Equipment, chlorination

Dangerous materials may require special equipment. Chlorination with gaseous chlorine requires quite expensive storage facilities. Chlorination with chlorine, thionyl chloride, sulphuryl chloride, phosphorus oxychloride, phosphorus trichloride, or phosphorus pentachloride, all of which are fairly hazardous, requires off-gas treatment. Some of these reactants can be recycled. Pyrophoric solids such as hydrogenation catalysts, anhydrous aluminium trichloride for Friedel-Crafts reactions, or hydrides used as reducing agents should usually be handled using special facilities. Therefore, all of the above proce.sses are usually carried out in dedicated plants. 

A wide range of paints and other organic coatings is used for the protection of mild steel structures. Paints are used mainly for protection from atmospheric corrosion. Special chemically resistant paints have been developed for use on chemical process equipment. Chlorinated rubber paints and epoxy-based paints are used. In the application of paints and other coatings, good surface preparation is essential to ensure good adhesion of the paint film or coating. 

An alternative chlorination process involves the use of sodium hypochlorite (NaOCl) as the oxidant. Reactions with sodium hypochlorite are similar to those of chlorine, except that there is no caustic requirement for destruction of free cyanide in the oxidation stages. Alkali, however, is required to precipitate metal-cyanide complexes as hydroxides. The entire oxidation-precipitation process is a typical chemical oxidation precipitation process system. All chlorination equipment, chlorine compounds, etc., are commercially available (27). 

A variety of polymers are used in engineering and medical applications which have relatively little impact on the environment. These are mainly high performance and relatively expensive polymers such as the silicones in rubbers, the specialised polyamides referred to above in gear wheels, polycarbonates (in office equipment), chlorinated and sulfonated rubbers, fluorinated polymers such as poly tetrafluoroethylene) Teflon ) in metal coating and the polyimides which, owing to their ladder structure, are extremely stable in high temperature apphcations. Since these polymers are high-cost durable materials, they rarely appear in the waste stream. 

In another process 117], 118) the same reactants are used, except at a higher temperature to take advantege of the oxidizing power of nitric add. In a complex process writh exotic corrosion-resistant equipment, chlorine is produced as a byproduct with the potassium nitrate. The process flowsheet is given in Figure 15.10. 

The volatile matter increases from less than 8% in antracite to more than 27 wt% in lignite. In addition, the content of water may vary from less than 5 wt% in antracite to about 60% in German brown coal. Nitrogen (0.5-2%) will be converted into ammonia. The sulphur content may typically vary from 0.5-5 wt%. Sulphur will be converted to COS and H2S. Sulphur will poison downstream synthesis catalysts and must be removed. Chlorine is normally below 1 wt%. Chlorine may cause corrosion problems in downstream equipment. Chlorine will react with ammonia from the nitrogen and deposition of ammonia chloride may foul waste heat boilers and limit their operating temperature [230]. 

Chlorine, which will be present as HCl or organic chlorine compounds, is a poison, in particular for copper catalysts [391] and it may cause stress corrosion in the equipment. Chlorine can be removed by promoted alumina. Chlorine may be present in certain refinery offgases and in landfill gas. Chlorine may also originate from failure in the water purification system. If so, it will pass the guard bed and should be captured by a guard in the low-temperature shift reactor (see Section 1.5.2). 

Chlorine is usually added upstream of a clarifier to oxidize organics, to improve the removal of color in the clarifier, and to control microbial growth in the clarifier and downstream equipment. Chlorine along with an alum feed at pH 4.5 to 5.5 is optimum for color removal. This is important for RO pretreatment, as color can irreversibly foul a polyamide composite membrane (see Chapter 8.2.1.1 and 8.5.2.1.1 for a more detailed discussions about chlorine for RO pretreatment). 

To begin with, we compare the stepsizes used in the simulations (Fig. 3). As pointed out before, it seems to be unreasonable to equip the Pickaback scheme with a stepsize control, because, as we indeed observe in Fig. 3, the stepsize never increases above a given level. This level depends solely on the eigenvalues of the quantum Hamiltonian. When analyzing the other integrators, we observe that the stepsize control just adapts to the dynamical behavior of the classical subsystem. The internal (quantal) dynamics of the Hydrogen-Chlorine subsystem does not lead to stepsize reductions. 

