Sulfite alternatives

Cavano, Robert. Panel Discussion on Oxygen Scavengers Non-Sulfite Alternatives. Association of Water Technologies 5th Annual Convention, USA, 1992. 

In an alternative industrial process, resorcinol [108-46-3] is autoclaved with ammonia for 2—6 h at 200—230°C under a pressurized nitrogen atmosphere, 2.2—3.5 MPa (22—35 atm). Diammonium phosphate, ammonium molybdate, ammonium sulfite, or arsenic pentoxide maybe used as a catalyst to give yields of 60—94% with 85—90% selectivity for 3-aminophenol (67,68). A vapor-phase system operating at 320°C using a siUcon dioxide catalyst impregnated with gallium sesquioxide gives a 26—31% conversion of resorcinol with a 96—99% selectivity for 3-aminophenol (69). 

Chemical recovery ia sodium-based sulfite pulpiag is more complicated, and a large number of processes have been proposed. The most common process iavolves liquor iaciaeration under reduciag conditions to give a smelt, which is dissolved to produce a kraft-type green liquor. Sulfide is stripped from the liquor as H2S after the pH is lowered by CO2. The H2S is oxidized to sulfur ia a separate stream by reaction with SO2, and the sulfur is subsequendy burned to reform SO2. Alternatively, ia a pyrolysis process such as SCA-Bidemd, the H2S gas is burned direcdy to SO2. A rather novel approach is the Sonoco process, ia which alumina is added to the spent liquors which are then burned ia a kiln to form sodium aluminate. In anther method, used particulady ia neutral sulfite semichemical processes, fluidized-bed combustion is employed to give a mixture of sodium carbonate and sodium sulfate, which can be sold to kraft mills as makeup chemical. 

An alternative route is the reaction of iodine or bromine in pyhdine with Hquid sulfur dioxide at 20°C, which gives good to high yields of sulfites (106). 

Calcium thiosulfate has been prepared from calcium sulfite and sulfur at 30—40°C, or from boiling lime and sulfur in the presence of sulfur dioxide until a colorless solution is obtained. Alternatively, a concentrated solution of sodium thiosulfate is treated with calcium chloride the crystalline sodium chloride is removed at low temperature. Concentrated solutions of calcium thiosulfate are prepared from ammonium thiosulfate and lime the Hberated ammonium ion is recycled to the ammonium thiosulfate process (85). 

Chromium Removal System. Chlorate manufacturers must remove chromium from the chlorate solution as a result of environmental regulations. During crystallization of sodium chlorate, essentially all of the sodium dichromate is recycled back to the electrolyzer. Alternatively, hexavalent chromium, Cr, can be reduced and coprecipitated in an agitated reactor using a choice of reducing agents, eg, sodium sulfide, sulfite, thiosulfate, hydrosulfite, hydrazine, etc. The product is chromium(III) oxide [1333-82-0] (98—106). Ion exchange and solvent extraction techniques have also... 

Salads. A combination of citric acid and ascorbic acid is used as an alternative to sulfites in prevention of enzymatic browning in fresh prepared vegetables (56). 

Alternatively, the metathesis can be effected by sulfites or bisulfites that convert cystine iato one cysteiae residue and one thiosulfate (Bunte salt) residue. Hair waving based on sulfites is slower than that based on mercaptans and is more likely to cause changes ia hair color. 

It is possible to introduce sulfonic acid groups by alternative methods, but these ate Htde used in the dyes industry. However, one worth mentioning is sulfitation, because it provides an example of the introduction of a sulfonic acid group by nucleophilic substitution. The process involves treating an active halogen compound with sodium sulfite. This reaction is used in the purification of m-dinitrohen7ene. 

Multiblended inhibitors based on tannins, for use in either closed loop HW systems or steam raising boiler plants. Tannin-based multiblends are often offered as an alternative to sulfite-based multiblends. 

Maintain adequate chelant reserve. Use sulfite or alternative oxygen scavenger, plus amine for program support. 

For HW, LP steam, and many lower pressure industrial operations, sulfite or sulfite derivatives have proved to be excellent scavengers and suitably cost-effective, provided the MU requirements are not too high and FW temperatures not too low. Alternatively, tannin-based products provide a similar degree of effectiveness without the contribution to TDS and, in practice, almost irrespective of FW oxygen content. 

Dissolved oxygen (DO) in the FW should be reduced to the lowest practical level before adding an oxygen scavenger. Hydrazine is recommended as an alternative to sodium sulfite only when it is dosed to the FW at a substantial distance from the boiler and where the FW is sufficiently hot to enable the removal of oxygen to be 90% complete before entry to the boiler. 

