Method of production of synthesis gas

FIELD: production of hydrogen and carbon oxide referred to as synthesis gas by selective catalytic oxidation of hydrocarbon raw material in presence of oxygen-containing gases.

SUBSTANCE: proposed method includes bringing the starting material in contact with catalyst at hourly volume rate of gas within 10,000-10000000 h-1; mixture contains organic material and oxygen or oxygen-containing gas in the amount ensuring ratio of oxygen to carbon no less than 0.3; electric current is passed through at least part of catalyst. Used as catalysts are complex composites including metallic carriers.

EFFECT: possibility of quick and safe ignition of catalyst; increased degree of conversion and selectivity under conditions of change of load in wide range.

24 cl, 7 ex

 

The invention relates to a process for producing hydrogen and carbon monoxide, a mixture which is called synthesis gas by selective catalytic oxidation of hydrocarbon (organic) raw material in the presence of oxygen-containing gases.

Currently, promising and rapidly developing new areas of utilization of synthesis gas and derived from it are hydrogen vehicles and small energy. Automotive synthesis gas or hydrogen can be used as a Supplement to the main fuel in internal combustion engines or as fuel for electric motor fuel cell. Energy synthesis gas and hydrogen can be used in combination with fuel cells or gas turbines for the production of environmentally friendly heat and power. For this kind of application requires catalytic processes implemented in compact reactors with high performance and, in addition, working autothermal, i.e. without additional heat supply from any other device.

These requirements fully comply with the process of selective catalytic oxidation of hydrocarbons with oxygen (RMS) [S.C. Tsang, J.B. Claridge and M.L.H. Green, Recent advances in the conversion of methane to synthesis gas, Catalysis Today, 1995, V.23 supported, 3-15; D.A. Hickman, L.D. Schmidt, Synthesis gas formation by direct oxidation o methane, in "Selective Catalytic Oxidation", ACS Symposium series, 1993, p.416-426; P.M. Torniainen, X. Chu and L.D. Schmidt, Comparison of monolith-supported metals for the direct oxidation of methane to syngas, J.Catal., 1994, v.146, 1-10], carried out at low contact times. Usually the reaction is carried out at atmospheric pressure and high gas hourly space velocities, such as 50×104-70×104h-1that correspond to the contact times 7-5 milliseconds. The experiments carried out at elevated pressures, showed no significant changes in the composition of the reaction products [A.G. Dietz, L.D. Schmidt, Catal. Lett., 33 (1995) 15; L. Basini, K. Aasberg-Petersen, A. Guarinoni, M. Ostberg, Catal. Today 64 (2001) 9; K.H. Hofsad, J.H.B.J. Hoebink, A. Holmen, G.B. Marin, Catal. Today, 40 (1998) 157]. The processes of partial oxidation were demonstrated for methane and higher alkanes [Basini, A. Guarinoni and A. Aragno, J.Catal. 190 (2000) 284; Y Ji, W. Li, H. Xu, and Y. Chem, Catal. Lett.71 (2001) 45; W.Yanhui and Diyong, Int.1. Hyd. Energy 26 (2001) 795; R.P. O'connor, E.J. Klein and L.D. Schmidt, Catal. Lett. 70 (2000) 99; S.S. Bharadwaj and L.D. Schmidt, Fuel Proc. Tech. 42 (1995) 109].

The main part of natural gas is methane. The relevant reaction is:

CH4+1/2O2=CO+2H2

ΔH°248=-35.7kJ mol-1

For gasoline and isooctane, which is usually expressed as the General formula C8H18the reaction of synthesis gas production has the form:

C8H18+4O2=8CO+9H2

ΔN°248=-158.1 kJ mol-1

The mixture coming into contact is the formation, may contain both pure oxygen and air. To increase the concentration of hydrogen in the synthesis gas mixture containing hydrocarbon fuel and oxygen-containing gas, add water vapor. In this case, the combined thermal effects of steam reforming occurring with absorption of heat (endothermic process), and partial oxidation (exothermic process). Even in laboratory conditions it is possible to produce several kilograms of product per day per 1 g of the catalyst during contact time is from 0.1 to 10 MS (volume of catalyst, for example, cubic centimeter divided by the flow rate of the gas mixture, expressed in cubic centimeters per second). The range of changes in the gas hourly flow rate in this case about 36×104-36×106h-1. In terms of energy for use in fuel cells hydrogen production in these experimental conditions is ˜ 1 kW of electricity [C.A. Leclerc, J.M. Redenius and L.D. Schmidt, Fast lightoff in millisecond reactors, Catal. Lett. 79, 1-4 (2002)39-44].

In order to obtain a high level of conversion and the desired selectivity of the process, the contacting with the catalyst is carried out at elevated temperatures. Typically, the temperature of the catalyst should be at least 800°C. the operating temperature is in the range of 800-1500°predominantly in the range of 50-1300° C.

The selectivity of the reaction RMSE for target products (carbon monoxide and hydrogen) depends on various factors, most important of which are the activity and selectivity of the catalyst. In addition, for the implementation of this process requires catalysts with low hydraulic resistance, resistant to thermal shocks and superusuario performed in the form of solid blocks.

