Systems, methods and compositions for producing synthetic hydrocarbon compounds
Abstract
FIELD: chemistry. SUBSTANCE: invention relates to a method of producing hydrocarbon compounds, which is characterised by that it includes the following: a) feeding water vapour with external supply of hydrogen gas and carbon dioxide gas into a first reverse conversion reactor, where the molar ratio of hydrogen gas to carbon dioxide gas is greater than one, in order to produce a first stream of synthetic gas which contains a mixture of at least carbon monoxide gas and hydrogen gas, water vapour and residual carbon dioxide gas; b) production of a second stream of synthetic gas from the first stream of synthetic gas through condensation and removal of at least a portion of water vapour from the first stream of synthetic gas; c) feeding the second stream of synthetic gas into a second water vapour reverse conversion reactor to produce a third stream of synthetic gas which contains a mixture of at least carbon monoxide gas and hydrogen gas, water vapour and residual carbon dioxide; d) production of a fourth stream of synthetic gas from a third stream of synthetic gas through condensation and removal of at least a portion of water vapour from the third stream of synthetic gas; and e) preparation of a mixture of at least hydrocarbon compounds from at least carbon monoxide gas and hydrogen gas from the fourth stream of synthetic gas. The invention also relates to a system for realising the said method. EFFECT: use of the invention reduces power consumption on producing hydrocarbons from synthetic gas. 20 cl, 1 tbl, 32 dwg
Term
Term ended
Expired 16 March 2026, 0.5 years ago.
- Priority and filed
- Granted
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- Today
20 claims: 6 independent, 14 dependent
- 1Способ получения углеводородных соединений, включающий в себя:a) подачу в первый реактор обратной конверсии водяного пара с внешней подачей газообразного водорода и газообразной двуокиси углерода, где молярное отношение газообразного водорода к газообразной двуокиси углерода превышает единицу, для генерирования первого потока сингаза, содержащего смесь по меньшей мере газообразной моноокиси углерода и газообразного водорода, водяного пара и остаточной газообразной двуокиси углерода;b) генерирование второго потока сингаза из первого потока сингаза конденсацией и удалением по меньшей мере части водяного пара из первого потока сингаза;c) подачу второго потока сингаза во второй реактор обратной конверсии водяного пара для генерирования третьего потока сингаза, содержащего смесь по меньшей мере газообразной моноокиси углерода и газообразного водорода, водяного пара и остаточной двуокиси углерода;d) генерирование четвертого потока сингаза из третьего потока сингаза конденсацией и удалением по меньшей мере части водяного пара из третьего потока сингаза и e) генерирование смеси по меньшей мере углеводородных соединений из по меньшей мере газообразной моноокиси углерода и газообразного водорода из четвертого потока сингаза.
- 2Способ по п.1, где рабочие температуры реакторов обратной конверсии водяного пара составляют между 350 и 500°С.
- 3Способ по п.1, где стадии с) и d) повторяют в одном или нескольких последовательно расположенных реакторах обратной конверсии водяного пара.
- 4Способ по п.3, где рабочие температуры реакторов обратной конверсии водяного пара составляют между 350 и 500°С.
- 5Способ по пп.1-4, где по меньшей мере часть двуокиси углерода отделяется от потока сингаза, находящегося в реакторе обратной конверсии водяного пара.
- 6Способ по п.5, где отделенная двуокись углерода подается в по меньшей мере один из реакторов обратной конверсии водяного пара.
- 7Способ по п.5, где по меньшей мере часть отделенной двуокиси углерода подается в первый реактор обратной конверсии водяного пара.
- 8Способ по пп.1-4, где двуокись углерода отделяется от смеси, генерируемой на стадии е), и подается в первый реактор обратной конверсии водяного пара.
- 9Способ по пп.1-4, дополнительно включающий подачу двуокиси углерода на стадии е) в качестве части потока, образующегося в необязательном реакционном процессе, который превращает двуокись углерода в по меньшей мере моноокись углерода.
- 10Система для получения углеводородных соединений, включающая по меньшей мере следующие узлы:а) узел реактора обратной конверсии водяного пара, в который подается газообразный водород и газообразная двуокись углерода с образованием сингаза, то есть смеси по меньшей мере газообразного монооксида углерода и газообразного водорода, потока воды и остаточной газообразной двуокиси углерода;b) узел для генерирования смеси по меньшей мере углеводородных соединений из по меньшей мере газообразной моноокиси углерода и газообразного водорода;где узел реактора конверсии водяного пара включает a) первый реактор обратной конверсии водяного пара, в который подается газообразный водород и газообразная двуокись углерода, где молярное отношение газообразного водорода к газообразной двуокиси углерода превышает единицу, для генерирования первого потока сингаза, содержащего смесь по меньшей мере газообразной моноокиси углерода и газообразного водорода, водяного пара и остаточной газообразной двуокиси углерода;b) узел для конденсации по меньшей мере части водяного пара из первого потока сингаза для генерирования второго потока сингаза;c) второй реактор обратной конверсии водяного пара, в который подается второй поток сингаза для генерирования третьего потока сингаза;d) узел для конденсации по меньшей мере части водяного пара из третьего потока сингаза для генерирования четвертого потока сингаза, который подается в узел для генерирования смеси по меньшей мере углеводородных соединений.
- 11Система по п.10, где рабочие температуры реакторов обратной конверсии водяного пара составляют между 350 и 500°С.
- 12Система по п.10, где модуль реактора обратной конверсии водяного пара содержит более двух последовательно расположенных реакторов конверсии водяного пара с узлами для конденсации по меньшей мере части водяного пара из находящегося в них потока сингаза.
- 13Система по п.12, где рабочие температуры реакторов обратной конверсии водяного пара составляют между 350 и 500°С.
- 14Система по любому из пп.10, 11, 12 или 13, включающая один или несколько разделяющих узлов, каждый из которых предоставлен после реактора обратной конверсии водяного пара и перед последующим реактором обратной конверсии водяного пара или узлом для генерирования смеси по меньшей мере углеводородных соединений, для отделения по меньшей мере части двуокиси углерода от имеющегося потока сингаза из по меньшей мере одного из реакторов обратной конверсии водяного пара и входящего в следующий реактор обратной конверсии водяного пара или узел для генерирования смеси по меньшей мере углеводородных соединений.
- 15Система по п.14, где удаленная газообразная двуокись углерода подается в по меньшей мере один из предшествующих реакторов обратной конверсии водяного пара.
- 16Система по п.15, где по меньшей мере часть удаленной газообразной двуокиси углерода подается в первый реактор обратной конверсии водяного пара.
- 17Система по п.10, 11, 12 или 13, дополнительно содержащая разделяющий узел для отделения двуокиси углерода от потока, имеющегося в узле, для генерирования смеси по меньшей мере углеводородных соединений, где поток содержит смесь по меньшей мере углеводородных соединений и двуокиси углерода, и где отделенная двуокись углерода подается в первый реактор обратной конверсии водяного пара.
- 18Система по п.14, дополнительно содержащая разделяющий узел для отделения двуокиси углерода от потока, имеющегося в узле, для генерирования смеси по меньшей мере углеводородных соединений, где поток содержит смесь по меньшей мере углеводородных соединений и двуокиси углерода, и где отделенная двуокись углерода подается в первый реактор обратной конверсии водяного пара.
- 19Система по п.10, 11, 12 или 13, дополнительно содержащая a) узел для генерирования моноокиси углерода, образующейся путем необязательного реакционного процесса, который превращает двуокись углерода в моноокись углерода, и b) узел для подачи имеющегося потока а) в узел для генерирования смеси углеводородных соединений из по меньшей мере газообразной моноокиси углерода и газообразного водорода.
- 20Система по п.14, дополнительно содержащая a) узел для генерирования моноокиси углерода, образующейся путем необязательного реакционного процесса, который превращает двуокись углерода в моноокись углерода, и b) узел для подачи имеющегося потока а) в узел для генерирования смеси углеводородных соединений из по меньшей мере газообразной моноокиси углерода и газообразного водорода.
Independent claims20
334 paragraphs in 4 sections, as filed
Data related applications U.S.
This application claims the benefit of provisional U.S. Patent Application №60 / 661 923, filed 16 March 2005, and provisional U.S. Patent Application №60 / 678 174, filed 6 May 2005, each of which is incorporated herein by reference.
TECHNICAL FIELD OF THE INVENTION
The present invention relates generally to the field of hydrocarbon compounds, and more particularly to energy efficient processes and systems that produce fuels based on hydrocarbon compounds. In a preferred embodiment, the present invention relates to an apparatus and method for converting electrical energy into such fuels based on hydrocarbon compounds such as gasoline, kerosene, jet fuel and diesel fuel, among others, which are obtained by recycling combustion products carbon dioxide and water.
BACKGROUND
Although the idea of developing synthetic hydrocarbon fuels discussed, at least over the last 30 years, the need to produce them was not due to availability, ease of preparation, transportation and processing of fossil fuels. However, the world market of fossil fuels varies due to a number of factors, including the ever-increasing global demand for energy, the increase in the concentration of production in the oil-producing areas and increased concentration dependent on oil supplies of the importance of energy sources.
There are several drawbacks to using fossil fuels. Firstly, there is a limited amount of fossil fuels available which, after use can not be regenerated. Additionally, hydrocarbon fuels made from fossil fuels may contain highly undesirable sulfur, nitrogen and aromatics. When these fuels are burned, sulfur, nitrogen, and particulates are released into the air, which leads to the formation of acid rain and smog. Later on, the concerns focused on the impact of carbon dioxide emissions from the burning of fossil fuels as a cause of global warming.
There are several well-established methods of direct hydrogenation of gases such as carbon monoxide or carbon dioxide to produce hydrocarbon fuels. One of the most successful of which was developed in Germany in the 1920s Franz Fischer and Hans Tropsch.
In 1938, early German plants produce approximately 5 million barrels per year of diesel oil and gasoline using the Fischer-Tropsch process, which is based on the interaction of carbon monoxide and hydrogen over a catalyst to produce liquid hydrocarbons and water. The problem with this and other methods is that they use fossil fuels such as coal or natural gas to produce carbon monoxide. The use of such fossil fuels as the primary raw material is accompanied by many of the same drawbacks as the production of fossil fuels such as limited supply and emissions.
For this reason, it can be seen that there is a long-term need for a production system that recycles the products of combustion of fuels based on hydrocarbon compounds. It is to such a system and methods for producing hydrocarbon compounds primarily addressed by the present invention, with concentration on energy efficiency.
SUMMARY OF THE INVENTION
The present invention comprises systems, methods and compositions for the production of synthetic hydrocarbon compounds, particularly hydrocarbon compounds that can be used as fuels. Typically, the types of oxides, carbon monoxide or carbon dioxide, are converted into one or more hydrocarbon compounds containing carbon and hydrogen, including but not limited to, diesel, gasoline, kerosene, liquefied petroleum gas, or compounds found in natural gas. A particular method includes generating electricity using a flow of hydrogen and in the presence of at least part of the hydrogen from the hydrogen stream, the conversion of at least part of the carbon monoxide contained in a flow of carbon monoxide, a hydrocarbon compound.
In a preferred embodiment, entering the system with the input of carbon dioxide, the relative amount of electrical energy input required to convert carbon dioxide into the higher calorific value of combustion energy of hydrocarbon compounds, at the outlet is between 1.4 and 1.1. In another preferred embodiment of the system with carbon monoxide input (thus eliminating the need to convert carbon dioxide to carbon monoxide), the external electric energy needed to convert carbon monoxide is between 0.64 and 0.84 of the total heat of combustion hydrocarbon compounds. Thus, in one embodiment of the present invention uses carbon dioxide as starting materials require more electrical energy than the total calorific value of combustion of hydrocarbon compounds. In another embodiment of the present invention uses carbon monoxide as the raw materials, require less electrical energy than the total calorific value of combustion of hydrocarbon compounds.
In accordance with one aspect of the present invention, it is possible to manufacture a single installation of the order of five hundred thousand gallons of fuel per day, or even more if available sufficient quantities of electric power, carbon monoxide and / or carbon dioxide.
One aspect of the present invention comprises systems and methods comprising an electrolyser and a Fisher-Tropsch reactor, and in some embodiments, the reverse shift reactor and steam to produce hydrocarbon compounds. The present invention includes methods and systems for producing hydrocarbon compounds comprising conversion of at least a portion of one of the species of carbon oxide, including but not limited to carbon monoxide, into hydrocarbon compounds, via a Fischer-Tropsch in the presence of at least a portion of the hydrogen stream; and transferring at least a portion of excess heat from the Fischer-Tropsch process to one of the other process steps in the method or system in a part of a method or system requiring energy, or one of the other nodes in the system, for example, to an electrolyser or reverse shift reactor steam.
