Chapter 7 - Wastewater Treatment
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381
CHAPER 7
WASTE TREATMENT
7.1
INTRODUCTION
Waste is a general problem in a chemical plant and it still remains a global problem in developed countries. Normally, a plant takes the raw materials to produce, through stages of processing steps, one or more products for sale with purpose to generate income. However, it is seldom possible to convert 100% of the raw materials into desired products, hence, there is almost always some waste or residual. Based on Second Law of Thermodynamic, there is no process can achieve 100% efficiency, so, the wastes are always to be taken into consideration. In the manufacturing and heavy industries, there have been rapid increases in the generation of pollutants and industrial wastes, resulting in the deterioration of environment. Waste treatment is an essential process in order to reduce and minimize the environmental pollutions, especially for those contains toxic components. It is a responsibility to treat the waste to an acceptable form or level before discharge into the ecosystem. Waste treatment is an economic burden to a process plant since it does not bring any economic advantage to the company participated. However, the implication implication of waste treatment plant becomes important with regards to environmental pollution. Thus, waste treatment is important in order to contribute to a safe environment. In Malaysia, Department of Environment (DOE) is responsible to make sure the all chemical plants design a waste treatment unit to treat the waste to an acceptable form or level before discharge them into the environment. Direct discharge of unwanted material into the natural ecosystem may pollute and destroy
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382 the balance of the ecosystem. Before the wastes are discharged to the environment, some consideration must be done. Firstly, we have to consider the economic aspect, whether the waste can be recover and sell as a by-product or not. There are 2 approaches to deal with waste produced from an industry: 1. Waste minimization 2. End-of-pipe Treatment Waste minimization is to eliminate or reduce the waste generated at the source or by not producing it in the first place. Therefore, it will eliminate any problems in treating it and at the same time we can save more on capital cost. On the other hand, end-of-pipe treatment means to transform the generated waste into another kind of materials or components that is harmless so that it can be released to the environment by using any physical, chemical, and biological or the combination of three methods. However, the treated waste is still hazardous to the environment; we can send it to waste treatment experts such as Kualiti Alam in Bukit Nenas, Negeri Sembilan. In this chapter, we will deal with the liquid wastes generated by Butyl Acetate production.
7.2
REGULATIONS
In Malaysia, the matters relating to the disposal of plant wastes regulated under Environment Quality Act 1974. Department of Environment (DOE) is the parties that responsible for managing matters that related to waste disposal. In order to ensure that the premises or plant obey the regulation regarding the waste disposal, the waste must be treated according to the parameter set as in (Appendix 7G: Parameter of Environment Quality Act 1974). Basically waste treatment plants are non-profitable. Hence, an optimum plant is needed to apply in order to minimize the expenses occur from the waste treatment plant. plant. It must be effective in order to comply with the standard sets by the authorities. The wastewater is essentially the water supply of the community after it has
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383 establishments, together with groundwater, surface water and other means may be present. If untreated wastewater is allowed to accumulate, the decomposition of the organic materials it contains can lead to the production of of malodorous gases. In addition, untreated wastewater usually contains numerous pathogenic microorganisms that dwells in human internal organs or may be present in industrial wastes. The selected method to treat these wastes must be suitable in order to control the concentration of chemical compound before releasing to environment. However, these wastes could be minimized while operation by considering several units operations where waste minimization can be utilized.
