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Nufarm DNBP as a Styrene Polymerization Retarder
DNBP (2,4-dnitro-6-sec butyl phenol) is the most commonly used polymerisation
control additive in the distillation of styrene monomer. It is used similarly in
divinylbenzene. Used on its own it is an effective and safe retarder that has been
proven over many years use, it can be used in all plant designs and at all
temperatures found in the distillation sections.
DNBP can be used as a direct replacement for 2,4-dinitrophenol (DNP), 2,4-dinitro-
o-cresol (DNOC) and 2,4-dinitro-p-cresol (DNPC). These other nitrophenols are
solids with very low solubility in styrene or ethylbenzene requiring manual handling of
the material on location. DNBP is a low melting point solid (35°C) and is very soluble
in ethylbenzene enabling it to be pumped from a container to bulk store tank with no
manual handling required.
Most widely used polymer control additive in styrene production.
A retarder that gives long lasting protection even under abnormal conditions
which can occur in plant outages such as pump failure, vacuum failure etc
Proprietary process that reduces residual free acid to very low levels
Nufarm DNBP can also be used in combination with Nufarm stable free radical
products for improved performance at reduced cost (see AHM 700 Series)
Nufarm registered DNBP under the European REACH regulations in November 2010
and will continue to support this useful and valuable product.
Nufarm DNBP is available in several different formulations. We are always ready to
evaluate new mixtures to suit specific customer plants.
H507A: DNBP technical, molten solid
H509A: 50% DNBP in Ethylbenzene
H510A: 70% DNBP in Ethylbenzene
H513A: 75% DNBP in Ethylbenzene
All Nufarm DNBP is produced at our own site in the UK and is quality controlled
before leaving site. It is available in 200L drums, 1000L intermediate bulk containers
(IBC) and in isotanks.
We aim for high quality at all times and in all areas; from production, through QC and
shipping, to technical service.
Nufarm AHM 700 Series Styrene Polymerization Inhibitors
The Inhibitor AHM 700 series are polymerization control additives specifically
designed to enable the most efficient trouble free operation of styrene monomer
production plants. They are a mixture of DNBP retarder with a true inhibitor that
offers greatly improved anti-polymerization performance compared to other
commonly used materials. The performance and economics have been proven at
many plant trials and conversion rate from plant trial to full time use is 100%.
Easily handled liquid products.
Superior polymer control, and can be used at a much lower dose, compared to
conventional nitrophenolic products
Reduced usage rate leads to superior economics and low NOx when residues
are burnt
Retarder and inhibitor properties in a single product so only one storage and feed
system is required
Nufarm AHM 700 series comprises several different formulations designed to suit a
variety of plant conditions and we can create bespoke formulations to suit specific
customer needs.
Inhibitors are selected from our range of stable free radical (SFR) products and
phenylenediamines.
The latest development from Nufarm is a liquid, solvent-free, mixture that reduces
shipping costs and the amount of product handling required.
Inhibitor AHM 700 series are available in 1000L intermediate bulk containers (IBCs)
and in isotanks.
Case History: Savings on plant >$500,000 per year
Parameter Pre-Trial With AHM700 % Change
DNBP in EB splitter, ppm 1250 900 -28
Polymer in EB splitter, ppm 3000 750 -75
DNBP in SM column, % 1.5 1.0 -33
Polymer in SM column, % 6.5 3.5 -46
Green Retarders as Styrene Monomer Polymerization Inhibitors
Retarder MB-1 is a Nufarm patented formulation for use in styrene in combination
with a true inhibitor.
Retarder MB-1 is not classified as toxic and offers a greener alternative to the
retarder DNBP.
The combination of Retarder MB-1 and a true inhibitor provides excellent control of
polymer during styrene distillation and is successfully used in several commercial
styrene distillation units.
Most effective at temperatures up to 110°C
Retarder MB-1 is not classified as toxic
Reduced NOx when distillation tars are burnt.
Easy to handle liquid product
H530A: Retarder MB-1, 55% solution in ethylbenzene
Retarder S450 (patent applied for) is a new retarder suitable for use in all styrene
monomer plants. It has been tested and shown to be effective up to 160°C and is
therefore ideal for plants operating at higher operating temperatures and those
operating with heat recovery systems.
Retarder S450 is not classified as hazardous for transport and offers a true Green
alternative to DNBP. Used in combination with a true inhibitor it offers excellent
performance.
This is a newly commercialised product and material is available for plant trials.
Nufarm’s experienced and skilled Technical Service Team will be on hand to guide
you through all aspects of a plant introduction.
Nufarm Crude C4 Inhibitors for Butadiene Units
Crude C4 cuts are produced by crackers and contain varying amounts of the
valuable monomer 1,3-butadiene. These can be processed on site but can also be
transported and traded for processing at sites remote from the crackers.