In the present invention, in some places, certain gases must be separated from the gas mixture, or for example, gas parameters such as temperature and pressure, must be changed to make one or both of these parameters are compatible with the previous or subsequent process. These separation or changes to gases of the present invention consume large amounts of energy. Another aspect of the present invention is that energy can be transferred within the invention to meet the energy requirements for the separation of gas and change settings.
One advantage of the present invention is energy efficient gas processing. There are generally two energy efficient thermodynamic processes used for gas processing. The first is an adiabatic process when all external work is converted to energy or gas obtained from it. The second is an isothermal process, when all external work is either converted into heat or derived from heat. By recycling external work through the distribution line for electricity and heat through several heat distribution lines, energy losses in gas processing are substantially reduced. It is also accompanied by the use of phase conversion of working fluids in heat distribution lines to for receiving or delivering heat.
The present invention includes systems and methods that provide the ability to produce a variety of hydrocarbon compounds, such as compounds for different fuels and a degree of control in the preparation of one or more specific types of hydrocarbon fuels that is not found in currently available methods of producing synthetic fuels. These and other objects, features and advantages of the present invention will become more apparent upon reading the following description in conjunction with the accompanying figures.
BRIEF DESCRIPTION OF DRAWINGS
1-4 illustrate generally the overall system of the present invention in accordance with preferred embodiments.
Figures 5-6 illustrate preferred embodiments of the present invention include systems in Figures 1-4.
7 shows various configurations of energy distribution lines of the present invention.
8 shows the principle of operation of unit RWGS reactor (conversion reactor steam) in accordance with a preferred embodiment of the present invention.
9 illustrates a three-stage RWGS reactor with carbon dioxide recycling, in accordance with a preferred embodiment of the present invention.
10 shows an RWGS reactor with a heater in accordance with a preferred embodiment of the present invention.
11 shows the principle of the FT reactor assembly according to a preferred embodiment of the present invention.
12 shows a two stage FT reactor, according to a preferred embodiment of the present invention.
13 illustrates an FT reactor with a water condenser according to a preferred embodiment of the present invention.
14 shows a portion of the hydrogen unit of the present invention, electrolytic cell in accordance with a preferred embodiment.
15 illustrates an example of electric power supply to the electrolytic cell of the present invention in accordance with a preferred embodiment.
16 illustrates various winding of phase shifting transformers.
17 is a graph of cell voltage in accordance with a preferred embodiment of the present invention.
18 shows a further fuel processing system according to a preferred embodiment of the present invention.
Figure 19 illustrates a combustion system according to a preferred embodiment of the present invention.
20 illustrates a block diagram of an energy efficient electro-mechanical gas separation process.
21 shows adiabatic machines according to a preferred embodiment of the present invention.
22 shows an apparatus for the isothermal pressure changes of the gas mixture in accordance with a preferred embodiment of the present invention.
23 illustrates a combination condenser and evaporator according to a preferred embodiment of the present invention.
24 illustrates the distribution line and the recycling of electrical energy in accordance with a preferred embodiment of the present invention.
Fig.25-26 illustrate the recycle line and heat distribution in accordance with a preferred embodiment of the present invention.
27 shows a cooling circuit for FT reactors according to a preferred embodiment of the present invention.
Figure 28 shows the introduction of steam / water in the electrolytic cell in accordance with a preferred embodiment of the present invention.
29 shows the main control circuit RWGS assembly in accordance with a preferred embodiment of the present invention.
30 shows the main control circuit unit CFT according to a preferred embodiment of the present invention.
Figure 31 shows the control of hydrogen supply RWGS assembly in accordance with a preferred embodiment of the present invention.
32 shows the control of hydrogen supply node TF in accordance with a preferred embodiment of the present invention.
Detailed description
The present invention comprises systems, methods and compositions for producing hydrocarbon compounds. Complete combustion of hydrocarbon fuels like coal, natural gas, liquid petroleum gas, ethanol, methanol, gasoline, kerosene, diesel fuel, and other known fuels, leads primarily to the production of two basic substances - carbon dioxide and water. During the combustion of such fuels, the main reaction is as follows:
CnH2n + 2 + (n + (2n + 2) / 2) · O2 → combustion energy (the total calorific value) + n · CO2 + (2n + 2) / 2 · H2O (water). (1)
For example, the average value for n = 10, is made 10% more moles of water than carbon dioxide. The amount used is the sum of the moles of oxygen per mole for oxidizing carbon and a half mole plus 10% to oxidize hydrogen, 1.55 moles in all. As used herein, "gross calorific value" (HHV) is the amount of heat produced by the complete combustion of a unit quantity of fuel when all products of the combustion are cooled down to the temperature before the combustion and the water vapor formed during combustion is condensed.
The present invention described herein, the products of combustion, carbon oxides and hydrogen are recombined in hydrocarbon compounds, such as transportation fuels, including but not limited to, diesel and gasoline. It is also possible to recombine as other compounds and compositions such as natural gas or liquefied petroleum gas. As used herein, hydrocarbon compounds include hydrocarbon compounds that may be used as an energy source such as fuels.
The hydrocarbon compounds may be prepared using the Fischer-Tropsch process. In this part of the method and system, carbon monoxide (CO) and hydrogen are ideally reacted as follows:
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wherein (-CH2-) is a building block for polymerization in the form of longer carbon chains. The primary products of this polymerization are linear paraffins, CnH2n, plus two hydrogen atoms to complete any chain at the ends. In this reaction, one hydrogen molecule is used for formation of hydrocarbons, plus approximately 10% for completing chains at the ends, and another hydrogen molecule is used for the recovery of carbon monoxide to carbon.
There are various methods for producing carbon monoxide from carbon dioxide. One method for this is a chemical process called reverse shift reaction of water vapor (RWGS). This reaction is as follows:
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In this reaction a hydrogen molecule is needed to recover the carbon dioxide to carbon monoxide.
For the reactions shown here, to produce hydrocarbon compounds used ratio of 1.1 + 1 + 1 = 3.1 hydrogen moles per one mole of carbon dioxide. If water is to serve as a hydrogen source, calculation may be as follows:
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In an ideal situation, the released amount of oxygen is the same amount as is consumed in combustion thereby completing the recycling process. The methods and systems considered here, all the water used or a portion thereof may also come from external sources. Various methods can be used to produce hydrogen from water, for example the electrolysis of water can be used for producing hydrogen, to produce hydrogen, photosynthesis may be used, as well as the heating of water to produce hydrogen. In a preferred embodiment, the electrolysis of water is chosen, although other methods of producing hydrogen are known to those skilled in the art and may be seen in the present invention.
One aspect of the present invention comprises systems and methods comprising preferably an electrolyser, a reverse shift reactor steam and Fischer-Tropsch reactor for producing hydrocarbon compounds. The present invention includes methods and systems for producing hydrocarbon compounds comprising conversion of at least a portion of one of the species of carbon oxide, including but not limited to carbon monoxide, into one or more hydrocarbon compounds by Fischer method Tropsch process in the presence of at least a portion of the hydrogen stream and transferring at least a portion of excess thermal energy from the Fischer-Tropsch process to one of the other process steps in the process requires energy, or one of the other units in the system, e.g. in an electrolyser or a reverse shift reactor steam.
The cell can be used to separate water on the hydrogen gas stream and a stream of oxygen gas.
The method may further include the conversion of various kinds of carbon oxides, including carbon dioxide. This step is the conversion of one or more species of carbon oxides can include carbon dioxide conversion in the inverse conversion process steam (RWGS). The conversion of CO2 takes place in the presence of hydrogen, and hydrogen may be provided on at least part of the hydrogen from the hydrogen stream from the electrolyser. The conversion of carbon dioxide to carbon monoxide may be accomplished by any means known to those skilled in the art and such processes are provided by the present invention.
Carbon monoxide stream for the present invention can be provided from any source, for example, the source may be a stream of carbon monoxide from a separate source, outside the present invention. A second source of carbon monoxide is carried out as part of the effluent stream from the optional reaction process converting carbon dioxide, among other species, carbon monoxide. Carbon dioxide stream for this process may come from a source such as carbon dioxide waste from a source outside the present invention.
The effluent from the Fischer-Tropsch process may be exposed to increasing quality, improving the spectrum of hydrocarbons into the hydrocarbon compositions desired, such as various liquid fuels. As used herein, "improving quality", "further processing" and "refining" or "improve the quality" "further processed" and "refine" are used interchangeably and mean division, separation, purification, or differentiation in some way by chemical or physical characteristics of various hydrocarbon compounds present in the synthesis reaction in the Fischer-Tropsch reactor, for example, fractionation and conversion of the compounds into useful products or raw materials for other methods. Examples of conversion processes include, but are not limited to, oligomerisation, hydrocracking, isomerisation, aromatization, hydrogenation, hydroisomerisation, and alkylation.
As used herein, "C 3 compound" means a compound having three carbon atoms. For example, propane, to represent a C3 hydrocarbon compound.
As used herein, "C4 compound" means a compound having four carbon atoms. For example, butane is to be a C4 hydrocarbon compound.
As used herein, "C5 + compound" means a compound having five or more carbon atoms. For example, hexane, octane, and compounds such as benzene, must be a C5 + hydrocarbon compound.
In one embodiment, the present invention describes systems and methods to produce hydrocarbon compounds from the products of combustion of fuel (carbon monoxide), and it includes supplying a quantity of electricity, such as electricity from a nuclear reactor, a plant using a portion of this quantity of electricity to produce a hydrogen stream from water; and reacting at least a portion of the products of fuel combustion, carbon dioxide and carbon monoxide in the presence of at least part of the hydrogen from the hydrogen stream to produce hydrocarbon compounds, where the use of electric energy is minimized by recycling energies consumed and released in various processes.
In a preferred embodiment, the methods and systems of the present invention converts electric energy into entryway to the heat of combustion of hydrocarbon compounds combustion energy output in a ratio of between 1.4 and 1.1, when carbon monoxide as the methods and systems used dioxide carbon, and it is between 0.64 and 0.84 when carbon monoxide is the carbon monoxide, or in the methods and systems without conversion of carbon dioxide to carbon monoxide.
In one embodiment of the present invention, electricity is used for the conversion of carbon dioxide and / or carbon monoxide and water into hydrocarbon compounds comprising carbon and hydrogen, wherein a water electrolyser is used to supply hydrogen to the conversion process. Carbon dioxide can be supplied from outside the process, and converted to carbon monoxide for further use in the methods and systems of the present invention. Carbon monoxide may also be fed into the process from the outside, and can be fed a mixture of carbon oxides.
Systems, methods and apparatuses of the present invention may include a number of subsystems, each of which increases the overall efficiency and productivity of the overall process, system or plant. For example, the present invention can include a source of electrical energy, an electrolyser, RWGS reactor, and FT reactor apparatus for further processing.
In one embodiment of the present invention has a source of electrical energy generated by the heat of the nuclear reactor. One example is the fast breeder reactor. This reactor can be filled once processed nuclear waste, and then its active zone can be recycled to the processing plant. This gives the advantage of increasing the energy output from the world's uranium reserves are about 25 times or so. Under typical processing intervals of five years, there is enough initial fuel to power the present invention until the end of the useful life of the physical units. Alternatively, the energy can be achieved by thermal conversion of waste nuclear reactor thermochemical method or other sources, including electricity that does not use fossil fuels, such as hydroelectric power, solar energy, ocean waves, wind, tides and currents and a combination of any of these sources.
Electrical energy can be used for water electrolysis to produce hydrogen and oxygen. In some embodiments, the electrolyser may need a sufficient amount of heat for operation. This heat, together with water for operation can be provided by steam generated elsewhere in the plant.
Although hydrogen can be produced in the usual electrolysis of water using electrodes may be used and other methods, including the thermolysis of water (for example using waste heat from nuclear reactors), thermochemical processes, and combinations of these methods. Oxygen produced in the electrolyser may be directed for use outside the system.
A method of electrolysis of water to produce hydrogen preferably includes an electrolyser having bipolar electrodes and a cell average operating temperature over 100 ° C or 130 ° C, where the internal pressure in the cell is greater than 10 bar or over 20 bar. Other embodiments include a current density of 3000 A / m2, the use of packet cells with voltages over 60 V, and / or the use of alternating current rectifier with an output voltage ripple of less than 3%.
In the apparatus, there are numerous uses for hydrogen produced in the electrolyser. Among them, hydrogen and carbon dioxide can be used together in the RWGS reactor to produce syngas, a mixture of carbon monoxide and hydrogen.
The source of carbon dioxide for the present process is the installation emitted carbon oxides such as carbon dioxide or carbon monoxide as a by-product, in particular an installation that should reduce its carbon oxide emissions. Examples of such devices include a blast furnace used to produce steel, and fossil fuel power plants using coal or gas to produce electricity. Carbon dioxide, carbon monoxide or carbon oxides or a mixture thereof may be provided by any method, including but not limited to, an external feed from any source.