However, even assuming the presence of a catalyst satisfying all the above conditions, there remains the problem of ignition of the catalyst, i.e. quick start of the reaction of partial oxidation of organic hydrocarbon fuel. Moreover, the ignition temperature depends on the fuel composition. Thus, for methane ignition temperature of approximately 600° [W.R. Williams, J. Zhao and L.D. Schmidt, Ignition and extinction surface of an homogeneous oxidation of NH3and CH4, A.I.Ch.E. Journal, 37, 5 (1991) 641-649], for isooctane ignition temperature is about 200° [R.P. O'connor, E.J. Klein and L.D. Schmidt, High yields of synthesis gas by millisecond partial oxidation of higher hydrocarbons, Catal. Lett. 70 (2000) 99-107]. When designing a small device, which is expected to produce hydrogen by oxidation of organic hydrocarbons for the production of electrical energy fuel cells in stationary conditions and means of transport are extremely important characteristics such as:/p>

the short time required for the ignition process;

- the suitability of the process to changes in load in a wide range.

The time required for the ignition process is determined mainly by the time during which the necessary heat is supplied to the catalyst to heat it to the desired temperature.

Usually the reaction mixture is served on the contacts after the catalyst has been heated to the desired temperature of the hot gas, the external flame or an electric heating in a special oven. Also used internal heating. To do this, first by homogeneous combustion before the catalyst is an organic hydrocarbon fuel at the proper stoichiometric ratio with oxygen. After a preset period of time, the ratio of air/fuel is changed to an appropriate value to produce synthesis gas [S.A. Leclerc, J.M. Redenius and L.D. Schmidt, Fast lightoff in millisecond reactors, Catal. Lett. 79, 1-4 (2002)39-44; L.D. Schmidt, E.J. Klein, C.A. Leclerc, J.J. Krummenacher, K.N. West, Syngas in millisecond reactors: higher alcanes and fast lightoff, Chem. Eng. Sci., 58 (2003) 10-37-1041]. It is obvious that all methods of external heating, be it flame or electric heating in a special oven, have considerable inertia, which does not allow to achieve the goals set by the leading automobile companies of the world - 0,5 min from the start to achieve the full n the load.

A method of obtaining a synthesis gas described in [L.D. Schmidt, E.J. Klein, C.A. Leclerc, J.J. Krummenacher, K.N. West, Syngas in millisecond reactors: higher alcanes and fast lightoff, Chem. Eng. Sci., 58 (2003) 10-37-1041]. The partial oxidation of hydrocarbons (methane, butane, cyclohexane, n-hexane, decane) is carried out at a gas hourly volume rate of 105-106h-1on the monolithic catalyst comprising a 5.0 wt.% Rh on foam α-Al2About3. The volume of the monolith catalyst 5.3 cm3. The ratio of air and hydrocarbon fuel varies in the interval O2/C=0.3-0.8. To heat the catalyst to a temperature of the beginning of the reaction the authors homogeneous combustion of organic hydrocarbon fuel before catalyst within 4 C. during this time the ratio of the air/fuel was approximately four times greater than that stoichiometrically required for the process for production of synthesis gas. Then the ratio of the air/fuel quickly change to the desired working mode value. Adiabatic heating during homogeneous combustion mixture air-fuel is on the order of 1500-2000°depending on the type of fuel. The art is to maintain such a flow of the reaction stream and such a time interval, so that the catalyst had to be heated to a predetermined temperature (200-600°) and no more. However, overheating at Asda catalyst, near which is homogeneous combustion can no longer be avoided. The authors noted that for some time there is a significant temperature gradient across the catalyst. It is obvious that during the implementation process, there are significant technical challenges. Very great danger of overheating of the catalyst. Possible overheating lead to irreversible damage to the catalyst. In addition, the resulting thermal stresses must inevitably lead to rapid loss of mechanical strength of the monolithic structure of the catalyst. For such a small amount of catalyst (5.3 cm3) the time required for ignition - start the process, 4-7 C. the Produced thermal power in the experiment is approximately 1 kW. The minimum power required for a vehicle, for example, equal to 50 kW. To obtain such power, the amount of catalyst will need to increase by about 50 times. In this case, will increase by approximately the same factor and the time to ignition of the catalyst and will account for an amount not less than 3 minutes This time much more than the required 0.5 min from the start to reach full load.

In the implementation of the specific device it is necessary to change the load over a wide range. The inlet temperature of the reactants - air, fuel, water - much nor the f process temperature, equal 800-1100°C. When the load changes on thermal conditions in the reactor will also be influenced by thermal inertia of the concrete structure. You must also take into account that the partial oxidation of hydrocarbon fuel includes a combination of exothermic and endothermic stages that determine the selectivity of the overall process and is very sensitive to temperature change. Thus, as with increasing load (expenses)and the decrease can occur cooling down individual sections of the catalyst. This can lead to changes in the selectivity of the process, and other undesirable phenomena, such as deposition of carbon with the deactivation of the catalyst, temperature stresses, etc.

The closest is a method of converting natural gas to the Nickel catalyst. The catalyst used in the form of a wire through which electric current is passed [SU 294795, C 01 b 1/18, 04.11.1971].