The cooled, dried chlorine gas contains - 2% HCl and up to 10% O2, both of which are removed by Hquefaction. A full scale 600-t/day plant was built by Du Pont ia 1975. This iastaHatioa at Corpus Christi, Texas operates at 1.4 MPa (13.8 atm) and 120—180°C and uses tantalum-plated equipment and pipes. Oxidation of HCl Chloride by JSHtricHcid. The nitrosyl chloride [2696-92-6] route to chlorine is based on the strongly oxidi2iag properties of nitric acid... 

Chlorine is stored and transported as a Hquefied gas in cylinders of 45.4-kg or 68-kg capacity that are under pressure and equipped with fusible-plug rehef devices. Quantities in the range of 15 to 90 t are transported in tank cars having special angle valves on the manhole cover on top of the vessel. Tank barges of the open-hopper type having several cylindrical uninsulated pressure vessels are used for amounts ranging from 600 to 1200 t. Road tankers are used for capacities of 15 to 20 t. 

HCl gas reacts with metal oxides to form chlorides, oxychlorides, and water. Therefore, all the steel equipment should be pickled to remove the oxide scales before it is put in service. Because oxidi2ing agents in the HCl gas such as oxygen or chlorine significantly affect the corrosion rate, it is essential that the operating temperature of the steel equipment be kept below the temperature (316°C) at which ferric chloride is vapori2ed from the metal surface. 

Another attractive commercial route to MEK is via direct oxidation of / -butenes (34—39) in a reaction analogous to the Wacker-Hoechst process for acetaldehyde production via ethylene oxidation. In the Wacker-Hoechst process the oxidation of olefins is conducted in an aqueous solution containing palladium and copper chlorides. However, unlike acetaldehyde production, / -butene oxidation has not proved commercially successflil because chlorinated butanones and butyraldehyde by-products form which both reduce yields and compHcate product purification, and also because titanium-lined equipment is required to withstand chloride corrosion. 

Fig. 2. The Dow magnesium cell. The steel container. A, is equipped with a ceramic cover, B, through which graphite anodes, C, pass. The magnesium is deposited on the cathode, D, and is diverted as it rises into the collection sump, E. The chlorine is withdrawn through a vent, F.

In the United States, the Clean Air Act of 1990 requires plants to reduce emissions of 189 toxic and carcinogenic substances such as chlorine, chloroform, and 2,3,7,8-TCDD (dioxin) by 90% over the 1990s. The U.S. Environmental Protection Agency is working to develop standards based on maximum achievable control technologies and the industry has invested bUHons of doUars in capital investments to retrofit or rebuUd plant equipment to meet these measures. 

Chlorinated Polyethylene. Chlorinating polyethylene under pressure results in a polymer having a chlorine content varying from 25 to 42%. The polymer requires the incorporation of carbon black and minerals for achieving good physical properties. The polymers handle like conventional polymers and can be mixed and processed on conventional mbber equipment. 

Chlorosulfonated Polyethylene. This elastomer is made by the simultaneous chlorination and chlorosulfonation of polyethylene in an inert solvent. The resulting polymer is an odorless, colorless chip that is mixed and processed on conventional mbber equipment. The polymer typically contains 20-40% chlorine and 1% sulfur groups (see ElASTOL RS, SYNTHETIC-Cm OROSULFONATEDPOLYETHYLENE) (8). 

Losses of selenium and tellurium from the solution are negligible, provided the reactor is equipped with a reflux condenser. The wet chlorination is easily controlled. The reaction is rapid, allowing fast turnover of the precious metals in the slimes and yielding all the selenium and tellurium in soluble form. 

Titanium metal is especially utilised ia environments of wet chlorine gas and bleaching solutions, ie, in the chlor—alkaH industry and the pulp and paper industries, where titanium is used as anodes for chlorine production, chlorine—caustic scmbbers, pulp washers, and CI2, CIO2, and HCIO storage and piping equipment (see Alkali and cm ORiNE products Paper Pulp). 

Under typical chlorination conditions, most elements are chlorinated. Therefore, for every metric ton of titanium tetrachloride produced, lower grade feedstocks requite more chlorine. Minor impurities such as alkaline-earths, where the chlorides are relatively involatile, may either inhibit bed-fluidization or cause blockages in the equipment and requite particular consideration regarding feedstock specification. 

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