Process for reducing propylene chlorohydrin in hydroxypropylated products

Patent metadata

Field	Value
Publication number	US-10626192-B2
Application number	US-201715584154-A
Country	US
Kind code	B2
Filing date	May 2, 2017
Priority date	May 2, 2017
Publication date	Apr 21, 2020
Grant date	Apr 21, 2020

Abstract

A method of reducing the amount propylene chlorohydrin produced in a reaction to make a hydroxypropylated/crosslinked starch comprising removing residual propylene oxide from alkaline slurry. The residual propylene oxide is removed by the dewatering the alkaline slurry or by washing the starch in slurry at a pH of around 10. The starch is then neutralized in an acid solution and recovered from the second slurry and may or may not be washed, depending on whether the slurry while at pH around 10 to make a hydroxypropylated/crosslinked starch having less than 1 ppm propylene chlorohydrin.

First claim

What is claimed is:

1. A method of making a hydroxypropylated/phosphate-crosslinked starch having a propylene chlorohydrin level of less than 1 ppm comprising:
a) obtaining an aqueous slurry having pH greater than 11 and a hydroxypropylated-phosphate-crosslinked starch by reacting in either order propylene oxide and phosphorous oxychloride with a starch;
b) adding an acid to the slurry to reduce the pH of the slurry from greater than 11 to between about 9.0 and about 10.4;
c) washing the slurry with a washing liquid at the pH between about 9.0 and about 10.4 to wash the hydroxypropylated/phosphate-crosslinked; and
d) neutralizing the washed hydroxypropylated/phosphate-crosslinked starch with sufficient acid to further reduce the pH of the slurry to less than 7.5.

2. The method of claim 1 wherein the pH of step b) is reduced to between 9.4 and 10.3.

3. The method of claim 1 wherein the pH of step b) is reduced to between 9.8 and 10.2.

4. The method of claim 1 wherein the washing liquid is added to the slurry in a ratio of between about 0.75:1 to about 6:1 by weight of liquid to starch.

5. The method of claim 1 wherein the washing liquid is added to the slurry in amount of between about 0.8:1 and about 1:1 by weight of liquid to starch.

6. The method of claim 1 wherein the pH is lowered from greater than 11 to between 9 and 10.4 over the period of about 1 hour.

7. The method of claim 1 wherein the acid used in steps b) and d) does not comprise chloride ions.

8. The method of claim 1 wherein the hydroxypropylated/phosphate-crosslinked starch is held in at pH of between 9.0 and 10.4 for between 1 and 24 hours.

9. A method of reducing the amount of propylene chlorohydrin produced in a reaction to make a hydroxypropylated or hydroxypropylated/crosslinked starch comprising:
a) mixing starch, water, and salt to make starch slurry;
b) adding sufficient base to the starch slurry to raise the pH of the slurry to greater than 11
c) adding a propylene oxide to the starch slurry to form a hydroxypropylated starch slurry;
d) optionally adding a crosslinking agent to the hydroxypropylated starch slurry to form a hydroxypropylated/crosslinked starch slurry;
e) adding an acid that does not comprise chloride ions to the hydroxypropylated or hydroxypropylated/crosslinked starch slurry in an amount sufficient to reduce the pH of hydroxypropylated or hydroxypropylated/crosslinked starch slurry to between 9.0 and 10.4;
f) washing the starch in the hydroxypropylated or hydroxypropylated/crosslinked starch slurry in water in amount of 0.8 to 1:1 by weight of the starch;
g) neutralizing the washed starch with sufficient acid to further reduce the pH of the slurry to less than 7.5;
h) dewatering the slurry to recover the hydroxypropylated or hydroxypropylated/crosslinked starch.

10. A method of making a hydroxypropylated/phosphate-crosslinked starch having a propylene chlorohydrin level of less than 1 ppm comprising:
a) obtaining an aqueous slurry having pH greater than 11 and a hydroxypropylated-phosphate-crosslinked starch by reacting in either order propylene oxide and phosphorous oxychloride with a starch;
b) adding an acid to the slurry the pH of the slurry from greater than about 11 to between about 9.0 and about 10.4;
b) dewatering the slurry to form hydroxypropylated/phosphate-crosslinked starch cake;
c) suspending the hydroxypropylated/phosphate-crosslinked starch cake in a liquid to form a second starch slurry;
d) in either order washing the second starch slurry and adding sufficient acid to the second slurry to reduce its pH to less than 7.5.

11. The method of claim 10 wherein the pH of step b) is reduced to between 9.4 and 10.3.

12. The method of claim 10 wherein the pH of step b) is reduced to between 9.8 and 10.2.

13. The method of claim 10 wherein the pH is lowered from greater than 11 to between 9 and 10.4 over the period of about 1 hour.

14. The method of claim 10 wherein the acid used in steps b) and d) does not comprise chloride ions.

15. The method of claim 10 wherein the hydroxypropylated/phosphate-crosslinked starch is held in at pH of between 9.0 and 10.4 for between 1 and 24 hours.

16. The method of claim 10 wherein the hydroxypropylated/phosphate-crosslinked starch cake is held at pH of between 9.0 and 10.4 for between 1 and 24 hours before being suspended to form the second slurry.

17. The method of claim 10 wherein the second slurry is held for between 1 and 24 hours before adding the acid in step d).

18. A method of making a hydroxypropylated hydrocolloid having a propylene chlorohydrin level of less than 1 ppm comprising:
a) adding an acid that does not comprise chloride ions to a slurry comprising a hydroxypropylated starch having pH greater than 11 to reduce the pH of the slurry to between about 9.0 and about 10.4;
b) washing the slurry with a washing liquid;
c) neutralizing the washed starch with sufficient acid to further reduce the pH of the slurry to less than 7.5.

Assignees

• Corn Products Dev Inc

Inventors

• Adeosun John
• Borkar Abhay
• Wei Qian
• Pantina John
• Vaz Judith M

Classifications

• C07D303/02

  Compounds containing oxirane rings · CPC title

• C01B25/455

  containing halogen {(completely halogenated alkali metal phosphates C01D, e.g. lithium hexafluorophosphate C01D15/005)} · CPC title

• C07C19/01

  containing chlorine · CPC title

• C08B31/12

  having alkyl or cycloalkyl radicals substituted by heteroatoms, {e.g. hydroxyalkyl or carboxyalkyl starch} · CPC title

• G01N30/7206

  interfaced to gas chromatograph (interfaces in general for introducing or extracting samples to be analysed with specially adapted mass spectrometer, see H01J49/04) · CPC title