The method of conversion of carbon dioxide to carbon monoxide is carried out by using a RWGS reactor. One aspect of the present invention comprises methods and systems wherein carbon dioxide and hydrogen are fed to the reactor RWGS and there is substantially complete conversion of carbon dioxide to carbon monoxide, e.g., greater than 70% conversion, more preferably greater than 80%, and still more preferably more than 90%. The output stream or effluent from the RWGS reactor comprises carbon monoxide and hydrogen at a ratio of H2 / CO ranging from zero to three. Also included means for separating the carbon dioxide at the outlet and the recycling of carbon dioxide to the input. Other preferred embodiments may include that the operating temperature is between 350-500 ° C, which provides for separation of water vapor by condensation and which can be coupled sequentially in a series of more than one reactor. One embodiment may include an intermediate separation of steam between the reactors connected in series RWGS.
As a byproduct RWGS reactor water is obtained, which can be used as starting materials for the cell.
Effluent syngas, which is typically a mixture of carbon monoxide and hydrogen and some residual carbon dioxide, is introduced from a RWGS reactor to the reactor FT. Additional hydrogen may be added to the synthetic gas or carbon monoxide, as required for the desired yield of products from the FT reactor. It is also possible to use carbon monoxide, such as waste carbon monoxide from existing industrial processes, and combine this carbon monoxide with hydrogen instead of syngas stream produced RWGS reactor, or in addition thereto. Position aspects of the present invention include methods that use carbon monoxide without the need for an intermediate step of conversion of carbon dioxide to carbon monoxide, thereby bypassing the RWGS process.
Installation FT of the present invention which may include more than one FT reactor, primarily provides conversion of carbon monoxide and hydrogen to hydrocarbon compounds, at proportions that are desired, for example, conversion more than 70%, more preferably more than 80%, and more preferably greater than 90%. In the present invention, methods and systems provide that the reaction heat removal occurs at substantially isothermal conditions. In addition, the hydrogen supply is controlled, for example, for minimum production of methane and ethane. Other embodiments include that provides separation at the outlet of steam and gaseous hydrocarbons using condensation caused by change of both temperature and pressure, and that more than one FT reactor may be connected in series or in a row, or more than one reactor, operating at substantially different temperatures and associated operating conditions.
The catalyst for the FT reaction can be a metal such as iron, cobalt, nickel, and combinations thereof; a metal oxide such as iron oxide, cobalt oxide, nickel oxide, ruthenium oxide, and combinations thereof; support-type material such as alumina or zeolites; metal on the carrier, mixed metals, metal oxides, mixed metal oxides, and combinations of these catalysts, or other catalysts known to those skilled in the art.
The main product of the output FT reactor is a mixture of hydrocarbon compounds with a byproduct of water that can have a variety of applications, for example, be introduced into the electrolytic cell. FT reaction is highly exothermic and heat can be used in a variety of ways. For example, at least part of the heat can be removed by a water stream that is converted into steam when that steam is then introduced into the electrolyzer, if necessary.
The mixture of hydrocarbon compounds, leaving the FT reactor may be fed to a plant for further processing, which may be similar to existing plants for processing of hydrocarbon fuels or to be in many ways simpler, since no removal of sulfur or nitrogen compounds. Some amount of hydrogen compounds can be used in this method, additional processing, refining, to give compositions containing combustible compounds. Such compositions can be used as fuel.
During further processing are fuel compositions for vehicles of the desired quality, which can include high-octane gasoline and diesel fuel of a composition reducing or even eliminating the need for additional processing in motor fuels. The fuel compositions produced from the present method eliminates many of the disadvantages of processing crude oil, i.e. these compositions have no sulfur content, no nitrogen content, and aromatics content. However, they have high bulk density and specific energy, excellent resistance to thermal oxidation processes, are fire safe (i.e., they are hard to ignite), and have good properties at low temperatures.
The present system further provides for methods using separators for separation of gases in gas mixtures, for example, in a new and form the subject invention, a combination of heat exchangers and compressors / expanders. The systems may include the use of compressors or expanders with heating or cooling gas mixtures to the required states for the condensation of the selected gas in a mixture, wherein expanders and compressors are used to condition gas mixtures to the desired temperatures. The systems may use heat exchangers for condensation or evaporation of a selected gas, with phase conversion of a cooling fluid until its vapor or steam as appropriate. Other embodiments include methods comprising phase conversion of a working fluid, which is used for heating or cooling, along with either compression or expansion of gases with. Heat machines, for example, heat pumps using a compressor, can be used to move heat from a low temperature region and high temperature region can be used teploudaliteli using an expander-generator (electric power generation).
The present invention provides energy efficient systems that use energy, such as electric energy, for the conversion of carbon oxides, including carbon dioxide and carbon monoxide, and water into hydrocarbon fuels on a commercial scale. The system of the present invention also includes the use of residual internal heat for electricity generation, electricity is used for the conversion of carbon dioxide, carbon monoxide and water into hydrocarbon fuels. The system may also comprise compressors and expanders used for conditioning and for separation of gas mixture components.
The present invention further includes one or more subsystems includes transferring heat or steam between components of the system, including the transfer of heat from the reactor (s) FT electrolyser either directly or via conversion to electric energy, introducing water pairs of reaction from the reactor (reactors) CFT for condensation in an electrolyser, transferring heat from the reactor (s) CFT for use in the heat consumers through the use of methods of heat transfer, transferring heat from the reactor (s) FT reactors RWGS together with the corresponding processing gas to inlet / outlet, heating reaction water from RWGS reactors and / or TF for use in an electrolytic cell and supplying heat to gas-phase conversion of the liquid for cooling and heating of process gases and liquids.
The present invention also includes the use of gas expanders with electric generators and gas compressors with electric motors for receiving and introducing electrical energy, i.e. recycling, to reduce substantially overall energy use in the plant.
The present invention, as shown in Figure 1, includes, in general, the process of the present invention 100, which is a process for the conversion of one or more species of carbon oxides into hydrocarbon fuels F using electricity as the energy input E. The output fuels F can include, for example, gasoline, diesel fuel and jet fuel. 1-4 illustrate the overall high-level system of the present invention 100, each of which embodies its own novelty and a step of the invention, as described below, and together form a preferred method of the present invention 100 as shown in Figures 5 and 6.
Although preparation of hydrocarbon fuels from coal and gas is known, the use of electricity for driving the conversion previously excluded. Industry refrain from developing methods of producing fuels from carbon oxides using electricity, simply because the efficiencies were too low to justify the cost. Also, the efficiency of the present invention is greater than 60%, i.e. the ratio of the higher calorific fuels F to the amount of electricity E required to actuate the transformation (transformation) is greater than 60%, and more preferably greater than 80% . The inverse relation, it means that the amount of electric energy of about 1.7 times (1/60%) is lower than the total calorific value of the fuel F, and more preferably more than 1.25 times lower.
In another form of the present invention, high level 100, as shown in Figure 2, the present method includes the step of supplying power 200 that provides power to process conversion step 300 that converts the one or more species of carbon oxides to fuel F, and a step of supplying hydrogen 400 providing hydrogen to efficiently implement the conversion 300 of the carbon oxides to fuel F.
Referring to the conversion step 300 converts carbon monoxide to fuel F, as shown in Figure 3, it can include at least two subsystems, a carbon monoxide conversion step 320 for the conversion of carbon monoxide to fuel F, and a second step conversion of the carbon dioxide 360, but the method of the present invention 100 be presented with carbon dioxide. The conversion step 360 converts carbon dioxide to carbon monoxide, and then enters the carbon monoxide in the carbon monoxide conversion step 320. Alternatively, or in combination with the carbon monoxide from the conversion step 360, carbon monoxide can be administered to conversion step 320 from outside the system of the present invention 100, for example, from the waste stream of carbon monoxide in the installation, or a mixture of CO2 and CO can be administered to step 360 to convert CO2 to CO.
Both conversion steps 320, 360 are used, at least part of the hydrogen from hydrogen input step 400 to perform corresponding conversion. In one preferred embodiment, the present invention is represented by 100 as the carbon dioxide and carbon monoxide, and thus, the method of the present invention 100 utilizes both conversion steps 320, 360.
4 shows an intermediate stage 500 located between the output of the conversion step 300 converts carbon monoxide and the final product fuels F. Typically, the product of the output of the conversion step 300 is a spectrum of hydrocarbon compounds HC, out of which only some can be used in fuels. Thus, additional processing comprising the steps 500 to improve their quality to a desired composition, for example, fuels F.
Preferred embodiments of various subsystems of the present invention 100 are shown in Figures 5 and 6, and includes recycling method and apparatus for the production of hydrocarbon fuels from the products of hydrocarbon fuel combustion. The present invention includes the energy input step 200 providing energy to the process, including the generation of electricity using nuclear power reactors 210, preferably using fast breeder reactors consuming existing nuclear waste. The reactor 210 can be loaded once processed nuclear waste, and then its active zone can be reprocessed, such as installing recycling 220, for extending the energy of the world's uranium reserves, about 25 times or more. As will be appreciated by those skilled in the art, at typical re-processing intervals of five years, there is enough initial fuel to power the present invention until the end of its useful life.
Electricity is supplied to the hydrogen input step 400, which may include electrolysis of water in the electrolyser 410 to form streams of hydrogen and oxygen. Heat, also called thermal energy, from other subsystems of the process of the present invention 100 can be supplied at this stage to improve efficiency. It can be supplied either directly to heat water when required or through conversion to electricity for electrolysis. Some known types of electrolysers 410 may require some heat for operation. This heat, together with water for electrolyser operation is preferably supplied primarily by steam generated elsewhere in the system of the present invention 100. There are numerous uses hydrogen produced in the electrolytic cell 410 in the system, although it is preferred that most of the product oxygen if not all, of the applications received for generating systems is the present invention 100.
At least a portion of the hydrogen is introduced into the conversion step 300, which, if the system 100 of the present invention deals with both carbon monoxide and carbon dioxide is a two step process. The first method uses a carbon dioxide conversion step 360, including a steam conversion process, namely a reverse shift reactor steam (RWGS) 362, to combine hydrogen and carbon dioxide to produce syngas, a mixture of carbon monoxide and hydrogen. As a byproduct produced RWGS reactor steam which is introduced into the electrolyzer 410.
The source of carbon dioxide for the conversion step 360 may be an installation emitted carbon dioxide as a byproduct, in particular, the installation for which it is necessary to reduce carbon dioxide emissions. Prime examples of such plants are blast furnaces used for steel production, and thermal power plants on fossil fuels, coal or gas to produce electricity.
Carbon dioxide can come in a mixture with carbon monoxide. This mixture can be either separated into carbon dioxide and carbon monoxide or processed as a mixture in the reactor 362, the final conversion of carbon dioxide to carbon monoxide.
Then, synthesis gas is introduced to the carbon monoxide conversion step 320, including a Fischer-Tropsch process to combine carbon monoxide and hydrogen to produce a spectrum of hydrocarbons based on a double bond radical. Carbon monoxide conversion step 320 can include a Fischer-Tropsch reactor (FT) reactor 322. While the FT 322 can use the syngas from step 360, is also possible to use waste carbon monoxide from existing industrial processes, and combine this waste carbon monoxide with hydrogen, instead of syngas, produced by RWGS reactor 362, or in addition thereto. As is known, there are number of processes that produce carbon monoxide as waste, especially in combination with carbon dioxide.
In one preferred embodiment of the system of the present invention 100, only carbon monoxide is processed, (not carbon dioxide), and this virtually eliminates the need for a RWGS process 360. The system of the present invention 100 can also use a mixture of carbon dioxide and carbon monoxide as a waste from industrial processes, giving this mixture. Additional hydrogen may be added to the synthetic gas at the output stage 360 and / or carbon monoxide at the input stage 320, as required, to adjust the composition of the desired output product 322 FT reactor.
The main output of the FT reactor 322 product is a mixture of hydrocarbon compounds based on the radical - (CH2) -, and a byproduct is water, which is preferably introduced into the electrolytic cell 410. The FT reaction is highly exothermic, so heat is removed at least by means of feed water which is converted into steam, which can be used directly or indirectly as a source of energy for electrolyser 410.
The hydrocarbon compounds output from the FT reactor can be characterized as some kind of crude oil that the hydrocarbon compounds, like crude oil, can be processed using known techniques to obtain compounds of the fuel. Thus, the hydrocarbons are subjected to quality improvement or processed at step 500, which includes the additional step of recycling the fuel to obtain the desired compositions of fuels F. Step 500 can include apparatus for further processing (increasing quality) 510, which is similar, but generally simpler, with fewer processing steps needed, than existing systems for crude oil processing. Such processing technology known to those skilled in the art. Again, some amount of hydrogen from step 400 may be used in this processing method 500.
