TECHNICAL INFORMATIONFULCAT HETEROGENEOUS CLAY CATALYSTS

CA-TI 1

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FULCAT heterogeneous clay catalysts

Contents
03 Introduction to FULCAT

11 Adsorbants

05 FULCAT product range

12 Brønsted acid catalysis

06 Antioxidants

14 FULCAT selection chart

07 Silicone fluids

15 FULCAT benefits

08 Oleochemicals

03

Introduction to FULCATFrom pharma to commodity chemicals, BYK’s FULCAT product range
provides only the best heterogeneous clay catalysts, with and withoutacid modification. The FULCAT catalyst product range, prepared fromsustainably sourced natural clays, is designed to be reused and recycled,providing an efficient and green solution for a range of chemistries.
Covering Brønsted and Lewis acidity, FULCAT catalysts have been
optimized to provide excellent activity in such reactions as Friedel-Crafts
alkylation, siloxane polymerization, dimerization, isomerization,dehydration, and more.
BYK’s experience in selecting clay minerals and acid processing ensureshigh-quality FULCAT products with low chloride content and high surface
area that consistently add value to chemical production. To support
customers in all kinds of applications, BYK has invested in a dedicatedcatalyst testing laboratory with capability for catalyst characterization andevaluation of FULCAT in a broad range of reactions. BYK’s catalyst testing
capabilities enable reaction-specific optimization of the FULCAT productrange, as well as a high level of quality assurance.

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FULCAT heterogeneous clay catalysts

BYK’s catalyst testing lab
Chromatography
analysis suite

High-pressurehigh-temperature
reactor

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FULCAT heterogeneous clay catalysts

FULCAT product range

FULCAT-22 B• BYK’s market leading FriedelCrafts alkylation catalyst• Potent Lewis acid active sites
provide exceptional alkylation
reactivity• Optimized particle size
distribution for extra-fast
filtration

FULCAT-22 F• BYK’s “all-rounder”• High reactivity in a large
range of reactions, including:Friedel-Crafts alkylation(trans)esterification
alcohol dehydration
alkene isomerization

FULCAT-435• High surface area, low acidvalue activated catalyst• For applications wherelow levels of free acidand high adsorption rates
are desirable, for example
fatty acid chemistry

FULCAT-22 S• High surface area, ultra-low sulfur
catalyst developed for the siloxane
polymerization market• Strong Brønsted acid sites provide
fast siloxane polymerization kinetics• Also recommended for fatty
acid isomerization reactions

FULCAT-22 D• Low-sulfur natural clay catalyst• Active Lewis acid sites within
the phyllosilicate structure provides
high reactivity in the dimerization oftall oil fatty acids
rapeseed oil fatty acids
soybean oil fatty acids

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FULCAT heterogeneous clay catalysts

Antioxidants
Antioxidants are an important class of materials that areused in almost all consumer markets. The FULCAT productrange is of particular importance to the production ofautomotive antioxidants. From rubber in the tires to oils in
the engine, antioxidants are crucial to ensure smoothrunning and longevity.

Example phenolic and aromatic amine antioxidant reagents
Diphenylamine (DPA)

PhenolOH
Phenolic/aminic antioxidants
Phenylamine and phenolic-based antioxidants are widelyused in rubber and/or lubricant formulations. The basearomatics are functionalized with a variety of organic
chemistries to provide antioxidant performance tailoredto their end-use environment.

Hydroquinone

Cresol
Ortho

MetaParaOHOHOHOHHNOHThe FULCAT product range is especially suitable for theproduction of antioxidants by alkylation of phenylaminesand phenolics (G. 02). These Friedel-Crafts type alkylation
reactions are catalyzed by Lewis acids. BYK recommends
FULCAT-22 B for this application. FULCAT-22 B has beendeveloped to have market-leading Lewis acidity combinedwith low catalyst deactivation and excellent filtration
properties. Furthermore, FULCAT-22 B is considerably lesstoxic than the traditional aluminum chloride Lewis acidcatalyst and is easily removed from the reaction mixture togive a pure end product.

