Hazardous Waste Management

(Class IUP) –Week 12

 Hazardous Waste Treatment:
Material Recovery and Utilization

Hazardous Waste Management

IDAA Warmadewanthi, PhD
Arseto Yekti Bagastyo, PhD ([email protected])

B.Eng Study Program

Dep. of Environmental Eng., FTSPK - ITS Week 12
www.its.ac.id INSTITUT TEKNOLOGI SEPULUH NOPEMBER, Surabaya - Indonesia
Books and References
• Trihadiningrum, Y., 2016. Pengelolaan limbah bahan berbahaya dan beracun.
Teknosain, Yogyakarta.
• Peraturan Pemerintah No. 101 Tahun 2014 tentang Pengelolaan LimbahBahan
Berbahaya dan Beracun.
• LaGrega, M.D., P.L. Buckingham, dan J.C. Evans, 2001. Hazardous waste
management. Second Edition. McGraw-Hill International Editions, New York
• Blackman, W. C., 2004. Basic hazardous waste management.- 3rd. Edition”. CRC
• Pichtel, J., 2005. Waste management practices - municipal, hazardous, and
industrial. CRC
• Other related books, references, and journal articles.

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 Course Learning Plan
Week Topic
9 Hazardous Waste Treatment – Stabilization and Solidification (S/S)
10 Hazardous Waste Treatment – Thermal/Incineration, in particular medical/infectious
wastes
11 Hazardous Waste Treatment – Biological, Remediation of HZW contaminated areas
12
Hazardous Waste Treatment – Material Recovery and Utilization of HZW (Review)
13 Secure Landfill for Long-Term HZW Storage
14 Case Study of Hazardous Waste Management; Households scale to Industrial/Manufacture
(Low to High scale)
15 Presentation of Case Study
16 Final-Semester Evaluation (EAS) Exam

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Treatment
and
Recovery

www.its.ac.idSource: David SNewby INSTITUT TEKNOLOGI SEPULUH NOPEMBER, Surabaya - Indonesia

 Teknologi Aplikasi Pada Industri
Pemisahan fisik
CONTOH TEKNOLOGI Gravity Settling Air limbah industri (tahap awal)
Filtration Penyamakan
UNTUK PROSES Flotation Kertas,mineral
Flocculation Kertas, pertambangan
RECOVERY MATERIAL Centrifugation Cat
Pemisahan komponen kimia
Distillation Perminyakan dan bahan kimia sejenis
Evaporation Plating logam, Smelting
Ion Exchange Plating logam, recovery krom
Ultrafiltration Coating logam
Reverse osmosis Garam
Electrolysis Plating logam
Carbon/resin adsorption Fenol
Solvent extraction Recovery zat warna, logam
Umumnya sistem recovery dan
Transformasi kimiawi
recycling menggunakan beberapa Precipitation Plating logam
jenis teknologi secara seri. Electrodialysis Pemisahan larutan asam dan logam
Chlorinolysis Pembuatan karbon tetraklorida
Reduction Plating Krom, merkuri
Chemical dechlorination Transformasi minyak
Thermal oxidation Recovery sulfur, HCl
(Office of Technology Assessment, 2005) Chemical dehalogenation Organik terhalogenasi
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 Ion Exchange
• Applications
• Removal of non-metal inorganic
• Removal or recovery of metal

Type of resin
a. Cationic resin - exchange positive ions
b. Anionic resin – exchange negative ions

(a) (b)

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ION EXCHANGE (Selectivity)
• Cations:
Ra2+ > Ba2+ > Sr2+ > Ca2+ > Ni2+ > Cu2+ > Co2+ > Zn2+ > Mn2+ > Ag+ >Cs+ > K+ >
NH 4+ > Na+ > Li+

