Method and apparatus for producing synthesis gas
FIELD: method and torch for producing synthesis gas at decomposition of liquid hydrocarbons such as oil and natural gas at elevated temperatures without usage of catalyst by CO and hydrogen.
SUBSTANCE: method is realized by partial oxidation of liquid and solid combustible materials at presence of oxygen and oxygen containing gases. Fuel, oxygen-containing gas and atomizing fluid are fed to torch separately. Atomizing fluid is expanded just in front of inlet opening for fuel by means of one or several nozzles providing speed of atomizing fluid in range 20 - 300 m/s. Relation of diameter of outlet opening of nozzle for liquid fuel to diameter of opening of nozzle for atomizing fluid is in range 1/1.1 - 1/5.
EFFECT: possibility for simplifying process.
2 dwg, 2 ex
The invention concerns a method and a suitable burner to produce synthesis gas, with liquid hydrocarbons, such as oil or liquid by-products of chemical production, as well as gaseous hydrocarbons such as natural gas or fuel gas, at high temperatures decompose without the use of the catalyst for carbon monoxide (CO) and hydrogen (H2).
This method is known as "multi-purpose gasification" (method MPG) and is implemented through the reactor section of the heat recovery, gas purification and washing plants for CO2and H2S. the Core of this technology is the burner, which are mixed and fed into the reactor of the original substance.
In the patent Austria at-In-369345 and European patent application EP-IN-0127273 described the principle of operation of the burner. Liquid fuel using high-pressure steam is sprayed in a special nozzle. Supplied with atomizing steam water participates in the reaction in the reactor MPG and is partially converted into hydrogen. When the non-catalytic decomposition of natural gas required water vapor to prevent damage to the burner as a result of overheating. At current natural gas ratio of carbon and hydrogen in the final product can be obtained only limited correlation WITH/N2. When using leading the CSO pair this ratio deteriorates even more. This is particularly disadvantageous in the case, if you want the synthesis gas with a high proportion of carbon monoxide or if the valuable gas itself is carbon monoxide.
In European patent application EP-IN-0380988 proposed burner adapted to supply liquid fuel to the reactor, in which the atomization of fuel is carried out using water vapor or, alternatively, carbon dioxide (CO2).
The disadvantage of this burner is required high excess pressure of from 100 to 250% critical compression, which couples and CO2must be submitted to the burner. In the case of use as a spray environment CO2this requires high energy and hardware costs for compression of CO2.
The basis of the invention lies task is to create an improved method for production of synthesis gas in which the fuel spray is required not only couples, but also other suitable gaseous medium type, carbon dioxide, natural gas, combustible gas, or mixtures thereof, and in which the atomization of fuel in the reaction chamber can occur cheaply and with little hardware overhead.
This task in accordance with the invention is solved due to the fact that for the production of synthesis gas by partial oxidation of liquid or gaseous combustible material in the presence of oxygen is whether oxygen-containing fuel gases containing oxygen gas and the spray medium is fed to the burner apart and spray environment extends directly in front of the entrance hole for the fuel using one or more nozzles, when this differential pressure expansion of the atomizing medium is only from 2% to 50% of the pressure in the reactor.
As a result of such low of the desired excess pressure for the expansion of the atomizing medium when it enters the burner achieved a significant reduction of costs for preparing the spray environment. If you use spray pairs, there is no need to select it from a separate network or boiler with a correspondingly high degree of pressure, as the gas environment may directly or after a minor overheating be used in pairs, or otherwise generated in the recovery boiler gasification reactor.
If the spray medium is carbon dioxide, it is possible to dispense external preparations of carbon dioxide, if it can be selected from the raw synthesis gas in the subsequent scrubber and fed again into the burner. It is particularly advantageous is required in the burner slight excess pressure of the atomizing medium. Required compressor for compressing separated in the scrubber carbon dioxide to the required in the burner pressure can have a small number of steps and requires less energy costs for the operation of the actuator. It's also better to slightly over-heating carbon dioxide plumage which it is supplied to the burner.