The present invention uses multiple energy distribution lines, contours recycling / feedback for gas flows and a medium of exchange of heat and electricity in the process. Overall results of various improvements in each of the subsystems of the present invention 100, and in the efficiency of the entire system, to create a system wherein preferably at least 60% of the energy input into the process (for example, from the electricity generated by the nuclear power plant) is ultimately It contains the highest heat of combustion from burning fuels produced at the output of F.
The system of the present invention 100 produces beneficial byproducts, as its outputs are fuels products and oxygen. In addition, the system of the present invention 100 provides a critical appearance properties so that it reduces the amount of carbon dioxide. Carbon dioxide is a greenhouse gas that is because it is the main cause of global warming, is the subject of a number of international treaties such as the Kyoto Protocol, and national and regional legislation.
As described, the final end products of the method of recycling of the present invention 100 are a plurality of desired fuel for vehicles, which can include high-octane gasoline containing no sulfur, and diesel fuel not containing sulfur with a composition reducing or even eliminating the need further processing in motor fuels. One advantage of the system of the present invention 100 is its ability to produce a variety of fuels based on hydrocarbon compounds. Another advantage is the level of control available to plant operators to alter the ratio of hydrocarbon compounds produced by setting specific parameters of the methods and system, for example, the relationship of carbon monoxide and hydrogen is introduced into the specific FT reactors. Varying amounts of the synthetic gas introduced into different types of FT reactors, it is possible to obtain different output relationship of diesel fuel, gasoline, kerosene and other fuels out of the total amount of synthetic gas inlet.
The system 100 of the present invention is described in more detail below, including preferred embodiments of the various subsystems of the present invention.
Distribution lines for energy
The system of the present invention 100 includes several energy distribution lines with two different types of energy lines - electric and heat. Examples of energy distribution lines used in the present system are shown in Figure 7. Use of at least one distribution line for electric energy (EDL). For example, one EDL is a conventional distribution line for electrical energy, three-phase alternating current in the normal operating voltage between phases in the 10-50 kV range, a range used in the commonly used electric power generators. However, there may be used other voltages as dictated by specific needs as would be clear to all skilled in the art.
Numerous generators and motors are connected to the EDL in this system. Generators are preferably of the synchronous type generators are usually controlled for matching the frequency, phase, and voltage amplitudes, so they can all be connected to the EDL in parallel. This type of control is used in the management of the existing electric power networks. The motors are preferably of the synchronous type motors for accountability and to realize higher efficiency, but may use other types of motors.
In a preferred system of the present invention 100, there are other energy distribution lines, distributing heat, or thermal energy (as opposed to electric energy) for installation. For heat distribution lines (HDL) in this system can accept heat from a heat sources, and deliver heat to heat consumers.
Conversion phase working fluid used for the heat distribution lines. Each line uses two reservoirs - one for liquid and one for vapor of this liquid, both of them are close to the boiling temperature and pressure of the working fluid. When necessary heat input, the pairs are selected from one half of the line, condensed and delivered to the liquid half of the line. The heat of condensation is released to the heat consumer. When there is a need for removal of heat, then liquid is taken, vaporized, and delivered as vapor to the vapor half of the line. External heat is consumed by evaporation of working fluid.
In a preferred embodiment, there are five distinct temperatures for each of the five heat distribution lines.
First HDL is preferably at the operating temperature of RWGS reactor 362, preferably in the range 280-800 ° C. In a preferred embodiment, the operating temperature of RWGS reactor 362 is approximately 400 ° C. When this temperature is preferred to use ethylene glycol as the working fluid or another fluid with a similar heat of vaporization and similar boiling pressure at 400 ° C. This first HDL is used at least to heat incoming gases into a RWGS reactor, and to deliver heat to this reactor itself, as the RWGS reaction is endothermic. In further description herein, this first HDL will sometimes be referred to in connection with this line as "RWGS-line" with a designation of its vapor portion "V", and its liquid part "L".
A second HDL is preferably at the operating temperature of the FT reactor 322, preferably in the range 180-350 ° C. It is preferred that the working fluid of this second HDL is water, as used in coal-fired and nuclear power plants. It is also possible to use a separate cooling loop for the FT reactor operating at higher temperatures using other working fluids, for example, ethylene glycol, and exchange some or all of its heat into this second HDL. In further description herein, this third HDL will sometimes be referred to in connection with this line as "FT-line" with a designation of its vapor portion "S", and its water part of "W".
A third HDL is at a temperature of water in the electrolyser 410. For example, it may be in a range 100-150 ° C, preferably in the range 130-140 ° C. The main purpose of this third HDL is powered electrolyser 410 with water and / or steam. This third HDL preferably uses water as the working fluid. In further description herein, this third HDL will sometimes be referred to in connection with this line as "E-line" with a designation of its vapor portion "S", and the aqueous portion "W".
A fourth HDL is at ambient temperature, at 25 ° C, in a preferred embodiment of the present system, but can be at other ambient temperatures at various locations and weather conditions of this system. The working fluid may be a conventional refrigerant used at such ambient temperatures. The primary use of this fourth HDL is the processing of incoming and outgoing materials. In further description herein, this fourth HDL will sometimes be referred to in connection with this line, as the "A-Line", with its steam part designation "V", and its liquid part "L".
A fifth HDL is preferably at the operating temperature of carbon dioxide separator 372 in Figure 8, preferably in the range from -50 to -55 ° C. When this temperature is preferred to use conventional refrigerants like ethylene. This fifth HDL is used for heating and cooling gases flowing to a separator for carbon dioxide and from it. In the description here is a line will sometimes be referred to as "line C", with its steam part designation "V", and its liquid part "L".
An additional source of thermal energy is available excess heat nuclear power, which can be used to convert it into electrical energy.
Balancing distribution lines for power
Distribution lines for energy must be balanced so that the incoming energy should be equal to the outgoing energy. Distribution line for delivering electrical energy to electricity for water electrolysis and numerous motors of the compressors and pumped. They receive electric energy from numerous gas expanders driving the electric power generators, including expanders converting heat energy released in the FT reactors or combustion residual gases. The remaining part of the electrical energy is delivered by an external source 210.
RWGS-line advantageously balanced heat pump, delivering energy from the FT reactor. The system 100 of the present invention include application of heat energy from this line by converting its vapor to liquid.
In a preferred embodiment, the FT-line is balanced by heat coming from cooling FT reactors.
In a preferred embodiment, the E-line is balanced by heat coming from cooling FT reactors.
In a preferred embodiment, the A-line is balanced by delivering energy to the environment. This line collects excess thermal energy not consumed by the process or converted into electricity. The primary use can be in space heating, especially in cold weather, by converting A-line vapor into liquid. If there is no need in this heat, then it can be dissipated to the environment using, for example, a conventional heat exchanger.
For economy of design, should be a typical temperature difference between the temperature of the environment - air or water - and the temperature of this line. Operating temperature (boiling point) in this line can be varied by adjusting the pressure.
In a preferred embodiment, the C-line is balanced by a heat pump bleed excess heat and delivering it to the A-line.
Power supply
Stage of energy supply 200 preferably includes power 210 that uses the heat generated by nuclear processes. Although can be used many types of nuclear processes, if not used for the fast breeder reactor type, then the installation would require the periodic supply of nuclear fuel.
The system 100 of the present invention does not use basic or excess heat of nuclear fission reactors, as to generate electricity can be used by other sources of energy. For example, the effectiveness of the system of the present invention 100 and the output requirements can be achieved not only by nuclear energy, but also, for example, by hydroelectric or wind generators, as there is no waste heat required from an external power source. Although not optimal, can be used with fossil-fueled power plants. The conversion of carbon oxides
The conversion of carbon dioxide
Conversion of carbon dioxide is preferably carried RWGS process 360. As shown in Figure 8, preferable carbon dioxide conversion system comprises RWGS reactor 362 that converts incoming carbon dioxide into carbon monoxide using hydrogen as a reducing agent.
The basic reaction is as follows:
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It is a reversible reaction, and its equilibrium constant is low. For this reason, in a preferred embodiment of the present invention, excess of incoming gases like carbon dioxide and hydrogen, is used to increase the amount of carbon monoxide.
The amount of hydrogen is enough for both (i) conversion to water inside the reactor, and for (ii) obtain a desired level of mixture H2 / CO (syngas) to be inserted into the FT reactor 322. In this embodiment, this ratio H2 / CO of about It is two, so the amount of hydrogen moles is approximately three times the number of moles of carbon dioxide at the inlet. Depending on the FT catalyst used, other values of H2 / CO when administered FT reactor are also acceptable.
The amount of carbon dioxide at the reactor inlet 362 is preferably sufficient to achieve complete conversion of incoming carbon dioxide at the selected operating temperature of the reactor 362. For example, in one embodiment, the RWGS process 360 has an operating temperature of 400 ° C, and a three-stage RWGS reactor with intermediate separation steam. With this structure requires about the same amount of carbon dioxide at the reactor inlet, as well as generally available incoming carbon dioxide, provided that the H2 / CO ratio on the output is near a value of 2. This additional amount of carbon dioxide, thus ensuring the recycling loop this reactor assembly as shown in Figure 8. This additional supply of carbon dioxide is not consumed in the reactor, but circulates through it to change the equilibrium conditions for as complete conversion of incoming carbon dioxide as possible or close to that. The two streams of carbon dioxide (fresh as well as recycled) can be mixed in a conventional gas mixer 366 or administered using separate nozzles or valves suitable design RWGS reactor.
The amount of carbon dioxide in the recycle loop depends on the amount of starting materials of hydrogen from the working RWGS reaction temperature and on the number of series-connected reactors with separation of steam between them. At lower receipt hydrogen or lower temperatures, or with fewer reactors in series, it has a substantially larger amount of carbon dioxide in the recycle loop, and vice versa. One advantage when there is minimal amount of gas in the recycle loop, is that there are lesser electric and heat losses needed to maintain gas circulation and separation.
RWGS reactor effluent 362 is first passed through a steam condensation section 368, and then through a carbon dioxide separator 372. In one embodiment, the steam condensation section can include a condenser (heat exchanger) followed by drum separator. The condensed water from the separator 368 can be introduced back into the electrolytic cell. Dedicated carbon dioxide is delivered to the mixer for the gas inlet 366. The direct product of the output of carbon dioxide separator 372 is a synthetic gas with a H2 / CO ratio approximately corresponds to that which is required mainly FT reactor 322 for the efficient conversion, and residual carbon dioxide, if available.
There are other well known methods for the conversion of carbon dioxide into carbon monoxide that can be used in the present invention without changing the functioning of the device.
Operating pressure in the reactors can be in the range 4-30 bar, 20-25 bar is preferred, GHSV-STP (Gas hourly space velocity at standard temperature and pressure) is 1500-15000, preferably 5000-8000.
Water vapor is preferably separated at ambient temperature or its vicinity, which leads to high separation ratio.
Branch of carbon dioxide from the output of the product can be traditional and modern methods. The predominant current methods include various methods of absorbing amines, as well as carbonate processes, pressure change with absorption, adsorption and penetration of gas, among others. In addition, it is possible to cryogenic separation by lowering the temperature and increasing pressure under appropriate processing conditions, so that only 15-35% of carbon dioxide may remain in the syngas, as a ratio to carbon monoxide, mol / mol, e.g., at a temperature from -50 to -55 ° C and a pressure of 50-100 bar.
More likely, the methods using cryogenics, methods mediated solvents such as Ryan-Holmes process, three-phase or methods such as CFZ (Controlled Freezing Zone), can be used to further lower the carbon dioxide. The remaining carbon dioxide is circulated through the previous steps or, better yet, mainly consumed under certain operating conditions in the TF node, and then more or less of it will go back to the input of the node. Furthermore, some of these methods may be used sequentially, for example, cryogenic liquefaction to separate most of the carbon dioxide, then either CFZ, or amine absorption to condition syngas to a desired carbon dioxide level of 3-10%, measured in mol / mol, compared with carbon monoxide. Before the cryogenic type separator should be carefully removed water vapor. Absorption dryer may be used such as is commonly used in cryogenic processes.
Another preferable carbon dioxide conversion system is shown in Figure 9 and comprises a three-stage RWGS. As shown, there are three steam separator sections, one after each reactor, and then a carbon dioxide separator at the end of the process.
RWGS reaction toward the formation of carbon monoxide is weak and therefore requires removal of at least one reactant.
To achieve conversions as close to 100% as possible, the system of the present invention 100 can use a three-stage RWGS reactor in conjunction with (i) steam removal on the output of each stage and (ii) an increase in the molar concentration on the input.
First, the hydrogen molar concentration is increased to such an extent that the resulting syngas will have greater than desired, the ratio H2 / CO for early Fischer-Tropsch reactor 322. In one example, this ratio is two or more.