• Anions:
HCrO4- > CrO42- > ClO4- > SeO42- > SO42- > NO3- > Br- > HPO4- > HAsO4- >
SeO32- > CO32- > CN - > NO2- > Cl- > H2PO4-, H2AsO4-, HCO3- > OH - >
CH3COO- > F-

Note: The least preferred has the shortest retention time, and appearsfirst
in the effluent and vice versa for the most preferred.
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Environmental
Electrochemistry

29/ 12/ 2020 10

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 ELECTROPLATINGWASTEWATER

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 ELEKTRODIALISIS

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 ELEKTRODIALISIS
• Digunakan untuk menyisihkan logam
mulia (emas, perak, platina)
• Prosesnya menggunakan arus listrik
untuk menggerakan ion terdisosiasi
melalui membran bermuatan
• Air limbah yang mengandung kation
dan anion dikontakkan di antara
membran
• Kation berpindah ke anoda negatif,
sedangkan anion berpindah ke katoda
positif
• Unit ini biasanya dapat menyisihkan
40-60% garam-garam pada air limbah

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 The EDunit represents a typical plate-and-frame (filter-press, sandwich) type device.
 The main core of this apparatus represents a membrane stack consisting of planar
plate anion (AM) and cation (CM) selective membranes.
 The individual membranes are separated by inert (electrically nonconducting) net-like
spacers providing mainly a mechanical support of the stack and determining the
geometry of the flow channel in the space between the membranes.
Generally, two independent hydraulic circuitries are considered:
(a) diluate stream (D) and concentrate stream (C) supplying diluate and concentrate
solutions into the diluate compartment (DC) and concentrate compartments(CC).

A part of the membrane stack consisting of one AM and CM with corresponding

compartments (DC and CC)then represents a repeating motive of the EDunit often
denoted as a membrane pair (MP).
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 ELEKTRODIALYSIS

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 ELEKTRODIALYSIS

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www.its.ac.id INSTITUT TEKNOLOGI SEPULUH NOPEMBER, Sur
 SOLVENTEXTRACTION IN METALS
• The practice of hydrometallurgy contains examples of a great number of diverse
solvent extraction processes.
• Solvent extraction of metals such as copper, uranium, cobalt and nickel, besides
being of great economic significance has been the spur for the development of
the engineering aspects of solvent extraction
• Besides the major metals there are commercial solvent extraction processes
operated for the recovery of metals such as tungsten, rare-earths, thorium and
vanadium.
• Metals for which solvent extraction has succeeded and the circumstances,
which caused these metals to become candidates for recovery by solvent
extraction, have some common features:

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 SOLVENTEXTRACTION IN METALS
• They are soluble in suitable lixiviants such as sulphuric acid, ammonia and
cyanide
• They are relatively valuable. Copper, which is the lowest priced metal recovered
in significant quantities by solvent extraction. Nickel, uranium and the precious
metals are more valuable.
• They can be recovered from the concentrated strip solution in a suitable
marketable or intermediate form by processes such aselectro-winning
• Suitable solvent extraction chemistry has been developed and available for
copper, nickel, uranium and other precious metals.

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 ELECTROWINNING
• Electro-winning involves the recovery and purificationof
metals using electrodeposition of metals at the cathode.
• The resulting products are metal cathode and leanelectrolyte
• The lean electrolyte is cooled and recycled back for stripping
unit.
• Metal cathode sheets are sent to for melting and casting

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THECHEMISTRYOFTHESOLVENTEXTRACTIONOFTHEMAJOR METALS

Classification of the four basic classes of metalextractants

These extractant classes on the basis of structure, extraction chemistry and the
metal species extracted

The four classes are:

• 1. Chelation Extractants
• 2. Ion Pair Extractants
• 3. Neutral or SolvatingExtractants
• 4. Organic Acid Extractants
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 EXTRACTANTCLASS:
FORMULA OR STRUCTURE CHELATINGAGENT

