High-pressure carbon monoxide process

While both SWNT and MWNT existed in small quantities from the first wood fires at the dawn of Earth s history, their discovery and methods of preparation are only recent, as described above. Briefly, some synthetic methods include nickel catalyzed pyrolysis of methane at bOO C (64) for MWNT, and the so-called HiPCO (high pressure carbon monoxide) process for SWNT.This latter involves thermal decomposition of iron pentacarbonyl in a flow of CO at 800-1200°C (65). 

The preparation of single-walled nanotubes succeeds more easily by the so-called HiPCo-process that was published for the first time in 1998. The name is deduced from high-pressure carbon monoxide and signifies a crucial aspect of the method Here the carbon source is not a hydrocarbon, but carbon monoxide that does not suffer pyrolysis at the relevant temperatures. The formation of carbon material is based on the Boudouard equilibrium (3.9) ... 

CNTs can be made by means of arc-discharge, laser ablation, high pressure carbon monoxide decomposition (HiPCO), and chemical vapor decomposition (CVD) processes. The HiPCO process delivers high quality SWCNTs but the upscaling is difficult. Arc-discharge, laser ablation and CVD systems are currently used to produce SWCNTs as well as MWCNTs in laboratory scales. However, until now only CVD processes have been upscaled successfully to produce MWCNTs in commercially relevant amounts. For this purpose the synthesis is usually performed in fluidized beds [10-12]. Currently (2011), industrial grades of MWCNTs can be purchased for less than 130 USD/kg. 

A number of methods have been developed to produce single- and multiple-wall carbon nanotubes. The most prominent are laser ablation, arc discharge, and catalytic growth (vapor deposition (CVD) and high pressure carbon monoxide (HipCO) process). 

The carbon monoxide purity from the Cosorb process is very high because physically absorbed gases are removed from the solution prior to the low pressure stripping column. Furthermore, there is no potential for oxidation of absorbed carbon monoxide as ia the copper—Hquor process. These two factors lead to the production of very high purity carbon monoxide, 99+ %. Feed impurities exit with the hydrogen-rich tail gas therefore, the purity of this coproduct hydrogen stream depends on the impurity level ia the feed gas. 

The low-pressure acetic acid process was developed by Monsanto in the late 1960s and proved successful with commercialization of a plant producing 140 X 10 metric tons per year in 1970 at the Texas City (TX, USA) site [21]. The development of this technology occurred after the commercial implementation by BASF of the cobalt-catalyzed high-pressure methanol carbonylation process [22]. Both carbonylation processes were developed to utilize carbon monoxide and methanol as alternative raw materials, derived from synthesis gas, to compete with the ethylene-based acetaldehyde oxidation and saturated hydrocarbon oxidation processes (cf. Sections 2.4.1 and 2.8.1.1). Once the Monsanto process was commercialized, the cobalt-catalyzed process became noncom-... 

Principally, as the wear of engine parts increased after a certain lime of operation, compression pressure reduced and more combustion products blew to crankcase, the combustion process of the engine deteriorated causing worse engine performance, high hydrocarbon, carbon monoxide, and particulate matter were formed, whilst nitrogen oxide reduced due to lower temperature. 

Carbon Monoxide. Processes patented by Loder and Larson claim that glycolic acid can be produced in high yield by the reaction of carbon monoxide under pressure ith formaldehyde and 1. atei in the presence of an acid catalyst. 

Reppe s work also resulted in the high pressure route which was estabUshed by BASF at Ludwigshafen in 1956. In this process, acetylene, carbon monoxide, water, and a nickel catalyst react at about 200°C and 13.9 MPa (2016 psi) to give acryUc acid. Safety problems caused by handling of acetylene are alleviated by the use of tetrahydrofuran as an inert solvent. In this process, the catalyst is a mixture of nickel bromide with a cupric bromide promotor. The hquid reactor effluent is degassed and extracted. The acryUc acid is obtained by distillation of the extract and subsequendy esterified to the desked acryhc ester. The BASF process gives acryhc acid, whereas the Rohm and Haas process provides the esters dkecdy. 

