Water gas production

Reactivity to steam It must be reactive to steam, a requisite if used for water-gas production. 

Reservoir engineers describe the relationship between the volume of fluids produced, the compressibility of the fluids and the reservoir pressure using material balance techniques. This approach treats the reservoir system like a tank, filled with oil, water, gas, and reservoir rock in the appropriate volumes, but without regard to the distribution of the fluids (i.e. the detailed movement of fluids inside the system). Material balance uses the PVT properties of the fluids described in Section 5.2.6, and accounts for the variations of fluid properties with pressure. The technique is firstly useful in predicting how reservoir pressure will respond to production. Secondly, material balance can be used to reduce uncertainty in volumetries by measuring reservoir pressure and cumulative production during the producing phase of the field life. An example of the simplest material balance equation for an oil reservoir above the bubble point will be shown In the next section. 

When a customer agrees to purchase gas, product quality is specified in terms of the calorific value of the gas, measured by the Wobbe index (calorific value divided by density), the hydrocarbon dew point and the water dew point, and the fraction of other gases such as Nj, COj, HjS. The Wobbe index specification ensures that the gas the customer receives has a predictable calorific value and hence predictable burning characteristics. If the gas becomes lean, less energy is released, and if the gas becomes too rich there is a risk that the gas burners flame out . Water and hydrocarbon dew points (the pressure and temperature at which liquids start to drop out of the gas) are specified to ensure that over the range of temperature and pressure at which the gas is handled by the customer, no liquids will drop out (these could cause possible corrosion and/or hydrate formation). 

Routine production tests are performed, approximately once per month on each producing well, by diverting the production through the test separator on surface to measure the liquid flowrate, water cut, and gas production rate. The wellhead pressure (also called the flowing tubing head pressure, FTHP) is recorded at the time of the production test, and a plot of production rate against FTHP is made. The FTHP is also recorded continuously and used to estimate the well s production rate on a daily basis by reference to the FTHP vs production rate plot for the well. 

As a field matures, bottlenecks may appear in other areas, such as water treatment or gas compression processes, and become factors limiting oil or gas production. These issues can often be addressed both by surface and subsurface options, though the underlying justification remains the same the NPV of a debottlenecking exercise (net cost of action versus the increase in net revenue) must be positive. 

If gas export or disposal is a problem gas re-injection into the reservoir may be an alternative, although this implies additional compression facilities. Gas production may be reduced using well intervention methods similar to those described for reducing water cut, though in this case up-dip wells would be isolated to cut back gas influx. Many of the options discussed under water treatment for multi-layered reservoirs apply equally well to the gas case. 

Process 2, the adsorption of the reactant(s), is often quite rapid for nonporous adsorbents, but not necessarily so it appears to be the rate-limiting step for the water-gas reaction, CO + HjO = CO2 + H2, on Cu(lll) [200]. On the other hand, process 4, the desorption of products, must always be activated at least by Q, the heat of adsorption, and is much more apt to be slow. In fact, because of this expectation, certain seemingly paradoxical situations have arisen. For example, the catalyzed exchange between hydrogen and deuterium on metal surfaces may be quite rapid at temperatures well below room temperature and under circumstances such that the rate of desorption of the product HD appeared to be so slow that the observed reaction should not have been able to occur To be more specific, the originally proposed mechanism, due to Bonhoeffer and Farkas [201], was that of Eq. XVIII-32. That is. 

The commercial production of carbon monoxide in the form of water gas is now largely obsolete. The production by the reaction between steam and hydrocarbons is considered later (p. 180). 

Methanol (qv) is one of the 10 largest volume organic chemicals produced in the wodd, with over 18 x 10 t of production in 1990. The reactions for the synthesis of methanol from CO, CO2, and H2 are shown below. The water gas shift reaction also is important in methanol synthesis. 

Secunda discharges no process water effluents. AU. water streams produced are cleaned and reused in the plant. The methane and light hydrocarbons in the product are reformed with steam to generate synthesis gas for recycle (14). Even at this large scale, the cost of producing fuels and chemicals by the Fischer-Tropsch process is dominated by the cost of synthesis gas production. Sasol has estimated that gas production accounts for 58% of total production costs (39). 

The technology of urea production is highly advanced. The raw materials requited ate ammonia and carbon dioxide. Invariably, urea plants ate located adjacent to ammonia production faciUties which conveniently furnish not only the ammonia but also the carbon dioxide, because carbon dioxide is a by-product of synthesis gas production and purification. The ammonia and carbon dioxide ate fed to a high pressure (up to 30 MPa (300 atm)) reactor at temperatures of about 200°C where ammonium carbamate [111-78-0] CH N202, urea, and water ate formed. 

