Sulfuric acid, supported

Nitration of o-xylene with N02 has been performed in the gas phase over several zeolites (HBeta, HY, HZSM-5 and HMordenite), as well as on sulfuric acid supported on silica and sulfated zirconia at temperatures between 50 and 130°C.[72] HBeta was found the most active and selective catalyst for the production of 4-o-NX giving ratios of 4-o-NX 3-o-NX as high as 6 1, whereas no dinitro-o-xylene compounds were detected. 

Tapia et al. [23] described the use of nitric acid supported on silica gel for the mono-nitration of activated aromatic compounds such as phenols and aryl methyl ethers. Riego et al. [24] used sulfuric acid supported on silica gel for the mononitration of a variety of aromatic compounds. The reaction was performed at ambient temperature with 70 % nitric acid or isopropyl nitrate as reagents and yielded mono-nitrated products within short reaction periods. Toluene was quantitatively converted to NT in 0.1 h, without a solvent, by use of a catalyst containing 10 mmol g as supported 70% H2SO4. A comparative study of the reaction kinetics of the nitration using supported and unsupported liquid acids revealed that the performance of supported sulfuric acid is comparable with that of 90 % sulfuric acid in the classical liquid phase reaction where complete protonation of nitric acid occurs [25]. 

The most likely explanation is the effect of radiation on the electrolytic solution. The study of the effect of radiation on the hydrogen evolution reaction on platinum in sulfuric acid supports this view. 

Reddy et al. (2009) documented a novel protocol for a Pechmann reaction involving the synthesis of substituted coumarins from phenols and P-ketoesters catalyzed by sulfuric acid supported on the silica gel surface (Scheme 5.28). The method has several distinct advantages such as a clean reaction profile, operational simplicity, use of nontoxic catalysts, and higher yields in short reaction time and provides a valuable addition to the existing methods for the synthesis of coumarins. 

Heravi MM, Ramezanian N, Sadeghi MM, Ghassemzadeh M (2004) Synthesis of [1,3,4] thiadiazolo[2,3-c][l,2,4]triazin-4-ones using sulfuric acid supported onto silica gel in sol-ventess system. Phosphorus Sulfur Silicon Relat Elem 179 1469-1472... 

Mellor et al. (1997, 2000) found that when well-dried CAN supported on silica gel, sulfuric acid supported on silica gel, and naphthalene were stirred at room temperature in dichloromethane in presence of tetrabutylammonium nitrite, 1-nitronaphthalene was rapidly... 

Catalytic gas-phase reactions play an important role in many bulk chemical processes, such as in the production of methanol, ammonia, sulfuric acid, and nitric acid. In most processes, the effective area of the catalyst is critically important. Since these reactions take place at surfaces through processes of adsorption and desorption, any alteration of surface area naturally causes a change in the rate of reaction. Industrial catalysts are usually supported on porous materials, since this results in a much larger active area per unit of reactor volume. 

Processes for Triacetate. There are both batch and continuous process for triacetate. Many of the considerations and support faciUties for producing acetate apply to triacetate however, no acetyl hydrolysis is required. In the batch triacetate sulfuric acid process, however, a sulfate hydrolysis step (or desulfonation) is necessary. This is carried out by slow addition of a dilute aqueous acetic acid solution containing sodium or magnesium acetate (44,45) or triethanolamine (46) to neutrali2e the Hberated sulfuric acid. The cellulose triacetate product has a combined acetic acid content of 61.5%. 

Starting from Benzene. In the direct oxidation of benzene [71-43-2] to phenol, formation of hydroquinone and catechol is observed (64). Ways to favor the formation of dihydroxybenzenes have been explored, hence CuCl in aqueous sulfuric acid medium catalyzes the hydroxylation of benzene to phenol (24%) and hydroquinone (8%) (65). The same effect can also be observed with Cu(II)—Cu(0) as a catalytic system (66). Efforts are now directed toward the use of Pd° on a support and Cu in aqueous acid and in the presence of a reducing agent such as CO, H2, or ethylene (67). Aromatic... 

