Smopex Fibres for Metal Recovery

1
Smopex Fibres for Metal Recovery

• Dr Mark Danks

2
Catalysis

• Johnson Matthey is a world leader in precious and
  base metal catalysis
• homogeneous, heterogeneous, chiral, supported
  homogeneous
• Catalysts widely used in pharmaceutical and fine
  chemical processes
• Clean and efficient routes to high value products
  
• Requirements are maximum conversion and high
  selectivity
• But what happens to the metal??

3
In the Product Stream?

• Requirement for metal to be removed from Product
• EMEA Guidance Note (2002)
• Product must be fit for its end use
• Residual metal can catalyse formation of
  by-products in
• work-up
• consecutive reaction steps

4
In the Waste Stream?
Example of Catalyst Cost Contribution 5 Rh/C at
6 metal loss
REFINING
RHODIUM
RHODIUM
17
RETURNED
30
CATALYST PURCHASE
PRICE
14
CYCLE DURATION
METAL LOSS
12
27
5
In the Effluent Stream?

• Metal will find its way to the site effluent
  plant
• Need to manage the removal of metals from these
  high volume streams
• Often an environmental or regulatory requirement
• Not limited to PMs - also Ni, Hg, As
• Shipped for special waste treatment if limits
  exceeded

6
Use a Selective Scavenger
7
Aims

• Introduce Johnson Mattheys scavenging
  technology - Smopex - by
• explaining what Smopex is and how it is made
• highlighting the benefits that it offers over
  technologies currently used for metal removal and
  recovery
• explaining the filing of Smopex with the FDA
• describing how a scavenging process is developed
• showing examples of how it can be incorporated
  into your process

8
What is Smopex?
Unique metal scavenging system where
metal-binding functionality is grafted onto
polyolefin fibre

• Graft co-polymerisation of polyolefin fibres
  using functionalised monomers.
• Metal binding properties bound to the exterior of
  the fibre.

The open fibrous structure of the Smopex polymer
enables greater metal recoveries in faster times
9
Smopex Product Range
Smopex-101
Smopex-110
Smopex-111
Smopex-102
Smopex-112
Smopex-103
Smopex-113
Smopex-105
Smopex-107
Smopex-234
10
Manufacturing Capability
Johnson Mattheys plant in Turku, Finland can
manufacture tonnage quantities of the full
Smopex range
11
Smopex Benefits

• Excellent functional group accessibility

• Accessibility of reactive sites

• Good mechanicalstability

• Mechanical stability

• Easily separated from solution

• Filtering characteristics

• Stable across the pH range

• Chemical stability

• Dispersion in organic media

• Easy to handle

12
What can Smopex do?

• Selectively remove ionic and non-ionic species
  from aqueous and organic solutions
• Removal from liquors containing low levels of
  precious or non precious metal - even down to ppb
  levels!
• Benefits include fast reaction kinetics and high
  metal loading

Ion-exchange of Cu2 in batch reaction
13
Process Economics
1kg Pd, Euro 8649 (24th March 2006)
Metal return ()
Carbon (0.5)
IEX (2)
Smopex (6)
Adsorbent (loading)
14
Technical Performance

• Pd/C catalyst used in a nitro-aromatic
  hydrogenation.
• Scavengers screened for Pd removal from a process
  stream containing 30 ppm leached Pd.
• S-105 gives greatest removal in a faster time
  than equivalent amounts of other scavengers.

Remaining 15 of Pd exists as a cation, this is
easily removed with S-101 to give
non-detectable Pd in solution
15
Technical Performance

• Homogeneous palladium catalyst precursor in the
  presence of triphenylphosphine, dibuytlamine and
  THF.
• S-111 allows superior metal recovery in faster
  time.
• An equivalent commercial resin is unable to
  remove more than 40 of Pd from solution.

