J. Ind. Eng. Chem, Vol. 11, No. 3, 2005) 380.346 REVIEW Manufacture of Chlorine Dioxide from Sodium Chlorate: State of the Art Bal Raj Deshwal’ and Hyung Keun Lee* Department of Chemistry, A. IJ. H. M. College, Rohtak -124 001, Haryana, India Flue Gas Treatment Center, Korea Institute of Energy Research, Daejeon 305-343, Korea Received October 8, 2004; Accepted February 3, 2005 Abstraet: Chlorine dioxide (CIO) has achieved a remarkable degree of commercial attention not only because of environmental concems but also because of its wide range of applications in the fields of bleaching, oxidation, and disinfection. There is a growing interest in the development ot ‘more efficient, and more cost effective techniques for the generation of chlo ous methods used for the manufacture of chlorine di prehensive review highlights the v. chlorate as the raw material and discusses their process chemistri ‘mechanisms of the various reactions responsible for ClO; generation, Efforts have been made t st recent developments in the manufacture of chlorine the pertinent details, including the m impler, more easily operated, dioxide. This present com- ide using sodium including the reaction kinetics and the incorporate all ide. This review not only provides a deep insight into the manufacturing processes but also it paves the ways for im- provements to the existing traditional processes and the design of advanced processes in the future. Keywords: Chlorine-dioxide, sodium chlorate, manufacturing processes, kinetics, mechanism Introduction iy of chlorine dioxide is complex and dif fers from that of other chlorine-based compounds. C10: is yellowish gas that is explosive at concentrations higher than 10% by volume in air or at a partial pressure above 76 mm of Hg (1.46 psig). It can be condensed to a reddish-brown liquid at 11°C and solidified to orange-red cexystals at -59°C. It is a neutral compound of chlorine in a +4 oxidation state and exists as a free radical, even in dilute aqueous solutions. It functions as a highly selective oxidant because of its unique ability to undergo one- electron transfer [1] ClO; is highly soluble in chilled water (~10 times ‘more so than chlorine), but it can be easily driven out of aqueous solutions with a strong stream of air. It is also soluble in sulfuric acid, acetic acid, and non-aqueous solvents such as CCL, hexane, cyclohexane, benzene, toluene, and xylenes. Solutions of ea. 1% ClO» (10 g/L) ‘may be stored safely if the solution is protected from * To whom all correspondence should be addeesse, (e-mail hlee@kerrekr) light and kept chilled. When an aqueous solution of chlorine dioxide is frozen, C1O>*8H0 crystals precipi- tate out. ClO: does not hydrolyze in water to any appre ciable extent in the pH range from 2 to 10; rather, remains as dissolved gas in aqueous solution [2]. ClO, is, thermally unstable and sensitive to light as well as, pressure. It decomposes spontaneously and exothermally to produce chlorine and oxygen when exposed to light, 2. C10) Ch +202 + heat a) ClO; may decompose violently if compressed, which, thus, makes store age and shipping impractical. Pure solutions of chlorine dioxide may also detonate if ex posed to bright light or an ignition source, such as heat, a spark, or an open flame. It is an extreme irritant and hazardous gas. On breathing air containing chlorine diox- ide gas, one may experience irritation to the nose, throat, and lungs. 1000 ppm of ClO> is fatal for short exposure. The odor of CIO; can be detected at as low as 14 t0 17 ppm. Adequate ventilation and proper care is therefore needed in the workplace. The properties of ClO; do not bar its use, but a high degree of caution is desirable. Aqueous solutions of ClO; are strong oxidants, ex-Manufacture of Chlorine Dioxide from Sodium Chlorate: State ofthe Art 331 tremely reactive, and corrosive, They attack all metals except platinum, tantalum, and titanium, ClO. is explo sive as a gas or solution at high concentrations. However, it can be handled easily when diluted with air to less than 15 w%. Chlorine dioxide is a highly reactive compound that does not exist in the environment for long periods of time. Major Applications of Chlorine Dioxide Chlorine is @ novel oxy-chlorine species that has emerged as a highly efficient chemical agent for bleaching, oxidation, and disinfection. It is used commer cially in textile, paper, fat, and pulp bleaching, waste- water treatment, Water purification, removal of iron, man= ganese, HS, and phenols from industrial wastes, medical treatment, sanitation, food processing, fumigation, deodo- tization, and aquaculture, among other applications. It is also popular as an algaecide, fungicide, gemicide, deo- dorant, and antiseptic agent The chlorine dioxide-based bleaching process, the so- called ECF technology, dominates the production of bleached chemical pulps [3]. Wood pulp bleaching is the prime use of chlorine dioxide because it is a unique selective oxidizer for lignin. Unlike other oxidizing agents, chlorine dioxide does not attack cellulose, and, thus, its use preserves the mechanical properties of the bleached pulp. Furthermore, chlorine dioxide functions via oxidation rather than chlorination; hence, it avoids the formation of chlorinated organic compounds. ‘Thus, there is growing interest for bleaching purposes in re- placing chlorine and hypochlorite with chlorine dioxide. Chlorine dioxide is quite effective as a biocide for industrial and municipal waste-water treatment. It rapidly ingetivates most microorganisms over a wide pH range, and it helps in eliminating the taste and odor problems, from drinking waters because it does not react with organic matter and, thus, avoids the formation of trihalo= ‘methanes (THMs). Undesirable tastes and odors resulting from algae, decaying vegetation, and phenolic compounds are controlled by using chlorine dioxide. The odors from rotten food wastes can also be eliminated, presumably through oxidation [4] of mercaptoethanol (the chemical responsible for the foul smell) by ClO». Chlorine dioxide is a good sterilizing agent for equip- ‘ment and tools. When ClO; is dissolved in a solution of sodium perborate, it forms a stable complex that can be used as an antiseptic. Recently [5], chlorine dioxide has been used to clean up acidic gases, like SO; and NO,, from flue gases. When a flue gas containing oxides of sulfur and nitrogen was treated with an aqueous scrub= bing solution containing ClO; in a lab-scale bubbling reactor, almost 100% SO» removal, 100% NO oxidation, and about 70% NO, removal efficiencies were observed, which is a result that is comparable with those of other additives used so far. ‘The EPA has set the maximum concentration of chlorine in drinking water at 0.8 mg/L. If inhaled, chlo- rine dioxide quickly changes to chlorite ions, which are broken down further into chloride ions in the body. Cur rently there is no evidence of the carcinogenic potential of drinking water disinfected with chlorine dioxide. Chlorine dioxide has been found to be superior to chlo- rine in a number of respects; for instance, it can also destroy some organisms, like bacteria, spores, and viruses, that are not attacked by