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IMT-Atlantique
Estelle Couallier
Membrane Processes for Industrial Wastewater Treatment
Jul 19, y

Veterinary Pharmaceutical Wastewater

Treatment through Nanofiltration
1. Paper Extract
1.1. Context and definition of objectives
Veterinary pharmaceutical wastewater is generating an important amount of contamination in
water bodies (specially affecting microbes) and so far it has not been taken into account.
That’s why we chose this industry and with the information available we will propose a
membrane process design for treating this polluted water, and eliminate the contamination.

The paper “Effect of water matrices on removal of veterinary pharmaceuticals by

nanofiltration and reverse osmosis membranes” by Davor Dolar, Ana Vuković, Danijela
Ašperger, Krešimir Košutić (taken from the Journal of Environmental Sciences - 2010), from
industry Veterina in Kalinovica (Croatia) propose an study for eradicating the following
veterinary pharmaceuticals:
1. Sulfamethoxazole (SMETOX)

2. Trimethoprim (TMP)

3. Ciprofloxacin (CIPRO)

4. Dexamethasone (DEXA)

5. Febantel (FEBA)

For the study they used 4 water matrices (Milli-Q water, model water, tap water and real
pharmaceutical wastewater) and for making the analyze they used 4 types of nanofiltration
membranes (NF90, NF270, NF and HL) and 2 types of reverse osmosis membranes (LFC-1
and XLE). The test was focused in Croatia, given the high level of contamination that is
being discharge on their aquifers. The study wanted to test the efficiency of the membranes to
remove the selected veterinary pharmaceuticals (VPs) and to investigate the effect of
different water matrices on the rejection of these VPs and flux. Finally it examined and
compared the rejection of VPs as a function of membrane type and compound properties.

The composition of the wastewater treated is the following:

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Pharmaceutical Wastewater (PWW) - Feed

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Pharmaceutical Wastewater (PWW) - Feed

SMETOX (mg/L) 8,22

TMP (mg/L) 27,68

CIPRO (mg/L) 17,48

DEXA (mg/L) 13,56

FEBA (mg/L) 1,02

Conductivity (µS/cm) 592

TOC (mg/L) 730,34

COD (mg O2/L) 1826

Fluoride (mg/L) 0,1151

Chloride (mg/L) 59,4974

Nitrate (mg/L) 0,138

Phosphate (mg/L) 0,4553

Sulphate (mg/L) 26,2266

Sodium (mg/L) 14,7979

NH4+ (mg/L) 7,5458

Potassium (mg/L) 1,7498

Magnesium (mg/L) 4,5697

Calcium (mg/L) 36,8147

pH 7,5

Table 1. Composition of pharmaceutical wastewater feed

There is no use of a synthetic solution and the aim is that the membranes retain the following
compounds: Fluoride, Chloride, Nitrate, Phosphate, Sulphate, Sodium, NH4+, Potassium,
Magnesium, Calcium and the veterinary pharmaceuticals.

WATER
COMPOUND MW (Da) dc (nm)
SOLUBILITY
Sulfamethoxazole
(SMETOX, 253,28 610 mg/L 0,734 nm
C10H11N3O3S)
Trimethoprim
(TMP, 290,32 400 mg/L 0,779 nm
C14H18N4O3)

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WATER
COMPOUND MW (Da) dc (nm)
SOLUBILITY
Ciprofloxacin
(CIPRO, 331,35 30000 mg/L 0,826 nm
C17H18N3O3F)
Dexamethasone
(DEXA, 392,46 89 mg/L 0,889 nm
C22H29FO5)
Febantel (FEBA,
446,48 322 mg/L 0,941 nm
C20H22N4O6S)

Table 2. Compounds to be retained by the membranes

The compounds that will go through the membrane are the clean water with negligible
compound concentrations. In order to make a design that works with the industry water
composition, from the comparison made in the paper we chose the nanofiltration membrane
for NF901, for the following reasons:
High rejection rate
Reduction of conductivity
High removal efficiency (VPs and other compounds)
Stability through the process
Cheaper treatment than reverse osmosis
Stable flux

The NF90 works with a dead-end filtration, the material of the membrane is polyamide thin-
film composite (with a MWCO of 100-200 Da and a diameter of 0.79 nm) and it’s form is
circular. The nanofiltration cell consists of two detachable parts: an upper part which is a high
pressure chamber provided with inlet and outlet openings for the flow of the feed solution
under pressure; and a lower part with an outlet opening for the membrane permeate. The
membrane is mounted on a stainless steel porous plate embedded in the lower part of the cell
and the surface layer of the porous membrane faces the feed solution on the high pressure
side.

