic. In sample C, 0.0964 g 1N NaOH was added to 9.9768 g solution. In sample D, 0.198 g 1N NaOH was added to 10.2325 g of the solution. The vials were sealed and allowed to stand at room temperature. Results are shown in Table 1.
PREPARATION OF 1,3-PROPANEDIOL-BASED POLYESTERS
This invention relates to the preparation of polypropylene terephthalate) ("PPT") and related copolyesters. In a specific aspect, the invention relates to the treatment of a byproduct-containing stream in a PPT preparation process.
The preparation of PPT involves the reaction of terephthalic acid and excess 1,3-propanediol (PDO) at about 250 °C under pressure to form an oligomer and water. The water is then distilled from the PPT. The major byproducts of the polymerization reaction, acrolein and allyl alcohol, are contained in solution in ,the distillate.
Although the amount of these byproducts is low, it would be desirable to further reduce the level of byproducts in the aqueous distillate especially for subsequent activated sludge treatment.
It is therefore an object of the invention to provide a process for preparing a 1,3-propanediol-based poly-esters~in which the level of acrolein byproduct in the aqueous stream distilled from the product polyester is reduced. This object is achieved by base treatment of the aqueous byproduct stream, optionally followed by biotreatment thereof.
The present invention therefore provides a process for preparing a 1,3-propanediol-based polyester, comprising contacting an aqueous stream containing acrolein byproduct with a base for a time effective to reduce the acrolein content of the aqueous stream. In a specific embodiment, the invention provides in a process QC~~.~'O.'v:HPA-MCvF_'CHE:\ t)4 ':.2U-- S-97 ' 7F;:~J ~ ~>, -~r) .'377t~141-.
+49 F39 '.>,39944Ei~:# 3 in which at least one dicarboxylic acid and 1,3-propane-diol are contacted at elevated temperature to produce a n aqueous product mixture comprising a 1,3-propanediol-based polyester and an aqueous solution of acrolein , which comprises:
' (a) removing a major portion of said aqueous solution from said aqueous product mixture;
(b) adding to the aqueous solution an amount of a bas e effective to form a basic solution havin a H
g 1G p greater than 7.5; and (c) mai:ltainirg the basic solution for a time effective to reduce the amount of acrolein therein;
(d) optionally, diluting the basic solution with water;
and 1S (e) optionally, biotreating the dilute basic sohition.
The process of the i~l:vention proz~-ides a by rodu t p c stream contair_ing reduced levels of acrolein.
The invention process involves forming a basic aqueous solution of the acrolein byproduct of the 3G condensation pclyrnerization of 1,3-propanediol and at least one dicarboxylic acid to prepare a 1,3-propane- -diol-based polyester. In addition to 1,3-propanediol, the polyester reaction product mixture can contain one or more additional diols such as ethylene glycol, 2S 1,~-bu~.anediol, 1,4-cyclohexane dimethanol and neopentyl glycol. Suitable dicarboxylic acids include for , example, terephthalic acid, isophthalic acid and 2,6-naphthaler~e dicarboxylic acid. The polyester and copolyester condensation products of such diol and diacid 3G monomers are referred to herein as 1,3-propanediol-based polyesters or PDO-based polyesters. "
Water-soluble byproducts are found in the a queous stream distilled from the PDO-based polyester reaction product mixture. The amount of typical byproducts in th e 35 aqueous distillate will generally be within th e range of AMENDED SHED
WO 96!26970 PCT/EP96/00809 about 100 to about 2500 ppm acrolein, 0.1 to 5 weight percent ally! alcohol and 0.1 to 10 weight percent PDO, based on the weight of the distillate.
The invention process involves addition of a base to the aqueous byproduct solution. The base is preferably an inorganic base, most preferably selected from alkali and alkaline earth metal hydroxides, including lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, and the corresponding carbonates and bicarbonates. The preferred base, because of its cost and effectiveness, is sodium hydroxide.