As the spray environment other suitable gaseous medium generated during the process or present in the installation, for example:
- the tail gas from the adsorption process with variable pressure (from the installation DWA) or membrane plants for hydrogen production,
- the tail gas from a plant for producing carbon monoxide (Cold Box)
gases that are byproducts of other processes, which are collected in the network combustible gas and to be burnt,
- natural gas.
These gases can individually, in a mixture or after enrichment steam fed to the burner as the atomizing medium.
To obtain effective sputtering rate of the gaseous atomizing medium at the outlet of the nozzle should be between 20 to 300 m/S. Mostly work with the speed of the atomizing medium at the outlet of the nozzle in the range from 40 m/s to 200 m/s variable output speed depends, among other things, on the ratio of the diameters of the nozzle, as will be discussed later. High output speed is provided by the structure which is the object of the present invention the burner, in which the diameter of the outlet nozzle for the liquid fuel is in a certain relation to the hole diameter of the nozzle for the spray environment. The ratio of the diameters of the pillar is t from 1/1,1 to 1.5, mainly from 1/1,3 to 1/3. Due to this design the cavity of the nozzle provides the speed required for mixing environments. Because of this high output speed can, as experience shows, to work with less significant extension.
Performance capabilities of the technology are illustrated by the drawings.
Figure 1 presents the technological scheme of production of carbon monoxide. In the reactor (1) is not illustrated in this case the burner. In the reactor (1) via the pipeline (2) is supplied with liquid fuel or gas. Pipeline (3) is required for the combustion of oxygen. Another pipeline (4) is designed to supply the spray environment necessary for spraying and cooling. This can be done, for example, by means not illustrated here the gas tank. In the reactor environment is subjected to gasification at a temperature of from 1000 to 1500°and a pressure of from 1 to 100 bar. The gasification gases are formed WITH N2and CO2. The gases are cooled and cleaned from dust (5) and enter then into the scrubber (6). The final gaseous products (CO and H2pipeline (7) served on the plot further processing. If the fuel contains sulfur, it is separated in the scrubber in the form of H2's and served in the usual way through the pipeline (8) in the Claus plant, while separated from the synthesis gas number of the first carbon dioxide by pipeline (9) first enters the compressor (10), and then by pipeline (4) back into the reactor.
Figure 2 presents a schematic diagram of the burner MPG. Liquid fuel through the nozzle (11) is fed into the pre-mixing chamber (12) and extends it. Spray medium is supplied through the annular chamber (15) and with high velocity into the chamber pre-mixing of the nozzle (13). Pulse stream spray environment provides additional atomization of the fuel flow into small droplets. Oxygen-containing gas is supplied via the annular chamber (21) and comes into contact with a mixture of fuel and atomizing medium at the mouth of the burner, just before entering the reactor chamber (20), which is not shown. The design depends on the characteristics of the liquid fuel and atomizing medium and their quantitative ratio. Axial length (A) mixing chamber (12)measured from the outlet for liquid fuel (11a) before entering the reaction chamber ranges from 10 to 300 mm, mainly from 20 to 200 mm, cone Angle (x) of the mixing chamber, measured parallel to the axis line (25)is from 2 to 20°usually from 5 to 15°. The maximum internal diameter of the mixing chamber (12) is located at the inlet and is from 10 to 150 mm, mainly from 20 to 90 mm are Crucial for fine races is ylenia liquid fuels and intensive mixing with the spray medium is the ratio of diameter (d) of the outlet nozzle (11) for liquid fuel to the diameter (D) of the hole of the nozzle (13) for the spray environment. The diameter ratio of d/D is from 1/1,1 to 1/5, mostly from 1/1 .3 to 1/3. The extension spray through nozzle (13) should be adjusted so that the output speed of the spray environment ranged from 20 to 300 m/s, typically from 40 to 200 m/S.