1 According to the paper the best performances come from the membrane NF90 (nanofiltration) and LF-C1 (reverse
osmosis) but nanofiltration is cheaper.

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The tested mode was a Batch mode, with a pressure of 15 x 105 Pa and a temperature of
30°C. Also from the information provided from the paper there’s no information of the VRR
or the time that it took to have the process completed.

1.2. Results
From the paper the NF90 membrane we have the water flux with the clean membrane (Jw) of
80,16 ± 5,15 L/(m2·hr) and a permeation flux of the real pharmaceutical wastewater of (J p) of
30,86 L/(m2·hr). The removal efficiency obtain was the following:

COMPOUND REMOVAL EFFICIENCY

SMETOX 0,99
TMP 1
CIPRO 0,995
DEXA 0,99
FEBA 1
TOC 0,602
COD 0,55
Fluoride 1
Chloride 0,991
Nitrate 0,609
Phosphate 1

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COMPOUND REMOVAL EFFICIENCY

Sulphate 0,989
Sodium 0,967
NH4+ 0,885
Potassium 0,872
Magnesium 0,976
Calcium 0,986
Conductivity 0,979
pH 0,605

Table 3. Removal efficiency of the compounds

1.3. Conclusions
The treatment is efficient to recover the wastewater, all veterinary pharmaceuticals were
effectively removed with a stable flux and with different water matrices (RR>90% under all
conditions).

The limitations we found were that when treating real pharmaceutical wastewater, the
membrane showed a flux decline of about 59%, mainly due to pore blocking and adsorption
onto membrane surface.

An enhancement of the process could be a regular cleaning of the membrane with alkali
agents is strongly recommended, in order to avoid pore blocking and allow the water flux
return to its initial value.

2. Process Design
2.1. Design considerations
· The industrial scale wastewater pilot plant is located in Croatia.
· The objective is to treat wastewater coming from the pharmaceutical industry
Veterina, (Kalinovica-Croatia) in order to be discharged in the nearest river.
· After the treatment all the veterinary pharmaceuticals (VPs) have to be removed from
the wastewater.
· The treated wastewater also has to comply with the concentration limits for the
different pollutants, legislated by the Ministry of Regional Development, Forestry and
Water Management of Croatia. This local legislation is aligned with the European
Commission’s Urban Waste Water Directive (Council Directive 91/271/EEC to

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protect the water environment from the adverse effects of discharges of urban waste
water and from certain industrial discharges). (European Commission, 2017)

2.2. Operation Mode: Batch

In order to define the operation mode of the pilot plant, the paper “Effective Wastewater
Treatment in the Pharmaceutical Industry” by Manfred Martz was consulted (Martz, 2012).
In this publication the author does and exhaustive revision of the current treatments for
wastewater in the mentioned industry and he also presents some case studies and data about
the wastewater flow rates in some countries in Europe and Asia.

In the following table some findings of (Martz, 2012) about the quantity of wastewater
produced per day are presented.

Plant location Wastewater treatment Process Flow rate

Weimer / Germany UV-activated H2O2 oxidation 35 m3/d (total

process for removal of active wastewater from
pharmaceutical ingredients. production)

Berlin / Germany UV-activated H2O2 oxidation 4 m3/batch (from

process for removal of active hormonal production
pharmaceutical ingredients. only)

France UV-activated H2O2 oxidation 12 m3/d (from hormonal

process for removal of active production only)
pharmaceutical ingredients.

Lahore / Pakistan Biological oxidation process 40 m3/d (total

realized by Rotating Biological wastewater from
Contactors (RBC) process. production and sanitary
wastewater)

Table 4. Quantity of wastewater produced per day in some countries

Based on this data we can estimate that the flow rate of wastewater coming from the
pharmaceutical industry is between 4 m 3/d and 40 m3/d. This is a very low rate for a
continuous wastewater treatment plant and taking into account that some production

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processes of this industry are carried out in batch mode, the most suitable operating mode for
the treatment of the wastewater is also batch mode.

