Treatment on Petrochemical Industry Waste Water

Presented by: RIMELI ROY CHOUDHURY

Roll Number: 14/CHE/416

AcknowledgementI would like to express my special thanks of gratitude to my teacher Dr. Parimal Pal for giving me this golden opportunity to give a presentation on such a wonderful topic. I learnt a lot of things from this. Secondly I want to thank my parents and friends and my seniors for helping me to complete this project.

AT A GLANCE: Introduction

Technologies to treat petrochemical industry wastewater

Physico-chemical treatment Oil –Water Separator–Treatment of oily effluent Coagulation/Flocculation Adsorption Fixed bio-film Reactor Electrosorption Membrane Technology

Biological treatment petrochemical industry wastewater Aerobic Treatment Membrane Bioreactor Sequenching Batch Reactor Anaerobic Treatment

Chemical Oxidation Classical Chemical Treatments and Advanced Oxidation Processes (AOPs)

Conclusion: A Membrane Integrated Hybrid System

References

Large quantities of wastewater are generated from petrochemical industries .

The discharge of petrochemical wastewater (PCW) could cause serious environmental pollution and human health concerns as it contains organic and inorganic matter in varying concentrations.

The quantity and characteristics of wastewater generated from a petrochemical complex is strongly dependent on individual process plants operating at the complex.

INTRODUCTION:

Technologies to treat petrochemical industry wastewater

In terms of wastewater treatment there are four classifications of treatment. Preliminary treatment: It involves the removal of large particles

as well as solids found in the wastewater. Primary treatment : The second classification is primary

treatment, which involves the removal of organic and inorganic solids by means of a physical process, and the effluent produced is termed primary effluent.

Secondary treatment: This is where suspended and residual organics and compounds are broken down. Secondary treatment involves biological (bacterial) degradation of undesired products.

Chemical process : The fourth is tertiary treatment, normally a chemical process and very often including a residual disinfection.

Physico-chemical treatment Oil –Water Separator–Treatment of oily effluent

Oil and grease in wastewater can exist in several forms: free, dispersed or emulsified. The differences are based primarily on size. In an oil–water mixture, free oil is characterized with droplet sizes greater than 150 mm in size, dispersed oil has a size range of 20–150 mm and emulsified oil has droplets typically less than 20 mm

Conventional approaches to treat oily wastewaters have included gravity separation and skimming, dissolved air flotation, de-emulsification, coagulation and flocculation.

Gravity separation followed by skimming is effective in removing free oil from wastewater.

Oil – water separators such as the API separator and its variations have found widespread acceptance as an effective, low cost, primary treatment step. The API oil – water separator is designed to separate the oil and suspended solids from their wastewater effluents. The API separator, however, is not effective in removing smaller oil droplets and emulsions.

Emulsified oil in wastewater is usually pre-treated chemically to destabilize the emulsion followed by gravity separation. The wastewater is heated to reduce viscosity, accentuate density differences and weaken the interfacial films stabilizing the oil phase. This is followed by acidification and addition of cationic polymer/ alum to neutralize negative charge on oil droplets, followed by raising the pH to the alkaline region to induce flock formation of the inorganic salt. The resulting flock with the adsorbed oil is then separated, followed by sludge thickening and sludge dewatering.

Coagulation/flocculation Coagulation/flocculation is one of the most important

processes in the primary purification of water and in petrochemical wastewater treatment .

Operation Procedure: Coagulants are added to the tank. The velocity of the water is lowered below the suspension velocity and the suspended particles settle down due to gravity. Settled solids are removed as sludge, and floating solids are removed as scum. Wastewater leaves the sedimentation tank over an effluent weir to the next step of treatment.

Governing parameters: Type and dosage of coagulant/flocculant, pH, mixing speed and time, temperature and retention time are the governing parameters to evaluate the efficiency of the process.

Examples of coagulants: Both inorganic and organic such as aluminum sulfate (alum), ferrous sulfate, ferric chloride and ferric chloro-sulfate are widely used as coagulants.