When spraying heavy VAT residue at a pressure of 60 bar as the atomizing medium is used WITH the2. For comparison, commonly used for spraying water vapor is replaced by an equal weight of CO2. This significantly improves the process of obtaining and reduces specific fuel consumption. The differences presented in table 1.
|Steam atomization||Spraying with CO2||Change (%)|
|The ratio of CO/H2in the synthesis gas||1.10||1.80||+64.0|
|Fuel consumption in kg VAT residue/||0.55||0.45||-18.2|
|The consumption of oxygen|
There has been a marked reduction is their production costs for obtaining, as consumed 18% less fuel and 19% less oxygen. A significantly higher ratio of CO/H2facilitates the extraction of pure CO in the system for producing carbon monoxide (Cold Box) and in the membrane installation.
Installation is obtaining pure hydrogen by gasification of VAT residue oil production. For this purpose, the carbon monoxide contained in the incoming of the installation MPG gas raw, converted into hydrogen in the reactor shift FROM using water vapor and with the participation of the catalyst. Pure hydrogen is extracted from the gas by adsorption with pressure variation in installing DWA. The formation of the exhaust gas, N2(56%), CO (28%), and CO2(10%). Instead to divert the exhaust gas in the network combustible gas for later burning, it is compressed, mixed with steam and is used as the atomizing medium. When using flue gas as the atomizing medium supply of steam in the reactor can be reduced by 40%. Thanks to the return of the exhaust gas installation DWA in the reactor achieved the following improvements in hydrogen production (table 2):
|DWA + couples||(%)|
|The consumption of oxygen in m3N-O2/m3N||0.28||0.25||-10.1|
|in kg VAT residue /m3N-H2||0.36|
Savings on VAT residue and the oxygen nucleus is greater than the flow rate of the compressed exhaust gas, resulting in the production costs of hydrogen are reduced by 3%.
1. The method for production of synthesis gas by partial oxidation of liquid or solid combustible materials in the presence of oxygen or oxygen-containing gases, and fuel, oxygen-containing gas and the spray medium is fed to the burner separately, with the spray medium expanded immediately before the inlet of the fuel through one or more nozzles, wherein using the nozzle or nozzles that provide(s) the speed of the atomizing medium is 20-300 m/S.
2. The method according to claim 1, characterized in that use, the nozzle or nozzles that provide(s) the speed u is extreme environment equal to from 40 to 200 m/S.
3. The method according to claim 1, characterized in that the spray environment of the use of carbon dioxide which is withdrawn from the subsequent scrubber, compressed and recycled to the burner.
4. The method according to claim 3, characterized in that the carbon dioxide is fed to the burner directly or after a minor overheating.
5. The method according to claim 1, characterized in that the spray environment of the use of the tail gas from the installation DWA or membrane installation, or from a plant for producing carbon monoxide (Cold Box).
6. The method according to claim 5, wherein the tail gas before it enters the burner squeeze.
7. Burner for the production of synthesis gas by partial oxidation of liquid or solid combustible materials in the presence of oxygen or oxygen-containing gases, and fuel, oxygen-containing gas and the spray medium is fed to the burner apart and spray environment extends directly in front of the entrance hole for the fuel through one or more nozzles, the ratio of the diameter (d) of the outlet nozzle (11) for liquid fuel to the diameter (D) of the hole of the nozzle (13) for the atomizing medium is from 1/1,1 to 1/5.
8. Burner according to claim 7, characterized in that the ratio of diameter (d) of the outlet nozzle (11) for liquid fuel to the diameter (D) of the nozzle holes 13) for atomizing medium is from 1/1,3 to 1/3.
9. Burner according to claim 7, characterized in that the axial length of the mixing chamber, measured from the outlet to the fuel before entry into the reaction chamber ranges from 10 to 300 mm, mainly from 20 to 200 mm
10. Burner according to claim 7, characterized in that the cone angle of the mixing chamber is from 2 to 20°mainly from 5 to 15°.
11. Burner according to claim 7, characterized in that the maximum inner diameter of the mixing chamber at the inlet is from 10 to 150 mm, mainly from 20 to 90 mm
FIELD: petroleum chemistry.