7.3
AIR AND WATER STANDARDS
7.3.1
Ambient Air Quality Standards
Ambient air quality standard is a national target for an acceptable concentration specific pollutant in air. Under the clean Air Act, EPA develops two standards pollutant of concern. 1. A primary primary standard is to protect public health. The clean clean Air Act mandated primary standards be based entirely on health-related information, without considering the cost of attaining the standard. 2. A second standard is to protect public welfare. Public welfare includes soils, water, crops, vegetation, buildings, property, animals, wildlife, weather visibility, transportation and other economic values as well as personal being. The Clean Air Act, which was last amended in 1990, requires EPA to set National Ambient Air Quality Standards for pollutants considered harmful to public health and the environment. The EPA Office of Air Quality Planning and Standards (OAQPS) has set National Ambient. (Appendix 7F: National Ambient Air Quality Standard). Units of measure for the standards are parts per million (ppm) by volume,
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384 7.3.2
Water Quality Standards
Water quality criteria based on present – –day standards and guides are presented to assist in the establishment of water system performance goals for any plant. Quality criteria are expected to change as new information on the nature and behaviour of water is is revealed. revealed. The trend is toward production of water water of higher quality. The quality of raw-water sources is not expected to improve substantially and indeed may worsen in many places as greater use is made of streams for waste disposal. The water treatment plant, therefore, will have an increasingly important role of production of water of high quality. (Appendix 7H: Optimum and Maximum Characteristics of Water for Industrial.).
7.4
WASTE MANAGEMENT HIERARCHY
The best waste management is illustrated by the waste management hierarchy. Pollution prevention or source reduction is always the top priority option in waste management decisions. The waste management is begin by source reduction and followed by recycling. Source reduction means the reduction of waste at the spot and this is most preferable because in recycling the generation still occurs. If these two preferred options are not possible then waste treatment should be considered before the final preferable option disposal is considered.
Source Reduction Recycling
Treatment
Disposal
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385 The four options of waste management above are more clearly defined as listed below: Source reduction
-
Procedures that either reduce or eliminate the generation of hazardous waste before the waste is produced.
Recycling
-
Reuse of waste stream as an ingredient ingredient in a productive process or recovery recovery of a reusable.
Treatment
-
The use of physical, chemical, biological, or thermal technologies to to reduce the volume, toxicity and/or mobility of waste.
Disposal
-
7.5
The placement placement of of waste into landfill or the underground injection injection of of waste.
WASTE MINIMIZATION AND POLLUTION PREVENTION PREVENTION
Waste minimisation is at our top priority option in effluent solution. The best solution to effluent problem is not to produce the waste in the first place or the waste production is minimised. Waste minimisation reduces waste treatment cost and reduces raw materials costs. Waste minimization and waste treatment can be defined as below: Waste Minimization Minimization
-
The reduction to extent extent feasible, feasible, of any solid or hazardous waste prior to any treatment, storage, or disposal.
Waste Treatment
-
The dealing of waste by means of certain techniques to achieve reduction of of volume, toxicity and mobility of waste after the waste has been generated
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386 7.6
OBJECTIVES OF MINIMIZATION AND TREATMENT
The waste minimization and treatment plant also have to fulfil the following objective below: 1. To reduce potential environment liabilities. 2. To protect public and workers health from any harmless regarding the pollution. 3. To meet and complies with the waste minimization minimization standard set up by Department of Environment (DOE). 4. To minimize the cost of plant by reducing waste treatment and disposal cost, raw material purchases and other operating costs including utility costs.
