Method of vapour reforming and device for its implementation

FIELD: chemistry.

SUBSTANCE: invention relates to two methods (two variants) of reforming process using oxidizing gas at temperature 980-1000°C. The recirculation of the flow part outgoing from the autothermic reformer to the flowrate vapour-hydrocarbon is described at that the said recirculation is implemented throught the instrumentality of thermocompressor ejector using heated beforehand supplied mix as operative fluid. For the optimization of general configuration the mole ratio of recirculating synthesis gas and operative fluid was chosen in the range 0.2-1.0. In order to prevent the carbon black formation in the reforming process recirculated hydrogen and vapour are fed to the input flow and the temperature of feeding is increased. Since there is a certain pressure drop between initial mixture of vapour and natural gas and the mix fed to reformer it is necessary to increase the pressure of initial mixture but it is compensated with the lower pressure drop in the heater and other equipment laid out upstream and downstream because of decreasing of vapour capacity.

EFFECT: reforming process is carried out without carbon black formation.

27 cl, 2 dwg, 1 tbl

 

The invention relates to the autothermal reforming of steam and hydrocarbon to obtain a synthetic gas used in the production of ammonia, methanol, synthesis reaction Fisher-Tropsch, the fortification of oil and other processes, and in particular for the autothermal reforming by recycling part of the synthetic gas in order to reduce the ratio of steam to carbon without the formation of soot.

Autothermal steam reforming is well known and has commercial success. The mixture of steam and hydrocarbon is fed to the autothermal reformer with air, oxygen-enriched air, or oxygen, and is subjected to incomplete combustion with the use of specially adapted burners on the top entrance. Products of incomplete combustion react on the fixed catalyst to form a synthetic gas, which typically includes steam, hydrogen, carbon monoxide and carbon dioxide. This method is basically simple, reliable and cost-effective technology for the production of synthetic gas.

One operating characteristic that you want to improve, however, is that the autothermal reformer may also be based on external supply of hydrogen for ignition when starting, for example, in an amount of 5 mole percent in feed is. Another characteristic is that a relatively high ratio of vapor-carbon is typically used to ensure operation without the formation of soot. High correlation of vapor-carbon can lead to increased capital costs, because it requires larger units for heating and supply in reformer, as well as for the regeneration of waste heat exhaust from reformer. High correlation of vapor-carbon are not attractive to modern plants for the production of magazinechicago gas, which minimized the size of the equipment necessary to obtain a single consistent process and save on space. It is also known that higher temperature pre-heat supplied to the mixture provides work without the formation of soot, but it may also be associated with high capital costs and energy consumption.

Recently it was proposed to establish a preliminary reformer in the feed stream of a mixture of steam-natural gas autothermal reformer. This can lead to the depletion of hydrocarbons and to provide a certain amount of hydrogen in the feed to the autothermal reformer, while a decrease in the ratio of vapor-carbon. However, this requires more intensive is the pressing to reduce the ratio of vapor-carbon.

The present invention includes a recirculation of a small part of the flow coming from the autothermal reformer, the feed flow steam-hydrocarbon, preferably with ejector thermocompressor, which uses pre-heated feed mixture as the driving fluid environment. Ejector adapted for operation at high temperature, can provide a molar ratio of recirculating synthesis gas driving fluid from 0.2 to 1. The flow of recirculating gas is, therefore, proportional to the supplied mixture of hydrocarbon vapor that produces a stable, well-mixed enrichment in hydrogen-steam at the outlet of the ejector. The exact ratio of the recycled product and the driving fluid may be selected for special applications, to optimize the entire structure.

By recirculating the product is introduced both hydrogen and steam, at elevated temperature, the flow in the autothermal reformer. The mixture emerging from the ejector has a higher ratio of vapor-carbon, but also contains hydrogen from recycled product and has a higher flow temperature (where the recirculated product is at a higher temperature), so that reformer can operate in a mode without the formation of soot in order to prevent clogging of the layer of catalyst and about the equipment downstream. There is a small difference between the pressure source is supplied by a mixture of steam-natural gas and fed into reformer due to losses in the ejector, which requires that the source of the feed mixture was entered under a slightly higher pressure, but this is compensated by a lower pressure drop in the heater process and other equipment upstream due to lower quantities of steam at the inlet end as compared with the prior art without recirculation of the product. The heater also has a lower load, reduced capital costs and energy consumption. Equipment downstream can also be reduced in size, because the water vapor content in the output stream from reformer is smaller, for example, can be used smaller HRSG waste heat and/or heat exchanger reformer, and can be used in other equipment smaller waste heat recovery and cooling. The size of the autothermal reformer in relation to the total product of synthetic gas is approximately the same compared to the size required to work without recirculating the exit stream.

In one design of the present invention provides a method of steam reforming, comprising: heating the feed stream ha is a, contains the original mixture of hydrocarbon and steam; heating a second stream containing the gas-oxidizer; feeding the heated feed stream gas pipeline feeding into the autothermal reformer with the heated second stream pipeline to supply oxidizer; catalytic reforming to produce synthetic gas with a temperature 980-1000°; removing the exit stream of synthesis gas from the autothermal reformer; the introduction of part of exhaust synthetic gas such as recycle gas in the feed gas stream, to obtain the feed mixture containing hydrogen; the ratio of recycle gas and the feed gas stream is from 0.2 to 1; and the process in the autothermal reformer when the ratio of steam and carbon is less than 3.6. The recirculated gas is preferably introduced into the ejector thermocompressor located in the supply line, using the supplied gas flow as a driving fluid. The recirculated gas preferably has a higher temperature than the feed gas stream. The hydrocarbon preferably is a natural gas. Gas-oxidizing agent may be selected from oxygen, air enriched with oxygen, and air. The second stream may include pairs. The feed mixture contains from 5 to 50 molar percent is in hydrogen. The initial mixture preferably has a ratio of steam and carbon from 0.6 to 3. The method of steam reforming may also include cooling the effluent stream of synthesis gas and the selection of recirculating gas from the exit stream of the cooled synthetic gas. The output stream of synthesis gas can be cooled in the exhaust-heat boiler waste heat or heat exchanger reformer. Preferably the ratio of recycle gas and the driving fluid is from 0.3 to 0.7, and the feed mixture contains from 20 to 40 molar percent of hydrogen. The method may also include the preliminary reformer feed gas stream upstream than the ejector, preferably prior to heating the feed gas stream.

