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Refining of Precious Metal Powder Spent Catalyst Waste
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Refining of Precious Metal Powder Spent Catalysts
Imprint
Published by:
Evonik Industries AGCatalysts Business Line
Rodenbacher Chaussee 463457 HanauGermany
Responsible for the content:
Dr. Jrgen [email protected]
Concept and design:
United ArtsAgency for Communication and Design
Bahnhofstrae 265239 HochheimGermany
Photography:
Robertino Nikolicwww.robertinonikolic.com
Contents
Accelerating Your Chemistry
Evonik A World Leader in Chemical CatalystsGlobal Sites
Introduction
Precious Metal Powder Catalysts
The Precious Metal Cycle
Precious Metal Management and Refining
The Recovery Process
Three Key Steps
Packaging, Transport and Legislation
Questionnaire andIneractive Calculation Tool
Evonik Brings Value to Your Company
Our ServicesBrochures available from Catalysts
0405
0809
1011
1213
1415
1617
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Evonik Industries, formerly known as Degussa, has been a leader in chemical catalysts for almost 40 years. Now as before, customers all over the world rely on Evonik as a competent and trusted partner. Today Evonik is a fully integrated partner in catalysis, with all three disciplines homogeneous and hetero-geneous catalysis and biocatalysis under a single roof. This makes Evonik unique, and gives our customers the flexibility of finding the most cost-efficient solution for their needs.
Evonik A World Leader in Chemical Catalysts
With its heterogeneous catalysts for batch, semi-batch and continuous processes, the Catalysts Business Line serves the life sciences, fine chemicals, industrial chem-icals and polymers markets. Our objective is to work with you to develop and scale up tailor-made catalysts that will make your production processes more reliable, more efficient and more predictable.
In this technology driven business, Evonik continues to invest in state-of-the-art equipment for development, testing and production. Evonik is continually broadening its portfolio of technologies and services to deliver op-timised catalysts for your process.
Accelerating Your Chemistry
Evonik is a member of the European Catalyst Manufacturers Association (ECMA), the Catalyst Manufacturers Association of Japan (CMAJ), the Synthetic Organic Chemical Manufacturers Association (SOCMA), the Drug, Chemical & Associated Technologies Association (DCAT) and the American Chemistry Council (ACC).
0405
Life Sciences and Fine Chemicals
Precious Metal Powder CatalystsActivated Base Metal CatalystsHomogeneous CatalystsDeloxan Metal Scavengers
Batch
Industrial Chemicals and Intermediates
Continuous Process Catalysts Fixed Bed catalysts Fluid Bed catalysts
Continuous
Polymers
Supports for Ziegler-Natta type catalysts
Silane donors
Batch / Continuous
Markets
Products
Processes
Sales officesProduction sites
Together we bring catalyst ideas to life, creating value by our passion and focus.
To be globally recognised as the preferred partner for major catalyst users, and to develop and attract talented people for our international team.
Our mission
Our vision
All over the world and always close to you
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Introduction
precious metal
PdPtRhRu
support
CAl2O3SiO2CaCO3
doping
FePbCuV
Precious Metal Powder Catalysts
examples of possible combinations
High activity High selectivity Good filterability Good recyclability
Safe and easy start-up No precious metal loss Easy precious metal recovery Quantitative precious metal recovery
The wide use of PMPC is due to ...
Precious Metal Powder Catalysts are heterogeneous catalysts for slurry type reactions that are carried out in batch or semi-batch mode. They are very popular in the fine chemicals and pharmaceutical industry, though there are applications outside these industries. For the overall economics of chemical processes that work with Precious Metal Powder Catalysts, the recovery of the precious metal is of vital importance. This brochure describes the recovery of the precious metals and the related services we offer. Recovery is essential to maintain the precious metal loop.
Evonik manages the whole precious metal cycle, which starts with the purchase of precious metal and management of the precious metal account, and ends with the coordination of all activities around recovering the precious metals. Our global network of metal refiners carries out the recovery and refining for you. They operate state-of-the-art audited and ISO-certified metal refineries. However, we keep it simple. There is a single interface between Evonik and you, our customer.
