Chromium conversion processes

Hexavalent chromium reduction through the use of sulfur dioxide and sodium metabisulfite has found the widest application in the metal finishing industry. It is not truly a treatment step, but a conversion process in which the hexavalent chromium is converted to trivalent chromium. The hexavalent chromium is reduced through the addition of the reductant at a pH in the range of 2.5-3 with a retention time of approximately 30-40 min (Figure 9.7). 

The initial treatment used in Europe was a chromium conversion coating process using a proprietary product called Iridite. This was a two-component system which contained a blend of highly toxic materials such as chromium salts and ferro- and ferricyanides. 

Conversion coatings are not as protective as anodized coatings. In most cases, conversion coated surfaces are subsequently primed or painted. Xraditionally, pretreatment of Al has relied on chromate-based systems. Xhere are two general classes of chromate conversion processes the activated acidic formulations such as the chromium chromate processes that use a sodium fluoride-chromic acid chemistry, and alkaline oxide processes based on a sodium chromate-sodium hydroxide or carbonate chemistry. 

Trivalent chromium conversion coatings Meets no conosion in 500 h lequiiemeni (ASTM B 117 salt spray test) Still contains ciromium Electrolytic process... 

C and 19,600 kPa (2800 psi). The catalyst is a complex aluminum—ca dmium —chromium oxide that has high activity and exceptionally long life. The process is claimed to give a conversion of ester to alcohol of about 99% retaining essentially all of the original double bonds. 

In order to circumvent this problem, there has been significant activity directed toward the search for a less environmentally toxic and more selective oxidizing agent than chromium. For example, Hoechst has patented a process which uses organorhenium compounds. At a 75% conversion, a mixture of 86% of 2-methyl-l,4-naphthoquinone and 14% 6-methyl-l,4-naphthoquinone was obtained (60). Ceric sulfate (61) and electrochemistry (62,63) have also been used. 

Dehydrogenation of /i-Butane. Dehydrogenation of / -butane [106-97-8] via the Houdry process is carried out under partial vacuum, 35—75 kPa (5—11 psi), at about 535—650°C with a fixed-bed catalyst. The catalyst consists of aluminum oxide and chromium oxide as the principal components. The reaction is endothermic and the cycle life of the catalyst is about 10 minutes because of coke buildup. Several parallel reactors are needed in the plant to allow for continuous operation with catalyst regeneration. Thermodynamics limits the conversion to about 30—40% and the ultimate yield is 60—65 wt % (233). 

Ammonia production from natural gas includes the following processes desulfurization of the feedstock primary and secondary reforming carbon monoxide shift conversion and removal of carbon dioxide, which can be used for urea manufacture methanation and ammonia synthesis. Catalysts used in the process may include cobalt, molybdenum, nickel, iron oxide/chromium oxide, copper oxide/zinc oxide, and iron. 

When a calcined Cr(VI)/Si02 catalyst is fed with ethylene at 373-423 K, an induction time is observed prior to the onset of the polymerization. This is attributed to a reduction phase, during which chromium is reduced and ethylene is oxidized [4]. Baker and Garrick obtained a conversion of 85-96% to Cr(II) for a catalyst exposed to ethylene at 400 K formaldehyde was the main by-product [44]. Water and other oxidation products have been also observed in the gas phase. These reduction products are very reactive and consequently can partially cover the surface. The same can occur for reduced chromium sites. Consequently, the state of sihca surface and of chromium after this reduction step is not well known. Besides the reduction with ethylene of Cr(Vl) precursors (adopted in the industrial process), four alternative approaches have been used to produce supported chromium in a reduced state ... 

More than three decades ago, skeletal rearrangement processes using alkane or cycloalkane reactants were observed on platinum/charcoal catalysts (105) inasmuch as the charcoal support is inert, this can be taken as probably the first demonstration of the activity of metallic platinum as a catalyst for this type of reaction. At about the same time, similar types of catalytic conversions over chromium oxide catalysts were discovered (106, 107). Distinct from these reactions was the use of various types of acidic catalysts (including the well-known silica-alumina) for effecting skeletal reactions via carbonium ion mechanisms, and these led... 

AH = 2.9 kj mol-1 at 300 K and 1 atm, there is no low-energy pathway for the transformation, so the process is difficult to carry out. However, synthetic diamonds are produced on a large scale at high temperature and pressure (3000 K and 125kbar). The conversion of graphite to diamonds is catalyzed by several metals (i.e., chromium, iron, and platinum) that are in the liquid state. It is believed that... 

There are essentially three main steps in a conversion coating process cleaning, conversion coating, and post-treating. These three different, but equally important, steps in the pretreatment of metal articles will be discussed in more detail for the purpose of providing a background for the main emphasis of this paper, the post-treatment part of the conversion coating process, and more specifically chromium-free polymeric post-treatments which have been developed in recent years to replace the environmentally unacceptable chromate systems. 

Reaction of CrCl3-6H20 with trien gives a blue-violet mixture from which some chromium(III)-trien complexes (electronic spectra given in Table 56) may be isolated as indicated in Scheme 53. While the conversion of cis-ar-[Cr(0H)(trien)H20]Cl2 to the cis-fi isomer in the temperature range 160-225 °C is reversed on cooling, the process is irreversible if the reaction is carried out above 225 °C. 

More recent research efforts have focused on the development of other possible catalysts such as promoted Raney copper,371,403 catalysts prepared from intermetal-lic precursors,362,371 386 404-406 and catalysts that tolerate high C02 content.407 Catalyst modifications allowed to shift the selectivity to the formation of higher alcohols.208,408 110 For example, in a process developed by IFP, a multicomponent oxide catalyst is applied with copper and chromium as the main components 410 By this method, 70-75% total alcohol selectivities and 30-50% of C2 and higher alcohol selectivities can be achieved at 12-18% conversion levels (260-320°C, 60-100 atm). 

The femtosecond fluorescence up-conversion setup has been described elsewhere [13,14]. Briefly, a second harmonic (SH) of a home-made chromium-forsterite femtosecond laser tunable from 610 to 660 nm was used to excite the sample (Fig.2) [14]. The pulse duration of the SH pulses was about 50 fs at the full width at half maximum (FWHM). We were successful in the cavity-dumping operation of this laser [14] and kept the repetition rate as low as 4 MHz. Reduction of the repetition rate was necessary to avoid multiple hits of the same location of the sample as small as possible. The excitation intensity, controlled by a neutral density filter before the sample cell, was (0.5-l)xl012 photons/cm2/pulse. Special care was taken to work at the lowest excitation light intensity so that the effect of the exciton-exciton annihilation process was negligible. 

A palladium(II)-exchanged polystyrene sulfonic acid resin (Dowex 50W, H form) catalyzes the oxidation of 2-methylnaphthalene with 60% aqueous H2O2 (reaction 27), affording 2-methyl-l,4-naphthoqu1none (menadione) in 55-60% yield at 90-97% conversion. 3 Menadione is a commercially important vitamin K intermediate and these results compare favourably with those obtained in existing industrial processes that employ stoichiometric quantities of chromium trioxide in sulfuric acid. 

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