7.7
METHODOLOGY
This chapter deals with the methodology of the evaluation work of waste minimization in Butyl Acetate plant. It consists of: 1) Waste Sources Definition 2) Waste Sources Description 3) Selection of Waste Management Methods 4) Waste Treatment Process Process Flow Diagram and Description 5) Calculation: Mass Balance 6) Wastewater Equipment Sizing 7) Wastewater Equipment Costing 8) Plant layout for the Waste Treatment System
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387 7.7.1
Waste Sources Definition
In the production of Butyl Acetate, there are two types of waste generate in Butyl Acetate plant: 1. Liquid waste (Figure 10.2: Source of Liquid Waste from Butyl Acetate Plant ) 2. Gaseous waste (Figure 10.3: Source of Gaseous Waste from Butyl Acetate Plant )
Figure 10.2: Source of liquid waste w aste from Butyl Acetate plant
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388 7.7.2
Waste Sources Description
Figure 10.7.1a shows the stream waste or stream 16 which decant from the bottom of the decanter (V-100) contains a variety of components such as butanol, acetic acid, butyl acetate and water as a major component. The other stream discharge from the decanter which is stream 17 will proceed to next distillation column (T-101) for further processes. In stream 16, the waste containing mostly liquid water which is about 98.86 mol%. The other components are butanol, acetic acid and butyl acetate. The composition for each component can be shown by referring to (Appendix 7A: Wastewater stream composition). In other hand, there are also a gaseous waste produce in our plant. This waste generate from the equipment such as reboiler especially at the distillation column. The utilities that pass through the reboiler will be converted into gas form. Therefore, the gases that may contain a toxic acid which must be treated first before it discharge to the environment. Figure 6.7.1b shows the source of gases waste from reboiler in Butyl Acetate Plant). 7.7.3
Selection of Waste Management Methods
This chapter deals with the selection of waste management methods that are considered in this Butyl Acetate plant. As mentioned above, there are two type of waste generate in our plant which is liquid waste and gaseous waste. Liquid waste Treatment
-
The method of wastewater treatment system chosen is Conventional Wastewater System treatment which consist of two type of treatment, Primary Treatment (Primary settling basin) and Secondary Treatment (Aeration Tank and Secondary Clarifier).
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389 7.7.4
Waste Treatment Process Flow Diagram Diagram and Description
The proposed wastewater treatment which is Conventional Wastewater Treatment System can be shown in the Figure 10.7.4b. There is one stream that produced waste in this plant which is stream 16. This stream contains mostly liquid water which is about 98.86 mol%. The composition of the stream 16 can be shown in (7A: Wastewater stream composition). For the gaseous waste, the proposed treatment is Gaseous waste treatment through direct thermal combustion. This type of treatment can be shown in Figure 10.7.4a. For the liquid waste treatment, the biological treatment is used because the waste that entering the treatment system contains of organic compound. Besides that, we can also say that biological treatment is suitable for treatment because the waste that entering the waste treatment has been neutralized first in the neutralization tank before it undergo further treatment. In other hand, the use of nutrients such as procaryotic sp. and eucaryotic sp. is preferable since it ability in dealing with the highly toxic and chemical waste.
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390
4
P-6
11 P-8
1
2
3
5
P-5
21
E-100 V-100 MIX-100
P-22
7
V-101 6 8
V-102
V-100
Incinerator
TITLE:
V-101
Caustic Scrubber
Gaseous Waste Treatment
V-102
Neutralization Tank
MIX-100
Mixer
DRAWN BY:
E-100
Heat Exchanger
Mohamad Razif bin Mohamad. Rodzi
Figure 10.4: Gaseous waste treatment process flow
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391 7.7.4.1
Gaseous Waste Treatment Description
The simplify flowsheet for gas treatment process is shown in the Figure 106.7.4a. The waste from reboiler at stream 11 and stream 21 is mixed in a mixer (MIX-100). After that the stream mixed is heated up to 500 C in the heat exchanger (E-100) before it been sent to incinerator (V-100) for combustion. In the incineration, waste stream contains mixture components of butanol, acetic acid, butyl acetate and water is mixed with fuel and combustion air. The process begins when this mixture reacted at high temperature (650800 C) under control by catalyst. catalyst. The catalyst is generally generally platinum platinum (noble metal) dispersed on the surface of a catalyst support. At this stage, most of the components are converted into NOX, CO, CO2 and H2O. Reduction of NOX in incinerator depends on selection of catalysts. Most of the conversion is around 50 to 90 %. Treated gas temperature temperature must must not be below than than 300 C in order to avoid avoid corrosion in the stack. After the t he incinerator process, the waste containing co ntaining dry acetic acid and an d a few gases is passed through a caustic scrubber (V-101). The caustic solution about 73% w/w concentrations was injected into the scrubber. The function of caustic solution is to absorb the toxic gases so that the clean air will discharge at the top of the scrubber. This type of clean air will be measured by comparing its concentration with the concentration set up by the Department of Environment (DOE) or referring to (7 F: National Ambient Air Quality Standard). Besides that, the dry acetic acid that passed through a scrubber will also be neutralized by the caustic solution so that the products obtain from the neutralization process will not contain high percent of water. It is easier to be sent to Kualiti Alam to be treated as a schedule waste.