chlorine, At the same level of concentration, the capability of chlorine dioxide to destroy spores and viruses is higher than that of chlorine. Unlike chlorine, it does not react with ammonia and amino compounds and, thus, avoids the formation of chloramines, which have a negative influence on the dise infection and taste of the treated water. Various fundamental studies have been carried out from time to time to investigate the reaction kinetics ‘mechanisms involved in ClO» production; such studies help to improve the manufacturing processes by deter ‘mining the optimum reaction conditions for obt better yield and a more rational utilization of raw mater tials. This paper is a continuation of our previous commu nication in which we discussed the process chemistries of ClO; generation from sodium chlorite (6]. In this present comprehensive review, we highlight various aspects of the process chemistry and technological developments in the manufacture of ClO; from sodium chlorate. This knowledge will be advantageous when attempting to ime prove existing processes and develop advanced processes, in the future. Chlorine Dioxide Manufacture The discovery of chlorine dioxide was reported in 1815 by Davy [7,8]. The author [8] suggested that euchlorine (a mixture of chlorine dioxide and chlorine in a molar ratio of 2 : 1) was produced when hydrochloric acid was reacted with chlorate. Millon [9] also noticed the forma tion of chlorine dioxide upon reaction of oxalic acid with chlorate; the stoichiometry of this reaction was later suggested by Calvert and Davies as follows [10] 2KCIO; + 2(COOH)» + 2C10, + 2CO.+ (COOK); + 24:0 2 Here, oxalic acid serves both as an acid as well as a reducing agent and the CO> formed renders the C1O> less likely to explode. Later, Schacherl [11] suggested the ad- dition of sulfurie acid to the mixture of chlorate and oxalic acid: 2KCIO, + (COOH), + 2H:SO, > 2C10; +20; + 2KHSO, + 2H:0 ®332 Bal Raj Deshwval and Hyung Keun Lee When concentrated sulfuric acid reacts with solid chlo- rate, an explosion of chlorine dioxide may result as foF lows [12} 3KCIO, + 3:80,» 2C10; + @ HCIO, + H:0 + 3KHSO, The discovery of the reaction between chlorate and acid \was the major milestone in the manufacture of CIO». The synthesis of chlorine dioxide has an extensive literature, especially in the patent area. Although many fundamental studies have been carried out in the past to develop simpler, more easily operated, efficient, and economical techniques for the generation of chlorine dioxide, there remains plenty of room for improvement in these proc sses. Chlorine dioxide is always generated on-site because of its unstable nature and risk of rapid decomposition. In all, processes, it is produced from acid solutions of either sodium chlorite or sodium chlorate. Most of the small- scale generators use sodium chlorite as the precursor ‘material, particularly for water treatment, chemical ox dation, and disinfection applications because they require high-purity (i.e., Ch-free) water. Other applications, where large quartities of chlorine dioxide are needed, utilize sodium chlorate as the raw material. The chlorate- based processes have traditionally been used in the pulp and paper industries. Conditions for the production of ClO; from sodium chlorite can be better controlled than those from sodium chlorate, but chlorite is a more expen- sive and unstable chemical and, therefore, from an indus trial point of view, sodium chlorate is a more suitable raw material for the generation of chlorine dioxide. In addition, sodium chlorite is itself produced [13-17] by reduction of chlorine dioxide gas in an alkaline medium: 2CIO» + H:O2 + 2NaOH — 2NaClO, +O: +2H:0 (5) Manufacture of CIO; from Sodium Chlorate Sodium chlorate is manufactured by the electrolysis of aqueous solutions of sodium chloride. Hypochlorite is, the intermediate species in this oxidation process. Sodium. chlorate is the prime agent used in ClO; generation; therefore the production of chlorate has increased mani- fold during the past decade. ClO; can be formed by reduction of chlorate with a suitable reducing agent in a relatively concentrated acid solution. ‘The reduction half- reaction for the production of ClO; from chlorate can be expressed as ClOs + 2H! +6 > ClO, + HO (6) The standard redox potential, £”, of this half-reactior 1.152 V [18]. The choice of reducing agent is very im- portant because it affects the optimum reaction cond tions, the by-products, and the economies of the process. In all chlorate-based processes, the chloride ion plays a crucial role, as evidenced by its presence in the reaction solution and by the traces of chlorine formed along with ClO. No chlorine dioxide is formed if chloride ion is not, present in the reaction medium. Chloride is either intro duced in the feed or it is produced by the reduction of chlorate, as follows: ClOy + 6H! + 6¢ — CI +30 a This side reaction occurs in all the chlorate-based pro= cesses, so steps must be taken to minimize this reaction by careful control of the reaction conditions or by the choice of reducing agent. The reducing agents that have been used so far in the ClO; generation include SOs oxalic acid, sulfur, NOs, methanol, NaCl, HCI, and hydro- gen peroxide. There are several processes that are used to generate chlorine dioxide from sodium chlorate. Some of them are listed below in the form of their chemical equations; + SO-Based Processes: 2NaCIO; + SO; + HSOs ~> 2C10; + 2NaHSO: + Methanol-Based Processes: 6NaCI0; + CHOH + 41,80, > 6C10; + CO:-+ NaH (SO.)> + SHO + NaCl-Based Processes: 2NaCIO; + 2NaCl + 4HLSO, > 2C1O; + Ch + 4NaHSO, + 2H,0 + HCI-Based Processes: 2NaCIO; + 4HCI —* 2C10; + Ch +2NaCl + 2-0 + Hydrogen Peroxide-Based Processes: 2NaClO; + H.03 + H:SO, > 2CIO; + O» + NasSOs + 2H40 Commercial chlorine dioxide generation processes can be broadly classified into atmospheric and sub-atmo- spheric processes. Atmospheric processes use air to strip and dilute the chlorine dioxide gas and have an overflow of spent acid. These processes need higher concentra tions of acid (> 8 N) and the major by-product is sodium bisulfate (NaHSO.). However, by performing these processes under a sub-atmospheric pressure or vac tuum, a suitable production rate and yield can be obtained at an acid strength = 4 N and the major by-product is neutral anhydrous sodium sulfate (NaSO,). The cor sumption of acid is comparatively lower in the sub- atmospheric processes; moreover, they require lower tem peratures. Periodic developments that have oacurred for the manufacture of ClO» using various reducing agents are presented here.Manufacture of Chlorine Dioxide from Sodium Chlorate: State ofthe Art [oven cites cv, Absorber steam T_, co, slain Nacio,} |x,s0,| |} Primary | ISencm| | ‘Tank ‘Tank — | sn Spe fad Pee Pump Figure 1.A schematic diagram of Mathieson chlorine-dioxide generator. SO;-Based Processes The Mathieson process was developed by Olin-Mathieson Chemical Corporation in the 1950s. [19-22}, an SO>-air mixture is sodium chlorate and si etry of the reaction is 2NaClO; + SO. + H:SO, — 2CIO; + 2NaHSO, ficiency in terms of chlorine dioxide because of several competing side reactions. Chlorine dioxide is vulnerable to sulfur dioxide contamination and some chlorine is also formed. Woodside and Macleod [19] determined the opti= ‘mum concentrations of sulfuric acid, chlorate, and SO; gas (diluted with air) to be 8 N, 0.2 mol/L, and ~12%, respectively, to provide a generator efficiency above 90%. Reduction of chlorate by sulfur dioxide is an exothermic process and it is accompanied by several competing side reactions at low acidity, leading to a considerable loss of yield. 