The disadvantage of this method is the low conversion and selectivity due to the use of Nickel catalyst in the form of a wire which has a low activity, is rapidly oxidized and supervised in operation.

The invention solves the problem of the ignition process when the initial state of the catalyst at ambient temperature with high conversion and is electively process when the load changes in a wide range.

The problem is solved as follows. Process for production of synthesis gas is carried out by catalytic oxidation of organic raw materials. A mixture containing organic feedstock and the oxygen or oxygen-containing gas in amounts providing a ratio of oxygen and carbon is not less than 0.3, is fed to a catalyst which is a complex composite, and at least through part of which electric current is passed. Electric current can be fed alternately to different parts of the catalyst. For heating use the current from the source voltage greater than 6 volts, mostly more than 12 volts. Electric current is passed through the catalyst or part thereof for at least 1 C. for at least 1 s, mainly 3-60, organic raw materials and oxygen or oxygen-containing gas can be fed in amounts providing a ratio of oxygen and carbon more than 0.8. The mixture is applied to the contacting may contain water.

Passing electric current through the catalyst is carried out, mainly for heating to a predetermined temperature, reaction start - ignition catalyst. Then the voltage can be turned off. The transmission of the electric current used in other situations - for heating areas of the catalytic layer in the case of cooling. In the case of cooling of any at Asda catalytic layer, for example, when the load changes, the electric voltage on it will allow you to raise the temperature to a predetermined and, thus, to keep the overall conversion and selectivity. Time passing an electric current depends on the amount of the catalyst and is at least 1 C.

Thus, in the proposed method, the catalyst or its part, in addition to its main function is to provide high speed and selectivity in the conversion of the reagents, have special properties, namely electrical conductivity and sufficient resistance so that, if necessary, be heated by supplying electric power from an external source.

It is obvious that such properties may have catalysts prepared on metal substrates. Such catalysts provide high thermal conductivity, which reduces the temperature gradients on the catalytic unit and, therefore, thermal tensions.

In the proposed method uses a catalyst which is a complex composite containing mixed oxide, a simple oxide, transitional and/or noble element and includes the media on a metal basis, representing layered termometricheskikh material containing non-porous or malabarista oxide coating, the ri ratio of the thickness of the metal base to the thickness of the non-porous or malabarista oxide coating is 10:1-1:5 (the first option).

Or use a catalyst which is a complex composite and contains a mixed oxide, a simple oxide, transitional and/or noble element, and includes the media on a metal basis, representing layered termometricheskikh material containing non-porous or malabarista oxide coating and a highly porous oxide layer, the ratio of the thickness of the metallic base to the thickness of the non-porous or malabarista oxide coating is 10:1-1:5, and the ratio of the thickness of the metal base to the thickness of the highly porous layer is 1:10-1:5 (the second option).

The used catalyst may be a complex composite containing alumina, oxides of rare earth and/or transition metals, complex composite includes a ceramic matrix and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix, and the catalyst has a system of parallel and/or intersecting channels (the third option).

Or the process is carried out on the catalyst comprising a complex composite containing mixed oxide, a simple oxide of the transition element and/or a noble element, the catalyst contains media, including ceramic matrix material consisting of coarse particles or aggregatively, dispersed throughout the matrix, the catalyst has a system of parallel and/or intersecting channels (the fourth option).

Used catalyst is a combination of catalysts according to any one of the above options.

Conductive material, such as nichrome spiral, may additionally be incorporated (nakativaetsa) in the structure of the monolithic catalytic converters.

The process for production of synthesis gas used in this method guarantees a quick and safe ignition of the catalyst. In terms of load changes in a wide range remain high as conversion and selectivity of the process.

The invention is illustrated by the following examples.

Example 1 (the prototype). Process for production of synthesis gas is carried out in a flow reactor in autothermal mode at atmospheric pressure over a Nickel catalyst. The catalyst volume 1330 cm3in the form of wire placed in a quartz tube. From a source voltage of 12 volts to the catalytic unit serves current within 2 minutes the temperature of the catalyst during this time reaches the set temperature ignition - start of the reaction - 500°C. Metal wire has a low heat capacity, so that the reaction mixture at room temperature, containing natural gas and air costs 24 l/min natural g is for and 62.9 l/min air, served on the catalyst without turning off the electric current. The value Of2=0,54. The contact time of 0.92, which corresponds to a gas hourly flow rate 40·102h-1. When the ignition process and the establishment of autothermal mode voltage switch off and stop the flow of current. The temperature of the catalyst due to the high thermal conductivity metal wire is supported along the entire length almost constant - 890°C. In the first 10 min, the conversion of natural gas is 93,6%. The concentration of hydrogen in the synthesis gas to 31.2% vol., the concentration of carbon monoxide is 13.4%. For further implementation process has been a gradual decrease in the temperature of the catalyst with the appearance of significant amounts of carbon dioxide and a simultaneous decrease in the content of the main components of synthesis gas: hydrogen and carbon monoxide. After 20 minutes, the process of methane conversion decreases.