It has been known since the early 1950s that butadiene reacts with CO to form aldehydes and ketones that could be treated further to give adipic acid (131). Processes for producing adipic acid from butadiene and carbon monoxide [630-08-0] have been explored since around 1970 by a number of companies, especially ARCO, Asahi, BASF, British Petroleum, Du Pont, Monsanto, and Shell. BASF has developed a process sufficiendy advanced to consider commercialization (132). There are two main variations, one a carboalkoxylation and the other a hydrocarboxylation. These differ in whether an alcohol, such as methanol [67-56-1is used to produce intermediate pentenoates (133), or water is used for the production of intermediate pentenoic acids (134). The former is a two-step process which uses high pressure, >31 MPa (306 atm), and moderate temperatures (100—150°C) (132—135). Butadiene,... 

Even though form amide was synthesized as early as 1863 by W. A. Hoffmann from ethyl formate [109-94-4] and ammonia, it only became accessible on a large scale, and thus iadustrially important, after development of high pressure production technology. In the 1990s, form amide is mainly manufactured either by direct synthesis from carbon monoxide and ammonia, or more importandy ia a two-stage process by reaction of methyl formate (from carbon monoxide and methanol) with ammonia. 

Early in the twentieth century, the first attempts to manufacture formamide directiy from ammonia and carbon monoxide under high temperature and pressure encountered difficult technical problems and low yields (23). Only the introduction of alkaU alkoxides in alcohoHc solution, ie, the presence of alcoholate as a catalyst, led to the development of satisfactory large-scale formamide processes (24). 

Ca.rbonylProcess. Cmde nickel also can be refined to very pure nickel by the carbonyl process. The cmde nickel and carbon monoxide (qv) react at ca 100°C to form nickel carbonyl [13463-39-3] Ni(CO)4, which upon further heating to ca 200—300°C, decomposes to nickel metal and carbon monoxide. The process is highly selective because, under the operating conditions of temperature and atmospheric pressure, carbonyls of other elements that are present, eg, iron and cobalt, are not readily formed. 

Ma.nufa.cture. Nickel carbonyl can be prepared by the direct combination of carbon monoxide and metallic nickel (77). The presence of sulfur, the surface area, and the surface activity of the nickel affect the formation of nickel carbonyl (78). The thermodynamics of formation and reaction are documented (79). Two commercial processes are used for large-scale production (80). An atmospheric method, whereby carbon monoxide is passed over nickel sulfide and freshly reduced nickel metal, is used in the United Kingdom to produce pure nickel carbonyl (81). The second method, used in Canada, involves high pressure CO in the formation of iron and nickel carbonyls the two are separated by distillation (81). Very high pressure CO is required for the formation of cobalt carbonyl and a method has been described where the mixed carbonyls are scmbbed with ammonia or an amine and the cobalt is extracted as the ammine carbonyl (82). A discontinued commercial process in the United States involved the reaction of carbon monoxide with nickel sulfate solution. 

The rate of hydroformylation increases with increasing hydrogen and decreases with increasing carbon monoxide partial pressures (9), suggesting that rates of hydroformylation would be satisfactory at high H2 and low CO partial pressures. In industrial practice, however, high pressures of both H2 and CO ate required in order to stabilize the HCo(CO)4 catalyst at the temperatures necessary for practical rates (10). Commercial processes, for example, operate at >24 MPa (3480 psi) and >140 C. 

Semiconductors. Phosphine is commonly used in the electronics industry as an -type dopant for siUcon semiconductors (6), and to a lesser extent for the preparation of gaUium—indium—phosphide devices (7). For these end uses, high purity, electronic-grade phosphine is required normally >99.999% pure. The main impurities that occur in phosphine manufactured by the acid process are nitrogen [7727-37-9] hydrogen [1333-74-0] arsine [7784-42-17, carbon dioxide [124-38-9], oxygen [7782-44-7], methane [74-82-8], carbon monoxide [630-08-0], and water [7732-42-1]. Phosphine is purified by distillation under pressure to reduce the level of these compounds to <1 ppm by volume. The final product is sold as CYPURE (Cytec Canada Inc.) phosphine. 

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