2NaClO; + SSO; + 41.0 —> Cl. + 2NaHSO, + 3H:S0, o NaClOs + 380; + 3H:0 + NaCl + 3H2S0, (10) The schematic diagram of a Mathieson unit is shown in Figure | ‘The Mathieson generator is a lined, jacketed steel tank designed with an external heat exchanger. The absorption tower for ClO» is refrigerated at around 40°F. The spent liquor overflows continuously to a waste liquor tank where it is treated with 26% soda ash solution to form the crude salt cake. CIOs is removed continuously by the ar stream. Because the effluent from the generator is wasted, it leads to ~5% loss of the chlorate feed. To recover this loss, a small secondary generator, into which the effluent from ‘main generator flows by gravity, is attached. By means ofa single porous plate and a drought tube, a stream of SO is introduced into it and the gas evolved goes to the top of main generator to be mixed with the gas produced there, Subsequently, several modifications to the SO:-chlorate process were suggested to improve the yield of CIOs, the utilization of chlorate, and the recovery of acid. Pemert [29] suggested the use of chloric acid a8 an input reactant to minimize the production of by-products and to reduce the expenditure of extra acid. Sodium chlorate can be treated with aqueous sulfuric acid to form a relatively concentrated solution of chloric acid. ‘This solution can be cooled further to below about -15°C to separate the crystals of hydrated sodium sulfate. When diluted S introduced into aqueous chlorie acid at a low pressure, relatively pure chlorine-dioxide will evolve: 2HCIO; + $0 > 2C10) + HO. ay In some other patents [30,31], @ mixture of SO: and Cl diluted with an inert gas, such as nitrogen, was bubbled through the reaction liquor to suppress the side reaction (9) that produces Cb at the loss of chlorate. The importance of chloride in all of the CIO» generation processes was later demonstrated by adding sodium sulfate to precipitate the chlorides. It is often observed in the Mathieson generator that the ClO) formation begins334 Bal Raj Deshwval and Hyung Keun Lee Naclo, —, + closainct, Gas Serubber 0, ale = = To 3 2 Stripper ‘water —+| E 3 Secondary Generator Generator 80, igure 2. Modified Mathieson chlorine dioxide generator fitted swith a gas serubber. at a very slow rate and gradually increases up to the desired rate. It is accounted for by the need to build up the chloride concentration to the required level. It is recommended to add 5~10% chloride [31,33] in the acidic chlorate solution in the Mathieson generator to im prove the reaction rate, utilization of chlorate, and effi ciency of CIO; production. If the chloride concentration is maintained at a suitable level, it will suppress the side reaction (10) that forms chloride at the expense of chlo» rate, With the same thought in mind, Hoekje and Welch [31] suggested an improved process whereby a mixture of SO> and Ch (diluted with an inert gas) is passed into an acidic solution of sodium chlorate containing some It is known that SO: can react with Cl, as well as C102, to produce HCI and 5. amount of SO> used SO. [52 Thus, if the high, then it may reduce Ch first Ms mney, and HCI and H,SO, will appear in the CIO; solution. This difficulty was overcome by installing a gas scrubber over the generator [34]. The gas scrubber contained a small tower packed with Raschig rings. It was designed in such a way that the chlorate solution passed down the packing on its way into the generator, while the gas passing upward through the packing was scrubbed by the chlorate solu- tion. Thus, no acid is carried from the generator to the ab= sorber. The HCI and H:SOs that formed by reaction of Ch and SO; were retumed back to the generator for reuse. The overall mechanism [34] of the SO,-chlorate process in the presence of chloride is suggested as follows: Step - 8a ClO; +2H' + CI > HCIO,+ HOCL Step - 8b HOCI + H,0 + SO, > HCI + H:SO, Step - Se HCIO; + Cl0s +H’ + 2C10; + H20 Cooling Water Control Valve $0,+Air NaCIO, Solution {> Raschig Ring Reaction Column Gas a Receiver Tube Column, Liquid Steam 55 Li pischarge Tube Figure 3, Mathieson chlorine dioxide generator packed with Raschig rings. ‘A little chlorine is also formed by the side reaction of HOCI and HCl as: HOCI+ HCI — Ch + H:0 (12) The design of a modified Mathieson generator is pre= sented re 2. The bubbling of SO> diluted with No or air into an aque- ous acidic chlorate solution is a batch process; it seems impossible to establish and maintain the conditions that are most favorable for ClO; generation because of the constantly decreasing chlorate concentration and increas ing concentration of other by-products, some of which ‘may favor Ch production. Wayman and Rapson [26,27] suggested that ClO» substantially free from Ch may be produced continuously and efficiently from a concen trated solution of chlorate and dilute SO» gas (10~15%) by passing these two reactants either counter-currently or co-currently, through a reaction tower packed with Raschig rings, verl saddles, glass beads, or any other ible packing. A Mathieson ClO; generator packed with Raschig rings, in which concentrated sodium chlo- rate solution and SO» (diluted with air or N:) gas are passed co-currently, is presented in Figure 3. There is tendency towards the formation of a little chlo rine along with chlorine dioxide in the above continuous process, but SO: gas will react with this chlorine rapidlyManufacture of Chlorine Dioxide from Sodium Chlorate: State ofthe Art 335 [5,25-27] in the aqueous solution: b+ Ch + 2440 > 2HCI + (13) SO; can also react with chlorine dioxide [5,25-27] 5802 + 2C10; + 6FLO —> SHRSO: + 2HCI co) The reaction of SO2 with ClO» is, however, much slower when compared to that with Ch and chlorate, so there is little loss of chlorine dioxide. Cowley [35] later treated sodium chlorate with SO; at sub-atmospheric pressure (80~ 100 mm of Hg) by coun tercurrent flow in a gas-liquid contact reaction zone at a temperature of 50~80°C at a total acid normality of 9.5 ~11N. A small amount of NaCl (~0.1% by wt of chlorate) was also added to aid in the initiation of the production of ClO;. A preheated aqueous acidic chlorate solution and a preheated stream of diluted SO are fed counter-currently from the upper and lower ends of the tower and contact between the down-flowing chlorate and upward-flowing gaseous SO; produces the CIO>. The gaseous products and liquid by-product effluent were withdrawn by water ejectors. This technology has been successfully applied to generate ClO» for use in waste- water treatment in a fully automated plant. Methanol-Based Processes Solvay, R-8, R-9, R-10, and SVP-Lite processes are the znames given to the methanol-based CIO» generation