Example 2. Process for production of synthesis gas is carried out in a flow reactor in autothermal mode at atmospheric pressure. The catalyst is a complex composite containing, wt.%: 4,5 mixed oxide of cerium and zirconium with the fluorite structure, 2,1 perovskite composition LaNi0,994Pt0,006and executed on the media on a metal basis, representing layered termometricheskikh material with a ratio of the thickness of the metal is ment basis to the thickness of the non-porous or malabarista oxide coating 5:1 (first option).

The catalytic unit, having a volume of 133 cm3placed in a quartz tube. To the catalytic unit down power supply circuit for supplying electric voltage. From a source voltage of 12 volts to the catalytic unit serves current within 2 minutes the temperature of the catalyst during this time reaches the set temperature ignition - start of the reaction - 500°C. Then the voltage is turned off to stop the supply of current to the catalyst serves the reaction mixture at room temperature, containing natural gas and air costs 24 l/min natural gas and 62.9 l/min of air. The ratio of O2=0,54. The contact time 0,092, which corresponds to a gas hourly flow rate 40·103h-1. The temperature at the beginning of the catalytic unit 1030°With, at the exit of the reactor 750°C. the Conversion of natural gas is to 96.6%. The concentration of hydrogen in the synthesis gas is 34.0% vol., the concentration of carbon monoxide, which is 16.3 percent. After 4 and 8 hours instrumental analysis showed the conversion of natural gas to 95.3 and 96.8 per cent, respectively, and the hydrogen concentration of 34.2 and 33.6% vol., carbon monoxide is 15.6% and 16.7%. respectively, which is within error of the instrumental analysis shows a stable conversion of natural gas with high selectivity of this catalyst.

Example 3. The process is conducted as described in example 2. The difference of the situation of the t is after submission of a current for 0.5 min on the catalyst serves the reaction mixture at room temperature, containing natural gas and air with the costs of 16.2 l/min natural gas and 62.9 l/min of air. The ratio of O2/S=0,8. When electric current is not switched off. Over the next 0.5 min the temperature of the catalyst reaches 800°C. After this, the voltage switch off, stop the power supply and increase the flow of natural gas to a preset flow rate 24 l/min, with a ratio of O2=0,54.

Example 4. Obtaining synthesis gas is carried out at a pressure of 3 ATM. The catalyst (the second option) cooked on a medium containing non-porous or malabarista oxide coating with a ratio of the thickness of the metal base to the thickness of the non-porous or malabarista oxide coating 10:1, and highly porous oxide coating with a ratio of the thickness of the metal base to the thickness of the porous oxide coating 1:1. The resulting catalyst contains, wt%: 9,0 mixed oxide of cerium and zirconium with the fluorite structure, 1.7 perovskite LaNi0,994Pt0,006.

To the catalytic unit volume of 1.13 ml, placed in a quartz tube with a diameter of 12 mm, down power supply circuit for supplying electric voltage. From a source voltage of 12 volts for 2 to catalytic unit serves current. The temperature of the catalyst during this time on steget predetermined temperature ignition - 200°C. Synthetic kerosene having a boiling point in the range of 150-200°With, sprayed into the air stream through the nozzle over two centimeters in front of the catalytic unit. The consumption of kerosene 112.3 g/h (154 ml/h)air flow 470 nl/h Ratio O2/S=0,55. The contact time 0,009 sec, which corresponds to a gas hourly flow rate 40·104h-1. The temperature at the beginning of the catalytic unit 1250°With, at the exit of the reactor 1020°C. the Conversion of kerosene to 95%. Performance monoxide - 4.8 mol/kg of catalyst, the performance of hydrogen - 3.7 mol/kg of catalyst. The process in the reactor is carried out in the course of the working day. The process indicators were stable within the measurement errors.

Example 5. Use of monolithic catalytic unit, prepared for the third option, having a structure with a system of parallel and intersecting channels. The number of concurrent channels per unit geometric surface of the end plane is 56 cm-2. The distance between the intersecting channels is 0.5 mm, Specific surface area equal to 5 m2/, the Composition of the catalyst is a complex composite containing alumina and dispersed material is a mixed oxide LaNiO3+xwith perovskite structure with an average size of aggregates of particles of about 15 μm. The content on sergiovanni material is 22 wt.%.

The volume of the catalytic unit of 91.8 cm3. The catalyst is wound nichrome coil through which electric current is passed within 2 min from the source voltage of 30 volts. The temperature of the catalyst during this time reaches the set temperature ignition 530°C. Then the voltage is shut off and the catalyst serves the reaction mixture at room temperature, containing natural gas and air costs 24 l/min natural gas and 62.9 l/min of air. The mixture is at room temperature. The ratio of O2/C=0,54. The contact time 0,063, which corresponds to a gas hourly flow rate 58·103h-1. The temperature at the beginning of the catalytic unit 1010°With, at the exit of the reactor 820°C. the Conversion of natural gas is 95.2 percent. The concentration of hydrogen in the synthesis gas by 34.2%, the concentration of carbon monoxide is 17.2%. After stopping the process after 7 hours of stable operation produced unloading of the catalyst. Microscopic analysis showed no traces of coking.