EXTRACTION CHEMISTRY

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 EXTRACTANTCLASS:
CHELATINGAGENT
• MODIFIERS
• ALCOHOLS,PHENOLS, ESTERS(TXIB) KETOXIMES/ALDOXIMEMIXTURES

SPECIALFEATURES
• Main commercial extractants for copper
• Operate on hydrogen ion cycle. Stripping is reverse of extraction
• Function with acid and ammoniacal leachsolutions
• More selective than other extractantclasses
• Kinetically slower than ion pairextractants
• Have good physical properties in terms of phase separation, low aqueous solubility, chemical
stability
• Relatively expensive to manufacture

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 EXTRACTANTCLASS: ION-PAIREXTRACTANTS
FORMULA OR STRUCTURE
Quaternary Amines R3R´N+Cl-
Primary Amines RNH2
Secondary Amines R2NH
Tertiary Amines R3N

EXTRACTION CHEMISTRY – QUATERNARY AND Tertiary Amines

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 EXTRACTANTCLASS:ION-PAIR
EXTRACTANTS
• MODIFIERSI
• SODECANOLORTRIDECANOL,AROMATICDILUENT

SPECIALFEATURES
• Commercial extractants foruranium, thorium, vanadium, gold, cobalt and other metals
• Modifiers promote solubility of the extractant - metal complex in the diluents
• Kinetics, both extraction and stripping arefast
• Extraction is usually of a metal anion complex
• Selectivity is not high. Other anions can compete with the metal being extracted
• Tertiary amines are more selective than primaryand secondary amines
• Selectivity can be pH dependent
• Primary, secondary and tertiary amines are relatively easy toproduce

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 EXTRACTANTCLASS:
FORMULAOR STRUCTURE NEUTRALORSOLVATING
• Tri Octyl Phosphine Oxide(TOPO)
• Tri Butyl Phosphate (TBP)
R3P= O
(RO)3PO
EXTRACTANTS
• Ketones (MIBK) R2CO
• Alcohols ROH
R= CH3and (CH3)2CHCH2
EXTRACTION CHEMISTRY
• Extraction is by adduct formation
•Stripping is with concentratedHNO3
SPECIALFEATURES
• TBPis used extensively in nuclear fuelreprocessing
• Kinetically fast
• Extract neutral metal complexes
• Selectivity is low
• Organometallic complex must be organic soluble

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 EXTRACTANTCLASS:
FORMULA OR STRUCTURE
• Phosphinic Acids R3P(O) OH
ORGANICACID
• Sulphonic Acids RSO2OH EXTRACTANTS
• CarboxylicAcids R3C- COOH, Versatic Acid
• PhosphoricAcids (C4H9CH(C2H5)CH2O)2 POOH,
D2EHPA

SPECIALFEATURES
• Phosphinic acids are widely used for cobalt extraction
• Versatic acids can be used for Cu and Ni extraction
• D2EHPAextracts a wide range of metals
• Operate on a hydrogen ion cycle but do not display hydrogen ion stoichiometry. Often
between 1 and 2 moles of extractant are required for each mole of hydrogen produced
during extraction.
• Selectivity is poor and careful pH control may be required toachieve reasonable selectivity

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PEMANFAATAN LB3
• Onsite Use & Reuse  Limbah dimanfaatkan kembali sebagai bahan baku
pengganti proses yang lain.
• Offsite Reclamation  Merupakan proses recovery material berharga yang
terkandung dalam limbah B3. Sistemnya mengangkut limbah keindustri
pemanfaat komersil yang kemudian akan memproses kembali limbah tersebut dan
menjualnya, atau mengembalikan kembali hasil olahan ke industri penghasil
limbah B3.
• Interindustry Waste exchange  Limbah B3 yang terolah atau belum terolah
ditransfer ke industri lain untuk digunakan sebagai bahanbaku.
• Energy recovery material limbah digunakan untuk produksi energi, misal di
industri aspal atau cement kilns atau incinerator yang dilengkapi dengansistem
energy recovery.

