Nonylphenol production

There are over 150 different producers and some 2 million tonnes of commercial nonionic surfactants manufactured worldwide of which at least 50% are alkoxylated alcohols. Ethoxylated nonylphenol production is falling and accounts for 20% of the market while alkoxylated fatty acids account for some 15%. Fatty acid amides and sugar esters account for another 10% and there are a large number of specialities making up the balance. In general, non-ionic surfactants are easy to make, relatively inexpensive and derived from a variety of feedstocks. 

Typically, soHd stabilizers utilize natural saturated fatty acid ligands with chain lengths of Cg—C g. Ziac stearate [557-05-1/, ziac neodecanoate [27253-29-8] calcium stearate [1592-23-0] barium stearate [6865-35-6] and cadmium laurate [2605-44-9] are some examples. To complete the package, the soHd products also contain other soHd additives such as polyols, antioxidants, and lubricants. Liquid stabilizers can make use of metal soaps of oleic acid, tall oil acids, 2-ethyl-hexanoic acid, octylphenol, and nonylphenol. Barium bis(nonylphenate) [41157-58-8] ziac 2-ethyIhexanoate [136-53-8], cadmium 2-ethyIhexanoate [2420-98-6], and overbased barium tallate [68855-79-8] are normally used ia the Hquid formulations along with solubilizers such as plasticizers, phosphites, and/or epoxidized oils. The majority of the Hquid barium—cadmium formulations rely on barium nonylphenate as the source of that metal. There are even some mixed metal stabilizers suppHed as pastes. The U.S. FDA approved calcium—zinc stabilizers are good examples because they contain a mixture of calcium stearate and ziac stearate suspended ia epoxidized soya oil. Table 4 shows examples of typical mixed metal stabilizers. 

Large volumes of monoalkylphenols are shipped in Hquid form by railcar, tank wagon, or export container. These shipping vessels must be stainless steel or phenoHc resin lined carbon steel. Eor smaller volumes, dmms and tote-tanks are used. Eor high freezing point alkylphenols, such as PTBP, the product is flaked and shipped in either bags or supersacs. Eor low freezing point products, such as -nonylphenol (PNP) (fp < 20° C), the product is shipped in dmms or tote-tanks. 

The use of 4-nonylphenol ia the production of tris(4-nonylphenyl) phosphite is also not expected to show much growth because of its replacement ia many polymers by higher performing and more hydrolytically stable phosphites. 

Non-ionic surfactants used in detergents, paints, herbicides, pesticides and plastics. Breakdown products, such as nonylphenol and octylphenol, are found in sewage and industrial efffuents Products of combustion of many materials Widely used as plasticisers for PVC. Common environmental pollutants... 

Cyprid major protein is a larval storage protein necessary for successful metamorphosis. " Production of cyprid major protein was increased in the barnacle Balanus amphitrite following exposure to both nonylphenol and estradiol, suggesting that it may be a potential biomarker of estrogen exposure in invertebrates such as barnacles. " "... 

Figure 12a gives the surface dilatational viscosities for a nonionic surfactant, namely, nonylphenol 10 EO, and for C12-C14 AOS. Both products were ad-... 

Alkylphenol ethoxylates (APEs) are nonionic surfactants that are used in the manufacturing of plastics, agricultural chemicals, cosmetics, herbicides, and industrial detergent formulations. Alkylphenols such as nonylphenol (NP) are the products of... 

Fenner K, C Kooijman, M Scheringer, K Hungerbiihler (2002) Including transformation products into the risk assessment for chemicals the case of nonylphenol ethoxylate usage in Switzerland. Environ Sci Technol 36 1147-1154. 

