Background

This invention relates generally to a method for reducing dilution effects in fluid treatment vessels.

Ion Exchange Resins are regenerated with a chemical solution once they are exhausted.

The volume of regeneration liquid depends in part on the concentration of the liquid. Free water present in a vessel will negatively influence the effectiveness of the regeneration, leading to lower operating capacity, increased chemical consumption and more waste. For example, US2014/0263069 discloses the use of filler material in the end portions of the vessel, i.e., those portions not containing a fluid treatment medium. However, this reference does not disclose an efficient method.

Statement of Invention

The present invention is directed to a fluid treatment apparatus comprising:

(a) a tank comprising a bed of at least one fluid treatment medium,

(b) a distributor plate separating the bed from an end portion of the tank, and

(c) at least one inert medium comprising amorphous particles having a harmonic mean diameter from 2.5 to 250 mm and a density from 0.57 to 0.998 cm ³ /g;

wherein volume of the end portion containing inert medium is from 25 to 95% of total volume of the end portion.

Detailed Description

All percentages are weight percentages (wt%), and all temperatures are in °C, unless otherwise indicated. Averages are arithmetic averages unless indicated otherwise. All operations are performed at room temperature (18 and 25 °C) unless specified otherwise. Weight average molecular weights, M _w , are measured by gel permeation chromatography (GPC) using polyacrylic acid standards, as is known in the art. The techniques of GPC are discussed in detail in Modern Size Exclusion Chromatography, W. W. Yau, J. J. Kirkland, D. D. Bly; Wiley- Interscience, 1979, and in A Guide to Materials Characterization and Chemical Analysis, J. P. Sibilia; VCH, 1988, p. 81-84. The molecular weights reported herein are in units of daltons. Percentages of monomer units in a polymer are based on total polymer weight (dry weight). The “harmonic mean diameter” (HMD) is defined by the following equation:

HMD

where i is an index over the individual beads; di is the diameter of each individual particle; and N is the total number of beads. A particle that is not spherical is considered to have a diameter equal to the diameter of a sphere having the same volume as the particle.“Sphericity” (Y) is the degree to which a particle is spherical and is characterized by using two of the three principal orthogonal axes of the object, a (longest), b (intermediate), and c (shortest), as follows: Y = c / a . “Roundness” (R) is defined as the ratio of the average radius of curvature of the corners and edges of an object’s silhouette to the radius of the largest circle which can be inscribed within the silhouette. Sphericity and roundness are described in more detail in H. Waddell, The Journal of Geology, vol. 41, pp. 310-331 (1933).

The volume of the end portion containing inert medium is defined by the upper boundary of the inert medium when at rest. For example, if one defines a plane touching all of the uppermost particles of inert medium, i.e., a plane defining an upper surface of the inert medium, then the volume of the end portion below this plane is the volume of the end portion containing inert medium. For clarity, this is not the total volume of the particles themselves. Preferably, the volume of the lower end portion containing inert medium is at least 30% of the volume of the lower end portion, preferably at least 35%, preferably at least 40%, preferably at least 45%, preferably at least 50%; preferably no more than 90%, preferably no more than 85%. Preferably, the amorphous particles have an average sphericity from 0.7 to 1.0 and an average roundness from 0.4 to 1.0. Preferably, average sphericity is at least 0.75, preferably at least 0.80; preferably no more than 0.95, preferably no more than 0.92, preferably no more than 0.90. Preferably, average roundness is at least 0.45, preferably at least 0.50, preferably at least 0.55; preferably no more than 0.95, preferably no more than 0.90, preferably no more than 0.85, preferably no more than 0.80, preferably no more than 0.75, preferably no more than 0.70.

Preferably, the average sphericity and the average roundness are not both greater than 0.95, preferably 0.90.

Preferably, the amorphous particles have a harmonic mean diameter no greater than 150 mm, preferably no greater than 100 mm, preferably no greater than 50 mm, preferably no greater than 25 mm, preferably no greater than 10 mm, preferably no greater than 6 mm.