Other methods have been developed for the removal of oxygen (particularly from flowing streams). These include the use of electrochemical or chemical (zinc) scrubbers, nitrogen-activated nebulizers, and chemical reduction (by addition of sodium sulfite or ascorbic acid). Alternately, it may be useful to employ voltam-... 

Elemental sulfur dissolves in boiling aqueous sodium sulfite solutions with the formation of sodium thiosulfate (Na2S203). The reaction proceeds quantitatively if sulfur and excess sodium sulfite are boiled for some time in weakly alkaline solutions. In the cold, however, practically no reaction occurs. Alternatively, thiosulfate can be produced quantitatively in solution phase by using organic solvents to first dissolve sulfur and then accomplish the reaction with aqueous sulfite. In a parallel reaction, elemental selenium dissolves in alkaline sulfite solution to produce selenosulfate, SeSO ... 

Dioxygenation may result in the elimination of nitrite in reactions that are analogous to the elimination of sulfite from aromatic sulfonates, or halogen from 2-halobenzoates. As an alternative to dioxygenation, toluene-3- and toluene-4-monooxygenases can transform nitrobenzene to 4- or 3-nitrophenol, with the former dominating (Fishman et al. 2004) ... 

The most commonly employed routes for the preparation of the / -sulfatoethylsulfone group, which is the essential structural feature of vinylsulfone reactive dyes, are illustrated in Scheme 8.5. One method of synthesis involves, initially, the reduction of an aromatic sulfonyl chloride, for example with sodium sulfite, to the corresponding sulfinic acid. Subsequent condensation with either 2-chloroethanol or ethylene oxide gives the / -hydroxyethylsulfone, which is converted into its sulfate ester by treatment with concentrated sulfuric acid at 20 30 °C. An alternative route involves treatment of an aromatic thiol with 2-chloroethanol or ethylene oxide to give the /Miydroxyethylsulfonyl compound which may then be converted by oxidation into the /Miydroxyethylsulfone. 

Scale formation in the scrubber can lead to sodium carbonate as an additional dry sorbent in the scrubber. Alternatively, limestone is also introduced into combustion chambers to treat sulfur dioxide emissions. Decomposition of CaC03 into CaO and CO2 occurs in the combustion chamber, and the resulting CaO combines with S02 to produce calcium sulfite. Notice that this process produced another potentially environmentally harmful pollutant (CO2) as it gets rid of a definite environmentally harmful pollutant (SO2). 

A variation of the pathway in which 2 -hydroxybiphenyl-2-sulfinate is converted to 2 -hydroxybiphenyl-2-sulfonate (HBPSo) has been reported [26,62], In this alternate desulfurization pathway, the HBPSo further spontaneously cyclizes to sultone , BPSo. The latter is a substrate for DszA (Fig. 2), and is desulfurized to 2, 2 -dihydroxybiphenyl (DHBP) and sulfite. 

Quench the oxidation reaction by the addition of at least a 4-fold molar excess of N-acetylmethionine or sodium sulfite over the concentration of periodate in the reaction mixture (e.g., 40mM). Pre-dissolve the quencher in buffer at a higher concentration prior to adding an aliquot of it to the reaction solution. React for 10 minutes. Alternatively, the oxidation reaction may be stopped by the removal of excess periodate by gel filtration using a desalting column. 

O-Alkylation of 4-hydroxy-3-morpholino-l,2,5-thiadiazole 132 has been achieved with the chiral cyclic chloro-methyl sulfite 133 which subsequently suffers ring opening on treatment with simple alcohols <2001RCB436> or alkylamines <2002RJ0213> to afford the timolol analogues 134 with very little racemization (Scheme 20). This indicated an almost exclusive attack of the oxy anion on the exocyclic carbon atom and is a significant improvement on the previous oxirane method, which suffers from racemization. An alternative biocatalytic asymmetric synthesis of (A)- and (R)-timolol has also appeared <2004S1625>. 

The three rate constants for Eq. (98) correspond to the acid-catalyzed, the acid-independent and the hydrolytic paths of the dimer-monomer equilibrium, respectively, and were evaluated independently (107). The results clearly demonstrate that the complexity of the kinetic processes is due to the interplay of the hydrolytic and the complex-formation steps and is not a consequence of electron transfer reactions. In fact, the first-order decomposition of the FeS03 complex is the only redox step which contributes to the overall kinetic profiles, because subsequent reactions with the sulfite ion radical and other intermediates are considerably faster. The presence of dioxygen did not affect the kinetic traces when a large excess of the metal ion is present, confirming that either the formation of the SO5 radical (Eq. (91)) is suppressed by reaction (101), or the reactions of Fe(II) with SO and HSO5 are preferred over those of HSO3 as was predicted by Warneck and Ziajka (86). Recently, first-order formation of iron(II) was confirmed in this system (108), which supports the first possibility cited, though the other alternative can also be feasible under certain circumstances. 

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