2.3. Draw a flow sheet with a clear definition of the abbreviations

used

Figure 3. Diagram of the process

2.4. Definition of the inlet parameters:

· Volume: As presented in the operation mode section the volume to be treated in the
pharmaceutical industry oscillates between 4 m3/d and 40 m3/d. For this specific
design the upper limit of 40 m3/d is going to be used.

· Composition of the feed: For the pilot design the composition of the real
pharmaceutical wastewater presented in the reference paper (Dolar, Vukovic,
Asperger, & Kosutic, 2011) is going to be used (to see the values please refer to Table
1). As presented in the design considerations section, the aim of the design is to treat
the effluents of the industry Veterina, but this time at industrial scale.

2.5. Definition of the outlet parameters:

Since the main objective of the treatment is to be able to discharge the treated water into the
river, the PWW treatment plant has to comply with the corresponding legislation for urban
wastewater discharge in Croatia. Therefore the permeate concentration of the different
compounds have to be always lower than the maximum concentration value stated in the
ORDINANCE ON LIMIT VALUES OF HAZARDOUS AND OTHER SUBSTANCES IN
WASTE WATER of the (Ministry of Regional Development, Forestry and Water Management
- Croatia, 2017). In the next table the maximum concentration value for the compounds
present in our raw wastewater is presented:

Substance and unit of Max. Concentration to be

measurement discharged in surface water
TOC (mg/L) 30

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COD (mg O2/L) 125

Fluoride (mg/L) 10

Chloride (mg/L) No information about this substance

Nitrate (mg/L) 2
Phosphate (mg/L) 1
Sulphate (mg/L) 250

Sodium (mg/L) No information about this substance

NH4+ (mg/L) 10

Potassium (mg/L) No information about this substance

Magnesium (mg/L) No information about this substance

Calcium (mg/L) No information about this substance

pH 6,5 - 9

Table 5. Maximum concentration values for compounds present in wastewater2

It can be observed that for some substances the legislation does not provide any information
about concentration limits, however, the permeate concentration reached for those substances
is really low so there is no hazard.

2.6. Define the process: membrane used, retention rate for all the
compounds, VRR, time of filtration, permeation flux and
membrane area
As stated before, from the different membranes tested, the NF90 displays a good performance
regarding the retention efficiency and the pressure drop compared to the others. Therefore,
the membrane NF90 would be chosen as the main component of the wastewater treatment.

If we assume that the retention rates of the compounds calculated during the test in the pilot
plant remain constant at industrial scale for the membrane NF90, then the concentrations in
the permeate will be:

Retention Permeate Retentate

Compound
Rate (RR) Concentrations Concentrations

2 Obtained from (Ministry of Regional Development, Forestry and Water Management - Croatia, 2017)

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SMETOX (mg/L) 0,9900 0,0822 316,8920

TMP (mg/L) 1,0000 0,0000 1107,2000
CIPRO (mg/L) 0,9950 0,0874 686,4219
DEXA (mg/L) 0,9900 0,1356 522,7561
FEBA (mg/L) 1,0000 0,0000 40,8000
TOC (mg/L) 0,6024 290,6753 6729,2274
COD (mg O2/L) 0,5504 821,7000 13887,8101
Fluoride (mg/L) 1,0000 0,0000 4,6040
Chloride (mg/L) 0,9910 0,5355 2302,1809
Nitrate (mg/L) 0,6094 0,0540 1,3048
Phosphate (mg/L) 1,0000 0,0000 18,2120
Sulphate (mg/L) 0,9890 0,2885 1007,3475
Sodium (mg/L) 0,9671 0,4883 524,0734
NH4+ (mg/L) 0,8852 0,8678 197,4824
Potassium (mg/L) 0,8722 0,2240 43,6500
Magnesium (mg/L) 0,9760 0,1097 167,3009
Calcium (mg/L) 0,9860 0,5154 1398,4676

Table 6. Permeate concentrations and Compounds Retention Rate

From the paper, the following equation were used to determine retention rate (RR):

C O−C P
RR=
CO

Where C0 and Cp correspond to the membrane inlet and permeate concentrations. Then
solving for Cp and Cr (retantate concentration):

C P =( 1−RR )∗C O

C r=C O∗VR R RR

Finally, the VRR would be

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VO
VRR= =40
Vr

Incidentally, it may be noted that the membrane process does not meet the legislation limits
for the TOD and COD concentrations because they are too high and with a retention rate
around 55-60%. For cases of high organic compounds normally a pretreatment of the
wastewater is required and in fact, DoW Chemical’s strongly suggest it when the TOC for
instance exceeds 3ppm (DOW, 2014). Consequently, a viable solution would be a biological
treatment based on an activated sludge tank.