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392
23
19 V-104
V-101 16
17
18
20 P-102
V-101
V-102
V-103 P-101
21
22
24
MIX-100
V-101 Neutralization Tank
TITLE:
V-102 Primary Settling Basin
Conventional Wastewater Treatment System
V-103 Complete-Mix Reactor V-104 Secondary Clarifier
DRAWN BY:
P-101 Pump to Complete-Mix Reactor
Mohamad Razif bin Mohd. Rodzi
P-102 Pump to Secondary Secondary Clarifier MIX-100 Mixer Figure 10.5: Conventional wastewater treatment system using activated sludge system
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393 7.7.4.2
Liquid Wastewater Treatment Description
Like the other chemical plants, Butyl Acetate plant also produces wastewater where in form of liquid phase. The wastes discharge from the bottom of decanter (V-100) contains several components such as butanol, acetic acid, butyl acetate and water which flow at the rate of 1931 kg/h. The process flow diagram of wastewater treatment proposed is shown as in Figure 10.7.4b, we have selected Conventional Wastewater System as our treatment of the waste since it is contain an organic compound which can be treated through biological microorganisms. This wastewater treatment system consists of equipment such as Neutralization Tank, Primary Settling Basin, Complete-Mix Reactor, Secondary Clarifier and mixer. The process begins with the incoming waste from the stream 16 is flow into a Neutralization Tank (V-101). The function of installing this tank is to ensure that the pH of waste is in the range required which is 5.5 – 9. The small amount of Sodium Hydroxide (NaOH) was injected into the tank to neutralize the acidic acid. The pH indicator must also be installed inside the tank to measure the value of pH. If the value of pH obtain was complies with the range needed, the wastewater will then be allowed to discharged into the Primary Primary Settling Basin (V-102). The main objective of this basin is to decrease the amount of BOD5 and SS by some percent and also separate the heavy organic in form of sludge. Efficiently designed and operated
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394 The biological treatment of wastewater stream is based on the ability of a mixed population of microorganisms to utilize organic contaminants as nutrients. Organic constituents can be removed by aerobically converting them into carbon dioxide and water (mineralization) or by other mean we can anaerobically decompose them into methane and carbon dioxide; or bio transferring to less toxic or non-toxic organic compounds. Because of aerobic process, air which contains oxygen (O2) from atmosphere is bubbled into the tank. Besides that, the aeration tank also equipped with the mechanical stirrer which function to saturate the wastewater with the oxygen. Besides that, it also important for the well distribute of the oxygen in order to ensure the biological microorganism got enough oxygen supplied before react with the incoming influent. Biological microorganism requires specific ratios of carbon and nutrients. The most important nutrients are nitrogen, phosphorus, sulphur, potassium, calcium, and magnesium.