Precious Metal Powder Catalysts
0809
powdered,heterogeneous catalysts
catalysts for slurry phase reactions
precious metal mounted on a support
highly dispersed, stable metal crystallites
The Precious Metal Cycle
Refining the Spent Catalyst
The precious metal cycle starts with the manufacture of precious metal salt solutions from pure precious metals. The solutions are used as a raw material in the manufacture of Precious Metal Powder Catalysts, which are shipped to you for use in your catalytic processes. The spent catalysts are shipped to a metal refinery, where the precious metals are extracted. This process leads to a complete destruction of the catalyst, so this is not a regeneration step, in which the material remains intact. Once the precious metal is recovered this takes several weeks it is booked to your precious metal weight account. You own the precious metal weight account and can close this account at any time. Precious metal is taken from this account for the production of fresh catalyst. This completes the precious metal cycle.
There is no recycling process without losses. As des-cribed, they can occur in the catalytic process and in the metal refinery. Typically, the precious metal loss in the catalytic process lies between 2 and 3 %. Figures above 5 % are considered high. Also, in the refining and recovery process small losses cannot be avoided. The precious metal loss depends on the nature of the spent catalyst, the type of precious metal, and the refining process. To keep the cycle filled with precious metal and to compensate the unavoidable losses, small amounts need to be bought.
Please note, you have to own only approximately 40 % of the precious metal that is turned over in your process to keep the cycle running. For example, if you consume 1 tonne of catalyst containing 50 kg of precious metal, you only have to buy approximately 20 kg precious metal to maintain the cycle.
Precious Metal Losses in the Process
The fresh Precious Metal Powder Catalyst is used in the catalytic process and recycled (i.e. re-used) where this is applicable. In the chemical process precious metal losses may occur which has various reasons: Losses while handling the powder catalysts Precious metal leaching in the process Losses of fine catalyst particles in the filtration stepHowever, our technical experts are more than happy to assist you to minimise the precious metal losses.
Treatment of Spent CatalystsAfter the final usage of the catalyst, it is filtered off and collected. The spent catalyst does not only contain the precious metals, but also other chemicals originating from the chemical process. These compounds can be solvents, reactants and any other chemical that was in contact with the catalyst. The spent catalysts should be contaminated as little as possible with product and solvents. As a rule of thumb, the cleaner a spent catalyst is, the lower the refining costs.
Precious Metal Powder Catalysts need to be washed or steamed before being packed and shipped to the refinery. The spent catalyst should not be too wet or contain a separate water layer. The filter cloths can be shipped in the same drum as the spent catalyst if the filter cloths can be burnt and if this is compatible with the refining process (precious metal sampling after combustion, process 2, below). If the precious metal content is determined directly from the spent catalyst (precious metal sampling before burning), no filter cloths or any other solids apart from the catalyst are allowed. If the spent catalyst drums contain filter cloths, it is advisable to use material that is combustible. Filtration aids based on silica may entrap precious metals, which lowers the recovery rate.
precious metal loss precious metal recovery catalyst production
precious metal losscatalytic process
substrate product
precious metal purchase
precious metal account
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The Recovery Process
The Recovery Process
chemicaldesintegration
electrolysis
chemicaldesintegration
Process 1spent catalystscombustible
Process 2spent catalystscombustible
Process 3spent catalystsnot combustible
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homogenisationof spent catalyst
sampling
sampling
homogenisationof spent catalyst
homogenisationof ash
combustion
combustion
pyrometallurgical processing in high temperature furnace
sampling
precious metal analyticssampling credit to your weight account
Refining and recovery is a complex process which comprises several steps that are briefly described here. After the spent catalysts have arrived at the metals refinery, the material is inhomogeneous and needs to be pre-treated before the actual recovery process can start. In this pre-treatment the spent catalyst material is homogenised.
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Three Key Steps
chemicaldesintegration
electrolysis
chemicaldesintegration
production offresh catalyst
separation of Pt, Pd, Rh, Ru
preciousmetal sponge
preciousmetal solution
1. Homogenisation and samplingThe amount of precious metal contained in the spent catalyst is determined at the beginning of the recovery process, not at the end. This is necessary because later in the process the precious metal from different customers can no longer be distinguished. In process 1, the spent catalyst is homo-genised to slurry or a free flowing powder. A sample taken from the slurry is analysed, and the precious metal content determined. In process 2, the spent catalyst is combusted, the resulting ash is sieved and the coarse fraction milled. Subsequently, the ashes are unified and mixed. A sample is taken from the final ash and the precious metal content determined. In process 3, the spent catalyst is homogenised by sieving, screening, milling and blending, and an analysis is made from the original homogenised spent material.