Several processes are available for the recovery of platinum and palladium from spent automotive or petroleum industry catalysts. These include the following. (/) Selective dissolution of the PGM from the ceramic support in aqua regia. Soluble chloro complexes of Pt, Pd, and Rh are formed, and reduction of these gives cmde PGM for further refining. (2) Dissolution of the catalyst support in sulfuric acid, in which platinum is insoluble. This... 

In past years, metals in dilute sulfuric acid were used to produce the nascent hydrogen reductant (42). Today, the reducing agent is hydrogen in the presence of a catalyst. Nickel, preferably Raney nickel (34), chromium or molybdenum promoted nickel (43), or supported precious metals such as platinum or palladium (35,44) on activated carbon, or the oxides of these metals (36,45), are used as catalysts. Other catalysts have been suggested such as molybdenum and platinum sulfide (46,47), or a platinum—nithenium mixture (48). 

Esterification. Extensive commercial use is made of primary amyl acetate, a mixture of 1-pentyl acetate [28-63-7] and 2-metliylbutyl acetate [53496-15-4]. Esterifications with acetic acid are generally conducted in the Hquid phase in the presence of a strong acid catalyst such as sulfuric acid (34). Increased reaction rates are reported when esterifications are carried out in the presence of heteropoly acids supported on macroreticular cation-exchange resins (35) and 2eohte (36) catalysts in a heterogeneous process. Judging from the many patents issued in recent years, there appears to be considerable effort underway to find an appropriate soHd catalyst for a reactive distillation esterification process to avoid the product removal difficulties of the conventional process. 

Isopropyl Alcohol. Propylene may be easily hydrolyzed to isopropyl alcohol. Eady commercial processes involved the use of sulfuric acid in an indirect process (100). The disadvantage was the need to reconcentrate the sulfuric acid after hydrolysis. Direct catalytic hydration of propylene to 2-propanol followed commercialization of the sulfuric acid process and eliniinated the need for acid reconcentration, thus reducing corrosion problems, energy use, and air pollution by SO2 and organic sulfur compounds. Gas-phase hydration takes place over supported oxides of tungsten at 540 K and 25... 

Thermal decomposition of spent acids, eg, sulfuric acid, is required as an intermediate step at temperatures sufficientiy high to completely consume the organic contaminants by combustion temperatures above 1000°C are required. Concentrated acid can be made from the sulfur oxides. Spent acid is sprayed into a vertical combustion chamber, where the energy required to heat and vaporize the feed and support these endothermic reactions is suppHed by complete combustion of fuel oil plus added sulfur, if further acid production is desired. High feed rates of up to 30 t/d of uniform spent acid droplets are attained with a single rotary atomizer and decomposition rates of ca 400 t/d are possible (98). 

Catalysts. Commercial sulfuric acid catalysts typically consist of vanadium and potassium salts supported on sUica, usually diatomaceous earth (see Diatomite). Catalyst peUets are available in various formulations, shapes, and sizes depending on the manufacturer and the particular converter pass in which they are to be used. A detailed discussion of oxidation catalysts for sulfuric acid production is available (107). 

The level of technical service support provided for a given product generally tracks in large part where the suppHer considers thek product to be located within the spectmm of commodity to specialty chemicals. Technical service support levels for pure chemicals usually provided in large quantities for specific synthetic or processing needs, eg, ammonia (qv), sulfuric acid (see SuLFURic ACID AND SULFURTRIOXIDe), formaldehyde (qv), oxygen (qv), and so forth, are considerably less than for more complex materials or blends of materials provided for multistep downstream processes. Examples of the latter are many polymers, colorants, flocculants, impact modifiers, associative thickeners, etc. For the former materials, providing specifications of purity and physical properties often comprises the full extent of technical service requked or expected by customers. These materials are termed undifferentiated chemicals (9),... 