pro= cesses. The complete oxidation of methanol in acidic chlorate solution [36-45] follows the stoichiometry ONaCI0; + CHOH + 41:80, —* as) 6C10 + CO; + 2NagH (SO): + SHO The methanol-chlorate processes do not produce much chlorine, but they have several shortcomings. Firstly, chlorate oxidizes methanol in a stepwise manner: first forming formaldehyde, then formic acid, and finally carbon dioxide [36,46-50]. The oxidation of formic acid to carbon dioxide is a very slow step. It forms volatile ‘methylformate, which escapes along with chlorine- dioxide and, thus, reduces the efliciency of the process. HCOOH + CH:OH + HCOOCH; + H:0 (16) Secondly, it requires high sulfuric acid concentrations, to achieve the desired production rate of chlorine di oxide, which results in the formation of an acid salt cake. Thirdly, when the ClO» product is used in bleaching, the unreacted methanol constitutes a pollution load to the final user's secondary effluent treatment system. Fourthly, ‘methanol is a combustible and hazardous substance for the workplace. It has been observed that only about 40% of the meth anol fed is used efficiently in the above process. A thorough study [36,37,48] revealed that a part of the ‘methanol feed leaves the reactor unreacted. This loss ‘may be as high as 30 to 40%. The major source of these losses is the incomplete oxidation of methanol, which leads to the formation of formic acid or formaldehyde [36,37,42,45,47,48} 12NaCIOs + 3CHsOH + 8HLSO, —> on 12C10; + 3HCOOH + 4NaiHl (SO.): + 9H.0 6NaC IO; + 3CHLOH + 41:80. > as) 6C10; + 3HCHO + 2NasH (SO.): + 64:0 It is believed [36] that losses also result from side reactions that result in the formation of chlorine: 6NaC10 + SCH.OH + 41:80, > (19) 3Ch + SCO; + 2NasH (SO,)) + 13H:0 12NaCIO; + ISCH:OH + 8H2SO, —> (20) 6Ch + ISHCOOH + 4NasH (SOs)2 + 211.0 2 Norell [36] observed that methanol losses are strongly dependent on the mode of its addition in the reactor. When methanol and chlorate were fed at the same point, i.e., before the heat exchanger, which is the normal feed point of the reducing agent, the methanol loss was ~ 37%, However, when it is added in the crystallization zone of the reactor, the loss reduced to only ~3%. Norell also suggested the addition of small amounts of catalysts to influence the complete oxidation of methanol to COs[36] It is noteworthy here that the direct reaction between chlorate and methanol is very slow and the true reducing agent in this case is chloride ions, which are formed in situ [36-38] by the reaction of methanol with the chlorine formed in reactions (19) and (20), and so significant quantities of chlorine do not appear in the by-products. CHAOH + 3Cb+ H:0 ~ 6CI'+ CO: + 6H enn) If, for some reason, all the chloride ions are consumed, then the production of chlorine dioxide will cease until chloride ions are produced by the reduction of chlorate with methanol. This loss of chlorine dioxide production is termed a “white-out”, Thus, it is often necessary [36- 38,51] to add a small amount of chloride ions con tinuously to avoid the incidence of *white-outs” and to obtain a steady production of chlorine dioxide. The overall mechanism for the methanol-chlorate process shown in equation (15) is suggested as follows [34,4348]336 Bal Raj Deshwval and Hyung Keun Lee COs Air Ch Absorption > “Tower — pony Tel] Recovery Generator 1B) J secondary 18 | Genrer cot BE wor ‘Water iet | Water xc, Ho, cof Ai Figure 4. Solvay chlorine dioxide generators operated in series ina cascade fashion. Step -I5a_ ClOs + 2H" + CI + HCIO;+ HOC! Step -I5b HOCI + CHOH — HC1+ HCHO + FLO Step-15¢ HCIO: + ClO; +H —> 2C10, + H.0 Step -I5d_ HOCI +HCHO — HCI + HCOOH A small amount of chlorine is also formed by the side reaction of HOC! and HCI as expressed in equation (12). The possible reactions that can produce carbon dioxide are Step -I5e 2H’ +2C10s+ HCOOH + 2C10; + 2H20 + CO» Step-15f Cl + HCOOH — 2H’ + 2CT + COs A typical Solvay chlorine dioxide generator is shown in Figure 4. It consists of two jacketed lead-line steel reac tion vessels operated in series in a cascade fashion, over flowing by gravity from one to other. Each vessel agitated vigorously by an air stream, which also serves to remove ClO» at a lower partial pressure. Concentrated solutions of chlorate, methanol, and ~9 N H)SO, are introduced into the first reactor. The solution overflows, to the second reactor, which is maintained a at slightly higher temperature to ensure the complete utilization of chlorate. Subsequently, several modifications were suggested for the methanol-based process. Some researchers [36,37,39, 50,51] suggested the use of a high sulfuric acid normality (4.8 to LN), recirculation of the condensed by-products, and a single vessel generator-evaporator-crystallizer to enhance the efficiency of chlorine dioxide production where the reaction solution is subjected to a sub-atmom spheric pressure sufficient to evaporate the water. ‘The ‘mixture of chlorine dioxide and water vapor is withdrawn from an evaporation region and alkali metal sulfate is precipitated in the crystallization region. The purity of the chlorine dioxide formed, in terms of contamination by chlorine, increased with inereasing the acid normality The condensation of by-products and recirculation in the reactor not only favor the conversion of methanol to carbon dioxide but also reduce the methanol loss. The alkali metal sulfate (salt cake) formed under a high acid normality is either sodium bisulfate (NaHSO,) or sodium sesquisulfate [NasH(SO))]. In the past, most of the salt cake was consumed in kraft paper mills as a ‘make-up chemical for the sulfur values lost from mills, but, in recent years, most mills have made major equip- ‘ment and operating modifications because of environs ‘mental concerns, so the material is now an unwanted by-product. Because of their acidic nature, they can be disposed of only after neutralization, which makes the process costly. Several methods have been suggested to treat it such that the lost acid values can be recovered for recycling to the reaction zone. Norell [36] observed that when sodium sesquisulfate or the “acid salt cake” was heated to 400~600°C, it decomposed into gaseous SOs and neutral sodium sulfate or a “neutral salt cake” 2NasH (SOs). > 3Na\SO, (3) + SOs (g) + H20 (g) (22) The gaseous sulfur trioxide is then absorbed in water and the sulfuric acid that forms is recirculated to the reaction vessel. Sodium sesquisulfate can also be com verted by metathesis to form the neutral sodium sulfate Metathesis can performed using aqueous sodium chlorate, aqueous sodium chloride, aqueous methanol, or water alone. When the acid salt cake is dissolved in hot water in the metathesis tank, it dissociates into the neutral salt cake and weak sulfuric acid solution [49,50] as follows: 2NasH (SOs) ~“*—> 3NaSO, + H2SOs (23) ‘A schematic flow sheet diagram of a methanol-based w dioxide generator incorporating the metathesis shown in Figure 5. Yin and Ni [52] studied the effect of the addition of hydrogen peroxide in the methanol-chlorate process. Their study was conducted in the 3-mL. cuvette of a UV spectrophotometer under reaction conditions of 70°C, 3 M