G. 01

Friedel-Crafts alkylation reactions
NHNH
∆

R

FULCATRROHOH∆RR

R

FULCATR
G. 02

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FULCAT heterogeneous clay catalysts

Silicone fluids
Silicone fluids (polydimethylsiloxanes), typically preparedfrom cyclic dimethylsiloxane monomers, are widely used
as lubricants due to their low surface tension, heat
resistance, chemical resistance, shear resistance, water
resistance, and viscosity stability. FULCAT-22 F andFULCAT-22 S demonstrate excellent catalytic activity inthe polymerization of cyclic dimethylsiloxanes.

complex silicone-based molecules. Due to the very low
surface tension of the polydimethylsiloxane back bone,functional silicone fluids are excellent components of surface
additives. Such silicone-based surface additives are used ina broad range of applications, from personal care todecorative coatings. Modification of the functional fluids,
for example grafting polyethers on to hydride functionality
via hydrosilylation reactions, is often catalyzed by precious
metal catalysts. Such catalysts can easily be fouled by sulfur
species. FULCAT-22 S has been developed to combine
exceptional catalytic performance alongside ultra-low sulfur
content specifically to produce functional silicone fluids.

Functional silicone fluids
Replacing some of the methyl groups with reactive
organic functionalities like hydride (G. 03) or vinyl resultsin functional silicone fluids. Functional silicone fluids canbe used as building blocks in the manufacture of more

Siloxane polymerization
HMDSOMCS

OSi

Sim·pMHSOO

SiSiO+SiSi+SiOOSiO∆SiOSiOSiOSiFULCATHHn

OMCS = octamethylcyclotetrasiloxane  HMDS = hexamethyldisiloxane  pMHS = polymethylhydrosiloxane.

Sin4mG. 03

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FULCAT heterogeneous clay catalysts

Oleochemicals
Oleochemicals are compounds derived from natural oils
and fats. Typically talked about are glycerin, fatty acids, andtheir derivatives. Derivatives of fatty acids include fatty aciddimers, fatty acid esters, fatty alcohols, fatty amines, andmore. Fatty acids and their derivatives are used in a broad
range of applications, including detergents and surfactants,

paints, lubricants, and food stuffs. Intelligent andresponsible use of sustainably sourced oleochemicals is, andwill continue to be, an important part of a sustainableglobal chemical future. FULCAT clay catalysts add value tothe derivatization of fatty acids.

Oleochemical value chain
Raw material

Basic oleochemical

Derivatives

Sulfo fatty acid ester
Fatty acidmethyl ester

Fatty alcohol

Oil andfats

Guerbert alcohols
Alkyl chlorides
Fatty alcohol ethoxylate
Fatty alcohol sulfates
Technical esters
Alkyl polyglycosides

Fatty acid

Co-product
Glycerin

Conjugated fatty acides
Alkyl epoxyester
Dimer fatty acides
Fatty acid ethoxylates
Acelaine/Pelargon acid
Fatty acid ester

Fatty alcohol
EO–PO–adduct
Fatty alcohol ether
sulfates
Fatty alcohol ether
phosphate
Fatty alcohol ether
sulfosuccinates

Tricetines
Partial glycerins
Medium chain triglyceride (MCT)

G. 04

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FULCAT heterogeneous clay catalysts / Oleochemicals

Fatty acid dimers
Dimer acids are produced from mixed monounsaturated/
polyunsaturated starting materials such as tall oil fatty acids,
rapeseed oil fatty acids, and soybean oil fatty acids. Dimeracids are important raw materials for such chemical
processes as the production of: polyesters, polyamides,polyurethanes, inks, adhesives, lubricants, corrosion
inhibitors, and epoxy resin curing agents. The dimerization
reaction proceeds via a combination of dehydrogenation,isomerization, and Diels-Alder cycloaddition mechanisms.
FULCAT-22 D is a mineral acid-free natural clay catalyst
with excellent catalytic activity in the dimerization reaction.