Study of the mechanism of this complex reduction-Hquefaction suggests that part of the mechanism involves formate production from carbonate, dehydration of the vicinal hydroxyl groups in the ceUulosic feed to carbonyl compounds via enols, reduction of the carbonyl group to an alcohol by formate and water, and regeneration of formate (46). In view of the complex nature of the reactants and products, it is likely that a complete understanding of all of the chemical reactions that occur will not be developed. However, the Hquefaction mechanism probably involves catalytic hydrogenation because carbon monoxide would be expected to form at least some hydrogen by the water-gas shift reaction. 

Blue gas, or blue-water gas, so-called because of the color of the flame upon burning (10), was discovered in 1780 when steam was passed over incandescent carbon (qv), and the blue-water gas process was developed over the period 1859—1875. Successfiil commercial appHcation of the process came about in 1875 with the introduction of the carburetted gas jet. The heating value of the gas was low, ca 10.2 MJ /m (275 Btu/fT), and on occasion oil was added to the gas to enhance the heating value. The new product was given the name carburetted water gas and the technique satisfied part of the original aim by adding luminosity to gas lights (10). 

Prior to methanation, the gas product from the gasifier must be thoroughly purified, especially from sulfur compounds the precursors of which are widespread throughout coal (23) (see Sulfurremoval and recovery). Moreover, the composition of the gas must be adjusted, if required, to contain three parts hydrogen to one part carbon monoxide to fit the stoichiometry of methane production. This is accompHshed by appHcation of a catalytic water gas shift reaction. 

This reaction is first conducted on a chromium-promoted iron oxide catalyst in the high temperature shift (HTS) reactor at about 370°C at the inlet. This catalyst is usually in the form of 6 x 6-mm or 9.5 x 9.5-mm tablets, SV about 4000 h . Converted gases are cooled outside of the HTS by producing steam or heating boiler feed water and are sent to the low temperature shift (LTS) converter at about 200—215°C to complete the water gas shift reaction. The LTS catalyst is a copper—zinc oxide catalyst supported on alumina. CO content of the effluent gas is usually 0.1—0.25% on a dry gas basis and has a 14°C approach to equihbrium, ie, an equihbrium temperature 14°C higher than actual, and SV about 4000 h . Operating at as low a temperature as possible is advantageous because of the more favorable equihbrium constants. The product gas from this section contains about 77% H2, 18% CO2, 0.30% CO, and 4.7% CH. ... 

The final composition of the reactor product gas is estabUshed by the water gas shift equiUbrium at the reactor outiet waste-heat exchanger inlet where rapid cooling begins. Some units quench instead of going directiy to heat exchanger. 

Operating parameters of this German plant, on the basis of one cubic meter of raw gas, iaclude 0.139 m O2, 0.9 kg briquettes, 1.15 kg steam, 1.10 kg feed water, 0.016 kWh, and 1.30 kg gas Hquor produced. Gasifier output is 1850 m /h and gas yield is 1465 m /t dry, ash-free coal. The coal briquettes have a 19% moisture content, 7.8% ash content (dry basis), and ash melting poiat of 1270°C. Thermal efficiency of the gas production process is about 60%, limited by the quaHty and ash melting characteristics of the coal. Overall efficiency from raw coal to finished products is less than 50%. 

Gas and Hquid dehydrators employing molecular sieves provide product gas streams of <0.1 ppmv water and product Hquid streams routinely to <10 ppmv water. AppHcable pressures range from less than one to several hundred times atmospheric pressure. Temperatures range from subzero to several hundred °C. Processing units range in capacity from as Httle as 10 m /h to as much as 10 mr /d in multiple-train units. 

Shift Conversion. Carbon oxides deactivate the ammonia synthesis catalyst and must be removed prior to the synthesis loop. The exothermic water-gas shift reaction (eq. 23) provides a convenient mechanism to maximize hydrogen production while converting CO to the more easily removable CO2. A two-stage adiabatic reactor sequence is normally employed to maximize this conversion. The bulk of the CO is shifted to CO2 in a high... 

Tubular Fixed-Bed Reactors. Bundles of downflow reactor tubes filled with catalyst and surrounded by heat-transfer media are tubular fixed-bed reactors. Such reactors are used most notably in steam reforming and phthaUc anhydride manufacture. Steam reforming is the reaction of light hydrocarbons, preferably natural gas or naphthas, with steam over a nickel-supported catalyst to form synthesis gas, which is primarily and CO with some CO2 and CH. Additional conversion to the primary products can be obtained by iron oxide-catalyzed water gas shift reactions, but these are carried out ia large-diameter, fixed-bed reactors rather than ia small-diameter tubes (65). The physical arrangement of a multitubular steam reformer ia a box-shaped furnace has been described (1). 

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