2. AnalysisThe samples are analysed using state-of-the-art analytical methods. Our customers can also take a sample of the homogenised material to check the results independently. The result of the analytical investigation is the basis for billing and crediting the precious metal to the weight account. The amount of precious metal that is credited is calculated from the analytical result multiplied by the recovery rate. The recovery rate, which takes precious metal losses in the process into account, typically varies between 90 and 99 % depending on the process and the precious metal.
3. Precious metal recoveryThe analytical results also determine the process by which the ash is refined to provide the highest possible yield. The last step delivers the precious metals in powder or sponge form with a purity of 99.95 up to 99.99 %. From the pure precious metals, precious metal solutions are made, which are used in the manufacture of Precious Metal Powder Catalysts. This closes the precious metal cycle.
Packaging,Transport and Legislation
The spent catalyst must not be packed in small bags. The spent catalyst should be shipped in a large metal drum, which must not contain any solids apart from the spent catalyst (e.g. hand gloves, filter cloths, filter candles).
We recommend polyethylene bags with 25 kg content. The bags should be stable so that they cannot break or leak material in any way during transportation and handling. The polyethylene bags can be burnt together with the catalyst. The bags should be packed in drums for shipping. You can use the drums in which the fresh catalyst was sent. If you equip the drums with an inner bag, take care that no losses of valuable material can occur. Material that contains low amounts of precious metal (e.g. hand gloves, filter cloths, filter candles) should be packed separately and the drum labelled accordingly.
Process 1: precious metal sampling before burning
Processes 2 & 3: precious metal sampling after burning
Spent Precious Metal Powder Catalysts need to be packed with care. If the spent material is classified as hazardous goods, the package needs to be approved by the authorities.
Packaging
In addition, the spent catalyst shall: be thoroughly washed and steamed and delivered moist with water but solid for handling and shall not contain any excess liquid. not be self combustible. be packed and marked according to International transport laws. The spent catalyst shall be packed with no additional liquid in 60, 120 or 200 L steel or plastic UN-approved drums with metallic lid or in approved pails. Authorisation to use other packaging must be agreed to in advance of a shipment. be shipped together with a copy of the completed questionnaire, Information on Spent Precious Metals Catalyst, and a Material Safety Data Sheet (msds). Furthermore send the completed questionnaire 10 days in advance of dispatch if possible, but in any case before dispatch of shipment. be separated from all materials that are not spent carbon catalyst, but would be combustible, for example, cloths and filters. These materials shall be cleaned and disposed at the customers site or if included because of precious metal content, they must be packed and labelled separately. Additional cost or any change in conditions involved with the processing of these special materials will be passed on to the customer. be prepaid, packed and insured (DDU, duty unpaid, incl. Declaration T1).
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Classification as dangerous goods according to Transport Regulations
When shipped as dangerous goods, the catalyst has to be packed in approved drums that are not corrosive for the contents and are suitable for transport and storage. The shelf life of plastic drums must be good for at least half a year after arrival. Any receptacle must be no more than four and one half years old. Furthermore, all requirements concerning the trans-port and handling of dangerous goods shall be ob-served, particularly those for the receptacles, labels and documentation.For example, markings shall include: UN-number, consignor, consignee, gross and net weight, transport and dangerous goods classification. Furthermore, the corresponding transport emergency cards and instructions in writing have to accompany the shipment.
Legislation requires the sender of spent catalysts to obey national and international transport regulations and traffic laws for residual materials and waste. It must be checked, for example, if the residual chemicals in the spent catalyst need to be classified as dangerous goods. If necessary, special regulations and permits for packaging and transport may be required.
Transport and Legislation
Classification according to European Waste Legislation
Although your material has a high value and is sent for recovery of precious metals, it is considered waste according to the EU Regulation. Therefore the classification number according to European Waste Catalogue (EWC), new (AVV) must be stated in all shipping documents together with the material description.
The law says that the shipper of waste is responsible for the declaration: Based on experience your material could be classified as follows according to the European Waste Catalogue (EWC):
160801, spent catalysts containing gold, silver,rhenium, rhodium, palladium, iridium or platinum, if no disturbing elements and no dangerous transition metals or combinations in the sense of the Regulation 91/689/EWC are contained.
160807*, spent catalysts contaminated with disturbing elements. Here we refer to regulation 91/689/EWC, for example contaminations with corresponding amounts of organic compounds, acids, lead, bismuths, etc.