Butadiene can form polymers during storage and transportation, both poly-butadiene
rubber and, via reaction with oxygen, polyperoxides that are highly unstable and
hazardous.
Crude C4s are therefore stabilized during transport and the ideal product is one
which combines a phenolic anti-oxidant to remove poly-peroxides and a stable free
radical product that can prevent any polybutadiene formed from carbon radical
reactions.
Nufarm’s crude C4 stabilizer, Inhibitor AHM E870, is designed to perform these
functions and has been successfully used for several years.
Nufarm Polymerization Inhibitors for Butadiene Production
Butadiene is extracted and purified from a crude C4 stream using several different
technologies. The basic principle of them all is to use a solvent to extract 1,3-
butadiene from the other stream components, the solvent and butadiene are then
separated by distillation and finally polymer grade butadiene is purified in a final
distillation step.
There are two types of polymer that can form in a butadiene distillation unit
Polybutadiene rubber
o This is formed by carbon-carbon radical reaction and is characterised
by soft brown polymer. The process can be inhibited with stable free
radical inhibitors and Nufarm have been providing these compounds to
butadiene producers for over 10 years. It is normal to achieve 5 year
run-lengths between mandatory shutdowns using these products.
Nufarm can provide a bespoke product for your plant and advice is
available from our Technical Service Team.
o Products Available
Inhibitor AHM B238 (>10 years of commercial use)
Inhibitor AHM B247 (>7 years of commercial use)
Inhibitor AHM B239 (>5 years of commercial use)
Popcorn polymer
o This is formed when oxygen ingress occurs and is characterised by
white or yellow globular polymer that grows from the inside out and can
damage equipment through uncontrolled growth. Butadiene plants
rigorously exclude oxygen and operate under a positive pressure of
several bar. Excellent engineering and operator controls are required
to prevent oxygen ingress because there are no polymerization
inhibitors capable of preventing popcorn polymer growth once it has
seeded. The characteristic of the popcorn polymer of growing in the
vapour phase and containing internal radical sites means that
conventional inhibitors are ineffective. The Nufarm Technical Service
Team can advise on industry best practice to prevent popcorn polymer.
Nufarm Polymerization Inhibitors for Acrylonitrile
Acrylonitrile (ACN) is largely produced using the SOHIO process with propylene,
ammonia and air (oxygen) as the raw materials giving acrylonitrile, water and HCN
as products. The HCN can be recovered as a commercial product (a raw material
for MMA production) or incinerated. The purification of ACN is essentially split into
two sections (i) Recovery of ACN by quenching the gaseous reaction product in
water and (ii) Purification of ACN to give the polymer grade product. Purification of
the product includes a HCN column, a drying column and then the final product
column.
Fouling in the acrylonitrile plant can occur in the HCN column but this is largely
anionic polymerization of the HCN and cannot be controlled by free radical inhibitors.
It can be mitigated by addition of acids (usually acetic acid) and good engineering
techniques combined with dispersants are used to keep this column free of fouling.
Free radical polymerization occurs in the acrylonitrile, causing fouling of the column
plates and the reboiler, and can be inhibited using stable free radicals. Nufarm have
developed a proprietary product for acrylonitrile polymerization inhibition that has
provided excellent results as the case history below demonstrates.
2005: Hydroquinone/Phenylenediamine treatment
2008: Nufarm treatment, Inhibitor AHM N720
0
1
2
3
4
5
2005 2008
Frequency of Shutdowns
HCN
Drying
Product
The reduction in annual cleaning costs for this plant was in the order of US$570,000.
In addition to the reduced fouling, AHM N720 eliminated the need for manual
handling required for the previous treatment and reduced operator exposure to
acrylonitrile. The Nufarm treatment also increased ACN/water separation rates in
two decanters, thus increasing plant efficiencies.
Nufarm Polymerization Inhibitors for Acrylic Acid and Acrylic
Esters
Acrylic acid is a highly corrosive monomer that can polymerize extremely quickly and
violently. Thus the prevention of polymerization is not only critical to improving plant
efficiencies but also to the safety of the process. Polymerization is affected by many
competing influences including the metallurgy of the plant, the amount of water
present in different areas, temperature and the amount of air (oxygen) present, all of
which influence the tendency and rate of acrylic acid to polymerize.
Nufarm stable free radical inhibitors have been used in acrylic acid distillation and
through our own research, and working closely with our customers, Nufarm has
gained a high level of expertise in the prevention of acrylic acid polymerization in all
areas of the plant. Our Technical Service Team is available to give advice on the
best products for each area of the plant.
Acrylic esters are produced from the esterification of acrylic acid with a range of
different alcohols. Nufarm has products that will prevent polymer fouling in both the
esterification reactors and in the purification section.
The case history shown below shows what can be achieved with the correct
product selection.
Before treatment started with Nufarm, the customer had to clean the pump screens
many times per day, now the screens are checked only during plant maintenance.
