1
DSM Food Specialties
Enzyme formulations in the industrial fieldEnzyme formulations in the industrial field
From past to presentDr. Ir. Gabrie M.H. Meesters
Gabrie Meesters
DSM Food Specialties
1
15/06/2010 PaON
DSM Organizational ChartDSM Organizational Chart
DSM Innovation CenterDSM Innovation Center Corporate StaffCorporate Staff
Shared Competences &Business Support
Shared Competences &Business Support
DSM Nutritional Products
DSM Food Specialties
DSM Resins
DSM Engineering Plastics- DSM Dyneema
DSM Elastomers
DSM Agro
DSM Melamine
DSM Fibre IntermediatesDSM Special Products
DSM PharmaceuticalProducts
DSM Anti-Infectives
DSM Energy
DSM Nutritional Products• Human Nutrition and Health• Animal Nutrition and Health
DSM Food Specialties
Nutrition
DSM PharmaceuticalProducts
DSM Anti-Infectives
Pharma
DSM Engineering Plastics
DSM Dyneema
DSM Resins
PerformanceMaterials
DSM Fibre Intermediates
PolymerIntermediates
DSM Agro
DSM Elastomers
DSM Melamine
DSM Energy
Base Chemicals& Materials
Corporate Staff
Shared Competences &Business Support
DSM Managing Board
DSM Innovation Center
March 2009
DSM Food Specialties
2
15/06/2010 PaON
FactsFacts of theof the foodfood activitiesactivities
• DSM produces >50% of all vitamins in the world• Our products can be found in all kinds of personal care
products like (anti-wrinkle) crèmes, shampoos, sun blocketc.
• DSM makes ALL ingredients for cheese, except the milk• The top athletes of The Netherlands (soccer, hockey,
swimming, rowing, tri-athletes) use our PeptoProrecovery drink
DSM Food Specialties
3
15/06/2010 PaON
DSM Food SpecialtiesDSM Food Specialties’’ ingredients addingredients addquality to lifequality to life
Essential part of many every-day food & beverage products
2
DSM Food Specialties
4
15/06/2010 PaON
IntroductionIntroduction
• Since the early sixties, enzymes are produced for industrialpurposes.
• Especially in the solid formulations a lot of developmentshave taken place
• Leading in research are psd, dust formation, stability,solubility, application performance, compatibility, enzymeactivity
DSM Food Specialties
5
15/06/2010 PaON
What are enzymesWhat are enzymes
• Enzymes are proteins• Enzymes are bio-catalysts• Enzymes are used in all living organisms• Enzymes can be used in industrial surroundings• We modify micro-organisms to produce these enzymes in
large quantities• World market is about US$ 4 billion and growing ~5%
annually
DSM Food Specialties
6
15/06/2010 PaON
Per cell 200.000 – 500.000 !
1 nanometer (0,000001 mm)
How big are enzymes?How big are enzymes?
DSM Food Specialties
7
15/06/2010 PaON
Industrial enzymesIndustrial enzymes
• Enzymes for detergents• Enzymes for starch producing industries• Enzymes for baking• Enzymes for feed boosters• Enzymes for beverages, wines and beer applications• Enzymes for dairy industries• Enzymes for organic modifications and chemical processes
3
DSM Food Specialties
8
15/06/2010 PaON
Current production processesCurrent production processes
• Spray drying; esp.. in food and feed. Too high risks• Spray drying agglomeration. Food and feed applications;
State of the art• High shear granulation• Fluid bed coating layering• Extrusion spheronisation• Immobilisation for liquid applications in reactors (Also cross
linked crystals)• Ion exchange columns
DSM Food Specialties
9
15/06/2010 PaON
Single stage spray dryerSingle stage spray dryer
DSM Food Specialties
10
15/06/2010 PaON
Integrated Spray Dryer (Integrated Spray Dryer (NiroNiro))
DSM Food Specialties
11
15/06/2010 PaON
MechanismMechanism
4
DSM Food Specialties
12
15/06/2010 PaON
MSDMSD--materialmaterial
DSM Food Specialties
13
15/06/2010 PaON
Mechanisms during high shearMechanisms during high sheargranulationgranulation
DSM Food Specialties
14
15/06/2010 PaON
Typical growthTypical growth behaviourbehaviour of mixerof mixeragglomeratorsagglomerators
DSM Food Specialties
15
15/06/2010 PaON
Rotating Drum AgglomerationRotating Drum Agglomeration
5
DSM Food Specialties
16
15/06/2010 PaON
LLöödigedige agglomeratoragglomerator