Example dimerization for linoleic acid and oleic acid (major constituents of tall oil fatty acid)to produce cyclic and acyclic dimer acids
HOO

Oleic acidOOHOHO
230–260 °C
Linoleic acid

FULCAT

HOOOOHO

HOG. 05

10FULCAT heterogeneous clay catalysts / Oleochemicals

Isomerization/hydrogenation
Fatty acid hydrogenation is widely used to manufacture
saturated fatty acids and fatty alcohols. Of particular interest
for FULCAT is the conversion of oleic acid to isostearic acidvia an isomerization/hydrogenation mechanism (see G. 06).
Isostearic acid is a low-viscosity, high-stability base oil thatis used extensively in the cosmetics industry. Due to theirhigh surface area, strong Brønsted acid sites and low sulfurcontent, FULCAT-22 S and FULCAT-435 make excellent
isomerization acid catalysts for the initial conversion of oleic
acid to isostearic acid.

Conversion of oleic acid to isostearic acid via acid-catalysedisomerization and hydrogenation
OOH

Acid catalyst,p, ΔO

OH

Hydrogenation(e.g. H2 + Pd/C)

OOH

G. 06

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FULCAT heterogeneous clay catalysts

Adsorbants
Due to their high surface area and high surface affinity fororganics, acid-activated clays have a long history of being
used as adsorbants in the purification of hydrocarbons.
Examples of such purification processes include:• Oxide scavengers in the processing of fatty acids• Purifying white mineral oils (or paraffin oils)• Removal of isoprene and azo-compounds frombenzene streams
The high surface area and low free acid content of
FULCAT-435 and FULCAT-22 S make them an ideal choice
as high-performance adsorbants for a wide range ofpurification processes.

12FULCAT heterogeneous clay catalysts

Brønsted acid catalysis
Clay catalysts, especially after acid activation, display very
high levels of surface acidity. A combined effect of residual
protons and ionization of bound water means that FULCAT
clay catalysts can achieve surface pKa’s as low as -8. Thishigh surface acidity ensures FULCAT acid clay catalysts
display good reactivity in a range of Brønsted acid-catalyzed
reactions. BYK’s first recommendation for Brønsted acidcatalysis is FULCAT-22 F.
Carbonyl chemistry
The broad range of carbonyl chemistry makes it one of thecornerstones of chemical production. Carbonyl chemistry
includes functionalities such as: esters, carboxylic acids,amides, ketones, and aldehydes. Carbonyl chemistry isdriven by Brønsted acid activation of the carbonyl carbonoxygen bond. The carbon-oxygen bond is activated by theuptake of a proton by a lone electron pair on the oxygen.

FULCAT-22 F is a an excellent source of Brønsted acidity andas a result displays strong catalytic activity in such reactions
as esterification, transesterification, and reductive amination.
(Trans)esterification reactions are used in the production offine chemicals, agricultural chemicals, and pharmaceuticalchemicals. Example reactions include the production of fatty
acid esters from fatty acids or fatty acid methyl esters, andthe manufacture of polyesters. In the reductive amination ofan amine and a ketone, FULCAT catalyzes the formation ofthe imine intermediate. An important commercial exampleof this reaction is the reductive amination of methyl isobutyl
ketone with 4-aminodiphenylamine to produce 6PPD
(N-(1,3-dimethylbutyl)-N‘-phenyl-p-phenylenediamine) – anantioxidant for rubber compositions.