To meet the RWGS reaction, the first RWGS reactor 382 in this embodiment is fed in a molar ratio of 3: 1, relative to the molar content of carbon dioxide at the inlet 384. One mole is used to recover carbon dioxide to carbon monoxide, and two moles are synthetic effluent for gas.
Then, the introduction of carbon dioxide is increased in the first RWGS reactor 382 by creating a recycling line 386 from the output, and circulating it without conversion. Approximately one more mole needs to be added in the circulating loop to one mole of carbon dioxide at the inlet to generate about 100% conversion in three RWGS reactors 382, 388, 394 connected in series with the construction as shown in Figure 9.
Carbon dioxide conversion system 9 based on the removal of water vapor and carbon dioxide separation. The first steam separator 392 removes water vapor from the gaseous effluent of the first reactor RWGS 382, and in doing so, creates conditions for the continuation of the conversion of carbon dioxide in the second reactor RWGS 388. Because carbon monoxide is not removed, the percentage of conversion in the second reactor 388 will be smaller than in the first reactor 382.
The second steam separator 392 removes water vapor from the gaseous effluent from the second reactor RWGS 388, and in doing so, creates conditions for the continuation of the conversion of carbon dioxide into the third reactor RWGS 394. Because carbon monoxide is not removed, the percentage of conversion in the third reactor 394 will be smaller, than in the second reactor 388.
The third steam separator 392 is located at the output of the third RWGS reactor 394. On the output of this separator effluent gas contains syngas to a desired ratio of CO / H2 and carbon dioxide. Thus, carbon dioxide is separated using a separator 396, and placed in recycling line 386 to combine in a gas mixer 398 with incoming carbon dioxide 384.
If syngas contains smaller amount of hydrogen than necessary for administration to the FT reactors, then additional hydrogen to be added from the cell 410.
Reactors RWGS
RWGS reactors, used in the present system of the present invention 100 can operate efficiently at a number of operating temperatures, although, as in the preferred embodiment uses 400 ° C. An exemplary catalyst is a KATALCO 71-5, manufactured by Johnson Matthey. Operating pressures can be in the range of 4-30 bar, with preference for higher values to reduce overall size of the assembly. Used GHSV-STP, which is equal to 1500-15000, preferably 5000-8000.
The reaction is endothermic and requires external heat. In a preferred embodiment, the system of the present invention 100 uses an isothermal operation (being within plus or minus 10% of the ideal operating temperature as measured in ° K), with external heat delivered into a reaction zone from an external source. One example of the heat delivery system 810 generally illustrated in Figure 10. Conversion phase working fluid is used to deliver heat at a constant temperature or its vicinity, in particular, RWGS-line. RWGS-line vapors are delivered to condenser coil 812. The vapors condense and release condensation heat, while maintaining phase conversion temperature. The remaining working fluid is released into the liquid part of the RWGS-line. Release heat consumed interacting gases within the reactor by the heat transfer processes.
Preferably, reactors 322, 388, 394 in Figure 9 have the same general construction, although the second and third reactors can be smaller than the first, as they convert to smaller amounts of carbon monoxide and carbon dioxide recycle gas mixture smaller volume.
RWGS assembly can process not only pure carbon dioxide but also a mixture of carbon dioxide and carbon monoxide. The mixture may pass through one, two or all three serially connected reactors, depending on the ratio of carbon monoxide to carbon dioxide. If this ratio is smaller than this ratio on the output of the first reactor under the conditions of pure carbon dioxide conversion, then all three will be used in the reactor. The difference will be to reduce the amount of hydrogen needed to reduce the amount of carbon dioxide. The same rule will determine if two or require only one reactor for processing of this mixture. Ultimately, if only carbon monoxide is supplied, then no reactors are required.
Alternatives - the conversion of carbon dioxide
As discussed, carbon dioxide conversion is preferably carried out by RWGS process 360. There are number of modifications to this RWGS process, which does not significantly alter the outcome - the production of carbon monoxide components of syngas.
For example, the reaction temperature may be lowered into the reactor. This will decrease the equilibrium constant, and will cause thereby increasing amounts of carbon dioxide in the recycling line, or the number of reactors connected in series, or the like, and others.
In addition, the reaction temperature can be increased, and then may be possible to reduce the number of reactors in a preferred embodiment from three to two or only one with a sufficient amount of carbon dioxide circulation to provide 100% conversion of incoming carbon dioxide.
It is also possible to reduce the quantity of gaseous hydrogen introduced in this way with a consequent increase in carbon dioxide in the recycling loop. It is also possible to reduce the amount of circulating carbon dioxide by using more than three reactors in series at the same temperature.
The heat of reaction should not be delivered isothermally, but rather can be fed either by heat exchange with fluid from the hot side, at an appropriate temperature, flow rate, among other parameters.
Other methods of conversion of carbon dioxide to carbon monoxide, and such processes may be used in the present system 100 of the present invention.
The conversion of carbon monoxide
Carbon monoxide conversion is preferably performed by FT reactor process 320. The reactor assembly is shown in Figure 11. Job FT reactor 322 is as follows:
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Dashes at (-CH2-) denote communication available for either adding hydrogen or for polymerization. There are numerous purely hydrocarbon and oxygenated hydrocarbon compounds produced in Fischer-Tropsch synthesis, depending on the type of catalyst used and the operating temperature, pressure and gas velocity in the reactor.
In one preferred embodiment, as an example, the reactor operates with a Cobalt catalyst at 220 ° C and produces a mixture of hydrocarbons, which after the increase in the quality of results, first of all, to a mixture of gasoline and diesel fuel in an approximate ratio of 1: 2.
In other embodiments of the present invention, at higher temperatures, e.g., about 330-350 ° C, more gasoline is produced, in a ratio of gasoline to diesel fuel of about 4: 1. Thus, by combining operation at different temperatures can be set to the ratio of gasoline to diesel fuel from 1: 2 to 4: 1. Establishing diesel fraction produced by the present invention includes adjusting the temperature, pressure and residence time (gas flow). The amount of residual hydrocarbons that is difficult to convert into desired liquid fuels varies, and generally is higher at higher temperature and lower at low temperature.
In one embodiment, a cobalt catalyst is used in a ratio of H2 / CO of 2.15, at an operating temperature of 220 ° C, a pressure of about 20 bar, and GHSV-STP, equal to 1500. The conversion of carbon monoxide to hydrocarbons is up to 75%. The pressure can vary between 10-30 bar and GHSV from 500 to 5000.
FT reactor 322 in Figure 11 produces both liquid hydrocarbons that is pumped to further processing, and gaseous hydrocarbons mixed with steam and input gases (carbon monoxide and hydrogen). The presence of input gases is due to incomplete conversion of syngas. For a more complete conversion can be used more than one FT reactor, in series with removal of steam and certain hydrocarbon gases between reactors. In one example of a preferred embodiment of a two-stage FT reactor is used to achieve higher conversion efficiency.
At the outlet of the reactor 322 the water vapor is separated from the gaseous effluent through a steam separator 324, then gaseous hydrocarbons with carbon numbers C5-C6 by a separator 326, and finally gaseous hydrocarbons with carbon numbers C3-C4 by a separator 328. These separation processes can be combined depending on the composition of gas mixtures before separation. The residual gas contains mainly natural gas compounds, methane CH4 and ethane C2H6, and residual gaseous carbon monoxide and hydrogen from syngas, and high amounts of unstripped carbon dioxide and C3 and C4 compounds.
In a preferred embodiment, most of the syngas is returned to the input of the FT reactor 322 through the recycle line, thereby improving conversion efficiency of incoming syngas into hydrocarbon fuels. This can be partially controlled by using a throttle or valve 332. This throttle is installed in the recycle line for the gaseous effluent and permits evacuation or removal of a portion of the effluent gas in equal molar proportions. In a preferred embodiment, a controlling parameter is the amount of natural gas compounds before pumping. The throttle is opened just enough to keep the number at a predetermined level. Other gases may be used for the same purpose.
The gas conditioner 334 in the recycling line can be provided to harmonize the temperature and pressure of the syngas coming from the RWGS assembly 360. Syngas is combined in a gas mixer 336 or a similar type of gas mixer 384.
Instead of syngas FT reactor 322 can be powered by an external source of waste carbon monoxide (from outside the system of the present invention 100) and hydrogen from the electrolyser 410, or by a mixture of these gases and syngas. Hydrogen is added on the input from the electrolyser 410 to adjust the H2 / CO ratio required for the FT reactor 322. In a preferred embodiment, this ratio H2 / CO is around two, and more specifically between 2 and 2.2.
Evacuates gases in this apparatus can be introduced into a burner-generator to produce electricity.
This FT assembly can be replaced with different designs of conventional Fischer-Tropsch reactor without altering the functions of this device. A more detailed preferred carbon monoxide conversion system is shown in Figure 12. Illustrates a system of two-stage FT reactor 340. In this assembly, there are two FT reactors 342, 344. The synthesis gas from the RWGS assembly, and a quantity of hydrogen from the electrolyser are introduced into the first FT reactor 342. A certain amount of liquid hydrocarbons is produced and drained from the reactor. The unconverted syngas, steam, residual carbon dioxide from the RWGS assembly, and all hydrocarbons produced in the reactor 342 that are gaseous at reaction temperature and pressure, are introduced into a steam separator 346. It is preferred to effect separation at ambient temperature, but other Temperature can also be used. It is possible that some hydrocarbon gases will be separated along with water. Then, residual water and hydrocarbons can be separated, as is usually done, for example by distillation or gravimetrically.
The residual syngas with some amount of hydrocarbon gases and residual carbon dioxide are introduced into a second FT reactor 344. A certain amount of liquid hydrocarbons is produced and drained from the reactor. The unconverted syngas, steam, residual carbon dioxide from the RWGS assembly, and all hydrocarbons produced in the reactor that are gaseous at reaction temperature and pressure, are introduced into a steam separator 348. It is preferred to effect separation at ambient temperature, but other Temperature can also be used.
In this position in the process are much smaller amount of syngas than the output FT reactor 342, and therefore the partial pressure of hydrocarbon gases with carbon number C5 and higher is larger, and they will condense along with steam in the separator to couple and C5 + 348. Cn is a hydrocarbon with n number of carbon atoms per molecule. Cn + means hydrocarbons with n or more carbon atoms per molecule. The condensed liquid is pumped out, and water is separated by a variety of known methods such as distillation or gravimetrically in a water separator 352.
The residual gases from the separator 348 are introduced into another separator 354 of hydrocarbons, including hydrocarbons with carbon numbers C3 and C4. They can be condensed and separated from this residual mixture, for example, 20-50 bar and at temperatures where most of such compounds are condensed. This temperature depends on amount of other gases in the gaseous effluent. When these amounts are large in comparison with the volume of separated gases can be used a low temperature, such as that used for the separation of carbon dioxide. Then may be separated not only C3 and Cn hydrocarbons, but also carbon dioxide. These gases can be easily separated from each other by pressure change and carbon dioxide recycled to the input of the RWGS assembly. The effluent syngas, components of natural gas, and residual carbon dioxide are introduced into the controlled discharge valve 332 (Figure 11). This discharge valve, under equilibrium conditions, the amount of syngas is substantially smaller than other gases, and therefore, whatever amount of mixture is not released, it will contain much smaller amount of syngas than is contained in the recycle loop. Presence of syngas in the recycling loop has the same effect on completion of conversion of the incoming syngas as presence of carbon dioxide in the recycling loop RWGS assembly. The amount of syngas in the pumped gases may also be used for controlling the ratio pump.
In other preferred embodiments may be used longer reactors to increase the percentage of conversion of synthesis gas, even at different operating parameters, to create a more desirable spectrum of produced hydrocarbons, like spectra at low temperature, about 220 ° C and the other about 340 ° C. Syngas can be directed in different amounts to reactors operating under different conditions to regulate composition of produced hydrocarbons, which in turn will affect the composition of fuels after improving the quality, i.e. on the relative amounts of gasoline, jet fuel, diesel fuel, and like.
FT reactor
The reaction is highly exothermic and requires substantial heat removal as the output product of the reactor is highly temperature dependent. In a preferred embodiment, phase conversion of water into steam in the FT-line is used to remove this heat, as illustrated in Figure 13. This leads to near isothermal operation of the reactor, and therefore, to the output of the product, since the output of products from this reactor is highly dependent on temperature, e.g., within 10 ° C.
Alternatives - the conversion of carbon monoxide
The conversion of carbon monoxide may be carried out by FT process 320. There are a number of modifications to this FT process that do not alter the output product, i.e. the production of hydrocarbon compounds out of syngas, but may significantly change the composition of the products obtained.
