Treatment of API effluent of Tehran refinery by a ceramic microfiltration

membrane
Mahmood Hematia*, Toraj Mohammadib, Fatemeh Rekabdar a,Sareh Rezaei Hosein Abadi b , Ali Gheshlaghi a, Mohammad Reza Sebzari b
a
Polymer Science and Technology Division, West Blvd., Near Azadi Sports Complex, Tehran, Iran
,Research Institute of Petroleum Industry (RIPI)
b
Research Centre for Membrane Separation processes, Faculty of Chemical Engineering,
Iran University of Science and Technology, Narmak, Tehran, Iran

ABSTRACT RESULTS and DISCUSSION

Large amount of oily wastewaters are generated by industrial sources.. In recent years, membrane processes have been Effect of TMP:
applied for oily wastewater treatment. Microfiltration (MF) was successfully used in oil-in-water separations. In this research, Based on Darcy's low, the increasing TMP increases permeate flux.
investigations were carried out for treatment of an oily wastewater. A tubular ceramic (α-Al 2O3) MF system equipped with However, an increase in TMP could also attribute to the fouling layer
backwashing for removing reversible fouling was employed for treatment of a typical oily wastewater comes from API compression [3, 5]. As it is shown in Fig.1 until TMP increases up to
effluent of Tehran refinery. The initial wastewater characteristics were total organic carbon (TOC) of 141 mg/L and oil and 1.25 bar, permeate flux increases; however, after that permeate flux is
grease content of 26 mg/L. This system could produce a permeate with oil and grease content of 4 mg/L that meets the nearly constant.
National Discharge Standard and exhibited TOC removal efficiency higher than 95%. Also, effects of operating parameters Fig.1 also shows TOC removal efficiencies under TMP values
such as transmembrane (TMP), cross-flow velocity (CFV) and temperature on permeate flux, TOC removal efficiency and changing. The value of TOC removal efficiency is higher than 95%.
fouling resistance (FR) were investigated. The recommended operating conditions are TMP of 1.25 bar, CFV of 2.25 m/s and Also it is shown that, until TMP of 1.25 bar, Rf increases slightly,
temperature of 32.5 °C. In this system, backwashing was used to remove oil droplets and particulates that block the however, after that it increases severely. This can also be due to
membrane pores, and the results showed that backwashing could prevents permeate flux decline significantly. Based on the tendency to cake / gel formation at TMP up to 1.25 bar and as a result, Fig.1. Effects of TMP on permeate flux, TOC removal and Rf.
(CFV: 2.25 m/s,T: 32.5°C)
results, this system was proposed to be replaced with the conventional wastewater treatment method. the Rf growth is low.

Effect of cross flow velocity CFV:

Keywords : Oily wastewater; Ceramic membranes; Microfiltration; Backwashing; Operating conditions. Increasing CFV promotes turbulency and mass transfer coefficient [3]. It can be observed that increasing CFV up to 2.25 m/s
increases permeate flux and simultaneously decreases fouling resistance (FR).
INTRODUCTION It is also shown that TOC removal efficiency slightly decreases with increasing CFV.