The amount of base added to the aqueous byproduct solution is that which is sufficient to impart a pH (at 25 C) of the aqueous solution of greater than 7.5, preferably greater than 8, most preferably greater than 10. For the preferred inorganic bases such as alkali and alkaline earth hydroxides, carbonates and bicarbonates, the amount added will typically be such that the weight ratio of base:acrolein is within the range of 0.01 to 20, preferably 0.1 to 10, most preferably 0.2 to 5. For a typical concentration of acrolein of up to 2500 ppm, the preferred amount of base will be up to 2.5o by weight based on the total weight of the aqueous solution, although higher levels of base can be used if desired for faster reaction and if not detrimental to subsequent biotreatment.
The temperature during the base treatment can affect the rate of disappearance of the acrolein and will generally be within the range of 0 to 50 C, preferably from 10 to 40 C. Temperatures above 50 C, i.e., near or above the boiling point of acrolein, are effective but generally to be avoided since this will increase the evaporation of acrolein. The process is effective at temperatures less than 0 °C, but treatment times may be prolonged.
After the addition of the base, the aqueous stream is held in a vessel such as a tank or pipe for a length of time to allow the acrolein to react with the base. The time will typically be from a few minutes to several days and will depend on the amount of base, the temperature, the initial concentration of acrolein and the final concentration of acrolein desired. Generally, treatment times will fall within the range of 1 to about 100 hours.
After a sufficient treatment time for reduction of the concentration of acrolein in the aqueous solution, the solution may be optionally diluted with additional aqueous fluid such as a second aqueous byproduct stream.
The treated aqueous solution can optionally be passed to a biotreatment process. Biotreatment will generally involve contact with activated sludge in an aeration basin at a temperature within the range of 1 to 40 °C, a dissolved oxygen content within the range of 0.5 to 8 mg/1, and a typical dilution ratio of 10-500:1. It is preferred that treatment with base combined with optional dilution be carried out so as to reduce the concentration of acrolein to less than 3 ppm, most preferably to less than 0.3 ppm, prior to any biotreatment.
Other treatment methods such as reverse osmosis, ultrafiltration and adsorption may be used in combination with the invention process.
The following examples will illustrate the invention.
Example 1 Treatment of PPT Byproduct Solution with NaOH
PPT byproduct solution (76.6427 g) was spiked with 0.1247 g acrolein (97a) to bring the acrolein level to about 1950 ppm by GC analysis. Two samples of this water in screw cap vials were treated with caustic. In one vial, 0.0980 g of 1N sodium hydroxide was added to WO 96/26970 PCTlEP96/00809 10.380 g of the solution. In the other, 0.2341 g of 1N
sodium hydroxide was added to 10.380 g of the solution.
The vials were sealed and allowed to stand at room temperature. The vials were sampled periodically and s 5 analyzed by gas chromatography using clean dioxane as a diluent and tetrahydrofuran as an internal standard. The results are shown in Table 1.
Example 2 Treatment of PPT Byproduct Solution with NaOH
Treatment of samples of PPT byproduct solution containing 1000 ppm acrolein was carried out essentially as in Example 1. Sodium hydroxide was then added to the solution to bring the concentration of NaOH to 1000 ppm.
The initial pH was 12.5. The sample vials were sealed, allowed to stand at room temperature and analyzed periodically for acrolein. Results are shown in Table 1.
Example 3 Treatment of Byproduct Solutions with NaOH
A simulated PPT byproduct mixture was prepared by mixing together 0.4809 g allyl alcohol, 2.6063 g 1,3-propanediol and 0.0484 g acrolein and diluting with distilled water to a final solution of 56.2798 g. Two samples of this solution in screw cap vials were treated with caustic. In sample C, 0.0964 g 1N NaOH was added to 9.9768 g solution. In sample D, 0.198 g 1N NaOH was added to 10.2325 g of the solution. The vials were sealed and allowed to stand at room temperature. Results are shown in Table 1.