SUBSTANCE: waste water from Fisher-Tropsh synthesis reactor is mixed with carbon for obtaining carbon-water suspension which is directed to gasifier and is subjected to reaction with water steam and oxygen at high temperature and pressure for obtaining synthesis-gas. Waste water may be returned to suspension preparation stage where carbon is ground and is mixed with process water and waste water for forming the suspension, after which this suspension is delivered to gasifier where it is subjected to reaction with water steam at high temperature and pressure for obtaining synthesis-gas. Method of obtaining the hydrocarbons is described when synthesis-gas is brought in contact with catalyst for synthesis of hydrocarbon for forming reaction products and waste water which is separated from reaction products and is returned to recycle for mixing with carbon and forming the suspension.
EFFECT: possibility of obtaining closed recirculation cycle of waste water from Fisher-Tropsh reactor; reduction of operational expenses.
10 cl, 1 dwg
FIELD: method for producing synthetic gas, which may be used in oil chemistry for producing motor fuels.
SUBSTANCE: method includes processing of biogas under temperature of 1420-1800°C and following cooling of resulting synthetic gas. Thermal processing of biogas is performed in liquid heat carrier with ratio of volume of liquid heat carrier to volume of barbotaged gas, equal to 10-100 during 0,3-2 seconds, or in boiling layer of solid particles, where the speed of biogas is selected to be greater than minimal speed of fluidization.
EFFECT: increased purity of produced synthetic gas.
8 cl, 6 ex
FIELD: alternative fuels.
SUBSTANCE: invention relates to catalysts and process of steam conversion of hydrocarbons to produce synthesis gas. Proposed catalyst for steam conversion of hydrocarbons contains nickel oxide (4.0-9.2%) and magnesium oxide (4.0-6.5%) supported by porous metallic nickel (balancing amount). Carrier has specific surface area 0.10-0.20 m2/g, total pore volume 0.07-0.12 cm3/g, predominant pore radius 1-30 μm, and porosity at least 40%. Described are also catalyst preparation method and generation of synthesis gas via steam conversion of hydrocarbons.
EFFECT: increased heat conductivity of catalyst resulting in stable activity in synthesis gas generation process.
8 cl, 1 tbl, 5 ex
FIELD: production of synthesis-gas.
SUBSTANCE: proposed method is carried out at temperature of 750-900 C due to external heating of tubular furnace reaction tubes filled with catalyst; mixture of natural gas and superheated steam is fed to reaction tubes. External heating of reaction tubes filled with catalyst is first performed by burning the natural gas in air; after attaining the required mode of operation, external heating is carried out by burning the synthesis-gas fed from tubular furnace outlet to reaction tube external heating chamber. Device proposed for realization of this method includes tubular furnace with reaction tubes filled with catalyst, chamber for mixing the natural gas with superheated steam and external heating chamber for heating the reaction tubes filled with catalyst for maintenance of conversion process; heating chamber is provided with air inlet. Device is also provided with gas change-over point whose one inlet is used for delivery of natural gas fed to chamber of external heating tubular furnace reaction tubes during starting the mode of steam conversion process; other inlet of gas change-over point is used for delivery of synthesis-gas from tubular furnace outlet through distributing synthesis-gas delivery point. Device is also provided with regulator for control of delivery of synthesis-gas to reaction tube external heating chamber required for combustion.
EFFECT: enhanced economical efficiency of process.
3 cl, 1 dwg
FIELD: steam catalytic conversion of natural gas into synthesis-gas with the use of thermal and kinetic energy of synthesis-gas.