Advantages: This method is widely used as the primary purification processes mainly due to the ease of operation, high efficiency, cost effective. Also, it uses less energy than alternative treatment .

Disadvantages: This treatment process can remove almost 90% of the suspended solids from the wastewater but fails to remove organic, inorganic particles, heavy metals present in the wastewater.

Adsorption techniques to treat wastewaterAdsorption is a natural process by which molecules of a dissolved

compound adsorbs to the surface of an adsorbent solid.

This adsorption method appears to be very promising for the remediation and recovery of “petrochemical” waste water.

Granular activated carbon zeolites, silica-aluminas and silicas are the most popular adsorbent mediums due to their high surface area to volume ratio.

Basic characteristics of good adsorbents: i) high selectivity due to a strictly defined chemical composition and porous texture; ii) tunable hydrophilicity; iii) proven stability under harsh conditions; and iv) in most cases, excellent regenerability.

Disadvantages: i) most of the adsorbent are temperature sensitive; ii) with time their adsorption ability may deteriorate; in that case adsorbents need to be changed after a certain time.

Fixed bio film reactor The fixed bio film reactor is nothing but a trickling filter that

consists of a bed of highly permeable media on whose surface a mixed population of microorganisms is developed as a slime layer.

Operation Procedure: Wastewater passes through the filter which causes the development of a gelatinous coating of bacteria, protozoa and other organisms on the media. The continual increase in the thickness of the slime layer with time which in turns produce anaerobic end products next to the media surface, and the maintenance of a hydraulic load to the filter, eventually causes sloughing of the slime layer to start to form. To prevent clogging of the distribution nozzles, trickling filters should be preceded by primary sedimentation tanks equipped with scum collecting devices. Trickling filters should be followed by secondary sedimentation tanks to remove the sloughed solids and to produce a relatively clear effluent.

Advantages: Simple design, trouble free, ease of maintenance

and control nature (as compare to activated sludge process) .

Disadvantages: excessive organic loading without a corresponding higher recirculation rate clogging of under drain system,  non-uniform media size or breaking up of media.

Electrosorption

Electrosorption is nothing but the absorption on surface of an electrode.

After the polarization of the electrodes, the polar molecules or ions can be removed from the electrolyte solution by the imposed electric field and adsorbed onto the surface of the electrode.

Pros: Electrosorption has attracted a wide interest in the adsorption processes for treatment of wastewater due to its environmental friendly and less power consuming nature.

Cons: It has been limited by the performance of electrode material.

Activated carbon fibre cloth with high specific surface area and high conductivity is considered to be the most effective material which can be used as electrode materials.

Membrane technology Application of membrane based separation processes such as

microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) for treating oily wastewater are increasing day by day.

There are three broad categories of oily wastes – free-floating oil, unstable oil/water emulsions, and highly stable oil/water emulsions

Membranes are most useful with stable emulsions, particularly water soluble oily wastes. Mechanical separation devices can remove the free oil by using gravitational force as the driving force whereas unstable oil/water emulsions can be mechanically or chemically broken and then gravity separated

Advantages: Disadvantages:1. Widely applicable across a

wide range of industries;2. Do not involve phase

change; 3. Higher degree of purity

(99%) can be achieved ; 4. No separation agent is

required, making subsequent oil recovery easier;

5. Membranes can be used in-process to allow recycling of selected waste streams within a plant;

6. Energy costs are lower compared to thermal treatments;

7. The plant can be highly automated and does not require highly skilled operators.

I. Scale-up is almost linear above a certain size.

II. Capital costs for very large effluent volumes can be high;

III. Fouling is the most important problem in case of membrane separation processes. Due to fouling the flux decreases with time;

IV. Clogging is another important phenomena which not only decrease the permeate flux but is also a reason behind membrane degradation during use. Thus membranes are required to be replaced frequently, which can increase operating costs significantly.

