Flame Spray Pyrolysis Facility

Guideline Notes on System Specification

Introduction

The DTI has, under its Micro and Nano Technology (MNT) Network initiative, provided grant funding for the creation of a development scale Flame Spray Pyrolysis Facility at Jonhson Matthey Technical Centre near Reading. This is a unique facility for the production for nanomaterials. 2 Purpose

The purpose of the Flame Spray Pyrolysis Facility is to allow the production of a wide array of nanopowders ranging from single metal oxides such as Al2O3 to more complex mixed oxides or catalysts with capacity of up to 100 g/hr. A number of process variables will enable the preparation of well-defined target materials. 3 Process

Liquid feed-Flame pyrolysis is a one-step process by which a metal precursor(s), dissolved in a solvent, is sprayed with an oxidising gas into a flame zone where the droplets are combusted and the precursor(s) converted into nano-sized metal or metal-oxides particles, depending on the metal and the operating conditions. This technique is flexible as it allows for the use of a wide range of precursors, solvents and process conditions and thus provides control over particle size and composition. Flame spray pyrolysis is versatile one-step process to producing nanoparticles and can be used to make metal, metal oxide and more complex nanoparticle materials. Johnson Matthey has specialised in using the technique to make metallic nanoparticle catalysts and has developed considerable in-house expertise in this area. This knowledge is also transferable into other application areas.

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Health and safety

The flame spray pyrolysis rig has been the subject of a thorough HAZOP, which has been carried out together with a study of the static hazards (e.g. the intrinsic toxicity of the precursor and product materials). In order to minimise the risk of any failure, trips and alarms have been, or are currently being, installed, including flame monitors, temperature sensors, pressure transducers and flow meters. When triggered these all shut down the rig. Due to the unknown health effects of manufactured nanoparticles, great care has been taken to minimise exposure and to prevent any emission to the atmosphere. The rig itself is enclosed within a glove box within a sealed, restricted access laboratory. The rig is operated remotely but, in order to recover product and clean the system, operators have to enter the room and break the containment of the glove box. Before this occurs, the product and product filters are removed and water spray nozzles within the rig clean the bulk of the internal surfaces. This removes most of the remaining contamination and ensures any trace material is wet, thus minimising dust generation. Within the room, operators wear Tyvek suits, gloves and FFP3 respirators. Operators change their clothing in a changing room on their way out of the laboratory to minimise the spread of contamination. The filters used to collect the product are posted out of the glove box and cleaned in a second glove box thus preventing any escape of dust. The product itself is collected in a container and removed via a continuous plastic sock such that the container is never open to the laboratory atmosphere. HEPA filters are used to prevent any material being emitted to atmosphere in the process gases or ventilation. The filters are ' safe change' ensuring that exposure is minimal during maintenance. Particle counters are installed in both the discharge ducting and in the room and are monitored to ensure that particle levels are low. These precautions are considered to be sufficient to reduce the exposure of operators and maintenance staff to a very low level, orders of magnitude below conventional Workplace Exposure Limits. 5 Confidentiality and Ownership of Data

Johnson Matthey attaches great importance to the protection of customers confidentiality in all aspects of the flame spray pyrolysis operation. Hence information exchanged from the earliest contact onwards may be subject to a Non Disclosure Agreement, and data generated in the course of the work commissioned by the customer may be assigned to the customer under the terms of a Services Agreement.

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In the facility itself access is tightly controlled not only for Health and Safety reasons but also to ensure highest levels of information security. Johnson Matthey has a flame spray rig built from standard equipment. JM has inputted engineering innovation into aspects of the construction of the rig for the sole purpose of making the rig suited to the flexible testing of a wide range of materials. This will enable a wide range of materials to be tested efficiently within an open access framework, however JM retain the right to IP in the particular construction of the rig. Such IP should not normally prevent scaleup of specific materials by a third party. JM intends to research into innovative process technology as part of their own flame spray pyrolysis programme and retain the right to IP that arises during such work. As such, IP will be highlighted to third parties where appropriate. JM has considerable background IP (including know-how) in the areas of precious metals and solution precursor chemistry. If JM considers their background IP to be relevant to any collaboration with a third party they will highlight this to the third party and discuss how best to proceed with the collaboration. 6 The Flame Spray Pyrolysis Facility