Questionnaire andInteractive Calculation Tool
Information on Spent Precious Metals Catalyst
from company / plant:
in case of several lots / catalyst types per shipment, please fill one questionnaire for each lot / type
1. Type of material / name of catalyst: Shipping weights: gross: kg Type and number of packing: net: kg Labelling:
2. Material condition: dry powder sludge filter cake spheres/extrudates
3. Material Composition (indications in weight-%, relative to original weight delivered): base material: ca % solvents: ca % moisture: ca % organic substances: ca % (besides chemical solvents) classification: filteragents: organic / combustible inorganic / non combustible expected precious metals (Pt, Pd, Ru etc) other elements (Pb, Bi, Zn, F, Sn, Cr, S, P, As, Sb, Hg + combinations
ca % ca % ca % ca % ca % ca % ca % ca % ca %
in form of: (e.g. salts, organic compounds, acids) 4. Properties of the material:
4.1 Technical: non combustible Flashpoint > 55 C 4.2 Physiological: harmless toxic LD 50 harmfull irritant corrosive
further information: effects:
4.3 Does the Material contain halogenated organic combinations? yes no
if yes:
5. Precautions to be observed when handling the material:
protective equipment and / or antidotes:
6. Classification according to transport regulations and dangerous substance- and preparations directives
6.1 Dangerous goods acc. to transport regulations: yes no
transport classification:
6.2 Dangerous material acc. to dangerous substance- and preparations directive: yes no
labelling acc. to dangerous material regulations
EU-Material Safety Data Sheet (msds) is available and attached: yes no as no dangerous material
7. Classification according to European Waste Regulation: AVV(EWC)-No OECD-No
We confirm that the above mentioned data are complete and correct
place date authorised signature and stamp
Some metal refineries require a completed questionnaire that describes the spent catalyst material. This is necessary to guarantee maximum safety for the operators in the metal refinery plant. Therefore, we recommend sending the questionnaire together with the spent catalyst. Questionnaire
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InteractiveCalculation Tool
On our web site we have installed an interactive calculation tool. This web-based tool takes the whole precious metal cycle and the catalyst productivity into account. Since you can use the actual figures for precious metal and recovery prices, interest rates, catalyst productivity and precious metal loss, this tool gives you a rather exact idea about the value catalysts from Evonik create. We would be happy to assist you in the application of this model.
Annual Catalyst demand
Calculation in g and prices in Euro in troy ounce and prices in US
Amount of precious metal contained therein
Percentage of the annually used amount of precious metalused to form the precious metal stock (typically 30 %)
Customers precious metal stock
Precious metal losses(estimated)
Catalyst price
Recovery price(per gram or troy ounce precious metal credited)
Precious metal price
Interest Rate(typically 2 % - 5 %)
1. Catalyst Costs
2. Recovery Costs
3. Make up for precious metal losses( balanced by additional purchase)
4. Interest
Total
Costs for minimum stock of precious metal
Amount of product made in catalytic reaction in one year
Catalyst costs per kg product
kg/a
kg
%
kg*
%
/kg
/g
/g
%**
*
*
*
*
*
*
/a
/kg
www.evonik.com/catalysts
Evonik Brings Value to Your Company
Brochures available from Catalysts
Products and Services Handling and Safety
Products and Services ReacToCat
Metal Scavengers
Activated Base Metal Catalysts Continuous Process Catalysts Deloxan
Evonik has built an extended service package around precious metal recovery and precious metal management. Our services help you to optimise logistics, purchasing and financing of the precious metals you need.
Our Services
Spot market orders (in most cases) Fixing orders (London fixing plus location-charges) Limit orders Split orders Options Forwards
Precious Metal Purchasing
Transition borrowing Long-term borrowing Sell and lease-back Options Forwards Futures
Please note: securities are necessary, e.g. a bank guarantee.