For example, reactor temperature can vary from 150 ° C to 350 ° C. Changes in the type of catalyst, catalyst bed type, pressure, residence time, and velocity of syngas will alter in varying degrees the composition of the products obtained. At higher temperatures, lighter hydrocarbon obtained composition. In one example, at 310 ° -340 ° C and using the circulating catalyst, 72% of the output product compositions comprise carbon number C5-C11, based on which petrol, 6% heavier hydrocarbons, 8% hydrocarbon gases, and 14% alcohols, ketones and acids.
FT assembly can be made to operate at different reactor temperatures by regulating water temperature and pressure in the FT-line, and pressure in the FT reactors and other components that affect separation of steam and gaseous hydrocarbons.
Type layer and the catalyst can also vary from time to time to match changes in operating characteristics. Two or more reactors may be used in the sequential assemblage and operate at the same or different temperatures, catalysts, and other operating conditions. Also, there may be two or more parallel lines of reactors, also operating at different or same conditions.
With this construction, installation, constructed with the system of the present invention 100 can respond to changing market needs over many years of operation.
Hydrogen generation
The present system 100 of the present invention further includes the step of introducing hydrogen 400 providing hydrogen to actuate the conversion 300 of the carbon oxides to fuel F. The cell is the preferred means for feeding hydrogen.
Part of an embodiment of electrolyser 410 is shown in Figure 14. It is preferred to use bipolar electrodes 412 for a package of the electrolytic cell with a high voltage and lower current. Electric current 414 flows through the surface of all bipolar electrodes into electrolyte 416, which causes electrolysis of water in each cell.
Each cell can be divided by a gas diaphragm 418. Hydrogen and oxygen are released on opposite sides of each bipolar electrode, collected in the space between electrode and diaphragm and pumped for use in the system 100 of the present invention.
In a preferred embodiment, the cell design is used with high current density, for example 5-20 kA / m2. In comparison with low current densities, for example, 1-3 kA / m2, this increase results in an electrolytic much smaller size, weight and cost. But this increased current density are high efficiencies due to the much higher overvoltage on electrodes and resistive losses in the electrolyte. Electrolyzers with high current density using the following constructional and operational parameters:
- The operating temperature is 130 ° C, and potentially up to 150 ° C, which decreases overvoltage potential on electrodes and decreases resistivity of the electrolyte;
- Operating pressure is in the range of 20-30 bar to decrease volume of evolving gases that is beneficial to electrolyte conductivity, and to decrease water vaporization and its recycling;
- Concentration of KOH in the electrolyte is about 30% by weight and
- The gap between electrodes can be made smaller by use of diaphragm materials for temperatures in the range 130-150 ° C.
Is it possible to obtain the cell voltage near its thermoneutral (isothermal) voltage with a high level of current. This means that if the supply of electrical energy is achieved by the thermoneutral potential, did not require additional cooling or heating the cells. If this potential is lower then require additional heat, and if the above - then require cooling.
The reaction in water electrolysis cell at high current density can be delivered in two ways, either traditionally as liquid, or by condensation of water vapor in the form of water directly in the cell or by a combination of water and steam. The choice depends on the specific design, depending on the current density, other auxiliary subsystem choice for the electrolyser, operating voltages, among others.
Selecting a high electrolytic current density leads to other effectiveness values in the overall plant due to lower temperature drops and especially pressure.
Electrical power electrolyser can use existing devices described herein. In a preferred embodiment, Figure 15 illustrates the use of several rectifiers connected in series, each fed from phase shifting transformers. This design results in a circuit with high efficiency rectifier, which converts AC voltage (AC) in the first EDL to DC (direct current) necessary for cells.
The high voltage electrolyser packet may be divided into multiple packets, working in parallel for convenience of construction, maintenance and safety. This can be done with a rectifier. Semiconductor rectifiers can be paralleled to carry higher current, or each of such parallel rectifiers can be connected to a single packet cells. This can be done with the transformers.
Referring to Figures 15 and 16, three transformers are used, but these transformers do not have to have any phase shift, and can be used in different amounts. High packets electrolytic cells can even be fed directly without any transformer if output voltage of the power plant is compatible with the voltage necessary for the package.
Phase shifting transformers use more than one phase on the input with phase shifts between phases not 0 ° or 180 °, but usually, 120 ° or 240 °, it is a conventional three-phase electrical distribution. In one example, transformer 432 with three input phases is fed by the distribution line for electric energy (EDL). The ratio between the phases shown in the vector diagram 434. This is a typical delta connection system.
The output (secondary) winding of one phase of the three-phase transformer 432 comprises typically two separate windings connected in series. A coil 436 is wound on top of one input phase winding, and the other 438 is wound on top of the other input to the phase winding. Phase of voltage in each secondary winding is in phase with the input voltage of the winding over which this secondary winding is wound.
By choosing the ratio of the number of turns or the conversion factor between the two windings and polarity can get a lot of the desired phase shift. Graph 442 shows the voltage conversion coefficient and polarity of the voltages converted from the corresponding input phase voltages of equal magnitude and phase shift of 120 °. The combined voltage in output phase XY is shifted in phase compared with the input voltage in phase XY. In this example, it is lagging behind. Graph 444 shows the change in the polarity of the output, which makes this phase shift advancing.
Rectifier
The present system may use a semiconductor rectifier is a typical three-phase rectifier. Instead Semiconductor rectifiers can also be used on the basis of vacuum diodes, which can straighten a much more current. Semiconductors can be connected in parallel using known circuits to obtain a reasonable separation of power semiconductors in parallel. The rectifier can also be made for more phases by adding more phase arms and connecting all phases from all phase shifting transformers in parallel.
Output voltage
Phase shifting transformers and rectifiers described herein are combined into a circuit shown in Figure 15. In a preferred embodiment, three rectifier circuits R are shown as connected in series, each fed from phase shifting transformers T. This circuit leads to a rectified DC voltage with very slight pulsation of voltage, 1.5% peak to peak, which is beneficial to optimize the parameters of all components in the electrical circuits of the electrolyser. There are other ways to create a connection, eg by a parallel connection of the three circuits. Another alternative is to use different numbers of circuits, with more or less phases and corresponding lower or higher pulsation of output voltage.
The resulting voltage is the sum of voltages from all three rectifiers. 17 illustrates, to scale, stress diagram 452 of one three-phase rectifier. During one period of the voltage distribution lines for electricity (360 °), there are six vertex straightened a sine envelope from the positive and negative half cycles of each phase. The depth of the ripple voltage is equal to cos (30 °) = 0,866, or 13.4% of the peak voltage. In the circuit with three rectifiers, the phase shift is maintained between phases leading or lagging 20 °. In this case, the depth of voltage pulsations is cos (10 °) = 0.985, or 1.5% of the peak value - the voltage diagram 454.
This pulsation is adequate for low current fluctuation in the electrolyser cells that, in turn, leads to higher utilization of the surfaces of cells and a lower cost of electricity for transformers and rectifiers.
The high voltage of the cell pack can be divided into several packets, working in parallel, for the sake of convenience, service and security, among other tasks. The same can be done with a rectifier. Semiconductor rectifiers can be connected in parallel to carry higher current, or each of such parallel rectifiers can be connected to a separate package of the cell. The same can be done with the transformers.
Additional processing
Typically, the output product of the conversion step 300 is a spectrum of hydrocarbons. It provides additional processing step 500 for increasing the quality of hydrocarbons to the desired mixture of fuels F. The process can use existing technologies to convert hydrocarbon streams from the FT assembly into desired fuels, and other products if so desired. 18 shows the entrances to and exits from such a facility. Typical units for improving the quality will involve hydrocracking of FT heavy ends (in the range of greases and waxes) to fuels primarily in the range of diesel fuel and gasoline. It should be noted that the need for processing installation in hydrogen can be preferably satisfied with hydrogen from the electrolyser.
Burner generator
In a preferred embodiment, the combustion system 520 is shown in Figure 19. The starting materials for the burner may be pumped gases from the FT reactor assembly, and / or residues of petroleum and / or natural gas compounds. All these compounds are burned in a gas turbine generator 522 with a relatively small portion of oxygen coming from the electrolyser. The output gases from the turbine exhaust are steam and carbon dioxide. Water vapor is separated into water and residue - carbon dioxide which is injected back into the gas mixer with incoming carbon dioxide. It is yet another gas recycling loop of the system 100 of the present invention.
The electrical energy derived generator injected back into the power line and further to the electrolyser.
As a result, there is a small amount of waste material exiting the system, or none at all, only the desired fuels and oxygen in an amount necessary for burning it.
The produced electrical energy is recycled back into production of hydrogen, this apparatus is less sensitive to incomplete conversion of syngas in the FT assembly. Also, because the carbon dioxide is recycled back to the input node RWGS, the device is less sensitive to separation efficiency. For the separation of carbon dioxide in the RWGS assembly.
Separation and processing of gas - a common part
In these methods, there are numerous places where certain gases must be separated from the gas mixture, or simply gas parameters, for example temperature and pressure, must be adjusted to make them compatible with the previous process step.
One advantage of this system is its energy efficient gas processing. There are two main energy-efficient thermodynamic processes used for gas processing. The first is an adiabatic process when all external work is converted to or from gas energy to it. The second is an isothermal process, when all external work is either converted into heat or derived from heat.
Those skilled in the art will appreciate that these are ideal processes. In practical applications, there are some changes in temperature, ideally isothermal process. These changes make the process nearly isothermal. As used herein, the term "isothermal" shall include an operation or process that is "almost", "about" or other such terms to modify the ideal isothermal operation, and more specifically relates to a change in absolute temperature measured in ° K, in a practical isothermal process in a range of plus and minus 10% from an ideal isothermal temperature. Similarly, in practical adiabatic processes, some of the thermal energy involved in addition to the ongoing work of the mostly foreign. Such "practical" adiabatic processes are similarly "near" and / or "approximately" adiabatic, and when it is involved heat energy is also in the range of plus and minus 10% of the amount of external work energy from the ideal process.
The present invention preferably includes one or more nodes to change the gas pressure "isothermally" that includes a range of plus and minus 10% from the ideal isothermal process temperature. The present invention preferably includes one or more nodes to change the gas temperature "adiabatic" that includes a range of plus and minus 10% from the ideal adiabatic process, as described above.
As shown in Figure 20, a block diagram of a universal gas separation using these two processes. First, three processes 610-614 conditioned gas mixture for separation of one or more of its components by condensation in the condenser 616. Then, three processes 618-622 conditioned residual gas mixture for further processing. The separated gas or gases are in the liquid phase in the condenser 616. If it is desired for further processing in the gas phase, some gases are evaporated in the evaporator 624, and then are conditioned for further processing by processes 626-630.
Each group of processes or 610-614 or 618-620 or 626-630 are identical to the principles of their functioning. They focus on conditioning of gases for adiabatic processing to avoid any conversion phase component of the gas mixture or a liquid state or a solid. Each process begins with establishing the isothermal pressure. Then the gas or gas mixture is processed adiabatically to change temperature. After this process, the final isothermal process changes pressure as required for further processing. In summary, pressure is changed isothermally, and temperature adiabatically.
21 shows adiabatic machines, one to increase temperature and pressure by compression using power from the electricity distribution line, and one to decrease temperature and pressure and generating power to that line. In a preferred embodiment, electric power line is used as both the source and recipient of energy delivered to the adiabatic processes or derived from them. Compressor 632 is preferably a turbine driven by an electric motor, and the expander 634 is also preferably a turbine driving a generator of electric energy. Such generator must be synchronized in frequency and phase of voltage in the electric power line and consistent with that voltage value, very similar to other generators used in electric power grid. May also be used and other types of compressors and expanders, except the type of turbine.
22 shows isothermal machines, one for pressure increase and one to decrease it. The machine is used to increase pressure compressor 636 driven by an electric motor, and the resulting gas mixture receiving power from the electric power line is compressed and cooled. The heat is removed by the refrigerator 638. In theory, the amount of heat removed is equal to the electrical energy from the electric power line. For large changes in pressure may be several isothermal pressure change devices connected in series. In this case, they are called interleaved compressors. They alternate with refrigerators.
The opposite process is used for the isothermal mind nsheniya pressure. In this case, the gas mixture is expanded and this reduces both its pressure and its temperature. The change of temperature compensated heating. Again, in theory, the amount of heat supplied to the mixture equals the amount of energy supplied to the electric power line electric generator driven by an expander 640. It is preferred to use turbines as both compressors and expanders, but can also be used and other types of .
The system uses coolers 638 and heaters 642 in the isothermal machines. They are essentially heat exchangers. For isothermal operation is preferred to use phase conversion of a working fluid for supplying or removing heat from the gases passing through these heat exchangers, and to them. This enables the system to operate with heat from about zero change in temperature.
Referring to Figure 7, there are shown several examples of energy distribution lines used in the present invention. The first is an electric power line that supplies power for all applications electrolyser and all electric motors - and gets its energy from all sources - and all internal power generators of electricity.
