Method for preparing salt solutions having desired properties

• US 5,294,357 A
• Filed: 09/30/1991
• Issued: 03/15/1994
• Est. Priority Date: 09/30/1991
• Status: Expired due to Fees

• Current Assignee: Martin Marietta Energy Systems, Inc. (Martin Marietta Corporation)
• Original Assignee: Martin Marietta Energy Systems, Inc. (Martin Marietta Corporation)
• Inventors: Ally, Moonis R., Braunstein, Jerry
• Primary Examiner(s): Skane, Christine
• Assistant Examiner(s): OGDEN JR, NECHOLUS
• Application Number:
  US07/768,500
• Time in Patent Office: 897 Days
• Field of Search: 252/70, 252/67, 252/69, 62/101
• US Class Current: 252/67
• CPC Class Codes: C09K 5/04 the change of state being from liquid to vapour or vice versa

Abstract

The specification discloses a method for preparing salt solutions which exhibit desired thermodynamic properties. The method enables prediction of the value of the thermodynamic properties for single and multiple salt solutions over a wide range of conditions from activity data and constants which are independent of concentration and temperature. A particular application of the invention is in the control of salt solutions in a process to provide a salt solution which exhibits the desired properties.

Claims

1. A method of making a salt solution exhibiting a desired value of a selected thermodynamic property which comprises determining the water activity, a, in the solution at two different concentrations of the salt in solution at a reference temperature, T_r, wherein the water activity is related to the mole fraction of water, x_w, in the solution according to the general equation ##EQU18## calculating the value of the left-hand side of the general equation at each value of a and x_w, plotting the values of the left-hand side of the general equation versus a to obtain a line, setting the value of the slope of the line equal to the (c-1)/cr portion of the right-hand side of the general equation and setting the value of the intercept of the line equal to the 1/cr portion of the general equation to provide slope and intercept equalities expressed in terms of c and r, calculating c and r from the slope and intercept equalities, calculating ε

from the equation c=exp[ε

/TR_r ], selecting a test condition of concentration x_x and test temperature T_x, calculating the value of c_x at T_x from c_x =exp[ε

/RT_x ], calculating a at T_x and x_x from the general equation at r=r, c=c_x and x_w =1-x_x, calculating the value of the thermodynamic property from the value of a at x_x and T_x according to a thermodynamic expression relating the value of a and the value of thermodynamic property at x_x and T_x, determining the extent of any variation between the desired value of the thermodynamic property and the calculated value and, to the extent of any variance between the calculated and desired values of the thermodynamic property in excess of the an acceptable maximum variation, adjusting the value of at least one of the test conditions to reduce the variance between the calculated and desired values of the thermodynamic property to at or below the accepted maximum variance to cause the solution to exhibit the desired value of the property within the accepted variance, and incorporating in water an amount of the salt which in its resulting concentration in the solution causes the thermodynamic property to be within the accepted variance based on the adjusted value of X_x or Tx which causes the solution to exhibit the desired property.

2. The method of claim 1, wherein the salt solution comprises a plurality of salts and the values of r, c and ε

for the solution are obtained by obtaining the values of r_i, c_i and ε

_i for each salt in an aqueous solution and calculation of r from r=Σ

(r_i x_i), ε

=[Σ

x_i (r_i e_i)]/Σ

(x_i r_i) and c=exp[ε

/RT], and the values of r, c and ε

are used to calculate the water activity at the test concentration x_x and T_x.

3. The method of claim 1, wherein the test concentration x_x and test temperature T_x are selected by measuring the temperature of the solution and measuring the concentration of salt in the solution.

4. The method of claim 1, wherein the concentration of the solution is known and the test concentration x_x is equal to the known concentration, and the selection of the temperature T_x comprises measuring the temperature of the solution.

5. The method of claim 1, wherein the adjustment in the value of at least one of the test conditions comprises adjusting the temperature and/or concentration of the solution.

6. The method of claim 1, wherein the adjusting of the value of at least one of the test conditions further comprises recalculating the value of the water activity and the value of the thermodynamic property at the adjusted test condition(s) to cause the value of the thermodynamic property to be at or below the acceptable maximum variance, and adjusting the temperature and/or concentration of the solution in accordance with the adjusted values of the test conditions.

7. The method of claim 1, wherein the salt solution is being used in a fluid stream in a process including means for measuring and means for changing the temperature and/or concentration of the salt solution in the fluid stream, the selecting of the test conditions of temperature T_x and/or concentration x_x comprising measuring the temperature of the solution and/or measuring the concentration of salt in the solution, and the adjusting of the value of T_x and/or x_x comprises adjusting the temperature and/or concentration of the salt solution.

8. The method of claim 7 wherein the values of r and ε

are stored in a computer memory, and these values are accessed and used in the computation of the value of the thermodynamic property at the test condition and the value of the property for any adjustments in the test condition.

9. The method of claim 8, wherein the value of the thermodynamic property is calculated for an array of test conditions to provide an array of values of the property corresponding to the array of test conditions, and the calculating of the value of the property at the measured value of the test condition and determining of the extent of variation between the calculated and desired values of the property comprises selecting a test condition in the array of test conditions corresponding to the measured values and comparing the value of the property at the selected test condition to the desired value.

10. The method of claim 1, wherein the thermodynamic property is vapor pressure and is calculated from the value of the activity at x_x and T_x by multiplying the activity times the vapor pressure of pure water at T_x.

11. The method of claim 1, wherein the thermodynamic property is selected from the group consisting of vapor pressure, enthalpy, molal volume and the state of the solution with respect to the formation of crystals.

12. In a process employing a salt solution of known concentration x_s flowing in a fluid stream, an improved method of controlling a thermodynamic property of the salt solution to maintain the value of the property at a desired level comprising determining the water activity, a, in the solution at two different salt concentrations at a reference temperature, T_r, wherein the water activity is related to the mole fraction of water, x_w, in the solution according to the general equation ##EQU19## calculating the value of the left-hand side of the general equation at each value of a and x_w, plotting the values of the left-hand side of the general equation versus a to obtain a line, setting the value of the slope of the line equal to the (c-1)/cr portion of the right-hand side of the general equation and setting the value of the intercept of the line equal to the 1/cr portion of the general equation to provide slope and intercept equalities expressed in terms of c and r, calculating c and r from the slope and intercept equalities, calculating ε

from the equation c=exp[ε

/RT_r ], temperature T_s of the solution, calculating the value of c_s at T_s from c_s =exp[ε

/R_s T], calculating a at T_s and x_s from the general equation at r=r, c=c_s and x_w =1-x_s, calculating the value of the thermodynamic property from the value of a at x_s and T_s according to a thermodynamic expression relating the value of a and the value of the thermodynamic property at x_s and T_s, determining the extent of any variation between the desired value of the thermodynamic property and the calculated value and, to the extent of any variance between the calculated and desired values of the thermodynamic property in excess of an acceptable maximum variation, adjusting at least one of the values of the temperature T_s and/or concentration x_s to reduce the variance between the calculated and desired values of the thermodynamic property to at or below the accepted maximum variance to cause the solution to exhibit the desired value of the property within the accepted variance and incorporating in the fluid stream an amount of the salt solution and adjusting the concentration of the salt solution to cause the thermodynamic property to be within the accepted variance based on the adjusted value of Xx or Tx which causes the solution to exhibit the desired property.

13. The method of claim 12, wherein the salt solution comprises LiBr in a mole fraction range of from about 0.1 to 0.9, CaBr₂ in a mole fraction range of from about 0.05 to about 0.76 and ZnBr2 in a mole fraction range of from about 0.05 to about 0.9.