DSM Food Specialties
17
15/06/2010 PaON
LLöödigedige: Choppers and plough shares: Choppers and plough shares
DSM Food Specialties
18
15/06/2010 PaON
MechanismMechanism
DSM Food Specialties
19
15/06/2010 PaON
Typical high shear granulateTypical high shear granulate
6
DSM Food Specialties
20
15/06/2010 PaON
Fluidised bed granulationFluidised bed granulation
DSM Food Specialties
21
15/06/2010 PaON
mechanismmechanism
DSM Food Specialties
22
15/06/2010 PaON DSM Food Specialties
23
15/06/2010 PaON
Low pressure extrusionLow pressure extrusion
Bextruder Hosokawafor low pressure extrusionØ = 0,3 – 1,5 mm
7
DSM Food Specialties
24
15/06/2010 PaON
SpheronisationSpheronisation
BexrollerHosokawa
for spheronization
DSM Food Specialties
25
15/06/2010 PaON
MechanismMechanism
DSM Food Specialties
26
15/06/2010 PaON
Topics of DiscussionTopics of Discussion
• Formulations for the detergent industry• Formulations for the starch and glucose processing
industries• Formulations for the baking, beverages and dairy
industries• Formulations for the feed industries• Formulations for the chemical processes
DSM Food Specialties
27
15/06/2010 PaON
Detergent enzymes in the 1960Detergent enzymes in the 1960’’ss
• 60’s : Protease powder• end 60’s, severe allergic reaction and irritation• Collapse of the market to almost zero• Development of granules
8
DSM Food Specialties
28
15/06/2010 PaON
Early granule developments in the 1970Early granule developments in the 1970’’ss
• Gist-brocades: uncoated prills, later switching to coatedprills
• Novo-Nordisk: prills, switched to coated extrudates
DSM Food Specialties
29
15/06/2010 PaON
GistGist--brocadesbrocades--prillprill formulationformulation
Compounds of the prill formulation Wt %
Non-ionic or PEG 6000Soy oilTiO 2
BHTPVPCaSO 4
Enzym e powderBuilder, Na2SO 4
42-5610.60.11.5525, max17-63
DSM Food Specialties
30
15/06/2010 PaON DSM Food Specialties
31
15/06/2010 PaON
••NovoNovo--granulationgranulation
• Due to tighter dust restrictions Novo switched to high sheargranulation
• Granule-T concept was developed• Fibres are essential• Coated with PEG
9
DSM Food Specialties
32
15/06/2010 PaON
Novo granuleNovo granule--T formulationT formulation
C o m p o u n d s o f t h e e x t r u d a t ef o r m u la t i o n
W t %
E n z y m e p o w d e r o r l i q u idC e l l u l o s e f ib r e sW a t e rF i l l e rC o l o u r i n g a g e n t
5 - 9 02 - 4 01 0 , m a x .0 - 7 01 - 3
DSM Food Specialties
33
15/06/2010 PaON
Granulation in the 1980Granulation in the 1980’’ss
• Gist brocades develops its MOM-technology• Novo sticks to and improves its Granule-T concept• Showa-Denko develops similar process based on artificial
fibres• Solvay develops technology on basis of LP extrusion• Miles develops technology on basis of fluid bed
coating/layering
DSM Food Specialties
34
15/06/2010 PaON
GistGist--brocades MOMbrocades MOM--formulationformulation
C o m p o u n d s o f t h e M O M -f o r m u l a t i o n
W t %
M o d i f i e d s t a r c hE n z y m e p o w d e rS u g a rS o r b i t o lT i O 2G l y c e r i nP a r a f f i nL o r o l C - 1 8
4 52 01 664432
DSM Food Specialties
35
15/06/2010 PaON
Granulation in the 90Granulation in the 90’’ss
• Low enzyme dust levels (60ng/m3)• New enzymes in detergents• Henkel joins the field of enzyme producers, using HP-
extrusion• Novo sees limitations to amount of enzyme added to its
granules• Gb-prill formulation sees its end coming• Gb-MOM-technology not for 90’s
10
DSM Food Specialties
36
15/06/2010 PaON
Granulation in the 90Granulation in the 90’’sscontinuedcontinued
• Solvay extrudates see end coming (too high dust levels)• Gb develops a coating layering technique• Genencor International comes on the marked with new
formulation called Enzoguard®, based on fluid bedcoating/layering technology
DSM Food Specialties
37
15/06/2010 PaON
EnzoguardEnzoguard
• Solid core ……20-80%• PVA-layer ……. ~1%• Enzyme layer + PVA 0.1-20%• (NH4)2SO4 layer 10-30%• Polymer + pigment ..1-10%• Neodol coating 0.1-2%
DSM Food Specialties
38
15/06/2010 PaON
