Method and device for the determination of film forming amines in a liquid

Patent metadata

Field	Value
Publication number	US-11474045-B2
Application number	US-201817043001-A
Country	US
Kind code	B2
Filing date	Apr 3, 2018
Priority date	Apr 3, 2018
Publication date	Oct 18, 2022
Grant date	Oct 18, 2022

Abstract

A photometric method for determination of a concentration of a film forming amine in a liquid, including providing a buffer solution of a weak acid having a pKa≥4.5 and a strong acid having a pKa≤1; diluting an aliquot of the buffer solution with water, and determining the pH of the diluted buffer solution; adding reagent to the diluted buffer solution and measuring an initial absorbance of the diluted buffer/reagent solution; preparing a sample solution by adding liquid containing the film forming amine to an aliquot of the buffer solution and measuring the pH of the sample solution; adjusting the pH of the sample solution to match the pH of the diluted buffer solution by adding strong acid; and adding the reagent to the pH adjusted sample solution to form a colored complex, and measuring the absorbance of the resulting solution in a photometer.

First claim

The invention claimed is:

1. A method for the determination of a concentration of a film forming amine in a liquid by adding a reagent to the liquid to form a colored complex of the amine and the reagent, wherein the colored complex is measured photometrically, the method comprising the steps of:
a) Providing a buffer solution of a weak acid having a pKa≥4.5 and a strong acid having a pKa≤1;
b) Diluting an aliquot of the buffer solution with a given volume of water, and determining a pH value of said diluted buffer solution;
c) Adding a given amount of said reagent to said diluted buffer solution and measuring an initial absorbance of said diluted buffer solution containing the reagent;
d) Preparing a sample solution by adding a given volume of the liquid containing the film forming amine to an aliquot of the buffer solution and measuring a pH value of the sample solution;
e) Adjusting the pH value of the sample solution to match with the pH value of the diluted buffer solution by adding a calculated amount of the strong acid, wherein the amount of the strong acid to be added to the sample solution is calculated using a first calibration curve or an algorithm based on the formula:
log[Ac − ]=log([HAc] total /K HAc )+pH sample ,
wherein
[Ac − ] is an anion concentration of dissociated weak acid in the sample solution,
[Hac] total is a total concentration of the weak acid in the sample solution,
K HAc is an association constant of the weak acid, and
PH sample is a measured pH of the sample solution; and

f) Adding a given amount of said reagent to the pH adjusted sample solution to form the colored complex and measuring an absorbance of the pH adjusted sample solution containing the reagent and the colored complex,
wherein the concentration of the film forming amine in the liquid is calculated from the measured absorbance of the pH adjusted sample solution containing the reagent and the colored complex using a second calibration curve or an algorithm based on the formula:
[Amine]=( A sample −A o )/ f;

wherein
[Amine] is the concentration of the film forming amine in the pH adjusted sample solution,
A sample is the measured absorbance of the pH adjusted sample solution containing the reagent and the colored complex,
A o is the measured initial absorbance of the diluted buffer solution containing the reagent, and
f is a factor corresponding to a slope of the second calibration curve.

2. The method of claim 1 wherein the film forming amine is represented by the formula R—(NH—R 1 ) n —NH 2 , wherein R is an alkyl having 12 to 24 carbon atoms, R 1 is methylene or alkylene having 2 to 4 carbon atoms, and n is an integer from 0 to 7.

3. The method of claim 1 wherein the liquid is feed water or industrial water.

4. The method of claim 1 wherein the reagent is a xanthene dye.

5. The method of claim 4 wherein the xanthene dye is fluorescein, eosin, rose bengal, or Phloxine B.

6. The method of claim 5 wherein the xanthene dye is Phloxine B.

7. The method of claim 1 wherein the weak acid is acetic acid, and wherein the strong acid is hydrochloric acid.

8. The method of claim 1 wherein the pH of the diluted buffer solution is from between 2.5 to 2.9.

9. The method of claim 1 wherein the method is carried out manually or semi-automatically.

10. A device for determining an amount of a film forming amine using the method of claim 1 , wherein the device comprises:
a mixing chamber and a photometer connected to the mixing chamber;
a pH sensor provided in the mixing chamber; and
a control unit connected to the mixing chamber and the photometer and being configured to perform the steps of claim 1 ;
wherein the mixing chamber is connected to a feedstock of a strong acid and water, and further comprises an inlet line for a buffer solution, an inlet line for a processing liquid and an inlet line for a reagent solution; and
wherein the control unit comprises means for controlling an amount of the buffer solution, the processing liquid and the reagent solution supplied to the mixing chamber, as well as means for calculating and introducing an amount of the strong acid and water into the mixing chamber based on an input signal received from the pH sensor, wherein the amount of the strong acid to be added to a sample solution in the mixing chamber is calculated using a first calibration curve or an algorithm based on the formula:
log[Ac − ]=log([HAc] total /K HAc )+pH sample ,

wherein
[Ac − ] is an anion concentration of dissociated weak acid in the sample solution,
[HAc] total is a total concentration of the weak acid in the sample solution,
K HAc is an association constant of the weak acid, and
pH sample is a measured pH of the sample solution;
and wherein the control unit further comprises means for calculating an amount of a film forming amine in the processing liquid based on an input signal received from the photometer, wherein the amount of the film forming amine in the liquid is calculated from the measured absorbance of the pH adjusted sample solution containing the reagent and the colored complex using a second calibration curve or an algorithm based on the formula:
[Amine]=( A sample −A o )/ f;

wherein
[Amine] is the amount of the film forming amine in the pH adjusted sample solution,
A sample is the measured absorbance of the pH adjusted sample solution containing the reagent and the colored complex,
A o is the measured initial absorbance of the diluted buffer solution containing the reagent, and
f is a factor corresponding to a slope of the second calibration curve.

Assignees

• Framatome Gmbh

Inventors

• Ramminger Ute
• Nickel Ulrich
• Fandrich Jörg

Classifications

• G01N31/221

  for investigating pH value · CPC title

• G01N21/78

  producing a change of colour · CPC title

• G01N33/1826

  Organic contamination in water · CPC title

• Y10T436/173845

  Amine and quaternary ammonium · CPC title

• G01N31/22 Primary

  using chemical indicators (G01N31/02 takes precedence) · CPC title