Preferably, the amorphous particles have a density of at least 0.60 cm ³ /g, preferably at least 0.65 cm ³ /g, preferably at least 0.70 cm ³ /g, preferably at least 0.75 cm ³ /g, preferably at least 0.80 cm ³ /g, preferably at least 0.85 cm ³ /g. Preferably, the amorphous particles have a density no greater than 0.997 cm ³ /g, preferably no greater than 0.996 cm ³ /g.

Typical end portions (also known as dish heads) of tanks used for fluid treatment include, e.g., Klopper heads, elliptical heads and spheroid heads. Typically, dish head water volume is 15 - 35% of the installed resin volume in the main portion of the tank and dish head water volume is 40 - 100% of the resin void water in the main compartment. Preferably, the main portion of the tank is cylindrical.

Reduction of void water due to the presence of inert material in the end portions is calculated as follows for a spheroid end portion.

Vs = spheroid compartment volume

Vsx’ = the spheroid remaining free water after (partial) filling of X ml IF62 (ml)

Sx = the solid fill of the spheroid volume due to the X ml filling with IF62 (ml)

X = inert filling (ml)

Fw = free water (%)

Vsx = Vs - (X*F _W )

Sc = Vs-Vsc ^, Preferably, the fluid treatment medium in the main (center) compartment of the tank is an ion exchange resin, activated carbon, an adsorbent, a non functionalized co polymer or a zeolite. Preferably, the fluid treatment medium is an ion exchange resin, preferably in the form of spherical beads. Preferably, the beads are crosslinked polymer beads.

Depending in the technology applied:

Co-flow systems have 10 - 60 % filling

Countercurrent systems:

Packed beds: 85% - 97,5 % filling

Blocked beds 25 - 60% filling

Mixed beds 25 - 60% filling

Inert filling in the main compartment (cylinder) depends on the system technology and is either a fixed value ranging from 10-12 cm in an Amberpack/ Schwebebett or a range of heights depending on the vessel diameter. Typically <1000mm : 150 mm; <2500 : 200 mm and all other over 2500 : 300 mm

Or 15 - 25 cm as block layer in a blocked bed system with air hold down.

Examples

The equipment used in the present examples was as follows:

* 2 PYC columns in parallel for the comparison; Outer diameter 6 cm and column height 1000 mm

* Top and bottom compartments 160 mm wall height equipped with nozzle plates. The compartment represent the vessel spheroid dish head net volume V _s = 350 ml; the compartment is physically separated from the resin column by a nozzle plates to retain the filling.

* Instrumentation: 8 rotameters,

2 manometers

* Other equipment: 2 water tanks (lm ³ ),

2 chemical tanks (NaOH 30% HC1 37%),

4 pumps (2 feed, 2 dosing)

2 conductivity meters [We should describe how the PE particles are made, since this is not a commercial productl

IWAKI Electromagnetic Metering pumps Model EWN-

B16VCER

Capacity 65 mL/min · 3.9 L/h · 0.09-0.18 Power 100-240 VAC

mL/stroke supply

Disch. Press. 7 bar Frequency 50/60 Hz

Pressure 8 bar Current 0.8 A

Max. (Input)

Stroke 50-100% (0.5-1.0 mm) Power 20 W

Length (Input)

Stroke Rate 0.1-100 (1-360 spm) Materials PVC (head)

PTFE +EPDM

(diaphragm)