Example 6. Use of monolithic catalytic unit cell structures with a system of parallel and intersecting channels (the fourth option) mounted in it nichrome spiral. The composition of the catalyst is a complex composite containing alumina and dispersed material is mixed is th oxide LaNiO 3+xwith perovskite structure and contains 4.8 wt.% mixed oxide of cerium and zirconium with the fluorite structure and 1.0 wt.% Pt. The volume of the monolithic catalytic unit - 107 cm3.

From the source voltage 30 volts to the catalyst in the reactor serves current within 10 C. the temperature of the catalyst during this time reaches the ignition temperature 250°C. Then the voltage is turned off. Gasoline having a boiling point in the range from -42 to 192°C, mixed with hot air so that the temperature of the gasoline-air mixture fed to the reactor equal to 200°C. the Consumption of gasoline 0,893 kg/h, air flow to 3.58 m3/h Ratio of About2/S=0,53. The contact time 0,092, which corresponds to a gas hourly volume rate 39×10 h-1. Within 2 min set stable mode with a temperature of 1115°at the beginning of the catalytic unit and 1076°at the outlet of the catalytic unit. After 4 h of stable operation with full conversion of the gasoline and the concentrations of hydrogen and CO in the synthesis gas, respectively, and 26.3 22.2% vol. added the evaporated water in the fuel-air mixture in an amount of 1.14 kg/h so that the ratio of H2O/C=0,84. The temperature of the catalyst falls within the range 1063-1000°C. the Concentrations of hydrogen and CO in the synthesis gas is 27.5 and 17.4% vol. respectively. The concentration of carbon dioxide has increased from 0.3 to 7.1 is B.% due to steam reforming. At the end of the work shift was unloading of the reactor. The catalyst was found no trace of coking.

Example 7. Use two monolithic catalytic unit loaded into the reactor sequentially. The first downstream gas have the catalyst described in example 2, with the composition of the active component, wt.%: 4,5 mixed oxide of cerium and zirconium with the fluorite structure, 1 perovskite composition LaNi0,994Pt0,0061 LaRu. The second direction of gas flow have a monolithic catalytic unit cell structures with a system of parallel and intersecting channels described in example 6. The volume of the second downstream gas monolithic catalytic unit of 91.8 cm3.

From the source voltage 30 volts to the catalyst in the reactor serves current within 30 C. the temperature of the catalyst during this time reaches the set temperature ignition 230°C. the Gasoline is mixed with hot air and water vapor so that the temperature of the gasoline-vapor mixture fed to the reactor is equal to 200°C. the Consumption of gasoline 1.86 kg/h water flow 3,13 kg/h, air flow 6.9 m2/hours contact Time 0,059, which corresponds to a gas hourly flow rate 61×103h-1. Temperature directly after the filing of the reaction mixture is placed at the beginning of the first catalytic who Loka 800° Since, the output of the second catalytic unit 915°C. voltage is disconnected. The temperature at the catalyst gradually began to decline and after 5 min in the beginning of the first catalytic unit temperature is reduced to 400°With, at the output of the second catalytic unit 850°C. This is due to the fact that the ratio of a pair of water/fuel in the reaction mixture is (N2O/s=1,17), which is dominated by processes with absorption of heat. The value Of2=0,49. In the further process was inevitable decay process. Serves again the voltage only to the first block of the catalyst. The temperature in the layer at the beginning of the first catalytic unit after 1 min is set 890°With, at the output of the second catalytic unit 865°C. analysis of the composition of the synthesis gas shows that the conversion of gasoline full. The concentration of hydrogen is 34.0%, the concentration of carbon monoxide is 11.0%, the concentration of carbon dioxide formed due to the interaction of carbon monoxide with water vapor, up 14.2%. The process was carried out with these indicators within the accuracy of measurements during the work shift. As seen from the above examples, the proposed method of producing synthesis gas allows quick and safe ignition of the catalyst to its initial state at a temperature of OCD the global environment. The method of implementation of the process according to this invention allows to carry out the process with high conversion and selectivity, including when the load changes.

1. Method for production of synthesis gas by the oxidation of organic materials, comprising contacting a catalyst, through which electric current is passed, a mixture containing organic feedstock and the oxygen or oxygen-containing gas in amounts providing a ratio of oxygen and carbon is not less than 0.3, characterized in that the electric current is passed at least through a portion of the catalyst which is a complex composite that contains a mixed oxide, a simple oxide, transitional and/or noble element and includes the media on a metal basis, representing layered termometricheskikh material containing non-porous or malabarista oxide coating, with the ratio of the thickness of the metal base to the thickness of the non-porous or malabarista oxide coating is 10:1-1:5.

2. The method according to claim 1, characterized in that the electric current serves alternately to different parts of the catalyst.

3. The method according to claim 1, characterized in that for heating use current from a voltage source greater than 6, preferably 12 Century

4. The method according to claim 1, characterized in that the electric current is passed through a catalyst is or part thereof during at least 1 C.

5. The method according to claim 1, characterized in that for at least 1 with the organic raw material and the oxygen or the oxygen-containing gas is fed in amounts providing a ratio of oxygen and carbon exceeding 0.8.