HS, 0.97 M NaClOx, and a 0.01 M total reducing agent concentration. While maintaining the same total concentration of reducing agent, the rate of formation of ClO; increased considerably with the addition of HO>. In the case of a mixed reducing agent (0.007 M CH:OH +-0.003 M H:0;), the rate is much faster than the simple ‘mathematical addition of two individual runs. ‘The rate increased upon inereasing the proportion of HO. It was confirmed that the presence of H:O> increased formation chloride, prohibited the occurrence of the so-called white- out and eliminated Ch formation that is due to the following fast reaction [53,54Manufacture of Chlorine Dioxide from Sodium Chlorate: State ofthe Art 337 clio Chlorine dioxide Recycle se Figure 5. Schematic diagram of a methanol-based chlorine dioxide generator including a metathesis unit. H.0;+ Ch — 2Cl-+2H' +0; (24) Chloride has been suggested and confirmed [36-38] to be the catalyst for the methanol-based ClO» generation. Sodium Chloride-Based Processes The crucial role of chloride ions in chlorate-based pro= cesses led to the “Rapson R-2” process, which is also known as the "Hooker R-2” or “ER-2" It was, developed by the Hooker Chemical Corporation, together with Electric Reduction Company, and it became popular in the 1960s. The general form [55-73] of the chloride- chlorate reaction is 4H’ +2C10$ +2CT + 2C10;+ Ch+2H0 (25) This process gives the highest yield of ClO; at the lowest cost among all of the commercial processes; it is extremely simple to operate, responds immediately, and is highly cost effective. This process is much faster than the Mathieson and Solvay processes and can be carried out ina single vessel. Currently, most chlorine dioxide is, produced by reducing sodium chlorate using sodium chloride because most of the pulp bleaching processes Il make use of a mixture of chlorine and chlorine fioxide gases. In this continuous process, air is blown into the reactor solution to strip off the CIOs and Cl and through the porous plates over which draught tubes are placed to promote the circulation of the liquid. ClO: is preferentially absorbed in chilled water in a packed tower. About 10% of the Ch remains dissolved in the absorber. ‘The aqueous effluent contains sodium bisulfate, unreacted sodium chlorate, sodium chloride, and sulfurie acid. The R-2H, R-3, R3H, and R-S processes are ‘modified versions of the R-2 process. Brief descriptions of these processes is given in Table 1. ‘An R-2 chlorine dioxide generator has a very simple design (Figure 6) because no heat exchange is required. Concentrated solutions of sodium chlorate, sodium chloride, and sulfuric acid (equimolar ratio) are injected into a vigorously agitated reaction vessel. Air is blown into the reactor through the porous plates. Chlorine dioxide is absorbed in the packed towers in the chilled water, and chlorine leaves the system as the by-product. Chlorine can be further recycled to yield hydrochloric acid by reduction with hydrogen gas or neutralized with NaOH solution to produce sodium liquid effluent from the reactor is mixture mainly a of sodium sulfate and sulfuric acid. The R-2 process re quires more sulfuric acid, but if the acid salt cake in the liquid effluent is crystallized out and used for kraft make up, then the excess sulfuric acid can be recovered for reuse, which makes this process more economical. The R-2 process has been modified and optimized occasion ally to suit industrial requirements (70,74,75]. Currently, it is probably the most extensively used process for the production of chlorine dioxide. The form of sodium sulfate produced depends on the acidity and temperature of the reaction solution [64]. Sodium bisulfate is produced at an acidity of 10 N or above and at a temperature of about 75 to 100°C. The reaction can be represented by 2NaCIOs + 2NaCl + 4280, + 06) 2C10; + Ch + 4NaHSO, + 2HL0 ° In a lower acidity range (4.8 to 9 N) and at a tem perature between about 30 t0 70°C, sodium sesquisulfate is formed: 6NaCIO, + 6NaCl + 8H.SO,—> 2) 6C102 + 3Ch + ANasH(SO.)2 + 610 en However, in an acidity range from 2 to 4.8 N, anhy= drous neutral sodium sulfate is deposited: 2NaCIOs + 2NaCl + 2H:S0, > 2C1Os + Ch-+ 2NasSO, +2H:0 8) In all of the reactions above, chlorine and chlorine are formed in a molar ratio of two. This gaseous, ‘mixture is often termed “euchlorine”” Two mechanisms have been proposed to explain the chloride-chlorate reaction, i.e., the Taube and Dodgen (TD) mechanism and the Hong, Lenzi, and Rapson extended (HLRE) mechanism, The Taube and Dodgen (TD) mechanism, which is based upon the intermediate CLO, is outlined as follows [76]338 Bal Raj Deshwval and Hyung Keun Lee ‘Table 1. Brief Summary of Chlorate-Based Chlorine Dioxide Generation Processes Process Atte SO; Based Processes: NaCIO;+ 50; H3S0,—> 2C10;+ 2NaHSO, Mathieson ClO;stipped by ar at atmospheric pressure; low reaction rate; excess acid salt cake; Cl and SO» contamination, Modified NaCl up to 10 wi% of NaClOs is added to improve the reduction efficiency; gas serubber is installed on the top of Mathieson __ generator Batch process; chloride concentration is very low in the beginning, but increases gradually with time; solid sodium Holst(23.25] chorae is added; conversion efficiency is 83 Persson Chromic sulfate reduces chlorate to CIO; and is regenerated by treating with SOs in a separate cycle (2434) = Methanol Biased Procesen @NaTOs + CHGOH + 4HSO, > 6010+ COr+ 2Na(SOOSHO Sole Less Ch formed requirement o igh aid cone slow weeton rat; Formation oF aid salt cake Re Higher acidity needed (© 9 N); byproduct acide sodium sesquulte Extension of R-8; sodium sesquisulfate is diluted with water and separated into caustic soda and sulfuric acid in a Re membrane eel. 0 Sodium sesquisulfate is diluted with both water and methanol following the removal of sodium sulfate in a second filtration stage SUP-Lite Single vessel process; low acid requirement; operated at higher temperature biter effcieney and yield ‘SVP-SCW Additional salt cake wash stage; HSOs is recovered + NaClBased Processes: 2NaCIO; + 2NaCl + 2H380, > 2€103+ Ch + 2NasSO,+ 24:0 Air s used for agitation and dilution of CIOs; increased Ce formation; more salt cake; more consumption of water and & acid. me Modied 2 pros atebanowpe pti nd bling anpo sgl eal proce oer aly GAB Noland Re ty Ev and SVP Hoar company R odicd 3 pros Cs innate by rein th ex eu wih SOs the nly produ any das NaS, S1P Single procs unvane sid reactions suppres fomaton of eur st ake THC ased Prowse DNGCTO FACT > 30, Ch ¥INGCT HD Rai The NaCland half ofthe TSOva eR process else fy HL Rall_____The NaCland a of he SOs te R2 process else by HCL BS By ode NACE ble free hg operating npr Day-Kesting® Suitable for integration with an electrolyte plant producing NaClO; from NaCl svp® ‘The NaCl and half of the H:SO, of the SVP Standard Process is replaced by HCl, so there is a substantial reduction in Paria HCI theamount of y-prodt sodium sulle sip All of the NaCl and H:SOs is replaced by HCI; by-product is NaCl. SP uct ofthe NaC and FiSOuis replace by HCI; by-product is Na R6 Ineyated process used in conjunction wih an electrolyte plant producing NaCIO. Cris Untegrated