16
Purification of a Product Stream

• First Smopex Drug Master Files (DMFs) filed with
  the FDA
• Smopex-102 DMF 18441
• Smopex-105 DMF 18447
• Smopex-111 DMF 18099
• Smopex-234 DMF 18518
• Filed as a Type II (drug substance or
  intermediate)
• Allows Smopex to be used in contact with the API
• Can remove metal from process stream at source
• DMF available for review by customer through FDA

17
Lab-to-Plant
18
What is important to YOU?

• Why does the metal need to be removed from
  solution?
• Product purity or values recovery or both
• How important is metal removal?
• Effect downstream
• Effect on plant cleaning
• How important is selectivity?
• Co-extraction of product, or even other metals?
• Can you use less scavenger - but get a better
  financial return?
• Metal return  vs metal loss
• Strike a balance

19
Lab Scale - Screening

• Information about actual process solution
• Solution sampled prior to screen
• Soluton screened with Smopex range
• Johnson Matthey (expertise)
• In-house
• 1 w/v Smopex, 60 C, 2h
• Filter and analyse filtrate for PMs

20
Lab Scale - Optimisation

• Optimise scavenging in preparation for pilot
  trials
• How practical is the process?
• Where can Smopex be best implemented in the
  process?
• Statistical Experimental Design methods
• Use orthogonal arrays to investigate effect of
  factor whilst also changing other independent
  factors!
• Results are obtained by measuring the average
  response for each factor over the whole
  experiment
• Optimum conditions can be obtained quickly - and
  a lot of information is obtained
• Results are reproducible

21
Lab Scale - Optimisation
Case Study Johnson Matthey Effluent Plant
(Royston)

• Pt (2 mg/l), Pd (240 mg/l), Rh (1 mg/l), pH 10

22
Lab Scale - Optimisation

• Combined confirmation run
• 15 minutes, 80 ºC, mixture S-105 and S-112
• Residual concentrations
• Pt 0.14 mg/l (91.1 extraction)
• Rh 0.15 mg/l (73.7 extraction)
• Pd 0.23 mg/l (99.9 extraction)
• Pilot trials to maximise metal loadings
• first treatment with S-112 (Pd)
• followed by S-105 (Pd, Pt, Rh polish)

23
Lab Scale - Reaction Time
24
Pilot Scale - Metal Loading
25
Plant Process
240 ppm Pd 1.6 ppm Pt 0.5 ppm Rh

• Commissioned at JM Royston
• Plant generates gt10 MT per month
• gt99 PM recovery
• 13 w/w metal loading
• Saving gt100k/annum

S-112 (Pd)
S-105 (Pt,Rh)
1.39 ppm Pd 0.29 ppm Pt 0.32 ppm Rh
26
Using Smopex on the Plant
27
Batch and Fixed Bed Processes
28
Smopex Column Skid

• Plug and play principle
• Batch controller
• Temperature control
• Steam heated jackets
• Safety devices
• Compatible with organic and corrosive media

29
Purification and Values Recovery
Pd removal from process solution following
coupling reaction

• 280 ppm Pd in organic phase
• Development work Smopex-111 at 90 C
• Pilot scale treatment of 4.5 MT of waste liquor
• lt5ppm Pd in the treated mother liquor
• 98 Pd extracted from solution
• 1.2 kg Pd recovered with 6 w/w loading on Smopex

30
Rh Recovery
The refining of Rh from Oxo process waste liquors
can be challenging.

• Solution contains gt100 ppm Rh
• 2.5 MT circulated through Smopex column on
  recycle
• 1 w/w Rh-loading

31
Ru Removal
Removal of low levels of ruthenium from a polar
solution
80 ppm Ru

• Aqueous solution containing 35 acetic acid, 1
  sodium acetate, and 80 ppm Ru
• Pilot trial to treat 5 MT solution
• In a column at 85 C
• Ru loading is 4.5 w/w

500 mm
S-105
3 ppm Ru
32
Smopex in Bag Filters
Effluent polishing system to remove Pt, Pd, and
Rh from levels of only 2ppm

• Smopex-105 in bag filters
• High throughput 3000 litres/h
• Uses temperature from plant process 75 degC
• 25k CAPEX, but will recover 30k of metal in
  2005

33
Summary

• Imperative that metal impurities are removed from
  high value pharmaceutical substances
• Vital that precious metal catalysts are recovered
  from process streams or effluents..this will
  make the difference in process economics
• Smopex offers a real scavenging solution, with
  the open fibrous structure allowing fast reaction
  kinetics and extremely high metal loadings
• Johnson Matthey works closely with customers to
  give the best recovery solution from lab-to-plant

34
References
The Art of Meeting Palladium Specifications in
Active Pharmaceutical Ingredients Produced by
Pd-Catalysed Reactions C. E. Garrett and K.
Prasad, Adv. Synth. Catal., 2004, 346,
889-900. Removal of Metals from Process Streams
Methodologies and Applications J. T. Bien, G. C.
Lane and M. R. Oberholzer, Topics Organomet.
Chem., 2004, 6, 263-283.