Biological treatment petrochemical industry

wastewater In the wastewater treatment sector, biological processes deal primary with organic

impurities. Soluble organic sources of biochemical oxygen demand (BOD) can be removed by any viable microbial process, aerobic, anaerobic or anoxic process.

Aerobic treatment: Aerobic degradation is a simple, inexpensive and environment friendly way to

degrade wastes. Governing Parameters: Parameters which effect the aerobic treatment are

temperature, moisture, pH, nutrients and aeration rate that the bacterial culture is exposed to, with temperature and aeration being two of the most critical parameters that determine the degradation rates by the microorganism.

Advantages: i) Aerobic microbial reactions almost 10 times faster than anaerobic microbial reactions; ii) aerobic reactors can be built relatively small and open to the atmosphere, yielding the most economical means of BOD reduction.

Disadvantages: The major disadvantage of aerobic bioprocesses over anaerobic processes for wastewater treatment, is the large amount of sludge production due to accumulation of biomass (as biomass yield for aerobic microorganisms is relatively high, almost 4 times greater than the yield for anaerobic organisms).

Membrane bioreactors is a combination of the activated sludge process and a membrane separation process.

Advantages: 1)Decrease in sludge production, 2)improved effluent quality , 3) efficient treatment of wastewaters with varying contamination peaks are the different advantages MBRs offered over traditional activated sludge process.

Disadvantages: Disadvantages of this system include 1)this system needs frequent membrane monitoring and maintenance, 2)operates at relatively high running costs and 3) there is a limitation of the pressures, temperatures and pH the system . 4) Due to membrane fouling proper designing of these kind of reactor is very difficult. And because of these reasons MBRs are not being as widely used in large scale wastewater treatments in comparison to traditional activated sludge plants

Membrane bioreactors

Schematic of conventional activated sludge process (top) and external (side stream) membrane bioreactor (bottom)

SEQUENCING BATCH REACTOR A sequencing batch reactor (SBR) is a reactor in which an activated sludge process is carried out

in a time oriented, sequential manner using a single vessel for all the phases of the process. The same steps involved in a conventional, continuous activated sludge process (such as aeration, pollutant oxidation, sludge settling, and recycling) are now conducted in batch one after the other.

Operating Procedure: It has five discrete periods in each operation cycle: fill, react, settle, draw, and idle. Reactions start during fill with the reactor nearly empty except for a layer of acclimated sludge on the bottom and the reactor is then filled up with the wastewater and the aeration and agitation are started and complete during react. After react, the mixed liquor suspended solids (MLSS) are allowed to separate by sedimentation during settle in a defined time period; the treated effluent is withdrawn during draw and the time period between the end of the draw and the beginning of the new fill is known as idle.

ADVANTAGES: DISADVANTAGES:

1)Requirements of chemicals for the overall treatment process is low,

2) Low operating costs, 3) Eco-friendly and

4) Cost-effective alternative of conventional techniques and,5) Efficient at lower levels of contamination. 6) Can accommodate large fluctuations in the incoming wastewater flow and composition without failing which may not get from conventional activated-sludge processes7) Even the wastewater residence time in SBRs can be extended until the microbial population has recovered and completed the degradation process and settling time also can be varied to allow complete settling before discharging.

i) Higher level of sophistication is required (compared to conventional systems), especially for larger systems, of timing units and controls;

ii) Higher level of maintenance (compared to conventional systems) associated with more sophisticated controls, automated switches, and automated valves;

iii) Potential of discharging floating or settled sludge during the DRAW or decant phase with some SBR configurations;

iv) Potential plugging of aeration devices during selected operating cycles, depending on the aeration system used by the manufacturer;

v) Potential requirement for equalization after the SBR, depending on the downstream processes.

ANAEROBIC TREATMENT Anaerobic reactor differs from the aerobic reactors primarily

because the former must be closed in order to exclude oxygen from the system while oxygen plays a major role in case or aerobic reactor.To remove the gazes (mainly methane and carbon dioxide) produced during anaerobiosis an anaerobic reactor must provide with an appropriate vent or a collection system.