SUBSTANCE: proposed method includes external heating of reaction tubes of tubular furnace filled with nickel catalyst on aluminum oxide substrate by passing mixture of natural gas and superheated steam through them. External heating of reaction tubes filled with catalyst is performed by burning the natural gas in air at exhaust of flue gases from heating zone. After tubular furnace, the synthesis-gas is directed to gas turbine for utilization of thermal and kinetic energy; gas turbine rotates electric generator; then, synthesis-gas is directed to synthesis-gas burner of electric power and heat supply system; flue gases from external heating zone are directed to heat exchangers for preheating the natural gas and steam before supplying them to reaction tubes of tubular furnace. Device proposed for realization of this method includes sulfur cleaning unit, tubular furnace with reaction tubes filled with nickel catalyst on aluminum oxide substrate with inlet for gas mixture of natural gas and superheated steam; device also includes external heating zone for reaction tubes with flue gas outlet and gas burner for external heating of reaction tubes of tubular furnace with inlet for natural gas and air. For utilization of thermal and kinetic energy of synthesis-gas, device is provided with gas turbine and electric generator at tubular furnace outlet and synthesis-gas burner of electric power and heat supply system; device is also provided with heat exchangers for preheating the natural gas and steam before supplying them to tubular furnace.
EFFECT: improved ecological parameters; enhanced power efficiency of process.
3 cl, 1 dwg
FIELD: processing of hydrocarbon raw materials; oxidizing conversion of hydrocarbon gases into synthesis-gas.
SUBSTANCE: proposed method is carried out in flow-through two-chamber reactor in turbulent mode at combustion of mixture of hydrocarbon raw material and oxidizer. Superheated water steam is additionally introduced into said mixture in the amount of 5-20 mass-% relative to mass of carbon fed in form of hydrocarbon raw material. Three-component mixture is ignited in combustion chamber by jet of hot gas fed from external source where pressure exceeds pressure in first chamber during ignition. Combustion products from first chamber of reactor are directed to second chamber via nozzle at critical difference in pressure and combustion process is continued till content of oxygen in combustion products does not exceed 0.3 vol-%. Process is carried out in combustion reactor which is made in form of two coaxial cylindrical chambers with cooled nozzle located in between them; section of this nozzle ensures required pressure differential between chambers. Injector unit mounted at inlet of first chamber is used for delivery of working mixture components. Turbulator is mounted in first chamber. Lateral surface of first chamber has one or several holes for introducing the jet of hot gas from external source whose pressure exceeds pressure of first chamber and volume of second chamber exceeds that of first chamber. Proposed method makes it possible to produce synthesis-gas at H2/CO ratio approximately equal to 2.0; residual content of oxygen does not exceed 0.3 vol-% and content of carbon black does not exceed trace amount.
EFFECT: enhanced efficiency.
9 cl, 2 dwg, 11 ex
FIELD: carbon monoxide conversion catalysts.
SUBSTANCE: invention relates to a method of preparing catalysts for middle-temperature conversion of carbon monoxide, which can be used in industry when producing nitrogen-hydrogen mix for ammonia synthesis. Preparation of catalyst for middle-temperature conversion of carbon monoxide with water steam, comprising precipitation of iron hydroxide from iron nitrate solution with ammonia-containing solvent, washing of iron hydroxide with water to remove nitrate ions, mixing with calcium and copper ions, mechanical activation of components, molding, drying, and calcination of granules, is characterized by that, in the component mixing step, lanthanum oxide is supplementary added, in which case molar ratio of components is as follows: Fe2O3/CaO/CuO/La2O3 = 1:(0.8-0.9):(0.045-0.08):(0.005-0.01).
EFFECT: increased catalytic activity and more than thrice reduced content of by-products in condensate.
1 tbl, 3 ex
FIELD: alternative fuels.
SUBSTANCE: invention relates to autothermal conversion of hydrocarbon fuel to produce synthesis gas, which can be used in chemical production, for burning at catalytic heat plants, and in hydrogen power engineering. Proposed catalyst contains, as active components, cobalt oxide, manganese oxide, and barium oxide, and, as carrier, refractory reinforced metalporous carrier. Catalyst is prepared by impregnation of carrier with barium and manganese salt solution at Ba/Mn =5:4 followed by drying, calcination, impregnation with cobalt salt solution, drying, and calcination. Invention further describes generation of synthesis gas via autothermal conversion of hydrocarbon fuel performed utilizing above-described catalyst.
EFFECT: enabled catalyst exhibiting high heat conductivity, high activity in production of synthesis gas, and resistance to coking and deactivation with sulfur compounds present in diesel fuel and gasoline.