process; onsite electrolytic process to produce C10: from Cle and Hs + HhO;-Based Processes: 2NaCIO; + HO + H:SO, —>2C10s+ O3-+ NasSO, +2140 (Operated under vacuum; byproduct is neutral salt cake and Oss no chlorine; less acid required; faster rate; expensive sree reducing agen, SVP-HPA Operated at atmospheric pressure spent acid is discharged.Manufacture of Chlorine Dioxide from Sodium Chlorate: State ofthe Art Chilled Wat 339 ClO, Absorber cl, Absorber oj G0, Gr ch YY LI Pump NachNaCIO, I Tank El C10. c10, NaOCl H,S0, Generator solution solution Tank Stripper | Spent se —g—t Se Compressor Figure 6.A schematic diagram of a chloride-based R-2 chlorine dioxide generator. Taube and Dodgen (TD) mechanism [76} Step -25a CI + C10 + 2H" © ChOs+Hs0 Step = 25b 2CI0:— 2CI0) + Ch The first step is reversible and is followed by the rate- controlling step. An extensive amount of evidence for the existence of the unsymmetrical intermediate, CLO:, has been provided by Edwards [77]. This mechanism predicts that the [C1O:)/[Ch] ratio from the chloride-chlorate re= action should strictly be two. The rate equation for this, ‘mechanism was derived by Luther and MacDougall by applying a steady state approximation to the concen tration of the intermediate CLO: [62}: A ci0.) at closFiCrH}' 9) Subsequently, Hong and coworkers [55] determined the second-order dependence in chloride, the variable-order dependence (1 to 2) in chlorate, and the 12-to-13-order dependence in sulfuric acid, and also observed rate inhi- bition by chlorine. They found that the order with respect to chlorate increased from 1 to 2.6 as the acidity of the ‘medium decreased from 6.1 to 2.0 M. The authors also observed that the inhibiting effect of chlorine increased upon decreasing the acidity. To account for these facts, they proposed another mechanism, ie., the Hong, Lenzi, and Rapson extended (HLRE) mechanism [55], which involves HCIO: as the intermediate product: Hong, Lenzi, and Rapson extended (HLRE) mechanism [55} Step- 25a 3H! + 2CI + CIO; > Ch + HCIO; + H20 4 Step=25b H+ HCIOs+C10y~> 2C1O: + H20 Hong and coworkers [55] derived a rate equation by applying a steady state approximation to the concen tration of the intermediate HCIO: ACIO3) __ Bey HVECIOS PLC” a FALChI+ REA 1 CIOs eo) It is improbable that steps | and 2 are elementary steps, as treated by Hong and coworkers [55], although Equa tion (30) is consistent with the experimental observae tions, except for the acid order. The authors attributed the unusually high-order (12-13) acid dependence to vari ations in the activity coefficients with respect to the acid concentration. To reconcile the theory with experiments, the molal activity of acid, ay, was replaced by the molar concentration of acid and the order, with respect to sulfuric acid, reduced to about 4.5. It has also been observed [55,64,78,79] that at high chloride concentrations the production of chlorine is, enhanced because of a parallel side reaction: ClOy + SCI'+ 6H! > 3Ch+3H:0 GI) Equation (31) is a combination of steps (25a), (25b), and (25e) and it involves HOCI as an intermediate: “_, HOC! Step-25e H! +CI +HCIOs “—Ch+ HO Step=25d HW’ +C-+HOCI Hong and coworkers [55] observed an average exper imental [ClO:)[Ch] ratio (7) of 1.68 at a [ClOs){CT] ratio () of two in 3.8 M HSO, and they derived a340 Bal Raj Deshwval and Hyung Keun Lee tower Raton) 0 COIcr Rao) Figure 7. Variation in C1OyCl (7) ratio with respect to the chiorate/chloride () ratio, linear expressi n for the relative rate of production of ‘ClO, and Ch: [C10] _ ef OF «2 TCE] OP RECT BACT Equation (32) predicts that the [C1Os)/[Ch] ratio (7 ) is always less than 2, even at a high chlorate concentration. Later, it was suggested [77] that the [CIOs [Ch] ratio may be influenced by several factors, viz. the molar concen tration of sulfuric acid, the temperature, and the chlorate chloride (@ ratio. Therefore, some more intersive stu [79-80] were carried out to investigate the reaction ki neties, mechanism, side reactions, and optimal conditions for the best reaction yield in terms of chlorine dioxide production with minimal contamination of chlorine. The effects that the molar concentration of sulfuric acid, temperature, and chlorate/chloride (( ) ratio have on the ClO¥Cl (7) ratio has been examined critically [80] The experimental value ranged from 0.46 to as high as 3.4 under different experimental conditions. It was ob- served that the 7-value was not affected at all by the temperature and concentration of acid. ‘The sole factor found responsible for enhancement of the ClOYC was the chlorate/chloride ratio [80]. ‘The vari ClOyCh (7) ratio with chlorate’ chloride (@) ratio is shown in Figure 7. ‘At a chloratelchloride ratio of ~0.5, the reaction fob lowed the main stoichiometry with no side reaction, yielding a ClOCh ratio of ~2. When the @-value decreased to 0.05, the 7-value also reduced (to ~0.5) because of the enhanced contribution of the side reaction (31). Therefore the overall stoichiometry of the chloride- chlorate reaction at a high chloride concentration changes to 2NaCIO; + 2NaCl + 4H:S0, > 2Cl0; + Ch + 4NaHSO, +210 @3) When the chlorate/chloride ratio was taken as >1, the ClOCh (7) ratio exceeded 2 and touched the max ‘mum of ~3.4 at a @-value of 4. Thereafter, the ClO/CI> ratio decreased slightly, but its value remained higher than 2. The enhancement in the CIOyCb ratio was prom posed to be due to the following side reactions [80] 2HCIO, + Ch + 2HCI + 2C10, G4) HOCI+ 2HCIO; > 2C10; + HCI + H:0 (35) The hypochlorite-chlorite reaction has quite slow reac tion kineties [79] when compared to the chlorine-chlorite reaction; furthermore, formation of hypochlorite is favored only by a high chloride concentration, so Equation (35) does not contribute much to the enhancement of the ClOs/Cl, ratio at high chlorate/chloride ratios. In the light of the discussion above, the HLRE mech anism needs to include the following two additional steps to account for the ClOx/Ch (77) molar ratio being higher than 2: Step -2Se Ch +HCIO: “> ChO;+ HCI Step -25f 2ChO:—“— Ch + 2CI0; ‘A linear expression for the relative rate of production of ClO; and Ch: has been derived from a consideration of all of the six steps above, ie, steps (25a) to (25f) [80]: [G0] 2 thf WC} + RE Ch TORT RL TCIOs T+ AL CEI 3k CT 36) This equation is applicable under all conditions and explains very well the effect that the chlorate/chloride (@ ) ratio has on the ClOYCk ( 7 ) molar ratio. Subsequently, several modifications were suggested to improve the efficiency of the chloride-chlorate reaction, including a plurality of a reactors, selective removal of chlorine from the mixture of ClO> and Ch, and the use of some additional reducing agent along with NaC! or using, HCI in place of NaCl. Rapson [64] suggested the use of three generators in sequence: two operating at decreasing high acidity and one at low acidity. The acid salt cake formed in one generator is transferred to the next gener= ator. Although it may help in reducing the load of acid required, it does not appear practical from operational and economical points of view. Swindells and Fredette [81] and Rapson [64] suggested the use of HCI in place of NaCl because the former will not only behave as a reductant but also will provide part of the acid require ‘ment and reduce the production of sodium sulfate. HydroManufacture of Chlorine Dioxide from Sodium Chlorate: State ofthe Art 34 chlorie acid-based processes can be operated indepen dently (R-S, SVP-HCl) or integrated with an on-site chlorate plant (the R-6, Lurgi, Chemeties, and Day- Kesting processes). Swindells and Fredette [81] also suggested the addition of small quantities of methanol into a single-chambered generator-evaporator-crystallizer containing chlorate, chloride, and sulfuric acid; they observed that the ef ficiency increased rapidly upon inereasing the quantities of methanol. In one other patent [82], ClO: of high purity was generated by eliminating the concurrently formed chlorine by scrubbing the gaseous product with an aque- ous solution containing sodium hydroxide, sodium chlo= rate, and sodium chloride. 