Other lines are heat distribution lines. They deliver heat or taking heat from various sources and heat consumers. Each line preferably includes two parts, a liquid portion and a vapor portion. When heat must be delivered from a line, then vapors are taken into a heat exchanger adapted to receive this heat, condense in this heat exchanger and release heat, and condensed liquid is delivered in the other half of the distribution line to heat. When heat must be accepted, the reverse process is used, the liquid evaporates as vapor.
In the present process, examples of temperatures at which the conversion phases are;
a) When the reactor temperature RWGS - in the distribution lines for heat RWGS (RWGS-line);
b) at a temperature of the FT reactors - in the distribution lines for heat FT (FT-line);
c) temperature of water in the electrolyser - a distribution line for heat E (E-line);
d) at ambient temperature - in the heat distribution lines A (A-line); and
e) at a temperature of carbon dioxide separation - a distribution line for heat C (C-line).
The following are examples of working fluids for these lines:
a) Ethylene for RWGS-line;
b) Water for FT-line, or its substitute at higher temperature, like ethylene glycol;
c) Water for E-Line
d) Ammonia for A-line; and
e) Ethylene for C-line.
23 shows a combination condenser and evaporator, machines 616 and 624 in Figure 20. Part of the condenser 652 is a heat exchanger through which the gas mixture. Heat is removed from the gas mixture by means of evaporation of the working fluid through the evaporator 654, and this causes condensation of a desired component of a mixture, pre-conditioned for such condensation, in a collector part 656 of the heat exchanger 652. Liquefied gas is collected and removed in an evaporator, where the reverse process takes place. Heat is delivered to the evaporating heat exchanger from the same heat distribution line. Theoretically, the process of condensation and evaporation of gas emitted is energy neutral.
Figure 24 shows how the electrical energy is distributed and recycled. Line 1 is three-phase distribution line for electricity. It is powered by the main source of electrical energy 6, preferably powered by a nuclear reactor of the fast breeder type. It is also powered from residual energy released in the FT reactors by the generator 716 in Figure 27. Electrolysis cell in Figure 14 represent the major consumers of electrical energy. All devices expanders generators used in adiabatic temperature changes and isothermal pressure changes, the line feed, and all the motors of compressors used in adiabatic temperature changes and isothermal pressure changes are fed from this line. Naturally, all other accessory motors and generators are attached to this line. The authors show some processing, which uses a variety of motors and generators.
Figure 25 shows how the lines are used for the heat distribution and recycling. In the RWGS-line heat delivered by the heat pump 710 shown in Figure 27, heat is supplied from the energy released in the FT reactors. This heat is used to heat the RWGS reactors, as shown in Figure 10. All heaters and coolers shown in Figure 22 that are used in isothermal pressure changes of incoming and outflowing gases in these reactors use the heat from this line or deliver it therein.
In the FT-line heat exchanger 714 is delivered via 27, the heat is obtained from the energy released in the FT reactors. All heaters and coolers shown in Figure 22 that are used in isothermal pressure changes of incoming and outflowing gases in these reactors use the heat from this line or deliver it therein.
The potline heat delivered via the heat exchanger 712 in Figure 27, heat is obtained from the energy released in the FT reactors. The main consumer of heat is a heater / boiler for water in the electrolyzer 28. All heaters and coolers shown in Figure 22 that are used in isothermal pressure changes of incoming and outflowing gases in the electrolyser, use heat from this line or deliver it therein.
26 shows two distribution lines for recycling the heat. One is a line operating at ambient temperature. All heaters and coolers shown in Figure 22 that are used in isothermal pressure changes of incoming and outflowing gases at ambient temperature, using the heat from this line or deliver it therein. All evaporators and condensers shown on the separator 23 for gas like steam, or receive heat from this line or deliver heat to this line. There is also a receiving end of a heat pump that transfers excess heat from the carbon dioxide separation line. All unused heat in the overall plant will be delivered to this line and dissipated primarily as waste heat.
Another line in Figure 26 represents a carbon dioxide separation line. All heaters and coolers shown in Figure 22 that are used in isothermal pressure changes of incoming and outflowing gases at a temperature close to carbon dioxide separation by liquefaction, use heat from this line or deliver it therein. All evaporators and condensers shown in Figure 23 for the separation of carbon dioxide, or receive heat from this line or deliver heat to this line. Carbon dioxide separation line is used not only for separation of carbon dioxide from the gaseous effluent at the outlet of the RWGS reactor, but also for separation of C3 and C4 hydrocarbons and residual carbon dioxide in the gaseous effluent of the reactor FT. There is also the end to collect the excess heat of the heat pump, which takes away excess heat from the carbon dioxide separation line into the ambient line.
The preferred selection and processing of gas
Carbon dioxide can be delivered to this apparatus typically by a pipeline at a typical gas pipeline pressure of 50 bar and at ambient temperature. For administration to the node RWGS carbon dioxide must be heated to RWGS temperature, 400 ° C, in this embodiment, and to a working pressure of about 25 bar. To accomplish this, all processes can be used 610-614 in Figure 20 or some of them.
Hydrogen from the electrolyser exits at 130-150 ° C and 20-30 bar pressure, and must be conditioned for administration to the RWGS assembly. To accomplish this, all processes can be used 610-614 in Figure 20 or some of them.
At the output of each RWGS reactor steam must be separated. This should be done at a low temperature to remove most of the water vapor. In this embodiment, it is the temperature of the environment. To accomplish this separation can be used all of the processes 610-614 and process 616 in Figure 20 or some of them. Also, processes 614 and 616 may be combined in one machine. After separation, gases must be conditioned for re further processing using all processes 618-622 of Figure 20 or some of them.
Carbon dioxide present in the effluent stream at the outlet of the third separator to couple node RWGS, may be separated by various methods, such as amine absorption, carbonate absorption, adsorption with pressure variation, adsorption, gas penetration, cryogenics with auxiliary additives (e.g., Ryan Holmes-process), or three phase cryogenics (CFZ). When liquefaction is used to separate most of the carbon dioxide, then can be used by all the processes in Figure 20 or some of them. In this embodiment, the temperature T1 is the ambient temperature, the temperature of condensation T3 is in the range of -55 ° C, the temperature T4 is equal to the FT reactor temperature, 220 ° C, in this embodiment, and temperature T6 is equal to the RWGS reactor temperature, 400 ° Since, in this embodiment.
Hydrogen to the FT reactor assembly coming from the electrolyser at a temperature of 130-150 ° C and 20-30 bar pressure, and must be conditioned to 220 ° C and 20 bar as preferred for this embodiment. To accomplish this, all processes can be used 610-614 in Figure 20 or some of them.
If carbon monoxide is supplied to the FT likely it will be transported through the pipeline at a typical pressure of 50 bar and at ambient temperature. For input node TF in carbon monoxide must be heated to the FT temperature, 220 ° C, in this embodiment, and expanded to operating pressure like 20 bar. To accomplish this, all processes can be used 610-614 in Figure 20 or some of them.
At the output of each FT reactor steam is released when the ambient temperature in this embodiment. To accomplish this separation can be used all of the processes 610-614 and process 616 in Figure 20 or some of them. Also, processes 614 and 616 may be combined in one machine. After separation before the second FT reactor, gases must be conditioned again for further processing using all processes 618-622 of Figure 20 or some of them.
After the second FT reactor steam along with heavier residual hydrocarbons is also separated at ambient temperature. To accomplish this separation can be used all of the processes 610-614 and process 616 in Figure 20 or some of them. Also, processes 614 and 616 may be combined in one machine.
After this separation, C3 and C4 gaseous hydrocarbons must be separated using all processes 610-616 in Figure 20 or some of them. At low levels of carbon dioxide and syngas condensation may occur at ambient temperature. Otherwise it should be more likely at lower temperatures than at higher pressures. In a preferred embodiment, there is C-line for condensation of carbon dioxide and it is used for condensation of C3, C4, and CO2 in this mixture. As a result, when the pressure of the sealing liquid, CO2 will evaporate first, and will be processed through processes 624-630 20, to be introduced into the host RWGS. The condensate of C3 and C4 compounds can be used in liquid form or, if desired, evaporated and conditioned to gas using all processes 624-630 in Figure 20 or some of them. Finally, the residue of C1 and C3 hydrocarbons, syngas, and other gases must be conditioned for entry to a controlled release 322, again using all or some of processes 618-622 of them.
Then, in the recycling loop node FT gases must be converted from their state at the input to the temperature and pressure of the environment in controlled release to the input conditions of the first FT reactor - 220 ° C and 20 bar, in the present embodiment. Again, it can be used by all the processes 610-614 in Figure 20 or some of them.
Finally, if the oxygen from the cell must be delivered for use outside of this installation, then it must also be conditioned. It enters the cell at a temperature of 130-150 ° C and a pressure of 20-30 bar. For delivery by a pipeline oxygen must be conditioned to a typical pipeline pressure of 50 bar and ambient temperature. To accomplish this, all processes can be used 610-614 in Figure 20 or any of them.
Similarly, for oxygen delivery to the burner-generator, steam separation there, and delivery of carbon dioxide back to the input can be used by the processes described herein for such purposes and presented on Figure 20.
Similarly, hydrogen for use in refining can be processed in the same manner as described, but at a different temperature and pressure at the outlet.
Recycling of heat from the Fischer-Tropsch unit
Exothermic heat of reaction in the reactors of the Fischer-Tropsch synthesis is the major source of energy for actuating all gas processing in this plant and source of additional electric energy for water electrolysis. Figure 27 shows the authors of the cooling circuit for the FT reactor. In this embodiment, a pair of working fluid to cool the reactors are distributed for condensation in several heat machines.
The first machine 710 is a heat pump pumping heat derived from condensation of vapor in the heat distribution line RWGS for. At the outlet of the condenser, working fluid is in a liquid phase at condensation temperature.
The second machine is a heat exchanger to heat water to the electrolyser temperature. Again, this heat is delivered by condensation of the working fluid. This method may use all the processes 610-616 in Figure 20 or some of them, and the electric power that is generated is delivered through a distribution line for electrical energy to the electrolyser. Leaving liquid is reheated from the FT-line and compressed to match the temperature and pressure of the reactor FT.
Third machine delivers heat to a heat distribution line FT by condensation if such heat is required to balance heat flow in this line.
Residual pair is driven electric power generator 716 with outlet temperature, preferably at ambient. Electrical energy is delivered to the electric power line and via this line to the electrolyser, in addition to the energy delivered by the power plant. Liquefied working fluid is recompressed and reheated to the pressure and temperature of the liquid coming from other condensers, and returned back to the FT reactors for cooling them by evaporation. Water is reheated using heat from the heat distribution line FT. An example of this working fluid is water. At higher FT operating temperatures can be used by other fluids such as ethylene glycol.
Introduction of water to the electrolyzer
In Figure 28, the authors show processing of water to introduce into the electrolytic cell. Water comes from multiple sources. It is preferred to recycle as much as possible the amount of water from the other processes in this plant, in particular from the steam separators RWOS reactor, steam separators from the FT reactor, steam separators, from the burner-generator, and any water collected in refining. All these streams of water and incoming water are at different temperatures, mostly near ambient temperature, but the electrolyser water is at 130-150 ° C and compressed to 20-30 bar. In addition, the above certain high current density the electrolyser must be cooled, and below a certain current density the electrolyser must be heated.
In a preferred embodiment, the authors use the heating / boiling of the water and compressed air for this water to such temperature and at a pressure in the electrolytic cell, that this water either absorbs electrolyser excess heat or delivers the excess heat. In the heat delivery, part of it can be even vaporized to deliver more heat to electrolyser water via condensation. In the mode of heat absorption, water temperature is lower than in the electrolyser. For vapor compression can be used all the processes 610-614 in Figure 20 or some of them. For water heating use heat-E line.
Main controls
Electronic monitoring is inherently system of the present invention 100. Controls include a physical layer and control computers with software that includes algorithms control. The physical layer comprises sensors and actuators. Each functional block of the present invention 100 has sensors corresponding to its function - like gas flow, or specific gas flow or fluid pressure, temperature, velocity, among others.
The actuators are pumps for condensers and evaporators, electric generators actuated by means of expander turbines, electric motors driving the compressor, throttles or valves for gas and liquid flow, mechanical regulators like impeller with variable geometry turbines, and other as required for a particular function.
It is preferable to use a distributed computer processing with some margin to ensure the reliability and timeliness of management.
List of main control functions of this invention 100 include:
- Control complete conversion of incoming carbon dioxide into carbon monoxide in the RWGS assembly;
- Control gas release at the output node Fischer-Tropsch process to maintain a predetermined level of hydrocarbon or other gases in this output stream;
- Control of hydrogen supply inlet assembly RWGS;
- Control of the hydrogen supply at the input node TF;
Fig.29-32 illustrate various ways of controlling the system 1500 of the present invention 100. 29 illustrates the control unit RWGS. The main purpose of the control node RWGS is substantially as completely as possible, the conversion of incoming carbon dioxide into carbon monoxide using feedback control.