In laboratory preparations, sulfuric acid and hydrochloric acid have classically been used as esterification catalysts. However, formation of alkyl chlorides or dehydration, isomerization, or polymerization side reactions may result. Sulfonic acids, such as benzenesulfonic acid, toluenesulfonic acid, or methanesulfonic acid, are widely used in plant operations because of their less corrosive nature. Phosphoric acid is sometimes employed, but it leads to rather slow reactions. Soluble or supported metal salts minimize side reactions but usually require higher temperatures than strong acids. 

The use of an acidic solution of p-anisaldehyde in ethanol to detect aldehyde functionalities on polystyrene polymer supports has been reported (beads are treated with a freshly made solution of p-anisaldehyde (2.55 mL), ethanol (88 mL), sulfuric acid (9 mL), acetic acid (1 mL) and heated at 110°C for 4 min). The colour of the beads depends on the percentage of CHO content such that at 0% of CHO groups, the beads are colourless, -50% CHO content, the beads appear red and at 98% CHO the beads appear burgundy [Vdzquez and Albericio Tetrahedron Lett 42 6691 200]]. A different approach utilises 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (Purpald) as the visualizing agent for CHO groups. Resins containing aldehyde functionalities turn dark brown to purple after a 5 min reaction followed by a 10 minute air oxidation [Coumoyer et al. J Comb Chem 4 120 2002]. 

This solution Is heated to 65°C and barium hydroxide added in quantity sufficient to make the concentration of the barium hydroxide 0.2 mol/liter. The solution is agitated and maintained at 65°C for 6 hours after the addition of the barium hydroxide. It is then cooled and neutralized to a pH of 6.8 with sulfuric acid. The precipitated barium sulfate is filtered out. A quantity of activated supported nickel catalyst containing 5 g of nickel is added. 

UV spectra of a variety of 1 -alkyl-1 //-1-benzazepines,20,21 3//-l-benzazepines,20 l-acyl-l//-l-benzazepines,1 3,22,23 3-acyl-3//-3-benzazepines,22-23 3-alkyl-37/-3-benzazepines and their cations in concentrated sulfuric acid,24,25 and 3-mesyl-3//-3-bcnzazepine,2ft have been recorded. A comparison of the UV spectra of 3-alkyl-l, 5-dihydroxy-3//-3-benzazepinc-2,4-dicarboxylates and their bis-O-methyl ethers supports an enol rather than an amide structure for these derivatives.14... 

Water-free nitric acid is amphoteric, ie, it acts both as an acid and a base, or better as an electron donor or electron acceptor. This view, already suggested in the early Hantzsch papers, was supported by Walden (Ref 14) and later by Dalmon (Ref 30). Then Usanovich (Ref 25) demonstrated that nitric acid acts as a base with sulfuric acid and as an acid with water. 

However, the fact that the derived S—O bond dissociation energy in sulfuric acid is identical to that found in the acid derivatives, strongly supports the estimated enthalpy of formation for gas-phase sulfurous acid given by Benson18. 

Cationic polymerization of cyclosiloxanes is well known but used much less frequently than anionic reactions. The most widely used catalysts include sulfuric acid and its derivatives, alkyl and aryl sulfonic acids and trifluoroacetic acid1 2,1221. Due to their ease of removal, in industrial applications acid catalysts are generally employed on supports such as bentonite clay or Fuller s earth. 

Fig. 4 shows the current density over the supported catalysts measured in 1 M methanol containing 0.5 M sulfuric acid. During forward sweep, the methanol electro-oxidation started to occur at 0.35 V for all catalysts, which is typical feature for monometallic Pt catalyst in methanol electro-oxidation [8]. The maximum current density was decreased in the order of Pt/CMK-1 > Pt/CMK-3 > Pt/Vulcan. It should be noted that the trend of maximum current density was identical to that of metal dispersion (Fig. 2 and Fig. 3). Therefore, it is concluded that the metal dispersion is a critical factor determining the catalytic performance in the methanol electro-oxidation.

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