In another design of the present invention provides a method of steam reforming, which includes: heating the first and second gas streams supplied, containing the initial mixture of hydrocarbon and steam; heating the third stream containing gas oxidant flow of the first heated feed stream gas pipeline feeding into the autothermal reformer with the third thread on the pipe feeding the oxidant; removing the first effluent stream of synthesis gas from the autothermal reformer; supply of the second heated stream into the heat exchanger reform the nga for the endothermic catalytic conversion of the heat exchanger tubes of the reformer, to form a second output stream of synthesis gas; mixing the first effluent stream of synthesis gas with the second outgoing stream of synthesis gas to form a mixed synthetic gas; passing the mixed synthetic gas through pipe reforming exchanger in heat exchange with them, to serve chilled product synthetic gas pipeline product synthesis gas; introducing product a synthetic gas such as recycle gas into the first feed gas stream, to obtain the feed mixture containing hydrogen, in which the ratio of recycle gas and the first feed gas stream is from 0.2 to 1; and (i) carrying out the process in the autothermal when reformer the ratio of steam and carbon is less than 3.6. It is possible in this design due to the enrichment of hydrogen and steam, as well as any increase in flow temperature.

In this design the recirculated gas is preferably introduced into the ejector thermocompressor located in the supply line, using the supplied gas flow as a driving fluid. The recirculated gas preferably has a higher temperature than the feed gas stream. The hydrocarbon preferably is a natural gas. Gas-oxidizer can the t to be selected from oxygen, air enriched with oxygen, and air. The third stream may include pairs. The feed mixture preferably contains from 5 to 50 mole percent hydrogen. The initial mixture preferably has a ratio of steam and carbon from 0.6 to 3. Preferably the ratio of recycle gas and the first feed gas stream is from 0.3 to 0.7, and the feed mixture contains from 20 to 40 molar percent of hydrogen. The method may also include the preliminary reformer feed gas stream upstream than the ejector, preferably prior to heating the feed gas stream.

In an additional design of the present invention provides a device for steam reforming. The device includes a means for heating the feed gas stream containing the initial mixture of hydrocarbon and steam, and means for heating the second stream containing the gas-oxidant. Means are provided for supplying heated feed stream gas pipeline feeding into the autothermal reformer with the second thread on the pipe feeding the oxidant. Means are provided for extracting the exit stream of synthesis gas from the autothermal reformer. Means are provided for introducing part of the exhaust synthetic gas such as recycle gas to the feed gas flow varactor thermocompressor, located in the supply pipe using the supplied gas flow as a driving fluid to get the feed mixture containing hydrogen, in which the ratio of recycle gas and the driving fluid is from 0.2 to 1. Means are provided for carrying out the process in the autothermal reformer when the ratio of steam and carbon is less than 3.6. The invention can also include a preliminary reformer for pre-reformer feed gas stream upstream than the ejector, preferably prior to heating the feed gas stream.

In an additional design of the present invention provides a device for steam reforming, which includes means for heating the first and second gas streams supplied, containing the initial mixture of hydrocarbon and steam, means for heating the third stream containing gas, an oxidizer, means for feeding the first heated feed gas stream in the pipe feed to the autothermal reformer with the third stream in the pipeline feeding the oxidizer, means for extracting the first effluent stream of synthesis gas from the autothermal reformer, means for feeding the second heated stream into the heat exchanger reformer for endothermic catalytic conversion in Trou the Ah exchanger reformer, to form a second output stream of synthesis gas, means for mixing the first effluent stream of synthesis gas with the second outgoing stream of synthesis gas to form a mixed synthetic gas, means for passing a mixed synthetic gas through pipe reforming exchanger in heat exchange with them, to serve chilled product synthetic gas pipeline product synthetic gas, a means for inputting a part of the synthetic product gas such as recycle gas into the first feed gas stream in the ejector thermocompressor located in the supply line with the first feed gas stream as a driving fluid to get the feed mixture containing hydrogen, in which the ratio of recycle gas and the driving fluid is from 0.2 to 1; and means for conducting the process in the autothermal reformer when the ratio of steam and carbon is less than 3.6. The invention can also include a preliminary reformer for pre-reformer feed gas stream upstream than the ejector, preferably prior to heating the feed gas stream.

In another design of the present invention provides a way to start already described device for continuous operation. JV the property comprises: heating the first and second gas streams supplied before the start of the third stream, moreover, in the first and second feed streams essentially no added hydrogen; introduction of substances to produce hydrogen in the first thread, the second thread or a combination thereof, and it decomposes in the autothermal reformer, the heat exchanger reformer or their combination, respectively, to form hydrogen gas; researchproven product of synthetic gas from the reforming exchanger in the first feed gas stream; in this case, when the first feed gas stream reaches a minimum temperature of self-ignition or exceed it at the entrance to the autothermal reformer start a third thread to perform ignition in the autothermal reformer; and after will auto-ignition finish the introduction of the substance to produce hydrogen in the first thread, the second thread or a combination thereof.