Oily water emulsions are the main pollutants emitted into water by industry and domestic sewage. So far, there are several
techniques for oil separation. Typical ones include chemical emulsification, pH adjustment, gravity settling, centrifugal
settling, filter coalesce, heating treatment, electrostatic coalesce, membrane filtration, etc [1, 2, 4].
Membrane separations have been developed greatly over the last 30 years and are becoming a promising technology. They
are used in industrial processes, and are utilized currently for oilfield produced water treatment. They have high oil removal
efficiency, low energy cost and compact design compared with traditional treatment methods[2-4].
Many studies of membrane separation for oily wastewater treatment have been reported, particularly in microfiltration
(MF), ultrafiltration (UF) and reverse osmosis (RO) with organic membranes [1]. Recently, there have been several reports
using MF using organic / inorganic membranes. Ceramic (or inorganic) membranes have attracted interest due to their
superior mechanical, thermal, and chemical stability[3, 4]. Muller et al. [5] studied two ceramic membranes (0.2 and 0.8 μm
pore sizes) to treat the oily water Hueneme field in California. The oil removal efficiencies were about 98-99%. Zhong et al.
Fig.3. Effects of temperature on permeate flux, TOC removal and Rf. (TMP:
[6] studied the performance of MF using a 0.2μm ZrO2 ceramic membrane combined with traditional chemical flocculation 1.25 bar, CFV: 2.25 m/s)
Fig.2. Effects of CFV on permeate flux, TOC removal and Rf. (TMP: 1.25 bar, T:
32.5°C)
method as pretreatment. The oil removal efficiencies were about 99.4-99.9%.
Effect of temperature:
In this paper, treatment of oily wastewater was carried out using a ceramic membrane. The objective of this study were to
Temperature has double effects on permeation flux; increasing temperature decreases viscosity, and as a result increases
investigate the effects of transmembrane pressure (TMP), cross flow velocity (CFV) and temperature on permeate flux;
permeation flux [6]. From another point of view, increasing temperature increases osmotic pressure and this decreases
TOC removal efficiency and fouling resistance (FR) were studied.
permeation flux. Increasing temperature decreases fouling resistance (FR) and this is due to the higher oil solubility. On the
other hand, at higher temperature, oil and grease can more easily permeate through the membrane. Thus, TOC removal
MATERIAL efficiency of the membrane decreases. This can also be due to the viscosity effect [1].
membrane Process feed
A tubular ceramic membrane (α-AL2O3) with a stainless Outlet of the API unit of Tehran refinery was used as the Effect of Backwashing in long-term operation:
steel housing was used in this study. Table 1 lists the feed. The feed was taken daily and used immediately. Figure. 4 shows effect of backwashing on permeation flux decline, for the first 100 min of long-term operation. Permeate flux
properties of this ceramic membrane. Analysis of the feed taken from the wastewater of the API was plotted as a function of time at optimum conditions: TMP of 1.25 bar, CFV of 2.25 m/s and temperature of 32.5 °C. As
Table 1 unit is presented in Table 2. observed, permeation flux was significantly restored by backwashing [8]. It can be seen that the periodic backwashing of the
Material and properties of the ceramic membrane used in this investigation ceramic membrane with hot water is sufficient to maintain its performance satisfactory for long-term operation. As shown, it
is possible to recover over 95% of the original flux by backwashing.
Intersection shape Table 2
Characteristics of the wastewater
However, as operation goes on, more sever fouling is observed since oil and particulates that pass through the ceramic
Product code MF190
membrane are adsorbed and accumulate within the porous ceramic membrane. Figure.5 shows long-term operation of the
Number of channels 19 ceramic membrane at optimum conditions. As shown, for a very long operation, backwashing is not effective for flux
Parameter Unit Feed
Out diameter :mm 30 restoration and a flux decline up to 40% of original flux is observed. As a result, chemical cleaning should be used to
Channel diameter :mm 4 Total suspended
Dimension
Thickness: mm 1.5-2 solids (TSS)
mg/lit 92 regenerate the ceramic membrane.
Unit surface: m2/m 0.24
Porosity of support: % >33 Oil & grease content mg/lit 26
Mean pore size of membrane:
0.2 Total organic
Parameters µm
mg/lit 141
Compressive strength: Mpa 1 carbon (TOC)
Flux of water: L/h.m2 >500
material Al2o3 Turbidity mg/lit 21
Applied pH scaled: 0-
Max. Working Temperature: 1200˚C
14

EXPERIMENTAL METHOD
A schematic of the MF pilot is shown in Fig A. There were 3 loops in this system; the main loop, the backwashing loop and the
chemical washing loop. The main loop referred to cross flow MF processing as it started from TK-101. P-101, a horizontal
centrifugal pump, pumped the feed from TK-101 to the bottom of the membrane module and it was fed to the membrane
channels. The backwashing loop contained a backwashing tank (TK-102), a horizontal centrifugal pump and three valves. Hot
Fig.4. Effects of Backwashing on flux decline (TMP = 1.25 bar, CFV = Fig.5. Effects of Backwashing on flux decline (TMP = 1.25 bar, CFV = 2.25 m/s,
distillated water was used to backflash the MF membrane from TK-102 using P-102. In this loop, V-104 was opened to send 2.25 m/s, T = 32.5°C) T = 32.5°C)
the hot water into the membrane from the permeate side. To start cleaning, TK-103 was filled with chemical agents and it was
pumped toward the membrane using P-101. To control the feed temperature, there was a heater to heat the feed and also a coil Comparison of MF with conventional biological treatment Table 3
Characteristics of the wastewater and the treated wastewater (TMP = 1.25
of cooling water to keep it constant. Each tank was equipped with a thermostat to set its temperature. There were two analog method: bar, CFV = 2.25 m/s and T = 32.5 °C)
flow meters in the way of feed and permeate streams. The tank volume was 90 L. Table 3 presents the results of two different treatment methods
(MF and biological). Conventional biological method is being Parameter Unit Feed Treated Wastewater

(A) (B) used in Tehran refinery for the wastewater treatment. As shown,
the results of MF for almost all the measurements are better than MF Biological method

the results of biological method. The better preference is more Total mg/lit
92 Trace 4
considerable in TSS and turbidity removals. Only, oil and grease suspended
solids (TSS)
content and TOC are slightly less. It seems that more residence Oil & grease mg/lit
26 4 5
time in the API unit is necessary for all of these components to be content
Total organic mg/lit
removed. carbon (TOC) 141 7 24

Turbidity mg/lit
21 0.3 1.1

CONCLUSIONS
The microfiltration processes with ceramic membrane was successfully applied for the
oily wastewater treatment in this study. The results showed that a TMP of 1.25 bar, a
CFV of 2.25 m/s and a temperature of 32.5 °C are the best operating parameters.
Analysis of the MF process showed %85, %100 and % 98.6 reductions of oil and grease
content, TSS and turbidity, respectively. The TOC removal efficiencies were higher than
95% for all experimental conditions. So, comparison of performances of the MF process
and the conventional biological method showed that MF is more preferred rather than the
conventional method and it can be replaced with it.
Backwashing process was applied to remove reversible fouling. The results showed that
it is possible to recover over 95% of the original flux and prevent flux declined by using
periodic backwashing. However in long-term operation, it is necessary to use chemical
cleaning as the flux decrease to 40-50 % of the original value.
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