' TABLE 1 Example Sample NaOH pH Hours Acrolein (ppm) 1 Untreated 0 0 1950 Treated 380 1.5 380 A
Treated 880 2 240 B
Treated 880 2 240 B
2 Untreated 0 5.6 0 1000 5.5 96 430 Treated 1000 12.5 1 13 4 <1 24 <1 12.0 96 <1 3 Untreated 0 890 Treated 380 1 80 C
Treated 760 1 160 D
ND = not detected (estimated 10 ppm) <
Example 4 Treatment of PPT Byproduct Solutions with NaOH/Ethylene Glycol PPT byproduct solution (70.428 g) was spiked with 0.1690 g acrolein to bring the acrolein level to about 2630 ppm by GC analysis and 6.58 g was transferred to a screw cap vial. To the remaining solution was added approximately 0.3 g 1N sodium hydroxide solution to give a final solution of 64.24 g with a pH of about 10 ' (sample E). Ethylene glycol was added to portions of sample E to make sample F with about l.lo ethylene glycol and sample G with about 10~ ethylene glycol. The sealed _ 7 _ samples were allowed to stand at room temperature and were analyzed by GC. The results are shown in Table 2.
The presence of added ethylene glycol does not appear to affect the results. The samples treated with sodium S 5 hydroxide show lower levels of acrolein than the untreated sample. Note that the concentration of base was lower and the initial concentration of acrolein somewhat higher than in Example 1.
Sample NaOH Hours Acrolein Conc. (ppm) Untreated 0 1 2630 Treated 190 2 280 E
Treated 190 3 280 F
Treated 170 3 450 G I
Comparative Example 5 Treatment of PPT Byproduct Solutions with Acid For comparison, PPT byproduct solution (53.1842 g) was spiked with 0.090 g acrolein to bring the acrolein level to about 2610 ppm. Three samples were prepared from this solution. Sample H containing 10.1576 g byproduct solution with 0.512 g O.1N hydrochloric acid (final pH 3). Sample I contained 9.5485 g by product solution with 0.5212 g O.1N HCl and 0.1063 g ethylene glycol. Sample J contained 9.4565 g byproduct solution with 0.4976 g O.1N HC1 and 0.5092 g ethylene glycol. The sealed vials were allowed to stand at room temperature and analyzed by GC. Results are shown in Table 3. The acid treatment, with or without added glycol, had _ g _ relatively little effect on the concentration of acrolein.
C
Sample Hours Acrolein Conc. (ppm) Untreated 0 2610 Sample H 1 1970 Sample I 1 1960 Sample J 1 1870 Example 6 Treatment of Byproduct Solution at Zower Temperature Similar to the process described in Example 3, a simulated PPT byproduct solution was prepared by mixing together 0.41 g allyl alcohol, 2.75 g 1,3-propanediol and 0.052 g acrolein and diluting with 51.69 g distilled water. To test the invention process under low-temper-ature conditions, the solution was cooled to about 1 °C.
Samples of the solution in screw cap vials were tested with caustic. In sample K, 0.12 g 1N NaOH was mixed with 10.304 g of solution. In sample L, 0.266 g 1N NaOH was mixed with 9.760 g of solution. In Sample M, 0.504 g 1N
NaOH was mixed with 9.989 g of solution. The vials were capped and stored at about 1 °C in a refrigerator.
Results are shown in Table 4.
_ g _ Sample NaOH Acrolein Conc.