Figure 1 shows a simplified schematic view of the process steam autothermal reforming in accordance with one design, in which synthesis gas is cooled in the exhaust-heat boiler waste heat.

Figure 2 is a simplified schematic view of the process steam autothermal reforming in accordance with one design, in which the reforming exchanger is used with the autothermal reformera.

Figure 1 shows processprotocol autothermal reforming in accordance with one design. The mixture of hydrocarbon and steam is supplied by pipeline 100, and the gas-oxidizer is supplied by pipeline 102. The hydrocarbon may be any hydrocarbon that is subjected to steam reforming, but usually it is a naphtha or naphtha, subject to a preliminary reformer, or preferably natural gas. Gas-oxidizer can be any oxygen-containing gas, such as air, air enriched with oxygen, or oxygen. "Oxygen" means essentially pure oxygen, which can be obtained from a typical installation for air separation, for example 95-99% oxygen, preferably about 98% oxygen.

The mixture and the gas-oxidizing agent are heated in a conventional heater 104 process or any other conventional recovery system for waste heat of flue gas (for example, release of a gas turbine) and then fed through pipelines 106, 108 in the burner autothermal reformer 110, which contains a reforming catalyst, and this method is well known to specialists in this field of technology. Output stream pipeline 112 from reformer 110 then cooled in HRSG 114 waste heat is supplied by pipeline 116 in the cooler 118, and the synthetic product gas is recovered in the pipeline 120, as is well known in this technical field. As one not Ogre is socialnogo typical example of an oxidizing agent and a mixture of natural gas-steam in the pipes 106, 108 heated to about 500°With emerging flux 112 has a temperature of about 980-1000°With the exit from the boiler 114 waste heat has a temperature of about 350-700°and the temperature in the pipe 120 synthetic product gas is approximately 50-350°C.

In accordance with the present invention a portion of the effluent stream of synthesis gas is extracted downstream of reformer 110 and recycle through line 122 and the ejector 124 thermocompressor in the pipeline 106. Ejectors of thermocompressor are commercially available, and they can operate at temperatures in the pipes 106 and 112. The ejector 124 thermocompressor uses the fluid in the pipe 106 to continuously take the recirculated gas from the pipeline 122 at a constant ratio in the pipeline A. At the same time, the ejector 124 thoroughly mixed flows, in order to facilitate introduction into the burner reformer 110 for continuous burning.

The ratio of recycled product in the pipeline 122 and the exit stream from the heater in the pipeline 106 should be sufficient to maintain adequate hydrogen pipeline A downstream from the ejector 124, to prevent the formation of soot in reformer 110, preferably from 5 to 50 molar percent of hydrogen, more preferably from 20 to 40 mole about the clients hydrogen pipeline A excluding water vapor. The molar ratio of the fluid in the pipe 122 and the fluid in the pipe 106 is preferably from 0.2 to 1.0, more preferably from 0.3 to 0.6. The presence of hydrogen in the pipeline A, as well as increasing the water vapor content and temperature of the recycled product, thus provide the opportunity to reformer 110 to operate continuously with a lower molar ratio of steam and carbon than in the autothermal reformer prior art, i.e. below about 3.6, preferably from 0.6 to 3.0. The proportion of steam and carbon, therefore, is chosen to optimize the composition of the exit stream from reformer to process downstream, i.e. different ratio can be applied for the synthesis of ammonia in contrast to the methanol synthesis, the production of hydrogen for the refinery or Fisher-Tropsch, or the like.

The differential pressure between the pipes 106 and A in the ejector 124 to create the driving force for the introduction of the recirculating gas is usually about 150-300 kPa. Thus, the pressure at the outlet of the heater 104 in the pipe 106 will typically be at 150-300 kPa greater than without recirculation of the product. Also, since the recirculated gas in the pipe 122 may be hotter than the original feed mixture in the pipeline 106, the heat load on the motor 104 can be reduced. The recirculated gas can be selected anywhere in the lower stream than reformer 110, via one or more pipes 126, 128, 130 or 132, depending on the temperature and pressure required for recirculating gas in the pipeline 122. In General, the farther downstream the selected recirculating the product, the lower the temperature, pressure and water vapor content, and higher hydrogen content. For example, the gas in the pipes 112 and 126 contains high temperature output stream directly from reformer 110, while the gaseous product in the pipes 120 and 132 has a much lower temperature and lower pressure than the pipeline 106, and contains less steam and more hydrogen than in the pipeline 112, due to the condensation of water and separation. In the pipes 116 and 130 are higher temperature and higher pressure upstream from the heat exchanger 118 than in the pipes 120, 130. The pipe 128 is shown that the recirculated gas can also be selected from the boiler 114 waste heat, in an appropriate location corresponding to the desired temperature. Recirculating the product can also be selected from a variety of locations with corresponding valves (not shown)in order to obtain the desired ratio of each corresponding location for the required temperature is, pressure and composition of the resulting recirculating the gas mixture.