Advantages: Anaerobic microbial processes have several important advantages over aerobic microbial processes like (1) lower production rate of sludge, (2) operable at higher influent BOD and toxics levels, (3) no cost associated with delivering oxygen to the reactor, and (4) production of a useful by-product, methane (biogas).

Drawbacks of this process: Although anaerobic digestion provides numerous advantages, it is not extensively applied in the petrochemical industries due to slow reaction, longer hydraulic retention time and lack of process stability, higher capital and operating expenses than aerobic processes because the anaerobic systems must be closed and heated.

Chemical oxidation Chemical Oxidation is a process by which electrons are transferred from

one substance to another. which leads to a potential expressed in volts referred to a normalized hydrogen electrode. The chemical oxidation processes can be classified in two classes: -1. Classical Chemical Treatments and2. Advanced Oxidation Processes (AOPs)

Classical chemical treatment: Classical chemical treatments involves addition of an oxidant agent to the water containing the contaminant to oxidize it. Some widely used classical oxidants are chlorine, potassium permanganate, oxygen, hydrogen peroxide, ozonztion etc. This oxidizer has different advantages and disadvantages. For example,a) Chlorine is considered to be a good chemical oxidizer for water evaporation

because it destroys microorganisms. Though it is a strong and cheap oxidant, very simple to feed into the system. It also has some disadvantages like i) its little selectivity that high amounts of chlorine are required and ii) it usually produces carcinogenic organochloride byproducts.

b) Ozonation is a strong oxidant , does not introduce “strange ions” in the medium and has low solubility in water at standard temperature and pressure . Ozone plays a major role many applications, like the elimination of colour, disinfection, elimination of smell and taste, elimination of magnesium and organic compounds etc. As the pH increases, the rate of decomposition of ozone in water also increases. The major drawbacks of this oxidizer is that it has to be produced on site and needs installation in an ozone production system in the place of use due to which the cost of this oxidizer is extremely high.

Advanced Oxidation Processes (AOPs): Among various AOPs like UV/O3 process, UV/H2O2, O3/H2O2, Fe3+/UV-vis

process, UV/TiO2 (Heterogeneous photocatalysis), the Fenton reagent (H2O2/ Fe2+) is the most effective methods of organic pollutant oxidation.

Fenton process is widely used as a suitable treatment method for highly concentrated wastewaters due to its effectiveness in producing hydroxyl radicals.

Application of traditional Fenton process is limited by its acidic pH requirements, the formation of iron sludge and high cost of hydrogen peroxide.

But nowadays (EAOPs) based on Fenton’s reaction chemistry have received much attention for wastewaters remediation. EAOP is the electro Fenton (E-Fenton) process, the most popular electro-chemical advanced oxidation process which can proceed by the following chain reactions:

1) H2O2 + Fe2+ → Fe3+ + OH• + OH- (1)2) H2O → H+ + OH• + e- (2)3) Fe3+ + e- → Fe2+ (3)

Conclusion: Membrane integrated hybrid reactor: As the petrochemical industries effluents consist of different types of

wastes it cannot be treated by using only one conventional technique. Several physicochemical options and biological wastewater treatment processes are showed here which are technologically and economically feasible and have been widely utilised in the successful treatment of industrial wastewaters.

API – oil separator is an excellent technique for oil removal from industrial wastewaters whereas both aerobic and anaerobic treatment systems are feasible to treat wastewater from all types of industrial effluents. So a combination using an anaerobic process followed by an aerobic treatment system is a better option but those hybrid systems produce a high removal of toxic pollutants.

A membrane based integrated system followed by a coagulation/flocculation process can be applied where the membrane modules are in cross flow mode to increase the effectivity of the process; an ultrafiltration (UF) membrane is installed prior to reverse osmosis (RO) as a pretreatment where UF will remove emulsions, colloids, macromolecules or proteins (size under 100 nm) and (RO) will separate dissolved salts and small organics (size under 1 nm).

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Submitted by: Rimeli Roy Choudhury(14/CHE/416)