Example 1: Tests with Upper and/or Lower Compartments Filled

OPERATING CONDITIONS FOR THE TESTS

Configuration 1 column

Regen. technology UPCORE TM Resins DOWEX™ MARATHON™ 1200H

New commercial name Amberlite HPR1200 H

DOWEX™ UPCORE™ IF-62

New commercial name Amberlite 62i

Setups None compartment filled

Bottom compartment filled

Bottom + Top compartment filled

Feed water Raw water after sand filter treatment

Regenerant HC1 4.5% Cycles monitoring Conductivity measurement

DOWEX MARATHON™ 1200 - UPCORE™

Floating inert DOWEX™ UPCORE™ IF-62 Floating inert height ⁽¹⁾ (mm) 85

Freeboard (mm) 50

Filling inert DOWEX™ UPCORE™ IF-62

Volume of filling inert ⁽²⁾ (L) 0.350

Volume of resin in swollen form (L) 1.89

Resin height (mm) 865

COMPACTION

Direction UPFLOW

Influent Demineralized water

Flow rate (L/h) 60

Linear velocity (m/h) 30.6

REGENERANT INJECTION

Direction UPFLOW

Regenerant HC1 35% w/w %

Quantity (g/LiQ 120

Regenerant solution concentration (w/w 4.5

%)

Flow rate (L/h) 15.0

Specific flow rate (BV/h) 8.6

Duration (min) 18

Linear velocity (m/h) 7.6

Volume (L) 4.5

REGENERANT DISPLACEMENT (SLOW RINSE)

Direction UPFLOW

Effluent Demineralized water

Flow rate (L/h) 15.0

same as during regenerant injection

Specific flow rate (BV/h) 8.6

End point Conductivity <1000 pS/cm SETTLING

Duration (min) 10

FAST RINSE (RINSE TO QUALITY)

Direction DOWNFLOW

Influent Demineralized water Flow rate (L/h) 55.0

same as loading cycle

Specific flow rate (BV/h) 29.1

same as loading cycle

End point Conductivity after SB A < 10 m8/ah

LOADING CYCLE

Direction DOWNFLOW

Influent Water after sand filters

Flow rate (L/h) 55.0

Specific flow rate (BV/h) 29.1

Linear velocity (m/h) 28

End point Conductivity after SBA > 2 pS/cm

Results

Loading cycles Regeneration cycles

AVG BV for fast

BV for

Op. Cap. (eq/LR) rinse to reach 10

displacement

pS/cm

No compartment ^ 34 ± 0 01 5.9 ± 0.2 2.06 Fr = 0%

filled

Bottom

Fr =

compartment 1.47 ± 0.07 6.2 ± 0.3 1.58

66,5%

filled

Bottom and Top

compartment 1.58 ± 0.03 6.2 ± 0.6 1.41 Fr =66,5% filled

• [Cations] (eq/liter) = Total cation concentration obtained from the feed water analysis. . Yx = Throughput (liter): Total amount of water treated at the resin breakthrough point.

• VR = The volume of resin loaded (liter)

FT x [Cations]

Op. Capacity = WR (Eq/l _re sin)

Compared to F _Wr = 0% (no filling), the resin operating capacity improves at 100% filling of V _s at Fwr = 66,5%

Fwr= free water reduction in compartment

Vs = spheroid compartment volume

The fast rinse volume to reach 10 pS/cm is improved from 2.06 to 1.41 bed volumes.

Example 2: Tests with Gradual Filling of Lower Compartment

The operating conditions and fill in the main compartment were the same as in Example 1. Results

Operating Capacity

Cycles % of Compartment Op. Cap. (eq/L _R ) Standard

Containing Filling deviation inert filling 0 ml 0 1,31 0,06 inert filling 100 ml 28.6 1,44 0,06 Inert filling 200 ml 57.1 1,48 0,02 Inert filling 300 ml 85.7 1,48 0,01

Inert filling 350 ml 100 1,47 0,07

Displacement (BY)

Cycles % of Compartment Displacement (BY) St. Dev.

Containing Filling

Regen O 0 5.8 0,3

Regen lOO 28.6 6,2 0,4

Regen_200 57.1 6.9 0,3

Regen_300 85.7 6,3 0,2

Regen_350 100 6,2 0,3

Displacement performance is substantially independent of the percent of the compartment which contains fill.