Financing
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Products and Services Products and Services Products and Services Handling and Safety Refining of Spent Catalysts
Homogeneous Catalysts Olefin Polymerisation Catalysts Precious Metal Powder Catalysts
Precious metal hotline Market Statistics Cooperation with precious metal firms with outstanding reputation Logistics for precious metal transactions transfers swaps physical shipments Determination of the precious metal demand in the precious metal cycle critical (minimum) demand future demand
Related Services
Logistics for spent catalysts Shipping provisions Packaging Material constitution Contaminations Pick-Up Service Documentation Waste classification Transport classification Analysis and Settlement approved variety of analytical methods available quick assay possible, third party analysis high yields due to state-of-the-art processes settlement on due date and credit to weight account (free of charge)
Services around Recovery
This information and all further technical advice is based on our present knowledge and experience. However, it implies no liability or other legal responsibility on our part, including with regard to existing third party intellectual property rights, especially patent rights. In particular, no warranty, whether express or implied, or guarantee of product properties in the legal sense is intended or implied. We reserve the right to make any changes according to technological progress or further developments. The customer is not released from the obligation to conduct careful inspection and testing of incoming goods. Performance of the product described herein should be verified by testing, which should be carried out only by qualified experts in the sole responsibility of a customer. Reference to trade names used by other companies is neither a recommendation, nor does it imply that similar products could not be used.
Copyright 2009 Evonik Industries AGpmpc refining 0209
Evonik Industries AGCatalysts Business Line
[email protected]/catalystswww.evonik.com
EuropeEvonik Degussa GmbHCatalysts Business LineRodenbacher Chaussee 463457 HanauGermanyphone +49-6181-59-8721fax +49-6181-59-2699
North AmericaEvonik Degussa Corporation379 Interpace ParkwayP.O. Box 677Parsippany, NJ 07054-0677USAphone +1-800-422-8773fax +1-973-541-8504
ChinaEvonik Degussa (China) Co. Ltd.55 Chundong RoadXinzhuang Industry ParkShanghai 201108Chinaphone +86-21-6119-1461fax +86-21-6119-1142
South AmericaEvonik Degussa Brazil Ltda.Catalysts Business LineAlameda Campinas, 5795th floor01404-000 So Paulo-SPBrazilphone +55-11-3146-4114fax +55-11-3146-4199
AustraliaEvonik Degussa (China) Co. Ltd.55 Chundong RoadXinzhuang Industry ParkShanghai 201108Chinaphone +86-21-6119-1460 fax +86-21-6119-1142
IndiaEvonik Degussa India Pvt. Ltd.Krislon House,Opp. Marwah Centre,Saki Vihar Road,Saki Naka,Andheri ( E ),Mumbai 400 072Indiaphone +91-22-6723-8800fax +91-22-6723-8811
IndonesiaPT. Jebsen & Jessen ChemicalsGraha Inti Fauzi, 7th floorJl. Buncit Raya No. 22Jakarta 12510Indonesiaphone +62-21-2753-7177fax +62-21-2753-7188/89
IranDegussa Iran AGNo. 20 Kish St., Africa Ave.P.O.Box 15875-3998Jahan-E-Kudak CrossroadTehranIranphone +98-21-8877 5249 fax +98-21-8879 7815
JapanEvonik Degussa Japan Co. Ltd.Catalysts Business Line Shinjuku Monolith 12th floorP.O. Box 70162-3-1 Nishi ShinjukuShinjuku-kuTokyo 163-0938Japanphone +81-3-5323-7363fax +81-3-5323-8789
KoreaEvonik Degussa Korea Ltd.94, Galsan 1-dong, Bupyeong-gu403-081 IncheonKoreaphone +82-32-510-2419fax +82-32-505-2510
Middle EastEvonik Degussa Gulf FZEP.O. Box 293594 Location:Phase 6 A - East Block Office 511Dubai Airport Free ZoneDubai, UAEphone +971-4-204-5580fax +971-4-204-5581
RussiaOOO Evonik ChimiaZemljanij Val 58a, Building 2RF-109028 Moscowphone +7 095 721-2862fax +7 095 721-2852
SingaporeJebsen & Jessen Chemicals (S) Pte Ltd2 Corporation Rd. #06-03 (Main Lobby)Corporation PlaceSingapore 61894Singaporephone +65-6305-3488 fax +65-6305-3461
ThailandJebsen & Jessen Chemicals(T) Ltd.23/110-117 Sorachai Bldg., 25-29th floorSoi Sukhumvit 63 (Ekamai), Sukhumvit RoadKlongton Nua, Wattana, Bangkok 10110Thailandphone +66-2-787-8752fax +66-2-787-8777
TaiwanDegussa Taiwan Ltd.9th floor, 133, Min Sheng East Rd.Sec. 3, Taipei, Taiwan,105 R.O.C.phone +886-2-2717-1242fax +886-2-2717-2106