Industrial
wastewater
often
lacks
the
essential
macro-
and
micronutrients, which must therefore be added during treatment. Commonly biological microorganisms used in our activated sludge system are procaryotic and eucaryotic since their ability to treat an organic toxic. Because the bacteria deplete the substrate, flocculation takes place. The soluble substrate becomes a solid biomass. This is the place where the mixed liquor
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395 7.7.5
Calculations
7.7.5.1
Assumptions
1. Influent and effluent biomass X concentrations are negligible compared to biomass at other points in the system. 2. Influent food concentration So is immediately diluted to the reactor concentrations S because of the complete mix regime. 3. All reactions occur in the reactor. Example, Example, neither biomass production nor food utilization occurs in the clarifier. 4. Because of assumption (3) the volume represents the volume of reactor only. 7.7.5.2
Mass Balance
7.7.5.2.1
pH calculation
In wastewater treatment of Butyl Acetate, the pH value plays an important key to the wastewater treatment. According to Department of Environment, the wastewater that can be discharge to the sewage must in between pH 5.5 to 9. Thus, pH calculation before treatment is essential to determine how much alkaline solution
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396 Table 10.1: Concentration of acetic acid
CH3COOH
CH3COO-
H+
Initial
11.9192M
+xM
+xM
Change
-xM
xM
xM
Equilibrium
(11.9192-x)
xM
xM
Concentration
≈11.9192 M
ka for acetic acid = 1.8 x 10-5
(6.1)
Where x = [H+], so pH = - log [H+] = - log [0.01465] = 1.83
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397 7.7.5.2.2
Neutralization Tank S-16a
0.9527 kg NaOH /hr S-16
1931 kg WWT /hr 1845.8429 kg H2O /hr 1.3517 kg AA /hr 62.5644 kg BuOH /hr 21.241 kg BuAc /hr
Neutralization Tank
S-17
1931.9527 kg WWT /hr
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398 It can be concluded that the total flow rate of waste after neutralization process is 1931.9527 kg/hr. We can see in the process that the amount flow rate of NaOH required to neutralize the acid until it pH in the range of 5.5 – 9 is 0.9527 kg NaOH/hr. Besides that, we also used the pH indicator to measure the value of pH. The pH indicator will measure the reading and will released the wastewater after the range of pH was complies with the standard. 7.7.5.2.3
Calculation of COD and BOD in waste stream
Acetic Acid
CH3COOH + 2 O2 From the equation;
2 CO2
+ 2H2O
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399 7.7.5.2.4
Primary Settling Basin
S-17
S-18
Primary Settling Basin 1931.9572 Kg/hr
772.7811 kg/hr
S-22
1158.6 kg/hr Figure 10.7: Primary settling basin configuration
Efficiently designed and operated primary sedimentation tanks should remove from 50 to 70 percent of the suspended solids and 25 to 40 percent of the Biological
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400 7.7.5.2.5
Activated Sludge System (Complete-Mix Reactor and Secondary Clarifier)
S-23 V-104
S-18 Qo, Xo
V-103
O2 P-101
Xe, Se Q3=Qo-Qw
S-19
S-20
X, S Qo + Qr
Qu, Xw
S-20a Qw, Xw, S
S-21 Q r , Xw
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401 Effluent BOD5 for substrate for substrate concentration, S was calculated as below,
(6.5)
Assume suspended solids (SS) in effluent = 20 mg/l and VSS/SS=0.8. If degradable fraction of volatile suspended solids (VSS) =0.7, BOD5 of VSS in effluent, Xe = 0.7(0.8x20) = 11 mg/l. Thus, total effluent BOD5 = 13.6 + 11 = 24.6 mg/L (acceptable). The parameter for the growth constant for the Domestic wastewater can be shown
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402 Then, the food-to-mass ratios was calculated as below,
(6.7)
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403 Return Sludge flow rate, Qr . A mass balance around the secondary clarifier can be written as follows, (6.10) Rearrange the equation in term of Qr ,
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404 7.7.6
Equipment Sizing
7.7.6.1
Neutralization Tank
Wastewater neutralization plays an important part in a wastewater treatment process. It provides the optimum environment for microorganism activity between pH 6.5 to 7, and the right waste discharge to the public sewage as mandated by
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405 Let H = 2D, therefore,
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406 By taking a sidewall depth of 3.5 m, volume of tank is approximately,
The detention time at flow rate is
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407 Length of the reactor,
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408
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409 Where,
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410 7.7.7.1.5
Utilities
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411 7.7.7.2.2
Heat Exchanger
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