Figure 2 shows the preferred embodiment includes a reforming exchanger for additional generation of synthetic gas using the exit stream from the autothermal reformer to supply heat for the endothermic reforming reactions in the reforming exchanger. The mixture of the hydrocarbon/steam is supplied to the heater 200 process with hot heating through two different pipes 202, 204 for receiving the preheated feed mixtures in pipelines 206, 208, respectively. The feed mixture in the pipeline 206 is used as the driving fluid ejector 214 thermocompressor to take the recirculated gas from the pipeline 236, and the resulting mixture therefrom is fed through line 216 to the autothermal reformer 218. The mixture of steam and gas-oxidizer is supplied by pipeline 222, is heated in the heater 200 process and passes through line 224 to the autothermal reformer 218 in a manner analogous to that previously described with reference to figure 1. Hot exit stream of synthesis gas is obtained from the autothermal reformer 218 pipeline 220.

The feed mixture in the pipe 208 is served in a traditional heat exchanger 226 reforming, where she p is uhodit through the reforming catalyst, usually placed in each of the multiple tubes 228. Gas-reforming product leaves the tubes 228, where it is mixed in the annular heat the area with a hot gas product of the reforming of the autothermal reformer 218, which enters through the pipe 220. The resulting mixture then passes into the shell side of the heat zone through pipe 228 to apply heat to the endothermic reforming reaction that occurs inside the tubes 228. Mixed, partially cooled product synthesis gas is obtained via a pipeline 230 exit tube heat zone and may be further cooled in block 232 of convective heat transfer and extracted by pipeline 234. The recirculated gas is preferably selected from the pipeline 230 and fed through pipe 236 in the ejector 214 in a manner analogous to that previously described with reference to figure 1. The pipeline 236 may be an alternative and/or additional abstracted from any point of the heat exchanger 226 reforming in order to optimize the temperature and pressure.

In this design, the load in the process for the autothermal reformer 218, as well as on the heat exchanger 226 reforming, usually should not be increased compared with the prior art without recirculating the product, despite the increased flow of recirculating about the ukta, since the ratio of steam/carbon decreases.

Figure 2 also shows an embodiment variant of the preliminary reformer, which previously supplied the mixture in the pipeline 207 passes through the catalytic preliminary reformer 210 to facilitate partial conversion to hydrogen and oxides of carbon before the gas pipeline 202 to the heater 200, as described above. Preliminary reformer 210 may alternatively be placed in the pipeline 204 upstream from the heater 200 or in the pipeline 206 after the heater 200 and upstream from the ejector 214 thermocompressor.

Run the autothermal reformer 218 may be implemented in accordance with a preferred method according to one of the designs. A mixture of steam/natural gas pipelines 202, 204 are heated in the heater 200 of the process and fed into the heat exchanger 226 reforming and autothermal reformer 218, without feed gas-oxidant in the autothermal reformer 218 as long as the supply in the pipeline 216 will have a temperature above the auto-ignition. The temperature rises as much as is possible, for example, 550°With increasing heating of the heater 200 process. The temperature rises further, and the auto-ignition temperature is reduced by introducing the connection of the cat is, which turns hydrogen, for example, such as 1-5% methanol and/or ammonia in the pipe 202 and/or 204 upstream from the heater 200 through line 238, preferably at least in the pipeline 204. Hydrogen is formed in the preliminary reformer 210, the autothermal reformer 218 and/or the heat exchanger 226 reformer, and he then recycle in the pipeline 216 submission to the autothermal reformer through the ejector 214, which can operate at a higher ratio of recycled product and driving the fluid relative to normal operating conditions in order to maximize the hydrogen content in the pipeline 216. When used prior reformer 210, all of the connection, which is obtained from a hydrogen, or a part thereof preferably is added to the pipeline 206 upstream than the preliminary reformer (not shown). This trigger is convenient as it eliminates the usual scheme of the prior art without recirculating the product, which includes the introduction of hydrogen directly into the flow in the autothermal reformer.

Examples

A number of specific examples of working conditions for reforming in accordance with the design in figure 2 is shown in the table for a number of different ratio of steam/carbon and oxidizing agents

That is person 1
The ratio of the vapor-carbon in the original submission (line 206) (molar)The oxidant (line 222)The ratio of the recirculated product/feed (line 236/ pipeline 206) (molar)The ratio of the vapor-carbon in the total supply (line 216) (molar)H2after the preliminary reformer (line 220) (mol %)H2in total supply (line 216) (mol %)
2,7Air0,333,214,627,4
2,5Air0,332,913,926,7
2,5Air0,663,213,932,1
2,798%O20,333,314,634,8
2,098%O20,332,412,331,9
1,598%O20,331,710,529,2
1,598%O20,661,910,538,4
0,698%O20,660,646,6 30,2
0,698%O20,400,66,624,1
2,528%O20,332,913,928,6
2,528%O20,663,313,935,0

Although the invention has been described through design, pictured above, many variations and modifications of the invention will be obvious to a person skilled in this technical field. It is assumed that all such variations and modifications are within the range of the scope or the spirit of the attached claims should be covered by them.

1. The method of steam reforming, comprising heating a feed gas stream containing the initial mixture of hydrocarbon and steam, the heated second stream containing gas oxidant flow of heated feed stream gas pipeline feeding into the autothermal reformer with the second thread on the pipe feeding the oxidizer, catalytic reforming to produce synthetic gas with a temperature 980-1000°With, removing the exit stream of synthesis gas from the autothermal reformer, the introduction of part of exhaust synthetic gas such as recycle gas supplied through the OK gas to produce supplied to the mixture, containing hydrogen, the ratio of recycle gas and the feed gas stream is from 0.2 to 1, the process in the autothermal reformer when the ratio of steam and carbon is less than 3.6.

2. The method of steam reforming according to claim 1, in which the recirculated gas is introduced into the ejector thermocompressor located in the supply line, using the supplied gas flow as a driving fluid.

