ADSORPTION. Adsorption, the binding of molecules or particles to a surface.
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1 جذب
2 ADSORPTION Adsorption, the binding of molecules or particles to a surface.
3 Adsorption vs. Absorption Adsorption is accumulation / adhesion of molecules at the surface of a solid material (usually activated carbon) in contact with an air or water phase Absorption is dissolution of molecules within a phase, e.g., within an organic phase in contact with an air or water phase
4 Adsorption PHASE I PHASE 2 Absorption ( partitioning ) PHASE I PHASE 2 P K c gas H aq Henry s Law
5 If we have to remove soluble material from the solution phase, but the material is neither volatile nor biodegradable, we often employ adsorption processes. adsorbate: material being adsorbed adsorbent: material doing the adsorbing. (examples are activated carbon or ion exchange resin).
6 Steps in Preparation of Activated Carbon Pyrolysis heat in absence of oxygen to form graphitic char Activation The char is then activated by heating to o C in the presence of steam, oxygen or CO 2. Result: Activated carbon which is highly porous, micro-crystalline material which resembles graphite plates with some specific functional groups (e.g., -COOH, -OH)
7 Increasing magnification
8 Factors Influencing Adsorption 1. Surface Area: A large specific surface area is preferable for providing large adsorption capacity
9 2. Nature of the Adsorbate Adsorption of a solute is inversely proportional to its solubility in the solvent. The greater the solubility, the stronger the solutesolvent bond and the small the extent of adsorption. In general, the solubility of any organic compound in water decreases with increasing chain length.
10 3. Molecular sizes.
11 4. ph of zero pint charge
12 5. ph Because hydrogen and hydroxide ions are adsorbed quite strongly, the adsorption of other ions is influence by the ph of the solution. In general, adsorption of typical organic pollutant from water is increased with decreasing ph.
13 6. Temperature increases with decreasing temperature.
14 7. Adsorption of Mixed Solutes The degree of mutual inhibition of competing adsorbates should be related to the relative sizes of the molecules being adsorbed, relative adsorptive affinities, relative concentrations of solutes.
15 8. Nature of the Adsorbent
16 9. Pore size distribution micropores: <2nm dia mesopores: 2nm to 20 nm dia macropores: > 20 nm
17 10. Surface polarity adsorbents having affinity for polar substances such as water or alcohols are called as hydrophillic. Examples: aluminosilicates such as zeolites, porous alumina, silica gel or silica-alumina.
18 adsorbents having affinity for non-polar substances called as "hydrophobic" adsorbents. Carbon, polymer adsorbents and silicalite are typical nonpolar adsorbents.
19 Other parameters used for AC characterization Phenol Number: Index of carbon s ability to remove taste and odor compouns Iodine Number: Adsorption of low-molecular weight substances Micropores, radius <2 µm Molasses Number: Carbon s ability to adsorb high molecular weight substances Pores 1 50 µm
20 Other parameters used for AC characterization High iodine number Effective for ww with low molecular weight organics High molases number Effective for ww with high molecular weight organics
21 Types of adsorption Depending on the nature of attractive forces existing between the adsorbate and adsorbent, adsorption can be classified as: Physical adsorption Chemical adsorption
22 Physical adsorption the forces of attraction between the molecules of the adsorbate and the adsorbent are of the weak van der Waals' type. Since the forces of attraction are weak, the process of physisorption can be easily reversed by heating or decreasing the pressure of the adsorbate (as in the case of gases).
23 Chemical adsorption (Chemisorption) In chemisorption, the forces of attraction between the adsorbate and the adsorbent are very strong; the molecules of adsorbate form chemical bonds with the molecules of the adsorbent present in the surface.
24 Adsorption Isotherms Technical feasibility of Activated Carbon Adsorption tests Generate adsorption isotherms
25
26 Adsorptive Equilibration in a Pore Porous Adsorbent Early Later Laminar Boundary Layer GAC Particle Adsorbed Molecule Equilibrium Diffusing Molecule
27 Adsorption Isotherms Add Same Initial Target Chemical Concentration, C init, in each Control Different activated carbon dosage, C solid, in each q fin mg cinit cfin mg/l g csolid g/l An adsorption isotherm is a q vs. c relationship at equilibrium