(Trans)esterification

Reductive amination
R3RO

1FULCAT

R2O

R3RO

1OHO
R3R2

H2NO

R1G. 07

NFULCATOH
R2R3HN

Reducing agent

R3H2O
R1R2R1R2G. 08

13FULCAT heterogeneous clay catalysts / Brønsted acid catalysis

Alcohol dehydration
FULCAT-22 F provides excellent catalytic performance inthe acid-catalyzed dehydration of alcohols. This has a rangeof applications from forming alkenes and/or reactive
carbocation intermediates from secondary and tertiary
alcohols to forming ethers from primary alcohols.

redistribute double bonds statistically. BYK’s recommendation
for this application is FULCAT-22 F if low sulfur is not required
and FULCAT-22 S if low sulfur is required (for example in thepreparation of isostearic acid).
Hydrolysis
As the reverse of dehydration reactions such as alcohol
dehydration and esterification, hydrolysis is also catalyzed
by Brønsted acids. This means that FULCAT-22 F, as well as
being the recommended catalyst for dehydration reactions, isalso recommended as a catalyst for the hydrolysis of ethers,esters, and amides.

Isomerization
Alkene isomerization is catalyzed by Brønsted acids. Alkene
isomerization can be used to rearrange molecules to theirmost thermodynamically stable stereoisomer, for example:
the cis-trans rearrangement and alkene migration, or to

Alcohol dehydration

Hydrolysis reactions are critical depolymerization pathways
for polyesters, polyamides, and polyethers. As the global
chemical industry looks to move to sustainable chemical
feedstocks, the ability to break down polymers and biomass
will become increasingly important; FULCAT clay catalysts
offer the potential for a clean and green solution.

Alkene isomerization

OH

Example cis-trans rearrangement

Example thermodynamic bond migration

FULCAT
Toluene reflux
Dean-Stark trap

H+H+H2O

G. 09

G. 10

Hydrolysis
Ester hydrolysis

Ether hydrolysis

OO
R1Amide hydrolysis

R2H+H2O

R1OH

HOR2

R1O

H+OR

2H2O

HOR

1OH

R2R1HNH+R

2H2O

H2N
R

1R2OH

G. 11

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FULCAT heterogeneous clay catalysts

FULCAT selection chart
Product

Application
Antioxidants

Desired properties
Silicone fluids

Oleochemicals- Dimerization

Oleochemicals- Isomerization/
Hydrogenation

Absorbants

Brønsted
catalysts

Lewis catalyst

High surfacearea

Low sulfur

Low moisture

FULCAT-22 B
FULCAT-22 D
FULCAT-22 F
FULCAT-22 S
FULCAT-435
First recommendation  

Second recommendation

T. 01

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FULCAT heterogeneous clay catalysts

FULCAT benefits

FULCAT-22 B• Acid-activated clay catalyst• Market-leading Lewis acidityand filtration performance• Recommended for FriedelCrafts alkylation reactions,particularly in the productionof aminic and phenolicantioxidants

FULCAT-22 F• Acid-activated clay catalyst• Active Lewis and Brønsted acidprovide high reactivity in a large
range of reactions, including:Friedel-Crafts alkylation(trans)esterification
alcohol dehydration
alkene isomerization

FULCAT-435• Acid-activated clay catalyst• High surface area, low acid value• For applications where low levelsof free acid and high adsorption
rates are desirable, for example
fatty acid chemistry or
purification processes

FULCAT-22 S• Acid-activated clay catalyst• Combines high surface area andultra-low sulfur with strong Brønsted
and Lewis acid sites• Recommended for use when sulfur
would cause problems to concurrent
or downstream processes• Particularly developed for fatty acidisomerization and functional silicone
fluid production

FULCAT-22 D• Low-sulfur natural clay catalyst• Active Lewis acid sites within thephyllosilicate structure provides highreactivity in the dimerization of;tall oil fatty acids
rapeseed oil fatty acids
soybean oil fatty acids

01/2022
CA-TI 1BYK-Chemie GmbH
P.O. Box 10 02 4546462 Wesel
GermanyTel +49 281 670-0
Fax +49 281 65735

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