3. The method of steam reforming according to claim 1, in which the recirculated gas has a higher temperature than the heated feed gas stream.

4. The way the steam reformer of claim 1, wherein the hydrocarbon contains natural gas.

5. The method of steam reforming according to claim 1, in which the gas-oxidant selected from oxygen, air enriched with oxygen, and air.

6. The method of steam reforming according to claim 5, in which the second stream includes pairs.

7. The way the steam reformer of claim 1, wherein the feed mixture contains from 5 to 50 molar percent of hydrogen.

8. The method of steam reforming according to claim 1, in which the initial mixture has a ratio of steam and carbon from 0.6 to 3.

9. The method of steam reforming according to claim 1, additionally containing a cooled effluent stream of synthesis gas and the selection of recirculating gas from the cooled effluent stream of synthesis gas.

10. The way steam reform the ha according to claim 9, in which the output stream of synthesis gas is cooled in the exhaust-heat boiler waste heat.

11. The method of steam reforming according to claim 9, in which the output stream of synthesis gas is cooled in the heat exchanger reformer.

12. The method of steam reforming according to claim 1, in which the ratio of recycle gas and the feed gas stream is from 0.3 to 0.7, and the feed mixture contains from 20 to 40 mol.% of hydrogen.

13. The method of steam reforming, including the transmission of the first feedstock through the pre-catalytic reformer, subsequent heating the first stream containing hydrogen, and a second feed gas stream containing the initial mixture of hydrocarbon and steam, the heating of the third stream containing gas, an oxidizer, the flow of the first heated feed stream gas pipeline feeding into the autothermal reformer with the third thread on the pipe feeding the oxidant, removing the first effluent stream of synthesis gas from the autothermal reformer, the flow of the second heated stream into the heat exchanger reformer for endothermic catalytic conversion of the heat exchanger tubes of the reformer to form a second output stream of synthesis gas, mixing the first the exit stream of synthesis gas with the second outgoing stream of synthesis gas, that is to form a blended syngas, the transmission of mixed synthetic gas through pipe reforming exchanger in heat exchange with them, to supply the cooled synthetic gas product in the pipeline product synthetic gas introduction part of the synthetic product gas such as recycle gas into the first feed gas stream in the ejector thermocompressor located in the supply line, with the first feed gas stream as a driving fluid to get the feed mixture containing hydrogen, the ratio of recycle gas and the driving fluid is from 0.2 to 1.

14. The method of steam reforming in item 13, in which the recirculated gas is introduced into the ejector thermocompressor located in the supply pipe using the supplied gas flow as a driving fluid.

15. The method of steam reforming in item 13, in which the recirculated gas has a higher temperature than the heated feed gas stream.

16. The method of steam reforming in item 13, in which the hydrocarbon contains natural gas.

17. The method of steam reforming in item 13, in which the gas-oxidant selected from oxygen, air enriched with oxygen, and air.

18. The method of steam reforming in item 13, in which the third stream includes pairs.

19. The method of steam reforming in item 13, in which padave the th mixture contains from 5 to 50 mol.% of hydrogen.

20. The method of steam reforming in item 13, in which the initial mixture has a ratio of steam and carbon from 0.6 to 3.

21. The method of steam reforming according to claim 20, in which the ratio of recycle gas and the driving fluid is from 0.3 to 0.7, and the feed mixture contains from 20 to 40 molar percent of hydrogen.

22. Device for steam reforming for implementing the method according to claim 1, containing:

means (104) for heating the feed gas stream containing the initial mixture of hydrocarbon and steam,

means (104) for heating the second stream containing gas, an oxidizer,

means (108) for supplying heated feed stream gas pipeline feeding into the autothermal reformer (110) with a second thread on the pipe feeding the oxidant,

means (112) to retrieve the exit stream of synthesis gas from the autothermal reformer,

means (122) for the introduction of part of exhaust synthetic gas such as recycle gas in the feed gas stream in the ejector (124) thermocompressor located in the supply line, using the flow of the injected gas as a driving fluid to get the feed mixture containing hydrogen, in which the ratio of recycle gas and the driving fluid is from 0.2 to 1.

23. The device according to item 22, is AutoRAE further comprises a means for cooling the effluent stream of synthesis gas and a means for selecting the recirculating gas from the cooled effluent stream of synthesis gas.

24. The device according to item 23, in which the means for cooling the effluent stream of synthesis gas contains HRSG waste heat.

25. The device according to item 23, in which the means for cooling the effluent stream of synthesis gas comprises a heat exchanger reformer.

26. Device for steam reforming for the implementation of the method according to item 13, containing:

means (200) for heating the first and second gas streams supplied, containing the initial mixture of hydrocarbon and steam,

means (200) for heating the third stream containing gas, an oxidizer,

means (224) for filing the first heated feed stream gas pipeline feeding into the autothermal reformer (218) with the third thread on the pipe feeding the oxidant,

means (220) to extract the first effluent stream of synthesis gas from the autothermal reformer,

means (208) for the filing of the second heated stream into the heat exchanger reformer for endothermic catalytic conversion of the heat exchanger tubes of the reformer to form a second output stream of synthesis gas,

means (226) for mixing the first effluent stream of synthesis gas with the second outgoing stream of synthesis gas to form a mixed syngas;

means 228) for passage of the mixed synthetic gas through the tubes of the heat exchanger reformer with heat exchange with them, to serve chilled product synthetic gas pipeline (230) of the synthetic gas product;

means (236) for the introduction of product synthetic gas such as recycle gas into the first feed gas stream in the ejector (214) thermocompressor located in the supply line, with the first feed gas stream as a driving fluid to get the feed mixture containing hydrogen, in which the ratio of recycle gas and the driving fluid is from 0.2 to 1

27. The startup type of the device according to item 23 for continuous operation, including:

(a) heating the first and second gas streams supplied before the start of the third stream, and in the first and second feed streams essentially no added hydrogen

(b) introducing a substance to produce hydrogen in the first thread, the second thread or the combination of the first and second threads, and it decomposes in the autothermal reformer, the reforming exchanger or in combination, respectively, to obtain hydrogen gas,

(c) recycling of the product synthesis gas from the reforming exchanger in the first feed gas stream,

(d) whereby, when the first feed gas stream reaches a minimum temperature of self-ignition or exceeds its input the autothermal reformer, start a third thread to perform ignition in the autothermal reformer,

(e) the end of stage (b) after spontaneous ignition will occur.



 

Same patents:

FIELD: chemistry; processing of hydrocarbon material to synthesis gas.

SUBSTANCE: porous ceramic catalytical module represents the product of exothermic finely dispersed nickel-aluminium mixture exposed to vibration compaction and to sintering. The said product contains: nickel 55.93-96.31 Wt%; aluminium 3.69-44.07 Wt%. Porous ceramic catalytical module may contain up to 20 Wt% (based on the module weight) of titanium carbide as well as catalytic coating including following groups: La and MgO, or Ce and MgO, or La, Ce and MgO, or ZrO2, Y2O3 and MgO, or Pt and MgO, or W2O5 and MgO in quantity 0,002-6 Wt% based on the module weight synthesis gas is produced by conversion of methane and carbon dioxide mixture on porous ceramic catalytical module in filtration mode The process conditions are as follows: temperature 450-700°C, pressure 1-10 atm, rate of CH4-CO2 mixture delivery to catalytical module 500-5000 l/dm3*hr.

EFFECT: inventions permit to carry out the process at lower temperatures.

5 cl, 37 dwg

FIELD: hydrogen production processes.

SUBSTANCE: invention relates to catalysts for hydrolysis of hydride compounds to produce pure hydrogen for being supplied to power installations, including fuel cells. Invention provides catalyst for production of hydrogen from aqueous or water-alkali solutions of hydride compounds containing platinum group metal deposited on complex lithium-cobalt oxide and, additionally, modifying agent selected from series: titanium dioxide, carbon material, oxide of metal belonging to aluminum, magnesium, titanium, silicon, and vanadium subgroups. According to second variant, catalyst contains no platinum group metal. Described are also catalyst preparation method (variants) and hydrogen generation process, which is conducted at temperature no higher than 60°C both in continuous and in periodic mode. As hydrogen source, sodium borohydride, potassium borohydride, and ammine-borane can be used.

EFFECT: increased catalyst activity at environmental temperatures (from -20 to 60°C), prolonged time of stable operation of catalytic system, and reduced or suppressed platinum metals in composition of catalyst.

14 cl, 1 tbl, 20 ex

FIELD: method and torch for producing synthesis gas at decomposition of liquid hydrocarbons such as oil and natural gas at elevated temperatures without usage of catalyst by CO and hydrogen.

SUBSTANCE: method is realized by partial oxidation of liquid and solid combustible materials at presence of oxygen and oxygen containing gases. Fuel, oxygen-containing gas and atomizing fluid are fed to torch separately. Atomizing fluid is expanded just in front of inlet opening for fuel by means of one or several nozzles providing speed of atomizing fluid in range 20 - 300 m/s. Relation of diameter of outlet opening of nozzle for liquid fuel to diameter of opening of nozzle for atomizing fluid is in range 1/1.1 - 1/5.

EFFECT: possibility for simplifying process.

2 dwg, 2 ex

FIELD: method for producing synthetic gas, which may be used in oil chemistry for producing motor fuels.

SUBSTANCE: method includes processing of biogas under temperature of 1420-1800°C and following cooling of resulting synthetic gas. Thermal processing of biogas is performed in liquid heat carrier with ratio of volume of liquid heat carrier to volume of barbotaged gas, equal to 10-100 during 0,3-2 seconds, or in boiling layer of solid particles, where the speed of biogas is selected to be greater than minimal speed of fluidization.

EFFECT: increased purity of produced synthetic gas.

8 cl, 6 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to catalysts and process of steam conversion of hydrocarbons to produce synthesis gas. Proposed catalyst for steam conversion of hydrocarbons contains nickel oxide (4.0-9.2%) and magnesium oxide (4.0-6.5%) supported by porous metallic nickel (balancing amount). Carrier has specific surface area 0.10-0.20 m2/g, total pore volume 0.07-0.12 cm3/g, predominant pore radius 1-30 μm, and porosity at least 40%. Described are also catalyst preparation method and generation of synthesis gas via steam conversion of hydrocarbons.

EFFECT: increased heat conductivity of catalyst resulting in stable activity in synthesis gas generation process.

8 cl, 1 tbl, 5 ex

FIELD: production of synthesis-gas.

SUBSTANCE: proposed method is carried out at temperature of 750-900 C due to external heating of tubular furnace reaction tubes filled with catalyst; mixture of natural gas and superheated steam is fed to reaction tubes. External heating of reaction tubes filled with catalyst is first performed by burning the natural gas in air; after attaining the required mode of operation, external heating is carried out by burning the synthesis-gas fed from tubular furnace outlet to reaction tube external heating chamber. Device proposed for realization of this method includes tubular furnace with reaction tubes filled with catalyst, chamber for mixing the natural gas with superheated steam and external heating chamber for heating the reaction tubes filled with catalyst for maintenance of conversion process; heating chamber is provided with air inlet. Device is also provided with gas change-over point whose one inlet is used for delivery of natural gas fed to chamber of external heating tubular furnace reaction tubes during starting the mode of steam conversion process; other inlet of gas change-over point is used for delivery of synthesis-gas from tubular furnace outlet through distributing synthesis-gas delivery point. Device is also provided with regulator for control of delivery of synthesis-gas to reaction tube external heating chamber required for combustion.

EFFECT: enhanced economical efficiency of process.

3 cl, 1 dwg

FIELD: steam catalytic conversion of natural gas into synthesis-gas with the use of thermal and kinetic energy of synthesis-gas.

SUBSTANCE: proposed method includes external heating of reaction tubes of tubular furnace filled with nickel catalyst on aluminum oxide substrate by passing mixture of natural gas and superheated steam through them. External heating of reaction tubes filled with catalyst is performed by burning the natural gas in air at exhaust of flue gases from heating zone. After tubular furnace, the synthesis-gas is directed to gas turbine for utilization of thermal and kinetic energy; gas turbine rotates electric generator; then, synthesis-gas is directed to synthesis-gas burner of electric power and heat supply system; flue gases from external heating zone are directed to heat exchangers for preheating the natural gas and steam before supplying them to reaction tubes of tubular furnace. Device proposed for realization of this method includes sulfur cleaning unit, tubular furnace with reaction tubes filled with nickel catalyst on aluminum oxide substrate with inlet for gas mixture of natural gas and superheated steam; device also includes external heating zone for reaction tubes with flue gas outlet and gas burner for external heating of reaction tubes of tubular furnace with inlet for natural gas and air. For utilization of thermal and kinetic energy of synthesis-gas, device is provided with gas turbine and electric generator at tubular furnace outlet and synthesis-gas burner of electric power and heat supply system; device is also provided with heat exchangers for preheating the natural gas and steam before supplying them to tubular furnace.

EFFECT: improved ecological parameters; enhanced power efficiency of process.

3 cl, 1 dwg

FIELD: processing of hydrocarbon raw materials; oxidizing conversion of hydrocarbon gases into synthesis-gas.

SUBSTANCE: proposed method is carried out in flow-through two-chamber reactor in turbulent mode at combustion of mixture of hydrocarbon raw material and oxidizer. Superheated water steam is additionally introduced into said mixture in the amount of 5-20 mass-% relative to mass of carbon fed in form of hydrocarbon raw material. Three-component mixture is ignited in combustion chamber by jet of hot gas fed from external source where pressure exceeds pressure in first chamber during ignition. Combustion products from first chamber of reactor are directed to second chamber via nozzle at critical difference in pressure and combustion process is continued till content of oxygen in combustion products does not exceed 0.3 vol-%. Process is carried out in combustion reactor which is made in form of two coaxial cylindrical chambers with cooled nozzle located in between them; section of this nozzle ensures required pressure differential between chambers. Injector unit mounted at inlet of first chamber is used for delivery of working mixture components. Turbulator is mounted in first chamber. Lateral surface of first chamber has one or several holes for introducing the jet of hot gas from external source whose pressure exceeds pressure of first chamber and volume of second chamber exceeds that of first chamber. Proposed method makes it possible to produce synthesis-gas at H2/CO ratio approximately equal to 2.0; residual content of oxygen does not exceed 0.3 vol-% and content of carbon black does not exceed trace amount.

EFFECT: enhanced efficiency.

9 cl, 2 dwg, 11 ex

FIELD: carbon monoxide conversion catalysts.

SUBSTANCE: invention relates to a method of preparing catalysts for middle-temperature conversion of carbon monoxide, which can be used in industry when producing nitrogen-hydrogen mix for ammonia synthesis. Preparation of catalyst for middle-temperature conversion of carbon monoxide with water steam, comprising precipitation of iron hydroxide from iron nitrate solution with ammonia-containing solvent, washing of iron hydroxide with water to remove nitrate ions, mixing with calcium and copper ions, mechanical activation of components, molding, drying, and calcination of granules, is characterized by that, in the component mixing step, lanthanum oxide is supplementary added, in which case molar ratio of components is as follows: Fe2O3/CaO/CuO/La2O3 = 1:(0.8-0.9):(0.045-0.08):(0.005-0.01).

EFFECT: increased catalytic activity and more than thrice reduced content of by-products in condensate.

1 tbl, 3 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to autothermal conversion of hydrocarbon fuel to produce synthesis gas, which can be used in chemical production, for burning at catalytic heat plants, and in hydrogen power engineering. Proposed catalyst contains, as active components, cobalt oxide, manganese oxide, and barium oxide, and, as carrier, refractory reinforced metalporous carrier. Catalyst is prepared by impregnation of carrier with barium and manganese salt solution at Ba/Mn =5:4 followed by drying, calcination, impregnation with cobalt salt solution, drying, and calcination. Invention further describes generation of synthesis gas via autothermal conversion of hydrocarbon fuel performed utilizing above-described catalyst.

EFFECT: enabled catalyst exhibiting high heat conductivity, high activity in production of synthesis gas, and resistance to coking and deactivation with sulfur compounds present in diesel fuel and gasoline.

6 cl, 1 tbl, 3 ex

FIELD: hydrocarbon conversion catalysts.

SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.

EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.

4 cl, 1 tbl, 8 ex

FIELD: power engineering.

SUBSTANCE: method includes searching for continental or oceanic rift generation zones, supported by abnormal mantle with output of substance branches to earth crust. Drilling of wells by turbodrills into mantle substance. After well enters mantle substance a reaction hollow is formed in it by putting together force and product wells or by expanding force and/or product wells. Water is pumped into force well and gas-like hydrogen is outputted to surface through product well forming during reaction of inter-metallic substances fro mantle substance to water. Water is fed in amount, adjusting output of hydrogen, while reaction surface of reaction hollow is periodically regenerated, for example, by high pressure water flow, supplied through jets in reaction hollow, on remotely controlled manipulators. Expansion of well may be performed via explosions of explosive substances charges, and it is possible to separate forming gaseous hydrogen and water steam by separator mounted therein.

EFFECT: higher effectiveness of hydrogen production.

9 cl

FIELD: alternative fuel production and catalysts.

SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.

EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.

6 cl, 2 tbl, 16 ex

FIELD: autothermal catalytic reforming of hydrocarbon feed stream.

SUBSTANCE: method relates to method for reforming of hydrocarbon feed stream with water steam at elevated temperature to produce gas enriched with hydrogen and/or carbon oxide. Hydrocarbon stream is passed through water steam reforming catalyst bed wherein oxygen is fed through oxygen-permeable membrane followed by removing of finished product from this bed. Said catalyst bed contains in input region catalyst with reduced or without water steam reforming activity, but having hydrocarbon feed oxidation activity.

EFFECT: process with improved characteristics due to temperature controlling in reactor.

3 cl, 1 dwg

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: electric power and chemical industries; methods of production of the electric power and liquid synthetic fuel.

SUBSTANCE: the invention presents a combined method of production of the electric power and liquid synthetic fuel with use of the gas turbine and steam-gaseous installations and is dealt with the field of electric power and chemical industries. The method provides for the partial oxidation of hydrocarbon fuel in a stream of the compressed air taken from the high-pressure compressor of the gas turbine installation with its consequent additional compression, production of a synthesis gas, its cooling and ecological purification, feeding of the produced synthesis gas in a single-pass reactor of a synthesis of a liquid synthetic fuel with the partial transformation of the synthesis gas into a liquid fuel. The power gas left in the reactor of synthesis of liquid synthetic fuel is removed into the combustion chamber of the gas-turbine installation. At that the degree of conversion of the synthesis gas is chosen from the condition of maintenance of the working medium temperature at the inlet of the gas turbine depending on the type of the gas-turbine installation used for production of the electric power, and the consequent additional compression of the air taken from the high-pressure compressor of the gas-turbine installation is realized with the help of the gas-expansion machine powered by a power gas heated at the expense of the synthesis gas cooling before the reactor of synthesis. The invention allows simultaneously produce electric power and synthetic liquid fuels.

EFFECT: the invention ensures simultaneous production of electric power and synthetic liquid fuels.

2 cl, 2 dwg

FIELD: petrochemical industry.

SUBSTANCE: the invention is dealt with petrochemical industry, in particular with a method of catalytic preliminary reforming of the hydrocarbon raw materials containing higher hydrocarbons. The method provides for the indicated hydrocarbon raw materials gating through a zone of a catalyst representing a fixed layer containing a noble metal on magnesia oxide (MgO) and-or spinel oxide (MgAl2O4) at presence of oxygen and water steam. The technical result is a decrease of a carbon share on the catalyst.

EFFECT: the invention allows to decrease a carbon share on the catalyst.

3 cl, 2 tbl, 2 ex

FIELD: technology for production of methanol from syngas.

SUBSTANCE: claimed method includes mixing of hydrocarbon raw material with water steam to provide syngas by steam conversion of hydrocarbon raw material and subsequent methanol synthesis therefrom. Conversion of hydrocarbon raw material and methanol synthesis are carried out under the same pressure from 4.0 to 12.0 MPa. In one embodiment hydrocarbon raw material is mixed with water steam and carbon dioxide to provide syngas by steam/carbonic acid conversion of hydrocarbon raw material in radial-helical reactor followed by methanol synthesis therefrom under the same pressure (from 4.0 to 12.0 MPa). In each embodiment methanol synthesis is carried out in isothermal catalytic radial-helical reactor using fine-grained catalyst with grain size of 1-5 mm. Methanol synthesis is preferably carried out in two steps with or without syngas circulation followed by feeding gas from the first or second step into gasmain or power plant.

EFFECT: simplified method due to process optimization.

12 cl, 3 tbl, 3 dwg

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: chemical industry; petrochemical industry; oil refining industry and other industries; methods of production a synthesis gas.

SUBSTANCE: the invention is pertaining to the field of the methods of production of a synthesis of gas and may be used in chemical, petrochemical, oil refining and other industries. The method of production of synthesis gas using a vapor or a vapor-carbon dioxide conversion of a hydrocarbonaceous raw material provides for purification of the hydrocarbonaceous raw material from sulfuric compounds, its commixing with steam or with steam and carbon dioxide with formation of a steam-gas mixture. The catalytic conversion of the steam-gas mixture is conducted in a reactor of a radially-spiral type, in which in the ring-shaped space filled with a nickel catalyst with a size of granules of 0.2-7 mm there are the hollow spiral-shaped walls forming the spiral-shaped channels having a constant cross section for conveyance of a stream of the steam-gaseous blend in an axial or in a radially-spiral direction. At that into the cavities of the walls feed a heat-transfer agent to supply a heat into the zone of reaction. The invention ensures intensification the process.

EFFECT: invention ensures intensification the process.

4 cl, 4 dwg, 2 tbl, 3 ex

Up!