3Ch + 6NaOH —* NaClOs + SNaCl + 3H.0 en In the scrubbing solution, the concentration of sodium chloride is maintained near the saturation point to mine mize the solubility of chlorine dioxide. The chlorate and chloride formed in the above reaction are recirculated to the ClO; generator. This process also has one short coming: there is always a loss of some chlorine dioxide through its disproportionation in alkaline media [6, 83-85]; 2CIO» + 2NaOH — NaClO; + NaClO;+H.0 (38) Crump and Emst [86] suggested the addition of a small amount of hydrogen peroxide in the chloride-chlorate reaction and confirmed that, in the presence of H.03, the rate of the chloride-chlorate reaction increased not only due to the elimination of Cb inhibition by HkO> but also by the rapid reduction of intermediate ChOs, by HO: leading to ClO; formation: H.0; + 2ChO» > 2C10; + 0: + 2H" +21 (39) Furthermore, hydrogen peroxide reacts rapidly with the chlorine formed, as suggested in equation (24), and helps to reduce the chlorine contamination [53,54] Integrated HCI-Based Processes R-6 is an integrated process designed by ERCO. It is used in conjunction with an electrolytic plant producing sodium chlorate, Other versions of this process are the Day- Kesting, Lurgi, and Chemetics integrated processes. The overall reaction characterizing these processes is Ch + 44:0 + 2C10; + 4H» (40) The Lurgi process cons cally involves three steps: Step-1, Sodium Chlorate Synthesis: A solution enriched tutes a closed system, It basi Wati0, Sodivm Chlorate Chlorine dione Synthesis Generation cH, Tue 1 | wa Ly ‘Synthesis Figure 8. A schematic diagram of the Lurgi Process. with sodium chlorate is produced by electrolysis of som dium chloride solution: NaCl + 3H:0 — NaClO;+ 3H> (41) Step-2, Hydrochloric Acid Synthesis: Hydrogen gas generated in the chlorate electrolytic tank is treated with the chlorine gas produced as a by-product in the ClO; generation, leading to the formation of hydrogen chloride gas, which is absorbed and forwarded to the chlorine dioxide generator. Hy + Ch 2HCI (42) Step-3, Chlorine dioxide Generator: Production of ClO; is based on the reaction of HCl and NaClOs, according to the following reaction [87-91] 2NaCIOs + 4HCI + 2C10; + Ch + 2NaCl +2440 (43) HCI from the HCl absorber and NaClOs from the elec- trolytic tank are fed to the generator and the electrolyte containing NaCI and unreacted NaClOs is fed back to the chlorate electrolysis cell. Chlorine dioxide is absorbed in the chilled water. Chlorine is used in the HCI synthesis Thus, the only product of the electrolysis process is ClO, because all of the other chemicals produced internally are recycled. The Day-Kesting process also combines the production ide, by reducing sodium chlorate with hydrochloric acid, and the electrochemical production of sodium chlorate from sodium chloride. Schematic diae grams of the Lurgi and Day-Kesting processes are shown in Figures 8 and 9, respectively. Hydrogen Peroxide-Based Processes Hydrogen peroxide [45,92-104] is another reducing agent that can produce chlorine dioxide efficiently from chlorate without any contaminating chlorine. The general stoichiometry of the hydrogen peroxide-chlorate reaction depends on the acidity of the reaction medium. When the342 Bal Raj Deshwal and Hyung Keun Lee Compressor : Chilled Water— Nac Chlorate ey ebaee) a Synth clo, KY son Ce Absorber Synthesis c1o, ae I Nacto, Generator inf clo, Het Tank Tank Air Compressor Figure 9. Schematic diagram ofthe Integrated Day-Kesting Process, concentration of sulfuric acid sodium bisulfate (acid salt cake) is higher than 11 N, formed [95,96] 2NaCIO3 + H.02+ 2HS0,— 4a) 2C10; + Os + 2NaHSO, + 20 When the concentration of sulfuric acid is between 5 to IN, sodium sesquisulfate is formed [96} 6NaCIO, + 3H:02 + 41:80, > (45) 6C102 + 30; + 2NasH(SO:)2+ 6H20 Sodium sesquisulfate has a sulfuric acid content of about 18 wi%, so the recovery of the H.SO. content can be performed in an additional SCW (Salt Cake Wash) system, where it is treated in the metathesis tank to recover the acid. The sodium sesquisulfate solution can be utilized in a pulp mill recovery system for sodium and sulfur make up either after neutralization or directly It has been observed [95] that if the single-vessel proc= ss with reduced pressure is used together with hydrogen peroxide, then it is possible to produce essentially chlorine-free chlorine dioxide at a sulfuric acid normality between 2 and 5 N. This reaction is quite rapid and occurs without any catalyst; sodium sulfate (neutral salt cake) is formed [95]: 2NaC IOs + H202 + HO. —> 46) 2C10; + O: + NaSO, + 2H,0 Inall the cases above, the chlorine dioxide that forms is, essentially free from chlorine. Burke and coworkers [45] studied the rate of the hydrogen peroxide-chlorate reaction in both batch and well-mixed reactors over a range of temperatures and reactant concentrations. They deduced the following rate equation: ClO.) dt Avexp(— E/RD LH, SO" TOP LNacio;* (47) The kinetie parameters that best deseribe the data are A. 4.0% 10", E = 24.3 ki/mol, x= 4.4, y= 0.6, and 13. The authors found a poor agreement between the ‘measured rates and the rates calculated from Equation (47) in the presence of added NaSOs. To improve the ‘model, an acidity function, /_, was substituted in place of the molar concentration of sulfuric acid. It is known [105-108] that sodium ions increase and sulfate ions decrease the acidity of sulfuric acid, but chlorate ions have little or no effect. To account for the acidity funoe tion, the improved rate law that best fits the experimental data was deduced to be: ACi0-) a 1.510" exp (—SB0/RDU [#041 TNaCiO,) (48) There are number of advantages of using H:O-based process over other traditional approaches, including the lower production of salt cake (Na:SO,), elimination of an organic reducing agent, elimination of chlorine by-pro- ducts, smaller and cheaper reaction equipment, faster reaction rates at even lower concentrations of acid, and higher yields and efficiency (> 95%) in terms of chlorine dioxide based on the amount of chlorate reacted. ‘Although itis a better way to generate chlorine dioxide, this process has not attracted much commercial attention because of the expensive and relatively unstable natureManufacture of Chlorine Dioxide from Sodium Chlorate: State ofthe Art 343 of hydrogen peroxide. Hydrogen peroxide readily une dergoes decomposition, particularly at the elevated tem peratures, which makes the process quite expensive. 