Start of Nufarm
Inhibitor treatment
Nufarm Polymerization Inhibitors for Methyl Methacrylate
Methyl methacrylate (MMA) has been made principally using the Acetone
Cyanohydrin (ACH) route developed in the 1930s. Recently Lucite have introduced
the Alpha Process and started the first operational plants using this technology.
Nufarm has provided inhibitors for plants operating using both technologies and our
Technical Service Team can offer advice on product selection depending on the part
of the plant to be treated.
One of the main fouling locations in the ACH route occurs in the reactor section. The
data below compares the efficacy of two Nufarm products under typical conditions
encountered in this section
Methyl Methacrylate 15%w/w
Methacrylic acid 2%w/w
Sulphuric acid (36%) 32%w/w
Ammonium Bisulphate 51%w/w
Inhibitor 1ppm
Temperature 100oC
0
2
4
6
8
10
12
14
16
Inhibitor S4 P500 HQ
Po
lym
er
Inhibitor
1st Run
Data shows that both Inhibitor S4 and AHM P500 (a more acid stable inhibitor)
exhibit high efficacy in reducing MMA polymerization compared to the conventionally
used hydroquinone.
Nufarm Polymerization Inhibitors for Vinyl Acetate Monomer
Vinyl Acetate Monomer (VAM) requires inhibition to prevent polymerization in the
purification by distillation. Old inhibitor technology has now been displaced by the
use of stable free radical chemistry in this monomer.
Nufarm currently supplies inhibitor to a large VAM plant and can offer a range of
different inhibitor/solvent combination to suit your specific requirements.
0
1
2
3
4
5
TBC/BQ Inhibitor S4 P500
Po
lym
er
The above graph compares the efficacy of Nufarm inhibitor products (Inhibitor S4
and AHM P500) with the conventionally used treatment system of tert-butyl catechol
(TBC) and p-benzoquinone (BQ).
Both Nufarm products provide a significant reduction in the amount of polymer
formed.
Nufarm Inhibitors for the Ethylene Train
Naphtha or ethane are “cracked” to give the range of unsaturated monomers that are
used to produce many of our polymers used in everyday life. In various amounts,
ethylene, propylene and butadiene are produced and separated by distillation. C4s
including butadiene can be purified remotely and are often traded. C5+ materials are
also produced.
Stable free radicals are well established in the purification of ethylene and propylene.
They are also used in compressors to keep these clear of fouling. Nufarm staff have
many years of experience in the industry and can advice on dosing locations and
quantities to prevent fouling.
We currently supply products to both depropanisers and debutanisers.
Case History: In 2010 we were approached by a company with severe fouling
problems in their debutanizer unit. Typical run-lengths before shutting down to
clean the column were 150 days only. Nufarm treatment was started in September
2010 and to date there has been no indication of fouling, no pressure drops, no
change in steam valve settings etc.
Nufarm Inhibitors for Pygas and Pygas Hydrotreating
Pyrolysis gasoline (pygas) is the cut of heavier molecules (C5+) that is generated by
the cracking of naphtha or ethane. It is used as a feedstock for BTX units and is
transported and traded in bulk.
Nufarm supplies Pygas stabilisers that can be added to the pygas during transport to
prevent the formations of gums or polymer whilst in transit. These are particularly
useful if the pygas is to be stored for any significant time or transported through hot
climates.
Pygas can be hydrotreated (hydrogenated) to remove unsaturated compounds from
the stream. This process is hot, and fouling caused principally by styrene and
cyclopentadiene can occur in the reboiler and heat exchangers. Nufarm has been
supplying inhibitors to prevent fouling in this process for six years.
Nufarm Inhibitors for Chlor-Vinyls
Vinyl Chloride monomer (VCM) is a very large volume monomer whose polymers have a wide range of application in both flexible and rigid forms. The most common method of production is via ethylene dichloride (EDC).
EDC is prepared by reacting ethylene and chlorine. This process is very selective, resulting in high purity EDC and high yields. When the EDC is heated to 500 °C at 15–30 atm (1.5 to 3 MPa) pressure, EDC vapour decomposes to produce vinyl chloride and anhydrous hydrochloric acid.
Even though residence time and temperature are carefully controlled, it produces significant quantities of chlorinated hydrocarbon side products. In practice, EDC conversion is relatively low (50 to 60 percent). The furnace effluent is immediately quenched with cold EDC to stop undesirable side reactions. The resulting vapor-liquid mixture then goes to a purification system.
VCM itself does not cause significant fouling problems during purification but some of the by-products of the cracking process do so. Chloroprene can foul the Lights column and Nufarm can supply inhibitors to keep this column free of polymer and reduce the amount of valuable product lost to waste.
Vinylidene Chloride is produced by the alkaline de-chlorination of 1,1,2-trichloroethane and has a tendency to polymerize during purification. Nufarm Technical Services can offer advice on the best inhibitors to use to prevent this based on our past experiences in commercial units.