(ppm) pH Hours ( m) Untreated 4.5-5 0 1120 ' 25 1110 Treated K 460 10.5-11 2 230 Treated L 1060 11.5-12 2 260 Treated M 1920 12-12.5 2 170 Example 7 Effect of Alkali Pretreatment on Byproduct Solution Biotreatability Respirometric tests were conducted to compare the oxygen utilization rates of activated sludge or biomass under various feed conditions. The oxygen utilization rate is a direct measurement of the microbial consumption rate of the waste materials. The activated sludge was taken from a chemical manufacturing plant where polyester (PET) based on ethylene glycol is produced. A byproduct solution from the synthesis of polypropylene terephthalate (PPT) containing 1000 ppm acrolein was treated with sodium hydroxide as described above in Example 2 and used as a feed. The byproduct solution from the PET plant was used as a standard feed for comparison. Acrolein was added at various levels to the PET solution to show whether it had any adverse effect on oxygen uptake rates. The results of a typical test are summarized in Table 5. Oxygen uptake rates are in millilitres of oxygen at 20 °C and atmospheric (100 kPa) pressure.
The PPT solution treated with caustic did not affect the oxygen uptake rate, while 5 to 15 ppm of acrolein reduced the rate by 29-52~ in 12 hours and 34-65~ in 28 hours. These results indicate that the caustic treatment removed the inhibitory effect of the acrolein in the PPT byproduct solution and that the organic products formed in the caustic treatment were nontoxic to the biomass.
TABhE 5 Oxygen Uptake Oxygen Uptake Feed Source at 12 Hoursa at 28 Hours Endonenous (no feed) 14 26 PET plant byproduct 85 250 stream PET plant byproduct 82 255 + caustic PPT
byproduct stream (3~ of total COD) PET byproduct stream 60 168 + 5 ppm acrolein (0.3~ of total COD) PET byproduct stream 41 88 + 15 ppm acrolein (0.9~ of total COD) COD = Chemical Oxygen Demand aMillimetres 02 at 20 C, 1 atm.
i
Treated 760 1 160 D
ND = not detected (estimated 10 ppm) <
Example 4 Treatment of PPT Byproduct Solutions with NaOH/Ethylene Glycol PPT byproduct solution (70.428 g) was spiked with 0.1690 g acrolein to bring the acrolein level to about 2630 ppm by GC analysis and 6.58 g was transferred to a screw cap vial. To the remaining solution was added approximately 0.3 g 1N sodium hydroxide solution to give a final solution of 64.24 g with a pH of about 10 ' (sample E). Ethylene glycol was added to portions of sample E to make sample F with about l.lo ethylene glycol and sample G with about 10~ ethylene glycol. The sealed _ 7 _ samples were allowed to stand at room temperature and were analyzed by GC. The results are shown in Table 2.
The presence of added ethylene glycol does not appear to affect the results. The samples treated with sodium S 5 hydroxide show lower levels of acrolein than the untreated sample. Note that the concentration of base was lower and the initial concentration of acrolein somewhat higher than in Example 1.
Sample NaOH Hours Acrolein Conc. (ppm) Untreated 0 1 2630 Treated 190 2 280 E
Treated 190 3 280 F
Treated 170 3 450 G I
Comparative Example 5 Treatment of PPT Byproduct Solutions with Acid For comparison, PPT byproduct solution (53.1842 g) was spiked with 0.090 g acrolein to bring the acrolein level to about 2610 ppm. Three samples were prepared from this solution. Sample H containing 10.1576 g byproduct solution with 0.512 g O.1N hydrochloric acid (final pH 3). Sample I contained 9.5485 g by product solution with 0.5212 g O.1N HCl and 0.1063 g ethylene glycol. Sample J contained 9.4565 g byproduct solution with 0.4976 g O.1N HC1 and 0.5092 g ethylene glycol. The sealed vials were allowed to stand at room temperature and analyzed by GC. Results are shown in Table 3. The acid treatment, with or without added glycol, had _ g _ relatively little effect on the concentration of acrolein.
C
Sample Hours Acrolein Conc. (ppm) Untreated 0 2610 Sample H 1 1970 Sample I 1 1960 Sample J 1 1870 Example 6 Treatment of Byproduct Solution at Zower Temperature Similar to the process described in Example 3, a simulated PPT byproduct solution was prepared by mixing together 0.41 g allyl alcohol, 2.75 g 1,3-propanediol and 0.052 g acrolein and diluting with 51.69 g distilled water. To test the invention process under low-temper-ature conditions, the solution was cooled to about 1 °C.