Regarding the volume, the plant will be designed to have a permeate volume (Vp) of 39
m3/d, so the majority of the wastewater is discharged properly treated. The retentate volume
(Vr) is then 1 m3/d in which all the unwanted substances will be concentrated.

In order to determine the time of the process, an analysis of the flux decay over the time of
the test was made. As seen in the figure 3, the cleaning of the membrane with demineralized
water as well as with alkali solutions should be done after around 30h of operations in order
to avoid pore fouling. However, since the operation of the designed process is batch and the
PWW volume treated is given on a daily basis, it is an appropriate time 20h to treat the
wastewater produced in one day, so there would be time for the cleaning of the membranes of
around 4h before starting the process again for the volume produced of the next day.

Figure 3. Membrane flux (J) in treatment of the real PWW. A: initial flux, B: flux after
cleaning with demineralized water, C: flux after cleaning with alkali agent (Dolar, Vukovic,
Asperger, & Kosutic, 2011)

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Now, given the permeation flux (Jp) of 30,86 L/m2hr, according to the results of the
experiments, given the time (t) of 20h, the volume (V) to be treated of 40 m3 and the VRR of
40, the required area of the membrane can be calculated with the following equation:

Vp
J=
tA
Solving for A:

( )
V 0 VRR−1
A=
JA VRR
Then, the membrane area for the industrial scale process would be 63,15 m2.

2.7. Sensibility analysis

So as to carry out the sensibility analysis, some design parameters like the process time, the
treated volume and the VRR were changed in order to determine the required membrane area.
Figures 4 to 7 show the results:

Figure 4-7. Membrane area required varying design parameters (time, treated volume, VRR)

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· Time of the Process: it is inversely proportional to the required area and varying this
parameter has a strong impact on the required membrane area. It is important to now
that the higher the membrane area, the higher the pressure drop, thus, the costs of the
filters as well as the operational costs would be higher for shorter periods.

· Treated Volume: it is proportional to the required area. It is important to consider

changing from batch operation to continuous operation for larger volumes, since the
concentrations would not be homogeneous within the tank and control processes
would be more difficult.

· VRR: it is proportional to the required area but it should be noted that among the high
range of VRR values, the required area tends to have the value as if the total volume of water
would be treated. For PWW treatment aimed to discharge in the environment, normally the
higher values of VRR would not have that strong effect as for treatments whose aim is to gain
some benefits from the retentate. Here the low values of VRR should be taken more into
account.

All in all, more than a sensitivity analysis, these graphs could be used for quick estimations
when it comes to take decisions on whether to escalate or de-escalate the treated volume, as
well as determining a reasonable time for the process.

3. References

Dolar, D., Vukovic, A., Asperger, D., & Kosutic, K. (2011). Effect of water matrices on
removal of veterinary pharmaceuticals by nanofiltration and reverse osmosis
membranes. Journal of Environmental Sciences, 23(8), 1299–1307.
DOW. (2014, October 10). FILMTEC Membranes - Effect of Total Organic Carbon (TOC).
Retrieved from The Dow Chemical Company Web Site:
https://dowac.custhelp.com/app/answers/detail/a_id/441/~/filmtec-membranes---
effect-of-total-organic-carbon-%28toc%29
European Commission. (15th April 2017). Environment. Retrieved from Urban Waste Water
Directive: http://ec.europa.eu/environment/water/water-urbanwaste/legislation/
directive_en.htm
Martz, M. (2012). Effective Wastewater Treatment in the Pharmaceutical Industry.
Pharmaceutical Engineering-The official technical Magazine of ISPE, 32(6).
Retrieved from www.pharmaceuticalengineering.org
Ministry of Regional Development, Forestry and Water Management - Croatia. (14th April
2017). ordinance on limit values of hazardous and other substances in wastewater.
Retrieved from http://www.mvep.hr/zakoni/pdf/906.pdf

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