6 cl, 1 tbl, 3 ex
FIELD: gas treatment.
SUBSTANCE: invention relates to processes of removing carbon monoxide from gas mixtures containing, except hydrogen, carbon dioxide. This process is an important step for production of pure hydrogen or hydrogen-containing gas, e.g. in ammonia synthesis. Catalyst for removing carbon monoxide from hydrogen-containing gas represents permeable composite material containing combination of phases of catalytically active group VIII metal or their alloy, oxide-type carrier, and metallic copper or copper metal containing alloy, composite-forming grain size being less than 0.5 mm and permeability of composite exceeding 10-14 m2. Catalyst preparation procedure as well as processes of removing carbon monoxide from hydrogen-containing gas using it are also described.
EFFECT: increased activity and selectivity of catalyst.
20 cl, 3 dwg, 8 ex
FIELD: electronic industry; petrochemical industry; other industries; plasma converters of the gaseous and liquid hydrocarbon raw and the fuels into the synthesis gas on the basis of microwave discharge.
SUBSTANCE: the invention is pertaining to the microwave plasma converters of the hydrocarbon raw and the fuels into the synthesis gas of the low-power, for usage, for example, in the capacity of the source of the hydrogen and the synthesis gas in the developments of the mobile and self-contained power plants on the basis of fuel cells. The invention allows to simplify and to make cheaper production of the plasma converter. The plasma converter for transformation of the gaseous and liquid hydrocarbon raw and the fuels into the synthesis gas on the basis of the microwave discharge includes the plasmatron of the microwave spark plug consisting of the magnetron and the cylindrical coaxial bundle of the transportation line of the microwave emission of the magnetron to the discharge zone, formed beyond the butt the of the inner conductor of the coaxial transportation line, and the reactor of mixing connected to the discharge zone of the plasmatron by means of the hole of communication made in butt of the outer conductor, in which wall there are the holes for feeding of the plasma-forming gas. The magnetron has the antenna output terminal of the microwave emission made in the form of the cylindrical ceramic component having the metallic end cap. The inner conductor of the coaxial transportation line is fixed on the indicated metallic end cap. The outer conductor is fixed on the magnetron. In the outer conductor opposite to the ceramic component of the antenna output terminal of the microwave emission there are at least two tangentially directed holes for feeding of the plasma-forming gas. The inner diameter of the outer conductor D is equal to (2.3÷2.6)d, where d - is the diameter of the inner conductor. At that the length of the inner conductor makes no less than λ/4where λ is the wavelength of the microwave emission of the magnetron.
EFFECT: the invention allows to simplify and to make cheaper production of the plasma converter.
6 cl, 2 dwg
FIELD: petrochemical processes.
SUBSTANCE: invention relates to technology of processing hydrocarbon gas to produce pure carbon and hydrogen products. To that end, hydrocarbon gas is first preheated and then decomposed when affected by microwave electromagnetic field to isolate and separate carbon and hydrogen. Preheating of hydrocarbon gas is effected using energy of microwave electromagnetic field in thermal zone of elongated flow reactor uniformly filled with gas-permeable conducting substance serving as initiator and selected from titanium, nickel, titanium nickelide, aluminum nickelide, and molybdenum. Decomposition of hydrocarbon gas is effected at thermal zone outlet at elevated (as compared to thermal zone) intensity of microwave electromagnetic field. Apparatus comprises flow reactor with separately located hydrocarbon gas inlet and carbon/hydrogen outlet, and microwave emission source connected to microwave wave guide. Flow reactor is disposed within rectangularly-shaped microwave wave guide, said flow reactor being constructed itself as elongated cylindrical chamber made from radio-transparent heat-resistant material, partially filled with above-indicated initiator, and provided with microwave electromagnetic field concentrator disposed immediately behind initiator.
EFFECT: increased yield of desired products.
9 cl, 2 dwg, 2 tbl
FIELD: hydrocarbon conversion catalysts.
SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.
EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.
4 cl, 1 tbl, 8 ex