Samples of the solution in screw cap vials were tested with caustic. In sample K, 0.12 g 1N NaOH was mixed with 10.304 g of solution. In sample L, 0.266 g 1N NaOH was mixed with 9.760 g of solution. In Sample M, 0.504 g 1N
NaOH was mixed with 9.989 g of solution. The vials were capped and stored at about 1 °C in a refrigerator.
Results are shown in Table 4.
_ g _ Sample NaOH Acrolein Conc.
(ppm) pH Hours ( m) Untreated 4.5-5 0 1120 ' 25 1110 Treated K 460 10.5-11 2 230 Treated L 1060 11.5-12 2 260 Treated M 1920 12-12.5 2 170 Example 7 Effect of Alkali Pretreatment on Byproduct Solution Biotreatability Respirometric tests were conducted to compare the oxygen utilization rates of activated sludge or biomass under various feed conditions. The oxygen utilization rate is a direct measurement of the microbial consumption rate of the waste materials. The activated sludge was taken from a chemical manufacturing plant where polyester (PET) based on ethylene glycol is produced. A byproduct solution from the synthesis of polypropylene terephthalate (PPT) containing 1000 ppm acrolein was treated with sodium hydroxide as described above in Example 2 and used as a feed. The byproduct solution from the PET plant was used as a standard feed for comparison. Acrolein was added at various levels to the PET solution to show whether it had any adverse effect on oxygen uptake rates. The results of a typical test are summarized in Table 5. Oxygen uptake rates are in millilitres of oxygen at 20 °C and atmospheric (100 kPa) pressure.
The PPT solution treated with caustic did not affect the oxygen uptake rate, while 5 to 15 ppm of acrolein reduced the rate by 29-52~ in 12 hours and 34-65~ in 28 hours. These results indicate that the caustic treatment removed the inhibitory effect of the acrolein in the PPT byproduct solution and that the organic products formed in the caustic treatment were nontoxic to the biomass.
TABhE 5 Oxygen Uptake Oxygen Uptake Feed Source at 12 Hoursa at 28 Hours Endonenous (no feed) 14 26 PET plant byproduct 85 250 stream PET plant byproduct 82 255 + caustic PPT
byproduct stream (3~ of total COD) PET byproduct stream 60 168 + 5 ppm acrolein (0.3~ of total COD) PET byproduct stream 41 88 + 15 ppm acrolein (0.9~ of total COD) COD = Chemical Oxygen Demand aMillimetres 02 at 20 C, 1 atm.
i
Claims (8)
1. A process in which at least one dicarboxylic acid and 1,3-propanediol are contacted at elevated temperature to produce an aqueous product mixture comprising a 1,3-propanediol-based polyester and an aqueous solution of acrolein which comprises:
(a) removing a major portion of said aqueous solution from said aqueous product mixture;
(b) adding to the aqueous solution an amount of a base effective to form a basic solution having a pH greater than 7.5; and (c) maintaining the basic solution for a time effective to reduce the amount of acrolein therein.
(a) removing a major portion of said aqueous solution from said aqueous product mixture;
(b) adding to the aqueous solution an amount of a base effective to form a basic solution having a pH greater than 7.5; and (c) maintaining the basic solution for a time effective to reduce the amount of acrolein therein.
2. The process of claim 1 in which said basic solution has a pH greater than 10.
3. The process of claim 1 in which the base is selected from alkali and alkaline earth metal hydroxides, carbonates and bicarbonates.
4. The process of claim 3 in which the base is selected from sodium hydroxide and potassium hydroxide.
5. The process of claim 1 in which the temperature of the basic solution of step (c) is within the range of 0 to 50 °C.
6. The process of claim 1 in which step (c) is carried out over a time within the range of 1 to 100 hours.
7. The process of claim 1 which further comprises:
(d) adding an aqueous liquid to the basic solution to form a dilute solution containing less than 3 ppm acrolein and (e) subjecting the dilute basic solution to biological treatment.