General The Flame Spray Pyrolysis Facility is based at Johnson Matthey Technology Centre in Sonning Common near Reading. A laboratory has been specifically designed to house the new facility and contains two parts: the process and the preparation areas. Although the process area has a restricted access for containment purposes, viewing areas in the preparation laboratory have been accommodated for visitors. The process laboratory has its own air-handling unit to keep it under negative pressure while the process gases are exhausted through a separate ducting and filtered through HEPA filters prior to being released in the environment. The pre and post-filtered gases are being controlled with a pressure sensor by the filter and also with a particle counter from TSI, which will detect down to 5 nm particles. Finally, a clean room was built to access and exit the process area. The process itself has been automated and is ran and controlled from the preparation area. The preparation laboratory also contains the necessary equipment for the preparation of precursor(s) solutions and arrangements will be made to have the customer precursors delivered to this laboratory. The customer can also choose to prepare its own precursor(s) solutions. Equipment The flame spray rig contained in the process laboratory is described in the scheme below:

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It consists of a syringe and syringe pump system to introduce the precursors in the form of a solution, a nozzle made up of a liquid insert and a gas channel to spray the solution. The nozzle also includes 2 channels to introduce the flamelet gases (typically CH4/O2) for the ignition of the sprayed reaction mixture and a third channel to introduce a sheath gas when necessary. The resulting powder is collected via a duct collection into a hopper containing 12 candle bags. The powder is collected onto these candle bags by extraction and then blown down into a collection can at the bottom of the hopper using blasts of compressed air pulsed down the bags. Modes of Operation The operation is ran in a pseudo-continuous mode whereby 1 L syringes are processed at a time and switched over once the first injection is completed. The operation is repeated until the appropriate amount of product is collected. The current setup can process up to 200 g/h depending on the required specification of the nanomaterials. The powder is then isolated and the clean up process can take place. It is anticipated that the clean up operation will take up to 1 day. Feedstocks A wide range of precursors and solvents can used within constraints of safety, practicality and budget. Only solutions can be processed and the say solutions need to contain a combustible mix to produce a flame and to allow for the components to decompose and vaporise prior to growth and agglomeration during the cooling phase.

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If the customer forwards its own precursor(s) solutions, it is important for Johnson Matthey to know the composition of such solutions to assess the hazard associated with the chemicals, chemical mix and the combustion products. The system will handle a wide range of materials subject to the following constraints: Not containing pathogens Non-radioactive Non-carcinogenic or mutagenic Compatible with the materials of construction of the system

The above list is also valid for the end product. Operation and control The process is operate by one specialised scientist and supported by a labview program to operate and control the operation from outside the production room. Pre-run setup includes running of the air-handling unit on operation mode, pilot flame, the extraction and the dispersing gas. A 1 L syringe is filled up with appropriate solution containing fuel and precursor, placed in the holder with a driver. The precursor mix is fed into the nozzle and the solution is sprayed using a dispersing gas, typically air or O2. Both the precursor feed rate and dispersing gas flow rate can be adjusted to achieve a change in droplet size, which will in turn affect the particle size of the end product. With the high enthalpy organic solution used in our experiment, a small pilot flame is used as source to ignite and sustain spray combustion. The production of the powder is monitored using a particle counter in the extraction line, the temperatures pre and postcollection and the pressure in the precursor line as well as the pressure drop across the nozzle. The compressed air pulsations to the collection bags and extraction may be adjusted during the run to optimise powder collection. Once the run is completed, the precursor line and the nozzle are cleaned by spraying some EtOH. The can is finally isolated using a containment technique to avoid exposure and transported into a glove box area to be transferred into an appropriate container. A full Hazop study has been carried out and appropriate control and safety measures taken. Experimentation Typically the preparation of up to 100 g of product on the larger flames spray equipment will require 0.5 day experimentation. When minimal crosscontamination from one product to another (for instance in the case of oxide

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doping) is acceptable, several products may be prepared in one day. Downtime for cleaning the flame spray facility would typically require 0.5 to 1 day. 7 Key Contact Potential users of the Flame Spray Laboratory are advised that this document provides only guideline notes Dr Bndicte Thibaut Johnson Matthey Technology Centre Blounts Court Sonning Common Reading RG4 9NH Tel: + 44 (0) 1189242055 Email: thiebb@matthey.com

Disclaimer: All technical information in this document is provided in good faith but is subject to revision without notice and is not intended to form the basis of any understanding or agreement between Johnson Matthey and any client pr potential client of the Flame Spray Pyrolysis Facility.

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