6. The method according to claim 1, characterized in that the mixture supplied to the contacting, contains water.

7. Method for production of synthesis gas by the oxidation of organic materials, comprising contacting a catalyst, through which electric current is passed, a mixture containing organic feedstock and the oxygen or oxygen-containing gas in amounts providing a ratio of oxygen and carbon is not less than 0.3, wherein electric current is passed at least through a portion of a catalyst which is a complex composite that contains a mixed oxide, a simple oxide, transitional and/or noble element, includes the media on a metal basis, representing layered termometricheskikh material containing non-porous or malabarista oxide coating and highly porous oxide layer, the ratio of the thickness of the metallic base to the thickness of the non-porous or malabarista oxide coating is 10:1-1:5, and the ratio of the thickness of the metal base to the thickness of the highly porous layer is 1:10-1:5.

8. The method according to claim 7, characterized in that Thu is the electric current serves alternately to different parts of the catalyst.

9. The method according to claim 7, characterized in that for heating use current from a voltage source greater than 6, preferably 12 Century

10. The method according to claim 7, characterized in that the electric current is passed through the catalyst or part thereof for at least 1 S.

11. The method according to claim 7, characterized in that for at least 1 with the organic raw material and the oxygen or the oxygen-containing gas is fed in amounts providing a ratio of oxygen and carbon exceeding 0.8.

12. The method according to claim 7, characterized in that the mixture supplied to the contacting, contains water.

13. Method for production of synthesis gas by the oxidation of organic materials, comprising contacting a catalyst, through which electric current is passed, a mixture containing organic feedstock and the oxygen or oxygen-containing gas in amounts providing a ratio of oxygen and carbon is not less than 0.3, wherein electric current is passed at least through a portion of a catalyst which is a complex composite containing alumina, oxides of rare earth and/or transition metals, and includes a ceramic matrix and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix, with the catalyst has a system of parallel and/or intersecting channels.

14. --- The on clause 13, characterized in that the electric current serves alternately to different parts of the catalyst.

15. The method according to item 13, wherein for heating use current from a voltage source greater than 6, preferably 12 Century

16. The method according to item 13, wherein electric current is passed through the catalyst or part thereof for at least 1 S.

17. The method according to item 13, wherein for at least 1 with the organic raw material and the oxygen or the oxygen-containing gas is fed in amounts providing a ratio of oxygen and carbon exceeding 0.8.

18. The method according to item 13, wherein the mixture is applied to the contacting, contains water.

19. Method for production of synthesis gas by the oxidation of organic materials, comprising contacting a catalyst, through which electric current is passed, a mixture containing organic feedstock and the oxygen or oxygen-containing gas in amounts providing a ratio of oxygen and carbon is not less than 0.3, wherein electric current is passed at least through a portion of a catalyst which is a complex composite containing mixed oxide, a simple oxide, a transition element and/or a noble element that contains media, including ceramic matrix material consisting of coarse particles or aggregates of particles, the var is Giovanni on throughout the matrix, when this catalyst has a system of parallel and/or intersecting channels.

20. The method according to claim 19, characterized in that the electric current serves alternately to different parts of the catalyst.

21. The method according to claim 19, characterized in that for heating use current from a voltage source greater than 6, preferably 12 Century

22. The method according to claim 19, characterized in that the electric current is passed through the catalyst or part thereof for at least 1 S.

23. The method according to claim 19, characterized in that for at least 1 with the organic raw material and the oxygen or the oxygen-containing gas is fed in amounts providing a ratio of oxygen and carbon exceeding 0.8.

24. The method according to claim 19, characterized in that the mixture supplied to the contacting, contains water.



 

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5 cl, 2 dwg

FIELD: petroleum processing.

SUBSTANCE: hydrocarbon/steam mixture is subjected to preliminary reforming stage in contact with first steam reforming catalyst enclosed within externally heated preliminary reforming reactor in passage for furnace gas escaping from steam reforming reactor with flame heating. Stream subjected to preliminary reforming and escaping from preliminary reforming reactor comes into contact with second steam reforming catalyst enclosed within steam reforming reactor with flame heating. Process may further comprise stage wherein stream subjected to preliminary reforming interacts with third reforming catalyst disposed outside of furnace gas passage between preliminary reforming reactor outlet (in furnace gas passage) and inlet of steam reforming reactor with flame heating.

EFFECT: prolonged undisturbed process period.

3 cl, 1 dwg, 2 tbl

FIELD: gas and petroleum processing.

SUBSTANCE: invention relates to methods for decomposing and utilizing hydrogen sulfide and/or mercaptans, which methods can be used for production of hydrogen and sulfur from hydrogen sulfide as well as for purification of gas mixtures polluted by hydrogen sulfide and/or mercaptans. Method comprises passing hydrogen sulfide and/or mercaptan-containing gas at temperature below 200°C through solid catalyst bed placed in liquid capable of dissolving reaction intermediates and/or sulfur arising on catalyst surface to release hydrogen and/or hydrocarbons.

EFFECT: lowered reaction temperature and eliminated need of frequent solid catalyst regeneration.

7 ex

FIELD: chemical industry; conducting non-adiabatic reactions.