Fluid bed spray coating/layering (LA)Fluid bed spray coating/layering (LA)
DSM Food Specialties
39
15/06/2010 PaON
11
DSM Food Specialties
40
15/06/2010 PaON
Business consolidation in the early 1990Business consolidation in the early 1990’’ss
• Genencor acquired Gist-brocades- and Solvay Industrialenzymes (~35% market share)
• Novo acquires Showa Denko industrial enzymes (~40%market share)
• Henkel remains to produce for captive use only (~10%market share)
DSM Food Specialties
41
15/06/2010 PaON
Enzyme formulations from the mid 1990Enzyme formulations from the mid 1990’’ss
• Novo: Granule TX• GCI: fluid bed coating layering• Henkel: HP-extrusion• Use of granules in automatic dish washing matrix (higher
pH)• Use of enzymes in tablets
DSM Food Specialties
42
15/06/2010 PaON
Current statusCurrent status
• Dust requirements are met by current producers, levelsdecrease
• Storage stability• Formulation compatibility• GCI introdusing a new matrix granule, using fluid bed
technology
DSM Food Specialties
43
15/06/2010 PaON
12
DSM Food Specialties
44
15/06/2010 PaON DSM Food Specialties
45
15/06/2010 PaON
DSM Food Specialties
46
15/06/2010 PaON DSM Food Specialties
47
15/06/2010 PaON
13
DSM Food Specialties
48
15/06/2010 PaON
Formulations for the starch and glucoseFormulations for the starch and glucoseprocessing industriesprocessing industries
• Starch degrading enzymes• glucose isomerase• enzyme reactors operated at elevated temperatures (65º)• immobilised enzymes• Leading is cost and life time of formulated product
DSM Food Specialties
49
15/06/2010 PaON
Formulation development 70Formulation development 70’’ss--8080’’ss
• Novo developed a extrusion process, and cross linking• Gist-brocades developed a prilling in liquid process, and
cross linking• Miles developed a extrusion process, including cross
linking, using two cross linking agents
DSM Food Specialties
50
15/06/2010 PaON
Formulations in the 90Formulations in the 90’’ss
• Genencor acquired, Miles, Solvay and Gist-brocadesbusiness, making them the largest player
• Novo remained equal is size• Current formulations based on ion-exchange columns
DSM Food Specialties
51
15/06/2010 PaON
Future developmentsFuture developments
• Increase life time of enzymes• Increase reaction temperature• New better enzyme screening• Current ion exchange will be around for several years to
come
14
DSM Food Specialties
52
15/06/2010 PaON
Formulations for the baking, beverages andFormulations for the baking, beverages anddairy industriesdairy industries
• In baking enzymes are applied as powders or in breadimprovers
• Baking allergy is well known, has increased sinceintroducing enzymes
• In 80’s these enzymes were spray dried• Now advanced spray drying is used to agglomerate the
products
DSM Food Specialties
53
15/06/2010 PaON
Formulations for the baking, beverages andFormulations for the baking, beverages anddairy industries (cont.)dairy industries (cont.)
• bakers grade: 95%(w/w)<225 µm, less than 1%<63 um• Other grades: 100%(w/w)<1000 µm , less than 1%<63 um• These grades will produce enzyme dust• Dairy and beverages: spray drying changing to MSD,
mainly liquids are used.• Dosing in small quantities from sachets, tablets or boxes
DSM Food Specialties
54
15/06/2010 PaON
Baking formulation technologyBaking formulation technology
DSM Food Specialties
55
15/06/2010 PaON
Future developmentsFuture developments
• Cost is leading, but in baking enzyme dust will have to bereduced
• More fancy techniques for small granule coating will bedeveloped
• Stability is of little concern in this area
15
DSM Food Specialties
56
15/06/2010 PaON
BakingBaking enzymeenzyme examplesexamples
DSM Food Specialties
57
15/06/2010 PaON
Beverage EnzymesBeverage Enzymes
Retail
Grapes
JuiceConcentratesFruits
Grain
Wine
BeerAlcohol
Enzymes
Enzymes, Wine,Yeasts, Chemicals
Goals DSM Food Specialties, Beverage Ingredients :
Exploration of our capabilities in enzymes, yeast and fermentation in the beverage(wine, fruit, beer, alcohol) industry by innovation and market penetration.