SDSI is being developed to recognize companies, facilities, and others who voluntarily phase out or commit to phasing out the manufacture or use of NPE surfactants. NPEs are used in detergents in cleaning and other products. Both NPEs and their breakdown products, such as nonylphenol, can harm aquatic life. The Safer Detergents Initiative complements EPA s Aquatic Life Ambient Water Quality Criteria for Nonylphenol which are designed to protect aquatic hfe in both fresh and saltwater and can form the basis for state and tribal water quahty standards. 

PLE pressurized liquid extraction, SPE solid phase extraction, UE ultrasonic extraction, DSPE dispersive solid phase extraction, SBSE stir bar sorptive extraction, TD-GC-MS thermal desorption-gas chromatography-mass spectrometry, LAS linear alkylbenzene sulfonates, CDEAs coconut diethanol amides, NPEOs nonylphenol ethoxylates, DP degradation products, SPC sulphenyl carboxylates, PCDD dibenzo-p-dioxins (PCDD), PCDF dibenzofurans, PCBs biphenyls... 

Gonzalez S, Petrovic M, Barcelo D (2004) Simultaneous extraction and fate of linear alkylbenzene sulfonates, coconut diethanol amides, nonylphenol ethoxylates and their degradation products in wastewater treatment plants, receiving coastal waters and sediments in the Catalonian area (NE Spain). J Chromatogr A 1052(1-2) 111-120... 

Petrovic, M., Gehringer, P., Eschweiler, H., Barcelo, D. (2004). LC-MS-MS determination of oxidative degradation products of nonylphenol ethoxylates, carboxylates and nonylphenols in water. Water Sci. Technol. 50 (5), (Assessment and Control of Hazardous Substances in Water), 227-234. 

APEOs are used in domestic and industrial applications. They are applied as detergents, emulsifiers, wetting agents, dispersants or solubilisers. APEO derived from nonylphenol (NP), i.e. nonylphenol ethoxylates (NPEOs) comprises about 80% of the total market volume, while octylphenol-derived surfactants (OPEOs) account for 15-20%. Because of the persistence and toxicity of some degradation intermediates, their use has been reduced in several countries either through voluntary bans by the chemical industry or by legal regulations. However, excellent properties in combination with comparably low production costs hampers their complete replacement with other more environmentally acceptable alternatives. 

Octyl- and nonylphenol are well known raw materials used in the surfactant industry since the early 1960s, mainly for the production of their corresponding ethoxylated derivatives (APE). Today, these products have lost considerable importance in this industry as a consequence of substantial environmental threats, resulting from their relatively slow biodegradation, toxicity of their biodegradation metabolites and positive endocrine-disrupting reactions. 

The synthesis of commercial nonylphenols generally proceeds through an alkylation reaction of phenols with propylene trimer [124], which itself has a spread of isomers [47]. The alkylation occurs preferentially at the para position of the phenol, but 3-6% of ortho-nonylphenol can be found in commercial products [125]. Also meta and disubstituted species have been mentioned [47]. A common feature of the isomers appears to be a dimethyl substitution of the a-carbon atom [83]. 

The APCI-RP-C 1 s - h - i I S ( / ) separation of this mixture consisted of the anionic nonylphenol derivatives besides synthetic by-products to the total ion current traces and selected mass traces as presented in Fig. 2.11.23. By-products from synthesis could be confirmed as... 

As for the elimination efficiency of NPEO during wastewater treatment, values from 81 to 99.5% were calculated. However, the removal of parent NPEOs led to the formation of transformation products that are much more resistant to microbial degradation and overall elimination of nonylphenolic compounds during sewage treatment is very low. Ahel et al. [20] estimated that approximately 60-65% of all nonylphenolic compounds introduced to WWTP are discharged into the environment 19% in the form of carboxylated... 

Although the occurrence of the non-ionic surfactant nonylphenol ethoxylate (NPEO Fig. 6.7.1) and its biodegradation intermediates in the aquatic environment has attracted large interest [18] because of the potential of some biotransformation products to mimic estrogenic effects, their fate and distribution in soil environments has been only investigated in a few cases. 

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