SUBSTANCE: proposed method includes the following stages: introducing first flow of reagents in parallel into first reaction zone and second flow of reagents into second reaction zone; interaction of first flow of reagents with catalyst in first reaction zone is effected under condition of indirect heat exchange with heat exchange medium and interaction of second flow of reagents with catalyst is effected under condition of indirect heat exchange with heat exchange medium; gases formed due to reforming with water vapor are evacuated; catalyst in first reaction zone is located inside tubular reactor under conditions of indirect heat exchange with heat exchange medium due to introduction of this medium into tubular heat exchange zone located around tubular reactor with first reaction zone and catalyst in second reaction zone is located on side of heat exchange zone envelope under condition of indirect heat exchange with heat exchange medium.

EFFECT: enhanced compactness of reactors; reduced usage of expensive materials.

6 cl, 2 dwg

FIELD: chemical industry; conducting non-adiabatic reactions.

SUBSTANCE: proposed method includes the following stages: introducing first flow of reagents in parallel into first reaction zone and second flow of reagents into second reaction zone; interaction of first flow of reagents with catalyst in first reaction zone is effected under condition of indirect heat exchange with heat exchange medium and interaction of second flow of reagents with catalyst is effected under condition of indirect heat exchange with heat exchange medium; gases formed due to reforming with water vapor are evacuated; catalyst in first reaction zone is located inside tubular reactor under conditions of indirect heat exchange with heat exchange medium due to introduction of this medium into tubular heat exchange zone located around tubular reactor with first reaction zone and catalyst in second reaction zone is located on side of heat exchange zone envelope under condition of indirect heat exchange with heat exchange medium.

EFFECT: enhanced compactness of reactors; reduced usage of expensive materials.

6 cl, 2 dwg

FIELD: power industry, mechanical engineering and environmental control.

SUBSTANCE: the invention is pertaining to the field of high power industry, mechanical engineering and environmental control. In a explosion-proof chamber 1 with double-walls simultaneously feed a gaseous explosive mixture using pipeline 4 through channels 5 and inject hydrocarbons with the nucleuses of carbon crystallization using a pipeline 6 through an injector 7 with formation of a cone-shaped shell 8 with an inert cavity in the central zone. The shell 8 and the explosive mixture 9 form a cumulative charge. Conduct initiation of undermining of an explosive mixture 9, as a result of which the cumulative charge forms a cumulative spray 10 moving at a high speed along the axis of the cumulation. The gaseous products withdraw through pipeline 17. At collision of the cumulative spray 10 with a barrier having channels 11 of the cooling unit 2 the pressure and temperature there sharply increase ensuring growth of the formed crystals of diamond. Simultaneously conduct cooling with the help of pipelines 12 located in metal filings and granules 13. The atomized and cooled cumulative spray gets into the auxiliary chamber 3, where the diamonds 14 are separated, feed through the pipeline 15 to a power accumulator 16, in which they are settling. Separated hot hydrogen is removed for storing or utilization. The invention allows to magnify the sizes of dimensions crystals of diamond up to 800 microns and more, to decrease atmospheric injections, to reduce the net cost of the diamonds, to increase effectiveness of the device.

EFFECT: the invention ensures growth of sizes of diamonds crystals up to 800 microns and more, decrease of atmospheric injections, reduction of the net cost of the diamonds, increased effectiveness of the device.

2 cl, 2 dwg

FIELD: storage of gases in chemical, petrochemical ,and oil-refining industries.

SUBSTANCE: proposed oxygen storage method includes partial reduction of λ-Al2O3 on specific surface area of 200 - 400 m3/g doped with up to 0.5 mass percent of Sn during synthesis and subjected to oxidizing treatment at 500 °C in oxygen stream. Reduction is made by activated molecular, hydrogen, or hydrogen-containing hydrocarbon gas at gas temperature of 100 - 750 °C, pressure of 1 - 10 at., and humidity of 10-5 - 10-1 volume percent followed by freezing water produced in the process; storage of partially reduced λ-Al2O3 in arbitrary-humidity atmosphere at up to 50 °C or in vacuum, or in inert gas atmosphere at temperature of up to 750 °C and humidity of up to 10-5 volume percent; and oxidation of partially reduced λ-Al2O3 with water vapors at temperature of 100 - 750 °C or in vacuum at humidity of 10-5 - 10-2 volume percent.

EFFECT: enhanced holding capacity of hydrogen store at enhanced safety and low cost of its storage.

1 cl, 87 ex

FIELD: production of catalytic neutralizers.

SUBSTANCE: high-efficiency catalytic neutralizer has internal and external layers on inert carrier which contain noble metals of platinum group deposited on materials of base and oxygen-accumulating components. Inner layer of proposed catalytic neutralizer contains platinum deposited on first base and first oxygen-accumulating component and its external layer contains platinum and rhodium deposited on second base only; this second layer contains additionally second oxygen-accumulating component. Production of catalytic neutralizer includes application of coat on carrier made from composition containing powder-like materials including first material of base and first oxygen-accumulating component followed by drying, calcining, immersing the carrier with coat in solution of platinum precursor; coat is calcined and external layer is applied over previous layer. Specification describes two more versions of production of catalytic neutralizer.

EFFECT: enhanced ability of catalytic neutralizer for reduction of catalytic activity after aging due to discontinuation of delivery of fuel.