Specialty ingredients and processing aids for thebeverage industry
DSM Food Specialties
58
15/06/2010 PaON
Formulations for the feed industriesFormulations for the feed industries
• New field of application• Natuphos® best know product• DSM-Food Specialties was largest player in this field,
followed by Novo• DSM divested their business due to acquisition of Roche
Vitamins& Fine Chem.• Formulation recipe in relation to application is leading,
followed by dust reduction
DSM Food Specialties
59
15/06/2010 PaON
Feed formulation, BASFFeed formulation, BASF
Extrusion
Spheronisation
16
DSM Food Specialties
60
15/06/2010 PaON
ExtrudateExtrudate
DSM Food Specialties
61
15/06/2010 PaON
Feed applicationFeed application
• Enzyme granules are mixed with dry feed compounds,vitamins minerals etc.
• Steam injection to elevate (50-80ºC) temperature andincrease moisture content
• Pre-mix is pelletised using high pressures• Pellets are cooled down
DSM Food Specialties
62
15/06/2010 PaON
Current formulationsCurrent formulations
• Gist-brocades used spray drying in combination withmixing with inert
• DSM-FS uses low pressure extrusion combined with acoating
• Novo uses granule T process combined with additionalcoating
• Coatings stabilise product and reduce enzyme dustformation
DSM Food Specialties
63
15/06/2010 PaON
Formulation developmentsFormulation developments
• The combination of temperature and moisture is bad forenzyme stability
• Coatings need to prevent moisture uptake, but must allowdissolution of granules in stomach of animals
• Additives are added to increase stability
17
DSM Food Specialties
64
15/06/2010 PaON
Future developmentsFuture developments
• Better coating to increase pelleting stability from 60-80% to80-90 %
• lower dust formation• Enzyme stabilisation additives• New enzymes
DSM Food Specialties
65
15/06/2010 PaON
Formulations for the chemical processesFormulations for the chemical processes
• Chemical modifications of complex organic molecules• Stereo specific• “difficult” catalyst• Use in organic solvents is possible• Rapidly increasing marked
DSM Food Specialties
66
15/06/2010 PaON
Current formulationsCurrent formulations
• As a liquid (UF)• As a liquid, containing the micro-organisms• Immobilised in particles and cross-linked• Immobilised as enzyme crystals and cross linked (CLEC’s)
DSM Food Specialties
67
15/06/2010 PaON
Future developmentsFuture developments
• More types of enzymes will be used• Finding the right enzyme is the most important task
presently• In the case cost is important, immobilisation will take place• New immob techniques will be developed• CLEC’s seem not to have the potential to become big in
this field
18
DSM Food Specialties
68
15/06/2010 PaON
Enzyme forms in liquid phaseEnzyme forms in liquid phase
• Microbial stability• Lowering the water activity to levels where Aw<0.5 and or use anti-
microbial agents• Formulations based lowering water activity (Aw) by
• Salt addition + antimicrobial agent• Polyol addition (glycerol and or sorbitol)• Mixtures of salts and polyols
• Anti microbial agents used e.g. Na-benzoate, sorbate
• Enzyme stability
DSM Food Specialties
69
15/06/2010 PaON
Activity of antiActivity of anti--microbial agentsmicrobial agents
Figure 6; effect of the pH on the dissociation of benzoic (___) and sorbic (----) acid
DSM Food Specialties
70
15/06/2010 PaON
ConclusionsConclusions
• Use of enzyme applications is still growing• Different state of art per application field is seen• Enzymes for detergents are the best developed enzyme
products• Enzyme dust prevention in baking will be leading in this
field• In organic chemistry more enzymes are to be applied in the
near future
DSM Food Specialties
71
15/06/2010 PaON
We operate beyond the labels!We operate beyond the labels!
Yeast extract
Aroma’sYeast extract
Aspartame
Cultures
StarterCulturesRennets
AromasCoatings
Enzymes
Enzymes
YeastEnzymes
PUFA’s
ß-Carotene