Process and apparatus for producing hydrogen cyanide

Abstract: A process for producing hydrogen cyanide which comprises reacting methane or a gas containing methane as a main component, ammonia and an oxygen-containing gas in the presence of a platinum-containing catalyst, wherein the reaction gases are quenched by using an indirect heat-exchanger, preferably an indirect heat-exchanger made of a nickel alloy having an iron content of not more than 4.0 % by weight, without quenching them directly with water.

Description: This invention relates to an improvmenet in a process for producing hydrogen cyanide which comprises reacting methane or a gas containing methane as a main component, ammonia and an oxygen-containing gas, and to an apparatus for use in the process. Hydrogen cyanide has previously been used mainly as a material for methacrylic esters or for various organic syntheses, and recently as a material for the production of sodium cyanide which is used for metal refining. Its use in the production of pharmaceuticals such as biologically active substances has also increased. Industrial production of hydrogen cyanide involves the decomposition of formamide or the ammoxidation of methane. Hydrogen cyanide is also produced as a by-product in the production of acrylonitrile by ammoxidation of propylene. Production of hydrogen cyanide by ammoxidation of methane is described, for example, in JP-A-14128/1960. It is obtained by reacting a gas containing methane as a main component, such as natural gas, with a gaseous mixture of ammonia and air in the presence of a platinum-type catalyst at a temperature of as high as more than 1000 °C. In order to prevent decomposition of hydrogen cyanide in the reaction gas in this reaction, the reaction gas at a high temperature should be quenched to below 700 °C in a short period of time, and it is the general practice to inject quenching water into a site just below the catalyst bed. This method of quenching the high-temperature gas is not desirable because a large amount of thermal energy derived from a temperature of about 1000°C is lost. US-A-3 104 945 discloses a method of reducing the consumption of energy in such a hydrogen cyanide producing apparatus. According to this method, the starting gas is preheated to 400 to 525°C and then introduced into the reactor so that the conversion of methane and ammonia to hydrogen cyanide and the yield of hydrogen cyanide are increased. Processes for producing hydrogen cyanide in which the effluent gases are quenched in a heat-exchanger are described in US-A-3 056 655, FR-A-2 554 014, DE-B-1 159 409, US-A-3 505 030 and Ind. Eng. Chem., Process Design and Development, vol. 7, 1968, pages 53-61. The present inventors looked for a way of reducing the amount of energy used in the process of producing hydrogen cyanide by ammoxidation of methane, and found that (1) recovery of the heat of the high-temperature gas by providing a heat-exchanger instead of injecting quenching water into a site immediately below the catalyst bed is very advantageous because it permits effective use of the thermal energy; and (2) in this process the high temperature gas containing hydrogen cyanide makes contact with a heat-transfer tube of the heat exchanger, and if the heat-transfer tube is made of an ordinary material, hydrogen cyanide undergoes decomposition and its yield is decreased, but if the heat-transfer tube is made of a nickel alloy containing not more than 4.0 % by weight of iron, hydrogen cyanide scarcely undergoes decomposition and therefore its yield does not decrease. This finding has now led to the present invention. The present invention provides a process for producing hydrogen cyanide which comprises reacting methane or a gas containing methane as a main component, ammonia and an oxygen-containing gas in the presence of a platinum-containing catalyst at 1000°C or more; and quenching the reaction gases to a temperature of not more than 700°C using an indirect heat-exchanger without quenching them directly with water, the indirect heat-exchanger being made of a nickel alloy consisting of (a) 60 to 80% by weight of nickel, (b) 5 to 25% by weight of chromium, (c) 0 to 3% by weight of iron, and (d) 0 to 25% by weight of another metal, the total amount of components (a), (b), (c) and (d) being 100% by weight. There is also provided an apparatus for use in the above process. Generally, the reaction of synthesizing hydrogen cyanide by ammoxidation of methane is carried out by bringing a gaseous mixture composed of natural gas, ammonia and air or another oxygen-containing gas in which the methane/ammonia mole ratio is 1:1.2-1.4 and the oxygen/ammonia mole ratio is 1:1.2-1 into contact with a platinum-containing catalyst at a temperature of 1000 to 1200°C and a pressure of from normal atmospheric pressure to not more than 3.0 kg/cm²-G. To prevent decomposition of hydrogen cyanide in the reaction gas, it is necessary to quench it to a temperature of not more than 700°C. In the apparatus used in this invention, the above proportions of nickel and chromium are used because the nickel alloy is required to have excellent high-temperature heat resistance, corrosion resistance, and processability for making the heat exchanger, in addition to preventing decomposition of hydrogen cyanide. In addition to the nickel, chromium and optional iron, the alloy used in the invention may contain another metal such as molybdenum, manganese, niobium and tantalum. Examples of the material for the heat-transfer tube which meet the above requirements are Inconel 625 and Hastelloy W (Ni 69 wt%, Mo 23 wt%, Cr 5 wt%, Fe 3 wt%). Inconel 625 and Hastelloy W are Trade Names. In this invention, a gaseous mixture composed of methane, ammonia and air or another oxygen-containing gas is contacted with a platinum-containing catalyst, and then without quenching the gas using water, the gas is quenched using an indirect heat exchanger and the heat of the reaction is recovered effectively. The recovered heat may be utilized for generation of pressurized steam or for preheating the starting methane (natural gas), ammonia and air either singly or as a mixture. When it is utilized for preheating the starting gas to a high temperature, the amount of methane or ammonia burnt within the reactor can naturally be reduced, and the yield of hydrogen cyanide based on each of the starting gases can be increased markedly. Furthermore, since the amount of gas introduced can be decreased, the reaction apparatus can be built small. Hence, the process of this invention is very advantageous. The yield of hydrogen cyanide is high because in the hydrogen cyanide producing apparatus of this invention, the decomposition of hydrogen cyanide is little. Furthermore, in accordance with this invention, the heat of the high-temperature reaction gas at 1000 °C or more can be directly recovered, and can be effectively utilized to preheat the starting gases in the hydrogen cyanide producing apparatus or to recover pressurized steam. Consequently, the efficiency of the hydrogen cyanide producing apparatus can be increased, and the unit consumption of the starting materials and utility can be decreased. Accordingly, the present invention is of great industrial significance. The following examples illustrate the present invention more specifically. It should be understood that the invention is not limited to these examples alone. EXAMPLE 1 Test for decomposing hydrogen cyanide:- A quartz double tube having an inside diameter of 7 mm and a length of 775 mm was fitted to the inside of an electric oven. A sample of each of various nickel alloys was inserted into the double tube, and hydrogen cyanide decomposition was tested. A feed gas of a nearly constant composition composed of about 5 % of HCN, about 80 % of H₂O and about 15 % of N₂ prepared by evaporating an aqueous solution of hydrogen cyanide with nitrogen in an evaporator was fed into a reaction tube, and subjected to a decomposition test at a linear velocity of 1.5 m/sec and a temperature of 1040 °C under atmospheric pressure. The test results are shown in Table 1 below. EXAMPLE 2 A gaseous mixture composed of ammonia, methane and air in a mixing ratio of 1:1.3:6.4 was introduced at a rate of 150 m³/hour into a reactor having an inside diameter of 250 mm in which platinum gauze was placed as a catalyst on an alumina perforated plate, and hydrogen cyanide synthesizing reaction was carried out at a temperature of 1050 to 1150 °C. A heat-exchanger comprised of a heat-conducting tube made of Inconel 625 (Trade name) was set up just below the catalyst layer, and steam under a pressure of 15 kg/cm²-G was generated. In this reactor, the yield of hydrogen cyanide in the initial stage was 81 % (based on ammonia). After the initiation of the reaction, the reactor was operated continuously for 180 days. There was no decrease in the yield of hydrogen cyanide. The inside of the reactor was inspected after stopping the operation, and no change was observed in the heat-conducting tube.