24 cl, 1 dwg, 11 tbl, 5 ex, 3 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: catalyst contains, wt %: group VIII metal 0.01-2.0, group IVA metal 0.01-5.0, europium 0.01-10.0, cerium 0.10-10.0, halogen 0.10-10.0m and refractory inorganic oxide 63.00-99.86.

EFFECT: enabled preparation of catalyst with relatively high activity and selectivity, low carbon sedimentation velocity, and prolonged lifetime in naphtha reforming processes.

11 cl, 6 dwg, 4 tbl

FIELD: methods of production a synthesis gas.

SUBSTANCE: the invention is pertaining to the process of production of hydrogen and carbon oxide, which mixture is used to be called a synthesis gas, by a selective catalytic oxidation of the hydrocarbonaceous (organic) raw material in presence of the oxygen-containing gases. The method of production of the synthesis gas includes a contacting with a catalyst at a gas hourly volumetric speed equal to 10000-10000000 h-1, a mixture containing organic raw material and oxygen or an oxygen-containing gas in amounts ensuring the ratio of oxygen and carbon of no less than 0.3. At that the process is conducted at a linear speed of the gas mixture of no less than 2.2 · 10-11 · (T1 + 273)4 / (500-T2) nanometer / s, where: T1 - a maximum temperature of the catalyst, T2 - a temperature of the gas mixture fed to the contacting. The linear speed of the gas mixture is, preferably, in the interval of 0.2-7 m\s. The temperature of the gas mixture fed to the contacting is within the interval of 100-450°C. The maximum temperature of the catalyst is within the interval of 650-1500°C. The technical effect is a safe realization of the process.

EFFECT: the invention ensures a safe realization of the process.

10 cl, 5 ex

FIELD: alternate fuel manufacture catalysts.

SUBSTANCE: invention relates to generation of synthesis gas employed in large-scale chemical processes such as synthesis of ammonia, methanol, higher alcohols and aldehydes, in Fischer-Tropsch process, and the like, as reducing gas in ferrous and nonferrous metallurgy, metalworking, and on gas emission detoxification plants. Synthesis gas is obtained via catalytic conversion of mixture containing hydrocarbon or hydrocarbon mixture and oxygen-containing component. Catalyst is a complex composite containing mixed oxide, simple oxide, transition and/or precious element. Catalyst comprises metal-based carrier representing either layered ceramics-metal material containing nonporous or low-porosity oxide coating, ratio of thickness of metallic base to that of above-mentioned oxide coating ranging from 10:1 to 1:5, or ceramics-metal material containing nonporous or low-porosity oxide coating and high-porosity oxide layer, ratio of thickness of metallic base to that of nonporous or low-porosity oxide coating ranging from 10:1 to 1:5 and ratio of metallic base thickness to that of high-porosity oxide layer from 1:10 to 1:5. Catalyst is prepared by applying active components onto carrier followed by drying and calcination.

EFFECT: increased heat resistance and efficiency of catalyst at short contact thereof with reaction mixture.

13 cl, 2 tbl, 17 ex

FIELD: inorganic synthesis catalysts.

SUBSTANCE: invention provides ammonia synthesis catalyst containing ruthenium as active ingredient supported by boron nitride and/or silicon nitride. Catalyst can be promoted by one ore more metals selected from alkali, alkali-earth metal, or rare-earth metals. Ammonia synthesis process in presence of claimed catalyst is also described.

EFFECT: increased temperature resistance of catalyst under industrial ammonia synthesis conditions.

4 cl, 6 ex

The invention relates to a catalyst for the receipt of vinyl acetate in the fluidized bed

The invention relates to the process of obtaining mixtures of hydrogen and carbon monoxide by catalytic conversion of hydrocarbons in the presence of oxygen-containing gases and/or water vapor

The invention relates to catalytic chemistry, in particular to methods of producing catalysts for the process of reduction of nitrogen oxides, mainly in the presence of methane and oxygen, and can be used for purification of exhaust gases (NOx) in the production of weak nitric acid, flue gases of high-temperature furnaces and boilers

The invention relates to methods of producing the catalyst for purification of exhaust gases of internal combustion engines

FIELD: heterogeneous catalysts.

SUBSTANCE: catalytic system comprises (i) high-silica fibrous carrier characterized by 29Si MNR spectrum, in which lines with chemical shifts -100±3 ppm (line Q3) and -110±3 ppm (line Q4) are present at ratio of integral intensities Q3/Q4 from 0.7 to 1.2; IR spectrum, in which absorption bands of hydroxyl groups with wave number ν=3620-3650 cm-1 and half-width 65-75 cm-1 are present; which carrier has specific surface SAr=0.5-30 m2/g as measured by BET method from thermal desorption of argon, surface area SNa=10-250 m2/g as measured by alkali titration method, at SNa/SAr ratio 5 to 30; and (ii) at least one active element. The system represents geometrically structured one constituted by microfibers with diameter 5-20 μm and additionally has active centers characterized in IR spectra of adsorbed ammonia by presence of an absorption band with wave numbers ν=1410-1440 cm-1.

EFFECT: increased catalytic activity, resistance to deactivation, and selectivity.

3 cl, 7 ex

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