(d) adding an aqueous liquid to the basic solution to form a dilute solution containing less than 3 ppm acrolein and (e) subjecting the dilute basic solution to biological treatment.
8. The process of claim 1 in which the dicarboxylic acid is selected from at least one of terephthalic acid, isophthalic acid and 2,6-naphthalene dicarboxylic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/395,231 US5459229A (en) | 1995-02-27 | 1995-02-27 | By product stream purification in the preparation of 1,3-propanediol-based polyesters |
| US395,231 | 1995-02-27 | ||
| PCT/EP1996/000809 WO1996026970A1 (en) | 1995-02-27 | 1996-02-26 | Byproduct stream purification in the preparation of 1,3-propanediol-based polyesters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2213745A1 CA2213745A1 (en) | 1996-09-06 |
| CA2213745C true CA2213745C (en) | 2006-03-21 |
Family
ID=36101523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002213745A Expired - Fee Related CA2213745C (en) | 1995-02-27 | 1996-02-26 | Byproduct stream purification in the preparation of 1,3-propanediol-based polyesters |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2213745C (en) |
-
1996
- 1996-02-26 CA CA002213745A patent/CA2213745C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2213745A1 (en) | 1996-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0812337B1 (en) | Byproduct stream purification in the preparation of 1,3-propanediol-based polyesters | |
| KR100677784B1 (en) | Treatment of Aqueous Aldehyde Waste Streams | |
| Müller et al. | Architecture of biodegradable copolyesters containing aromatic constituents | |
| Pereira et al. | Molecular interactions in aqueous biphasic systems composed of polyethylene glycol and crystalline vs. liquid cholinium-based salts | |
| CA2629888C (en) | Storage-stable aqueous solutions of chlorine dioxide and methods for preparing and using them | |
| MX166409B (en) | POLYESTERS FOR PACKAGING FOR FOOD USE AND ITS PROCEDURE FOR OBTAINING | |
| JP2012512278A (en) | Copolyester with improved tear strength | |
| KR20110112339A (en) | Copolyesters with enhanced tear strength | |
| CA2213745C (en) | Byproduct stream purification in the preparation of 1,3-propanediol-based polyesters | |
| Eubeler | Biodegradation of synthetic polymers in the aquatic environment | |
| MXPA97006480A (en) | Purification of a sub-product current in the preparation of base polyesters of 1.3-propand | |
| TW201708303A (en) | Polyester resin | |
| Abate et al. | Polyhydroxyalkanoate recovery overview: properties, characterizations, and extraction strategies | |
| US7645722B2 (en) | Aloe derived scale inhibitor | |
| US20040222154A1 (en) | Treatment of non-aqueous aldehyde waste streams | |
| Salam | Metagenomic investigations into the microbial consortia, degradation pathways, and enzyme systems involved in the biodegradation of plastics in a tropical lentic pond sediment | |
| Gomes | Plastic degrading microorganisms: towards microbial biorecycling factories | |
| US8039421B2 (en) | Process using aloe for inhibiting scale | |
| Sullivan | Tossed at Sea: Plastic Degradation in Aquatic Environments | |
| Rathod et al. | Purification of halolipase from Haloferax larsenii (KP636736): an archaeon isolated from Gujarat, India | |
| Rani et al. | Plastic degradation and its environmental implications | |
| Pedrouso Fuentes et al. | Recovery of Polyhydroxyalkanoates from Cooked Mussel Processing Wastewater at High Salinity and Acidic Conditions | |
| Ramos | PHAs from mixed cultures as biopolymers for biodegradable films and flowerpots for plant transport | |
| El-Hassan et al. | Disinfection and disinfection by-products: a nuisance in desalination technology | |
| Lee | Formation of ketoacids and AOC during ozonation in drinking water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |