The way to obtain electricity, water vapour and carbon dioxide from hydrocarbon

 

The invention is intended for the chemical industry and energy. Thread 1 natural gas is heated, compressed and piped 2 served in the saturator 3, where it is mixed with water 4 coming from the device 14 to remove the water, and with fresh demineralized water from line 4b. The mixture is fed to the autothermal reactor 6 (APR) in the form of stream 5. There serves as a compressed air pipe 7. Before ATP can place the reactor prereforming. At least part of the air flow 29 can be pre-compressed to the pressure required for entry into the reactor. The synthesis gas from the Asia-Pacific region 6 is cooled in the steam generator 9, and then as stream 11 is fed to the installation of the 12 CO conversion. The obtained gas mixture 13 is cooled in the apparatus 14 in the form of stream 15 is fed into the absorber CO216, then desorber 19 as stream 18. The regenerated absorbent by pipeline 20 are returned to the absorber 16. In the apparatus 22 remove water from the stream WITH a221 and recycle it into the saturator 3. The resulting stream of highly concentrated CO2compress and brought on line 23. The gas flow 17 of the absorber 16 is used as fuel in a gas turbine 24, which also serves the air 25. Part of the stream 17 can be used in a fuel cell DPAR overheat in the heat exchanger 30 and the thread 31 is served in the generator 32. The exhaust gas 28 from the steam generator 27 can be recycled in the APR 6, or in conjunction with air 25 to submit to the turbine 24. The synthesis gas stream 11 can be selected for the synthesis of methanol, and from line 17 can be selected raw materials for the synthesis of ammonia. The invention allows to produce electricity with obtaining highly concentrated gaseous CO2and the quantity of nitrogen oxides is in the range adopted for gas turbines. The resulting gases are used as raw material for the synthesis of methanol and ammonia. The method is simple and economical. 10 C.p. f-crystals, 2 ill., table 1.

The invention concerns a method for production of electricity, water vapour and carbon dioxide in concentrated form from hydrocarbons. The invention also includes the optional receipt of the products on the basis of the synthesis gas associated with the specified method.

Power receive power plant with combined cycle, combined with the installation of the reforming process, where the fuel for the gas turbine serves as the hydrogen-containing gas (Integrated Reforming Combined Cycle (JRCC)). The main problem in this process is that the gas turbine is operated, giving the minimum of vydelenijami electricity, steam and a concentrated carbon dioxide published on the Internet, http:/www.hydro. com/konsern/news/eng/1998/980423e. htmi. This publication describes a process involving the reaction of natural gas with steam, which turns the hydrogen-containing gas, which is burned in a gas turbine combined cycle generating electricity.

In addition, because patent applications Japan JP 608041 is known about the use of turbines operating on hydrogen burning to generate electricity. Behind the scenes the application of natural gas and oxygen in a molar ratio of from 1:0.5 to 1:0.7 to react with the formation of hydrogen and carbon monoxide by partial oxidation of the specified fuel. Air is supplied to the separator of oxygen on the basis of the pressure difference absorption (RDA), and oxygen is fed to the autothermal reactor (ATR), where natural gas is converted into hydrogen and carbon monoxide. The resulting gas is fed into the reactor conversion, in which carbon monoxide is converted to carbon dioxide. Then the gas mixture is introduced into a membrane separator (gazorazdelitel), in which hydrogen is separated from the carbon dioxide. CO2after separation of hydrogen washed and then desorbed. Hydrogen, practically n the SSA needs oxygen, for which you want the separator of RDA that consume energy. In accordance with the technological scheme of the natural gas pressure must be reduced almost to atmospheric pressure, to be able to add oxygen. After the separation in the separator, RDA the oxygen you need to shrink a second time. All these additional compression reduces the efficiency of the process.

The main object of this invention is an improved method of generating electricity using reforming (conversion) of hydrocarbons with water vapor, in which the body is formed WITH2provided in the form of highly concentrated stream of gaseous CO2and where the amount of generated NOx is within accepted for conventional gas turbines.

Another object of this invention is the use of at least part of the synthesis gas generated in the specified process to produce electricity, to obtain products on the basis of the synthesis gas, particularly ammonia, methanol and/or dimethyl ether.

With regard to electricity generation, the real way to compete with conventional power plants, based singlebedroom is the emissions of carbon dioxide, because the exhaust gases after combustion contain only small amounts of carbon dioxide, which currently is not economically efficient to allocate from the gas mixture. Emission (emission) of nitrogen oxides (OXA), which varies depending on the process conditions, may also be part of the problem of emissions.

The main problem in reducing carbon dioxide emissions and OXA is to provide the desired reduction in emissions without unwanted decrease the efficiency of the process in relation to electricity generation. The first stage in assessing the main process from the point of view of the above requirements was the stage of a synthesis gas. Having considered various ways, the inventors have found that certain advantages can give the APR, and it was decided in future to conduct a study to determine the best way to work APR. In contrast to what is stated in the above application Japan, it was found that ATP must be a reactor operating with an air supply, not a reactor using oxygen supply. Application of ATP, apparently, gives some advantages from the point of view of degrees of freedom. So the working pressure can be determined from Koh is OK and, finally, the synthesis gas produced in the Asia Pacific region, may be relatively poor gas suitable for gas turbines and comparable with the fuel mixtures used in the already approved large industrial plants with combined cycle (JRCC).

Hydrocarbons that are applicable to such a process can be natural gas, naphtha, various petroleum distillates, etc. When using a reactor pre-reforming before ATP flexibility in the selection of raw materials is large enough. Preferred materials can be natural gas.

It was found that the problem OXA closely connected with the mode of operation of the gas turbine. Education OXA correlates with the temperature of combustion in the turbine. In accordance with this should include measures to regulate the specified temperature combustion. When designing the process, you can choose the composition of the gas mixture is combusted in the specified turbine so as to maintain the combustion temperature at the desired level, and still maintain at an acceptable level of electricity. The combustion temperature in the turbine is largely determined by the composition of the fuel gas. It was found that the ATP with the air supply gives poor Topli, what is useful to select the process air for the Asia-Pacific region at the outlet of the air compressor of the gas turbine and to compress it to the pressure required to enter in the Asia Pacific region. In addition, you can set the speed of the air flow, which provides the appropriate level of slippage of methane and composition of the fuel gas mixture that is compatible with an acceptable level of education of the OXUS in the combustion system of the gas turbine. Nitrogen emitted in the air from the gas turbine is returned to the turbine as a component of the fuel gas mixture, and thus largely supported the mass flow through the turbine.

If necessary, you can enter the fuel a small amount of water vapor to reduce the formation of OXA in the turbine. The burner design optimal design can also reduce the formation of OXA.

One of the alternatives in the concept of this invention is the combination of ATP with the reforming reactor - heat exchanger reformer). It was found that this option may increase the extraction of CO2in concentrated form.

In order to maximize the flexibility of the system, the basic concept of electricity generation can be combined with the synthesis of various what to use in the installation of the synthesis of methanol, and some part of the gas containing hydrogen and nitrogen, separated from the carbon dioxide after the reaction for the conversion of synthesis gas, can be used in the installation of ammonia synthesis. The only additional apparatus required for installation of the ammonia synthesis, will be conventional membrane separator (gas separation apparatus) and methanator (apparatus for the conversion of CO to methane), located in front of the reactor for the synthesis of ammonia.

In the scope of the invention includes the formation of synthesis gas in Asia Pacific with air flow, the heat generated synthesis gas and steam in the heat exchange. Then at least part of the cooled synthesis gas is processed in the reactor, the conversion of CO, which can be a single reactor or two reactors, the conversion of CO, one of which is low and the other high-temperature reactor. The specified gas stream is then processed in the plant extract carbon dioxide, which produce a flow of concentrated carbon dioxide and a stream representing a poor hydrogen-rich gas, which is at least partially burned in a gas turbine combined cycle to generate electricity. The air from ukazannogo pair, which together with the steam generated to the turbine, used in a steam turbine to generate electricity.

ATP can be combined with the reforming reactor - heat exchanger and raw materials can be distributed between the two devices, preferably 50-80% raw is served in the Pacific rim.

The reactor pre-reformer (prereforming) can be installed before the APR.

A minor portion of the steam produced in the process can be fed to the gas turbine for diluting the hydrogen-containing gas and the reduction in the result, the temperature of combustion in a gas turbine.

At least a portion of exhaust gas from the gas turbine can be returned to the ATP as a source of oxygen or mixed with air supplied to the gas turbine.

Part of the synthesis gas can be used for methanol synthesis, and the synthesis can be carried out in various ways, as described below in connection with the description of Fig.1.

Part of the gas from the apparatus for separation of carbon dioxide can be used to produce ammonia. In this case, one thread is fed to the membrane separator for the separation of hydrogen that is mixed with other hydrogen-containing gas stream so that mixed the hydrogen-containing gas, served then in the gas turbine.

This invention will be further explained and clarified on the basis of examples and descriptions of the accompanying drawings.

In Fig.1 shows a simplified process flow diagram of installation, reflecting the basic concept of electricity.

In Fig.2 shows a simplified flow diagram of the installation with this basic concept, combined with the installation of methanol synthesis and/or ammonia synthesis.

In Fig.1 shows an example implementation of this invention.

Gaseous hydrocarbons such as natural gas, is fed as stream 1, is heated and compressed, and then the pipe 2 enters the saturator 3, where it is mixed with water, formed in the process, 4, and fresh demineralized water supplied through line 4b. Then hydrocarbons, which at least partially saturated with water, served in Asia Pacific 6 in the form of stream 5. Compressed air is supplied to line 7 in the Asia-Pacific region 6. Optional before ATP can be located reactor prereforming. This will provide greater flexibility in relation to hydrocarbons. In this case, it may be acceptable high content of heavier hydrocarbons. At least part supplied in the Yes in the reactor. The reactor 6 can also be combined system, consisting of ATP and the reforming reactor - heat exchanger. The relative amount of hydrocarbons, which must be filed respectively in each of the reactors may vary within wide limits. Practically, the distribution of raw materials can be the following: 50-80% raw is served in the Pacific and the remainder in the reactor reformer - exchanger. The synthesis gas from the Asia-Pacific region 6 is cooled in the boiler (steam generator) 9 before serving in the installation conversion 12 as stream 11. This setting may consist of two conventional reactors conversion WITH - low-temperature (HT) reactor and high-temperature (VT) of the reactor, or may represent only one reactor conversion. The resulting gas mixture 13 is cooled, condensed water is removed in the apparatus 14, and the resulting gas mixture is fed in stream 15 in the absorber CO216, from which the CO2and absorbent served by pipeline 18 in desorber 19. Fresh absorbent material may be fed into desorber 19 as stream 20. The regenerated absorbent, for example the amine solution, is returned to the absorber 16 through the pipeline 20. Water is removed in the device 22 from the flow of CO221. Water, obrazuyte can be compressed and taken along the line 23 for subsequent use, for example, as a gas for injection into the oil and gas industry. The gas flow 17 of the absorber CO216 is composed mainly of hydrogen and nitrogen mixed with minor amounts of CO, CO2CH4. This stream can then be used as fuel for the gas turbine 24 combined cycle, in which air is injected 25. Optional can be fed into the turbine 24 water vapor 10 for reducing the number of OXA. At least part of the stream 17 can be used in a fuel cell to generate electricity in the form of direct current. If the electricity should be used for electrolysis, in the case of electricity generation in this form will not need to apply rectifiers. Exhaust gas from the turbine 26 24 transfers heat to water in the steam generator 27, and the water vapor from the steam generator can be overheated in the heat exchanger 30 before it in the stream 31 will be fed into the generator 32, which can also be fed pairs 10. The exhaust gas 28 from the steam generator can be recycled to the reactor 6, or may be combined with the 25 air supplied to the turbine 24.

In Fig.2 with the main process shown in Fig.1, the combined installation of ammonia synthesis and install sent may be selected from the stream 11 and fed into the methanol synthesis 35. Unreacted synthesis gas 37 may be returned to the stream of synthesis gas 11, and the resulting methanol can be discharged through the pipe 36. Synthesis gas 34 alternative can be processed in the gas-separating membrane apparatus for removing hydrogen and carbon dioxide, to obtain the initial mixture for the synthesis of methanol. To this mixture, optionally carbon dioxide from the stream 23. The other faction of membrane gas separation apparatus can then return to the stream 11.

The feedstock for the synthesis of ammonia can be extracted from the line 17. Stream 38 is first fed to the membrane unit 40 for supplying hydrogen 42 in line 39, in order to bring the ratio of H2:N2to 3:1; then, the gas mixture may be processed in methanator 43 before the ammonia synthesis apparatus 44, which is synthesized ammonia 45. Nitrogen membrane unit 40 recycle line 41 to line 17 to supply the hydrogen gas turbine 24.

Example 1 This example shows the effect of the present invention in relation to electricity generation, efficiency and the degree of extraction of carbon dioxide in the form of a concentrated stream in the process shown in Fig.1. In addition, this example shows the efficiency, the degree of Isle performance of the process with the use of primary - secondary reforming reactor to produce synthesis gas. This illustrative example shows the effects of recirculation of the gases leaving the turbine, the Pacific rim and it also shows the effect of combining ATP with the reforming reactor - heat exchanger. In the table the specified combination is denoted APR-RTO. The process according to this invention is compared using a combination of secondary and primary reactor reforming to produce synthesis gas, which is represented in the table BP/CR. The molar ratio of steam:carbon in the gas supplied to the reforming reactor, the table is denoted as pairs:S.

From the above results show that the method according to this invention, it is possible to allocate to 95.8% received CO2. In addition, the results show that within the concept of this invention, efficiency, power generation and the amount of emitted CO2change depending on the process conditions and the process is very flexible. Education OXA usually can depend on % hydrogen in the gas entering the gas turbine.

The present invention provides a method of obtaining purified carbon dioxide, suitable as the gas injected into oil reservoirs for the, this method gives poor fuel gas mixture on the basis of hydrogen, suitable for combustion in modern gas turbines. A small dilution with water vapor gas mixture supplied to the gas turbine, can be applied only when required reduction in the formation of the OXUS.

Claims

1. The way to obtain electricity, water vapour and carbon dioxide in concentrated form from a hydrocarbon feedstock, comprising the formation of synthesis gas in the autothermal reactor (ATR) with submission in the air, the heat generated synthesis gas and receiving the result of water vapor, characterized in that at least part of the synthesis gas is treated in the setting of CO conversion and the absorber and desorber of carbon dioxide to produce a concentrated carbon dioxide and poor hydrogen-containing gas, which is at least partially burned in a gas turbine combined cycle to generate electricity, and where the air from the gas turbine is served in the Pacific, and that the exhaust gases from the gas turbine are involved in the transfer of heat to produce steam, which together with the steam generated earlier in the process in ustanovka by p. 1, wherein using the installation reforming, consisting of ATP in combination with a reforming reactor - heat exchanger.

3. The method according to p. 1, characterized in that 50-80% of hydrocarbons are served in the Pacific, and rest of the raw material fed into the reforming reactor - exchanger.

4. The method according to p. 1, characterized in that before the APR using the reactor of the pre-reformer.

5. The method according to p. 1, characterized in that use only one installation of the conversion.

6. The method according to p. 1, characterized in that water vapor is served in a gas turbine for diluting the hydrogen-containing gas mixture.

7. The method according to p. 1, characterized in that the exhaust gas recycle from the gas turbine in Asia Pacific.

8. The method according to p. 1, characterized in that at least part of the exhaust gas from the gas turbine is mixed with air supplied to the specified turbine.

9. The method according to p. 1, characterized in that a portion of the synthesis gas is used to produce methanol, and that the rest of the synthesis gas is then treated in facilities located further along the technological scheme, before using it to generate electricity.

10. The method according to p. 1, characterized in that the part of the poor hydrogen-containing gas from the absorber deparate for to bring the ratio of nitrogen/hydrogen to the value required for the synthesis of ammonia, and returning the separated nitrogen in the main stream of hydrogen containing gas, and where the stream containing nitrogen and hydrogen in the ratio of 1: 3 is metastore before the synthesis of ammonia.

11. The method according to p. 1, characterized in that the part of the poor hydrogen-containing gas is supplied from the absorber of carbon dioxide for use as a fuel in a fuel cell producing electric power.

 

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