Claims: A process for producing hydrogen cyanide which comprises reacting methane or a gas containing methane as a main component, ammonia and an oxygen-containing gas in the presence of a platinum-containing catalyst at 1000 °C or more; and quenching the reaction gases to a temperature of not more than 700°C using an indirect heat-exchanger without quenching them directly with water, the indirect heat-exchanger being made of a nickel alloy consisting of (a) 60 to 80% by weight of nickel, (b) 5 to 25% by weight of chromium, (c) 0 to 3% by weight of iron, and (d) 0 to 25% by weight of another metal, the total amount of components (a), (b), (c) and (d) being 100% by weight. A process according to claim 1 wherein methane or the gas containing methane as a main component, ammonia and the oxygen-containing gas are preheated either singly or as a mixture in the indirect heat-exchanger. A process according to claim 1 or 2 wherein steam under pressure is generated in the indirect heat-exchanger. An apparatus for use in the process of claim 1 comprising a reactor and an indirect heat-exchanger therein, the heat-exchanging portion of the heat-exchanger being made of a nickel alloy as defined in claim 1.

Inventors: KOSEKI TOSHIO MITSUBISHI GAS C, OTAKE TAKESHI C O NIGATA FACTO, SAITO MASAO MITSUBISHI GAS CHE, TSUKAHARA KENGO C O NIGATA FAC, KOSEKI, TOSHIO MITSUBISHI GAS CHEMICAL COMP., INC., OTAKE, TAKESHI C/O NIGATA FACTORY, SAITO, MASAO MITSUBISHI GAS CHEMICAL COMPANY, INC., TSUKAHARA, KENGO C/O NIGATA FACTORY
Applicants: MITSUBISHI GAS CHEMICAL CO, MITSUBISHI GAS CHEMICAL COMPANY, INC.
Application year: 1989
Main classification: C01C3
IPC codes: F28F21, C01C3