The flow of carbon dioxide supplied is controlled by the valve device 1502 having a regulating element driven by the actuator means 1504. The flowmeter 1506 is envisaged for incoming carbon dioxide after throttle 1502. A second flow meter 1508 is provided for carbon monoxide on the output node RWGS. The output signals of both meters are fed to inputs of the error amplifier 1512 as shown, and those inputs are calibrated in molar velocity. The output of this amplifier drives the actuator 1504.
If the amount of carbon monoxide becomes smaller than the amount of carbon dioxide, the error amplifier output reduces drive of the throttle, and less carbon dioxide flows making difference between both flows smaller, within the error of this negative feedback loop.
Figure 30 shows the control unit FT. The main purpose of the control unit is maintaining FT certain levels of hydrocarbon or other gases like the synthetic gas at the output node with the goal of minimizing the release of the synthetic gas from the FT assembly recycling.
Controlling the gas flow meter at the output node 1522 FT is before the splitter 322. The signal from this flow meter is entered in the error amplifier in 1526, where it is compared with a reference level. The output of this amplifier feeds the actuator 1528 that controls the flow control element 322 in 1532 splitter.
This constitutes a negative feedback loop, and in a steady state, the flow control device 1532 allows a sufficient amount of gaseous effluent care, so that the amount of target gas is kept constant as determined by the reference level. If there are more control of gas flow control device then it opens more and reduces the surplus, and vice versa.
31 shows the control of hydrogen supply to the node RWGS. The main purpose of monitoring is to supply a sufficient amount of hydrogen to the desired H2 / CO ratio at the output node RWGS.
The flow of incoming carbon dioxide is measured by the same flow meter 1506. There is another flow meter 1544 hydrogen. The output of the flow meter of carbon dioxide is introduced into a multiplier 1546 that multiplies the signal to the desired ratio of hydrogen to carbon dioxide at the inlet RWGS assembly. In a preferred embodiment it is between 1.5 and 3.2. Signals from the multiplier and from the hydrogen flow meter are entered into an error amplifier 1548, and those inputs are calibrated in molar velocity. Output of this amplifier feeds the drive 1552 to control a hydrogen flow regulator 1554, which may be a simple throttle.
Hydrogen is supplied from the electrolyser. This constitutes a negative feedback loop. Its static condition is intended to allow flow of hydrogen when the output from amplifier 1548 is zero. If the amount of feed carbon dioxide is reduced, then there will be a signal to the output of the amplifier 1548 to reduce the flow through 1554. The reverse effect is also true.
Figure 32 shows the control of the hydrogen feed to the input node FT. The main purpose of this control is to regulate the ratio of hydrogen to carbon monoxide between the separator 328 and splitter 332 for the desired production of hydrocarbons in the node FT.
The stream of carbon monoxide is measured by a flow meter 1562 and hydrogen flow is measured by a meter 1564. Both meters are calibrated in molar velocity. A signal from meter 1562 is entered to a multiplier 1566 where the multiplier coefficient represents the desired ratio of hydrogen to carbon monoxide on the output. In a preferred embodiment, it is approximately two, similar to the ratio at the input node TF and varies as a function of operating conditions of a specific type of the FT reactor described here.
The outputs of multiplier 1566 and the flow meter 1564 are entered into the error amplifier 1568. Output of this amplifier receives the control actuator 1572 which feeds adjusting mechanism hydrogen flow control device 1574 that can be as simple as a throttle. The hydrogen is introduced from the cell through the flow controller 1574 to the input node FT.
This constitutes a negative feedback loop. At zero output of the amplifier 1568 the amount of hydrogen delivered to the node FT, corresponds precisely to the desired ratio multiplier. If more hydrogen is detected on the output node TF, then flow control device 1574 will be regulated to pass less hydrogen, and vice versa.
There is also a water level controller in the tank. It regulates the mechanism for pumping water, installed in the drainage pipe. It is a conventional controller used to maintain liquid level in storage tanks by pumping.
The utilization of electrical energy
Summary table, Table 1, illustrates the calculation of efficiency and electric energy usage as described herein.
Table Table 1Summarnaya energy flow in kJ starting material for the oxide uglerodaCO2CO2SOSOGranitsy effektivnostiminmaksminmaksEnergiya elektroliza853753578510Energiya reaction RWGS4137 - Energy from the FT reaction (146) (176) (146) (176) Energy pererabotki200150133100ELEKTRIChESKAYa for energy in general (TEE) 948764565434Polnaya heating value (HHV) hydrocarbon soedineniy670680670680Koeffitsient efficiency,% (HHV / TEE) 7189119157Koeffitsient use of electrical energy per unit of higher calorific value (TEE / HHV) 1,41,10,840,64Izbytok (deficit) TEE,% 4010 (16) (36)
Table 1 shows the calculations for the two species of carbon oxides. For each species, as explained further in the following exemplary description, all values leading to minimum efficiency are combined in one column, and all values leading to maximum efficiency in another. Efficiency is defined as the ratio of the higher combustion heat of combustion of hydrocarbon compounds (HHV) to the electrical energy is generally supplied to the process and the plant from an external source (TEE). The utilization of electrical energy is defined as the inverse of the efficiency as a TEE to the HHV.
The last line of Table 1 shows the excess or deficit of electric energy. For example, in the case of using carbon dioxide as raw materials and with a minimum required efficiency to 40% more electric energy than the total calorific value of combustion of hydrocarbon compounds. In the case of using carbon dioxide as raw materials and at the maximum efficiency will require only 10% more electric energy.
In the case of carbon monoxide as starting materials is clear that require substantially less electric energy, since carbon monoxide has certain combustion energy (versus carbon dioxide having no). For this reason, in the case of carbon monoxide as raw materials and with a minimum efficiency of 16% will require less electrical energy than the total calorific value of combustion of hydrocarbon compounds. In the case of using carbon monoxide as raw materials and at a maximum efficiency of 36% less.
The following description is a description of the items in Table 1, wherein for simplicity, all energies are shown per one carbon dioxide mole converted into hydrocarbon compounds.
Electric energy required for electrolysis of water is between 274 and 286 kJ per mole of hydrogen, as a function of temperature and under current density providing isothermal operation. In a preferred embodiment, it is estimated that it will be equal to 275 kJ. 3.1 moles of hydrogen is required to recycle one mole of carbon dioxide, thus, 853 kJ of electricity required is for isothermal operation. For lower current densities, this amount of electric energy will be lower, for example up to 100 kJ lower. In such a case, this deficiency will be supplied from the other processes in this plant. Of course, at higher current densities, there will be a need for more electric energy and additional heat must be removed. Some of this heat can be recycled with the introduction to the cell electrically, by generating electric power. Naturally, all heat can not be recovered and total energy consumption will increase.
RWGS reaction is moderately endothermic and requires 37-41 kJ per mole of converted carbon dioxide, depending on the operating conditions. It is another process that can use heat produced in this plant.
The Fischer-Tropsch reaction is highly exothermic and produces 146-176 kJ per carbon monoxide mole converted. This reaction is the main source of heat in this setting, methods and systems.
Other energy needs arise due to energy dissipation processes in which difficult its extract such as losses in the suspension, electric motors, transformers, rectifiers, losses by radiation and convection, and the like, and because of the difference in enthalpy of incoming and outflowing products . It is important to note that the only loss reversible processing of gases and liquids, which arise due to the processing, according to Figure 20. For this reason, it is estimated that these losses are in the range of 150-200 kJ per mole of carbon dioxide.
The output product from the FT reactors is a mixture of hydrocarbon compounds with different combustion energies. For this assessment uses the full heat of combustion of burning when water is used for recycling. The mixture of compounds of this energy is in the order of about 670-680 kJ per mole of converted carbon dioxide.
Using all these values, the magnitude of the electrical energy is calculated by the amount of the higher combustion heat of combustion of hydrocarbon compounds produced using that electric energy in the process and system as described herein. This range is between 1.4 and 1.1 when the input is only carbon dioxide. In turn, this means that the system requires 10-40% more electric energy from the external source than is contained in high heating value of combustion energy of hydrocarbon compounds with end products carbon dioxide and water.
Energy use is advantageous compared with the use of coal energy to convert the fluid - in the range of 2.5 - and the use of energy in the gas-liquid (GTL), approximately 1.7. In both cases, the inlet has a total heat of combustion or coal or gas.
In this system, there is a much lower usage utilization of electrical energy when carbon monoxide is used from an external source, versus using carbon dioxide. In this case, the system would require at least one mole of hydrogen and will not require heat for the steam reforming reactor. Then energy required for water electrolysis will be in the range of 275 kJ / mol, times the 2.1 mol, that is 578 kJ. In addition to this, the amount of losses in gas processing will be reduced at least by one-third due to elimination RWGS process and carbon dioxide separation process, so that it is equal to from 100 to 130 kJ. This leads to the fact that the need for external electric power will be between 0.64 and 0.84 of the maximum heat of combustion of hydrocarbon compounds.
To achieve this, the use of low-cost electricity coming from the outside, the following major internal energy flows:
- From Fischer-Tropsch to RWGS, using heat pump;
- From Fischer-Tropsch to the electrolyser as condensation heat of steam, if required;
- From Fischer-Tropsch to all processes using heat;
- From Fischer-Tropsch to the electrolyser, using residual heat for electric power generation;
- From the internal gas expander-generator to the internal compressor motor; and
- From internal gas coolers / heaters to the inner liquid for the gas / liquid using phase conversion of working fluids.
The preferred alternative for the system as a whole
In addition to using the reactor (s) FT conversion of synthesis gas into liquid fuels, it may be desirable to produce major components of natural gas, methane. This can be accomplished using the reaction catalyzed by
<img file="00000006.tif" he="5" wi="111" img-format="tif" img-content="undefined" />
In addition, from such synthesis gas may be obtained by other various hydrocarbon substances are widely known in the art.
In another preferred embodiment of the present invention, the installation may be located near natural gas fields, for selecting the carbon dioxide supply and CH4. In many gas wells, there is a sufficient amount of carbon dioxide and some of them are closed for that reason. These methods RWGS and FT may in some cases do using Sabatier reaction:
<img file="00000007.tif" he="5" wi="108" img-format="tif" img-content="undefined" />
In this process, similar amounts of heat are released as in the FT process (per carbon oxide mole) and conversion takes place at approximately 300 ° C.
Two different reactions can be used instead of the described processes and FT RWGS. The first is the process of Lurgi, also known as the process of Carnoles, and it can be used. Second is a process for producing gasoline from methanol (MTG).
While the reaction of the reverse water gas shift, carbon dioxide reacts with hydrogen to produce carbon monoxide and water, the process Lurgi or Carnoles uses the same reactants as the reaction of conversion of water vapor with other catalysts and reaction conditions to produce methanol . Thus, in another embodiment of the present invention, the RWGS reaction can replace or Carnoles Lurgi process, represent:
<img file="00000008.tif" he="5" wi="116" img-format="tif" img-content="undefined" />
Methanol is produced from this reaction is then used in the MTG process with high selectivity for light hydrocarbons forming basis of gasoline.
Although the present invention has been described in its preferred embodiments, those skilled in the art will recognize that many modifications and additions may be done abbreviations therein without departing from the spirit and scope of the invention and its equivalents as set forth in the following claims.
Contents4
Every citation, both ways
| Document | Relation | Office |
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| DE20320020U1 | Cites | Germany |
| DE19522083A1 | Cites | Germany |
| US6306917B1 | Cites | United States of America |
| RU2170776C2 | Cites | Russian Federation |
| RU2002118218A | Cites | Russian Federation |
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Numbers
- Publication
- 2394871
- Application
- 200713822104
Titles2
- Russian
- СИСТЕМЫ, СПОСОБЫ И КОМПОЗИЦИИ ДЛЯ ПОЛУЧЕНИЯ СИНТЕТИЧЕСКИХ УГЛЕВОДОРОДНЫХ СОЕДИНЕНИЙ
- English
- SYSTEMS, METHODS AND COMPOSITIONS FOR PRODUCING SYNTHETIC HYDROCARBON COMPOUNDS
Classification
- CPC, 22
- C10G2/32
- C10G2/00
- C10G2/30
- C10J3/18
- C10J2300/093
- C10J2300/1238
- C10J2300/1659
- C10G2300/1022
- C25B15/08
- C25B1/04
- Y02P20/129
- Y02P20/133
- Y02E20/18
- Y02E60/36
- Y02P20/10
- C01B3/16
- C01B2203/0294
- C10K3/026
- Y02P20/00
- C10J1/00
- C01B3/04
- C07C1/04
- IPC, 3
- C10G2 00
- C01B3 06
- C07C1 04