28 The Langmuir Isotherm model The Langmuir adsorption isotherm the most widely used isotherm for the adsportion of pollutants from a liquid solution based on the following hypotheses. (1) Monolayer adsorption. (2) Adsorption takes place at specific homogeneous sites on the adsorbent. (3) Once a pollutant occupies in a site; no further adsorption can take place in that site. (4) Adsorption energy is constant and does not depend on the degree of occupation of an adsorbent s active centres. (5) The strength of the intermolecular attractive forces is believed to fall off rapidly with distance. (6) The adsorbent has a finite capacity for the pollutant. (7) All sites are identical and energetically equivalent. (8) The adsorbent is structurally homogeneous. (9) There is no interaction between molecules adsorbed on neigh bouring sites
29 The Freundlich isotherm model The Freundlich equilibrium isotherm equation is an empirical equation used for the description of multilayer adsorption with interaction between adsorbed molecules
30 Commonly Reported Adsorption Isotherms Isotherms Equations Linear expression Plot Parameters Freundlich Langmuir qe amount of pollutant adsorbed at equilibrium (mg/g)
31 Example in excel file
32 مثال یک سفره آب زیرزمینی به مقادیر جزیی از نگهدارنده چوب به نام پنتاکلروفنل )PCP( آلوده شده است. از کربن فعال گرانوله برای تصفیه PCP این آب )با مقدار اولیه mg/l 10( در مقیاس آزمایشگاهی استفاده و نتایج زیر )جدول اکسل( حاصل شده است. الف( نتایج با کدام ایزوترم همخوانی بیشتری دارد ب( مقدار کربن فعال مورد نیاز برای تصفیه این آب بدست آورید
33 مثال در یک فاضالب صنعتی با دبی 200 m3/d غلظت فنل 100 mg/l می باشد. با فرض اینکه مقدار مجاز فنل در پساب خروجی 1 mg/l و بر اساس ایزوترم فروندلیچ برای رسیدن به این غلظت باقیمانده X/M= حاصل شده باشد. میزان کربن فعال مورد نیاز یک روز تصفیه خانه را محاسبه نمایید
34 Solution Phenol load= 200 m3/d 1000 L/m3 100 mg/l= 20,000,000 mg/d X= 20,000,000 mg/d 0.99= mg/d X/M= M=416.8kg/d
35 مثال در نتیجه کلریناسیون در یک تصفیه خانه آب مقدار mg/l 0.12 کلروفرم تشکیل می شود. چه مقدار پودر کربن فعال برای تصفیه میزان جریان 4000 m3/d مورد نیاز است تا مقدار کلروفرم به 0.05 mg/l برسد ضرایب ایزوترم جذب فروندلیج برای کلروفرم: kf=2.6 1/n=0.73
36 Solution q e q e X M k f. C 1 n e V M. C 1 n e C V ( C C ) e e 0 0 M k C f ضرایب ایزوترم را جایگزین می نماییم: V M (0.05) L g M V g / L مقدار کربن فعال برای تصفیه 4000 m3/d بدست می آوریم: 3 3 (0.24g / L)(4000m / d)(1000l / m ) PAC Re quired 960Kg / d 1000g / kg
37 مثال حداقل دوز پودر کربن فعال که برای حذف ژئوسمین )عامل ایجاد بو( مورد نیاز است را محاسبه نمایید. غلظت اولیه ژئوسمین 50 ng/l و هدف تصفیه کاهش ژئوسمین تا 5 ng/l است. مقادیر k و 1/nایزوترم فروندلیچ برای ژئوسمین به ترتیب 200 و 0.39 می باشد.
38 Applications of adsorption
39 استفادي اس جذب در تصفی فاضالب در چىدیه م رد اوجام می ش د: -1 الف- استفاده از جذب در تصفیه پیشرفته فاضالب در تصفیه فاضالب چندین مرحله داریم: تصفیه مقدماتی Preliminary treatment تصفیه اولیه Primary treatment تصفیه ثانویه Secondary treatment تصفیه پیشرفته Tertiary treatment
40
41 در تصفیه فاضالب معموال تصفیه ثانویه کافی است و ما را به استانداردهای مورد نظر می رساند. ولی در مواقعی که منابع آب به آلودگی کم حساس باشند نیاز به تصفیه بیشتر فاضالب )یا همان تصفیه پیشرفته( داریم. یعنی مقادیر BOD5 و SS را باید تا کمتر از 5 mg/l کاهش داد در صورتی که در تصفیه ثانویه کاهش این پارامترها تا mg/l 30 کفایت می کند.
42 ب- تصفی فیشیکی شیمیایی فاضالب این فرایند در صورتی بکار می رود که مواد آلی موجود در فاضالب قابلیت تجزیه بیولوژیکی نداشته باشند.
43 ج- بکار بزدن پ در کزبه فعال در لجه فعال
44 در تصفیه فاضالبهایی که درجه تصفیه پذیری یا تجزیه پذیری پایینی دارند مانند صنایع پتروشیمی و صنایع نفت مشاهده شده است که اگر به سیستم لجن فعال پودر کربن فعال اضافه نمایند تصفیه پذیری فاضالب باال می رود به این علت که کربن فعال بعنوان جاذب عمل کرده و همچنین ذرات کربن فعال سطح زیادی برای رشد میکروارگانیزم ها و در نتیجه تصفیه بیشتر فاضالب فراهم می نمایند.
45 د- ب عى ان محیطی در تصفی بی ل ژیکی در سیستمهای تصفیه بیولوژیک با رشد چسبنده محیطهایی وجود دارد که به آنها مدیا گفته می شود.,v c IN از کربن فعال گرانوله با قطر حدود mm می توان به عنوان مدیا یا بستر استفاده نمود. v, c OUT Packed Bed
46 ه- برای عملکرد بهتر حوضچه ته نشینی و لخته سازی PAC + Coagulants Settled Water Sludge Withdrawal PAC particles may or may not be equilibrated PAC + Coagulants Flocculated Water
47 - بزای کىتزل رط بت Silica and alumina gels are used as adsorbents for removing moisture and for controlling humidity of rooms.
48 - در ت ی ماسک ا Activated charcoal is used in gas masks as it adsorbs all the toxic gases and vapours and purifies the air for breathing.
49
50 Carbon Regeneration Objective: Remove the previously adsorbed materials from the carbon pore structure Methods: - Thermal - Steam - Solvent extraction - Acid / base treatment - Chemical Oxidation - Microbial regeneration
51 Thermal Regeneration Drying Desorption High temperature heat treatment ( o C) in the presence of water vapor, flue gas, oxygen - Multiple heat furnaces - Fluidized bed furnaces are used.
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