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 HZWASTEUTILIZATION
From Cradle From Cradle to CRADLE
to TheGrave (Pemanfaatan limbah B3)
PP101 of 2014
Permen LH No. 02/2008 concerning Hazardous WasteUtilization
 Every person producing hazardous waste must be made use of the
hazardous waste.
 In the event that everyone is not able to do it themselves, the hazardous
waste utilization will be submitted to the hazardous waste user.
 The utilization of hazardous wasteincludes:
© The utilization of hazardous waste as a substitute for raw materials;
© The utilization of hazardous waste as a substitute for energy sources;
© The utilization of hazardous waste as raw material; and
© Hazardous waste utilization is in accordance with the development of science and
technology.

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 HZWASTEUTILIZATION

 Hazardous waste is utilized by considering:

© availability of technology;
© product standard if the result of the hazardous waste utilization is a product; and
© quality standards or environmental standards.
 The criteria for utilizing hazardous waste are carried out by considering :
 Fuel Substitution:
© Calorie content: ≥ 2500 kcal / kg;
© Moisture content: ≤15%
© Does not contain halogenatedcompounds
© The type of waste and the level of pollutants in the waste meet the permit
requirements;
© Air emissions comply with air emissions from HZ wastetreatment
© Previously conducted a trial of burning HZwaste
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 UTILIZATION OF RAWMATERIALSFOR THE
PRODUCTIONPROCESS

• Solidification / Stabilization
• Utilization for a mixture ofpaving, brick
and red bricks.
• Requirements must pass the TCLPtest
(Attachment IV PP101 2014)
• Compressive strength test 10 ton/m2

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Recycle of HC- contaminated soil

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 CHALLENGESIN THEUTILIZATION OFHZWASTE

• The amount of waste continues to increase and the utilization /

treatment capacity is unable to accommodate HZwaste.
• The utilization permit already exists but what about the
implementation in the field? Influence on the surrounding
community?
• Utilization challenges in the community a technical point of view,
what is the safety of the use of raw materials containing HZ waste?

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 PENGOLAHAN DAN PEMANFAATAN LAHAN TERKONTAMINASILB3

Sumber: Direktorat Pemulihan Kontaminasi, DITJEN PSLB3KLHK–

Identifikasi dan Inventarisasi Lahan Terkontaminasi Limbah B3, 12 Agustus 2020
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 CHALLENGESIN THEUTILIZATION OFB3 WASTE

• The amount of B3 waste from

August to September 2015, which
has been managed is 102 million
tons, and only 1.82% is utilized
(KLHK, 2015).
• Utilization for fuel and raw
material substitution The use of used batteries, especially Pb,for
recycling (already licensed), but its
(solidification / stabilization) implementation is still far from the
requirements in PP1012014

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 CHALLENGESIN THEUTILIZATION OFHZWASTE

• Technical implementation challenges  utilization method to beused.

• The mixture of waste with other raw materials must be in such a way that
it produces a product of good quality (ex : passes the TCLPtest and
compressive strength)

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 CHALLENGESIN THEUTILIZATION OFHZWASTE

• Product use, for example paving and brick

or red brick. There should be no damage
such as broken or cut etc., so that the
waste does not spread to theenvironment .
• Supervision of utilization  is not an
excuse that it is only stockpiled fora long
time. The impact on the environmentis
enormous. Worker safety and worker
health also really need
supervision

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 Self-Evaluation/Review
Can you explain:
1. What characteristics/type of the hazardous wastes that can be
recovered and utilized?
2. What factors that need to be considered when applying
recovery technologies?
3. By choosing one example, how the recovery technologies
work?
4. What are the challenges for recovery and utilization of
hazardous waste?

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 Hazardous Waste Treatment

Learn and prepare:

• Long – term HZ waste storage(disposal)

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End of Course Week 12

- THANKYOU-