2H,0; + 2H:0 + 0; + 46.2 keal (49) This reaction is catalyzed by various metallic impur tities, in particular iron, which is typically present in the generator liquor. Decomposition of H,O> results in exces sive foaming, potentially leading to inefficient operation and uneven production rates of chlorine dioxide. Further= ‘more, H2O> is corrosive to titanium-based alloys, which are generally used in single-vessel proce claimed [97] that all of the above peroxide-chlorate process can be minimized to s extent by either pre-dilution of hydrogen peroxi water or by pre-mixing hydrogen peroxide with the sodium chlorate or sulfuric acid feed, All of the chlorate-based chlorine dioxide generation processes produce chlorine as one of the by-products, except for the peroxide-chlorate process. Recently, it has been found [109] that the chlorite-chlorate reaction may also be performed in a relatively concentrated acid solue tion; it yields 100% chlorine-tree chlorine dioxide gas. ‘The main stoichiometry of the chlorite-chlorate reaction is proposed [109] to be: NaClO; + NaClO + HsSO, > 2C102 + NaSO. + HO (50) This reaction is accompanied by a side reaction, ie. the acidic decomposition of sodium chlorite [110], which also yields chlorine dioxide gas: SCIO2 + 4H’ = 4CIOs + CI + 2420 1) Ithas also been found that under relatively concentrated acid conditions, the acidic decomposition of chlorite is a significantly slower process, but it remains unavoidable. SVP® Processes The Mathieson, Solvay, and R-2 processes operate at atmospheric pressure, use air to strip the chlorine diox- ide, and have an overflow of spent acid. Some unreacted NaCiO, also leaves the generator with the acid, which limits the yield and efficiency of the generator. It was recognized that a single vessel, Le. a reactor-evaporator- cystallizer, could also fumetion as a chlorine dioxide generator with the steam and a vacuum serving to control the CIO: partial pressure. This type of process is termed an SVP, ie., a Single-Vessel Process. The detailed come figuration of a commercial SVP chlorine dioxide generator is described elsewhere [45]. By performing the reaction under vacuum and at higher temperatures, a suitable ClO; production rate can be maintained at a solution acidity, below 4.5 N, namely the acidity below which neutral anhydrous sodium sulfate can be crystallized and filtered. The chemistry of the processes remains the same, ‘no waste acid is produced, and the yield is also enhanced. ‘An SVP chlorine dioxide generator is composed of four basic parts: 1) ClO> generator 2) ClO; recovery 3) 4) Sodium sulfate recovery The heart of the SVP process is a titanium ClO; gen erator, a large vessel in which NaClOs is reduced to ClO}. It is sized to optimize the reaction efficiency, promote salt cake crystal growth, and provide efficient Tiquid-gas separation and adequate facility for optimum control of chemical compositions. A titanium pump agitates the reaction solution through a titanium shell and tube heat exchanger, where water is evaporated, through indirect contact with low-pressure steam, The vapors in tum escape the generator along with ClO. The design of all of the components in this loop is critical to elim inating boil-out. The water evaporation rate is matched to the rate at which water enters the generator with the chemical feeds and from other sources. The vacuum is, created by means of a steam ejector, but a titanium liquid ring vacuum pump may also be used. The gas leaving the generator is a mixture of COs water vapors and some other gaseous by-products that depend on the reducing agent used, Water vapors are condensed, thereby enriching the ClO; concentration, which in tum is absorbed using chilled water in a packed tower absorber. The tail gas from the absorption tower consists of small amounts of different gases. It can be washed in a gas scrubber. ‘The neutral sodium sulfate crystals, which form in the generator, are pumped to a titanium bottom feed rotary drum filter for removal as a nearly dry solid. The filter is equipped with a hot water wash system to assist in re= covering the chemicals trapped in the salt-cake. The wash-water and mother liquor are withdrawn from the filter and retumed to the generator, leaving behind a dry salt-cake. A steam-operated titanium ejector provides the ‘motive force to remove the wash-water and chemicals, from the crystals. The SVP family consists of a number of similar pro= cesses all performed under basically the same experie ‘mental set-up and can be switched from one to the other. They can be distinguished from one another by the re= ducing agent and the acid used. Some of these processes are listed below:344 Bal Raj Deshwval and Hyung Keun Lee 1) SVP-LITE® 2) SVP"-SCW 3) SVP-HP” 4) SVP"-Standard 5) SVP®-Partial HCL 6) SVP"-Total HCL A brief summary of these processes is included in Table 1 The chlorate can also be provided by chloric acid, which also provides the acid requirement for the process. Moreover, no by-product salt is produced in this case. Considerable efforts are being made to develop electro chemical processes to split the by-product salt cake and the sodium chlorate feed into their respective acids and bases NasSO, +2H:0 + 2NaOH + H»SO, (2) NaClO; + HO + NaOH + HCIO; (53) For these technologies to be successful, the product acids need to be of sufficient strength not to cause water balance problems in the chlorine dioxide generation systems. The operating costs need to be competitive with purchased NaOH or acid and the process cost should be competitive with respect to capital. It is predicted that, because of their high cost, electrochemical processes will be adopted only if they are environmentally driven. The rapid growth in the applications of chlorine dioxide over the last twenty years primarily is due to its proven effectiveness as an environmentally friendly bleaching and disinfection agent. Chlorate-based processes have generally been used in pulp and paper industry, but recently they have been tested in full-scale municipal water-ireatment plants. The primary aim is to develop a process that has the following attributes: 1) Single chemical feed; 2) High efficiency; 3) Low operating cost; 4) Low capital investment; 5) High-purity chlorine dioxide; 6) Minimal chlorine contamination; 7) Maximum utilization of raw material; 8) Ease of operation and control. References 1. R. C. Hochn, A. A. Rosenblatt, and D. J. Gates, Considerations for Chlorine Dioxide Treatment of Drinking Water, Conference Proceedings, AWWA Water Quality Technology Conference, Boston, MA. (1996), 2. E, Aieta and J. D. Berg, J. AWWA, 78-6, 62 (1986). 3. D. C. Pryke and D. W. Reeve, Tappi J., 80-5, 153 (1997). 4.N. Khanna, T. D. Head, and B. D. Lowery, U. S. Patent No., 6,132,748 (2000) 5. D.S. Jin, B. R. Deshwal, and H. K. Lee, J. Hazard, ‘Mater, (2004) Submitted. 6. B. R. Deshwal and H. K. Lee, J. Ind. 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