WO2002030553A2 - Procede de reduction d"emissions nettes de gaz a effet de serre provenant de gaz de degagement industriels carbones et combustible de moteur a compression produit a partir desdits gaz de degagement - Google Patents

Procede de reduction d"emissions nettes de gaz a effet de serre provenant de gaz de degagement industriels carbones et combustible de moteur a compression produit a partir desdits gaz de degagement Download PDF

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WO2002030553A2
WO2002030553A2 PCT/SE2001/002211 SE0102211W WO0230553A2 WO 2002030553 A2 WO2002030553 A2 WO 2002030553A2 SE 0102211 W SE0102211 W SE 0102211W WO 0230553 A2 WO0230553 A2 WO 0230553A2
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fuel
gas
carbon
gases
bearing
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WO2002030553A3 (fr
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Andreas Eklund
Per Hedemalm
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Oroboros Ab
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0216—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/046—Purification by cryogenic separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process

Definitions

  • Patent references U.S. Pat. No. 4,678,860 "Process of producing liquid hydrocarbon fuels from biomass", issued 1987-07-07.
  • the present invention relates to a process for reducing net greenhouse gas emissions from carbon-bearing industrial off-gases and a compression engine fuel produced from said off- gases.
  • This invention relates to the reduction of emissions of greenhouse gases, and specifically to the reduction of net emissions of carbon-bearing gases from metallurgical industries, and to a fuel for compression engines produced from said carbon-bearing gases.
  • Off-gases from metallurgical industry such as blast furnace gas, coke oven gas, basic oxygen furnace gas, and aluminum smelter gas, often contain carbon-bearing gases, such as carbon . monoxide and carbon dioxide.
  • Carbon dioxide is a main contributor to the greenhouse effect, and is estimated to represent some 70%) of the total global greenhouse gas emissions. Carbon-bearing gases, such as carbon monoxide, will form carbon dioxide in the atmosphere, and thereby contribute to global warming.
  • Direct emission does not address the emission of greenhouse gases, which is the object of the present invention
  • Direct emission from a chimney has the disadvantage that toxic and corrosive substances, such as carbon monoxide and sulphuric acid, may be emitted without combustion, and also that there is a risk of accidental explosions, should the limit of combustion be reached at any time.
  • Gas turbines are often impractical to use on off-gases from heavy industries, since the off- 5 gases are often contaminated with dust, particles, or sulphur. When used, gas turbines tend to get very expensive both in terms of investment costs and in terms of maintenance costs.
  • nitrous oxides can be reduced using various catalysts, but this will always come at an investment cost, and a cost in terms of lower total efficiency.
  • Carbon monoxide separated from steelworks off-gases is successfully used in Japan by Kobe Steel for the production of polycarbonate and polyurethane polymers.
  • the demand for this application is small, and producing polycarbonate or polyurethane polymers from off- gases will therefore not yield any nationally nor globally significant decrease in greenhouse gas emissions.
  • the method also fails to take advantage of the hydrogen content of the off- gases. Nevertheless, this example shows that chemical production plants utilizing industrial off-gases can be competitive, providing that competing production plants are not several orders of magnitude bigger.
  • New fuel formulations include re-formulated diesels, rape-seed ester (RME) and di-methyl- ether (DME).
  • RME rape-seed ester
  • DME di-methyl- ether
  • MK1 Swedish diesel
  • MK1 shows a dramatic decrease in toxicity of emissions compared to standard European or U.S. diesel, a significant amount of toxic substances, such as polyaromatics, will nevertheless be emitted.
  • MK1 which is manufactured from crude oil, does not address greenhouse gas emissions at all.
  • MK1 The manufacture of MK1 is relatively energy-intensive , actually yielding higher net emissions of carbon dioxide from the production per kWh than standard European or U.S. diesels. 0
  • MK1 is known to cause wear of diesel fuel pumps, and the addition of synthetic lubricity improvers is therefore necessary.
  • RME made from rape-seed oil
  • Older engines will need to be 5 converted for use of RME, the production costs of RME are relatively high, and it is l ⁇ iown that the emissions have some mutagenic capacity [2].
  • the need for artificial fertilizers and pesticides, as well as the high usage of area for the culture of rape, contribute to giving RME environmental as well as economic disadvantages.
  • the cold flow properties of RME makes it unsuitable for use in arctic climates.
  • Methylated esters can be manufactured from many other natural triglycerides, such as soybean oil, sunflower oil, or even beef fat. However, all of them share some of the disadvantages of RME.
  • DME is a relatively clean fuel, with small emissions, but it is considerably more expensive to manufacture than conventional fuels.
  • DME is a gas, and conversion of vehicles is therefore necessary in order to use the fuel. Only a few experimental vehicles are currently run on DME, and there are still technical problems with the engines.
  • Many additives used in diesel can also be used in the paraffinic fuels of the present invention, additionally decreasing emissions.
  • oxygen-containing additives such as water (usually used with an emulgator), ethanol and PEG, are in no competition to the present invention.
  • Fuels consisting mainly of ethanol or methanol are not possible to use efficiently in compression engines, and are therefore not in competition to the present invention.
  • Bio-gas (methane from fermentation processes) is used in Otto engines, and is therefore not in competition to the present invention. Compression engines have a much higher efficiency 0 than Otto engines - around 30-50%) difference is not uncommon in commercial vehicles. Thus, limited fuel resources, in the form of clean fuels, can be used more efficiently in compression engines than in Otto engines.
  • a relatively inexpensive hydrogenation step can produce low-sulphur naphtha, diesel, and wax/lubricant. Since no gasoline is produced, no expensive isomerization equipment is needed.
  • Aromatics such as xylene, benzene, and bens(a)pyrene, are usually toxic. Many are also carcinogens or allergens. In many products, they must therefore be meticulously avoided, something which is very costly to achieve in an ordinary crude oil based refinery.
  • Figure 1 shows one embodiment of the invention using the off-gas from a basic oxygen furnace of a steelworks.
  • FIG. 1 shows one embodiment of the present invention.
  • the off-gas is in this case generated from a basic oxygen furnace 10 of a steel manufacturing plant.
  • the basic oxygen furnace is of a type that has a hood capturing off-gases from the process.
  • the off-gases are passed to a set of valves 12, which will pass on the gas to the next step only if the carbon monoxide content of the gas is above an adjustable limit.
  • valve constructions can in principle be used, a few examples of basic valve constructions are given in U.S. Patents 4,415,142 and 4,218,241.
  • the gas may be passed to a chimney or flare 28.
  • the off-gas is passed on to an expandable gas storage tank 14, of a size sufficient to give an essentially steady flow of gas out from the gas container.
  • the pressure of the gas storage tank is kept between approximately 1 and 3 bars. From the gas container, the gas is passed on to a compressor 16, where the gas is compressed to a pressure of approximately 10 to 50 bars.
  • the compressed gas is passed on to a shift reactor 18.
  • the function of the shift reactor is to convert some of the carbon monoxide of the off-gas to hydrogen, while the high temperature and the catalyst employed will simultaneously destroy any remaining traces of smelly hydrocarbons that may still be present in the gas.
  • An optional carbon dioxide separation step 20 is included in figure 1. This step is only necessary if there is a use for said carbon dioxide, since all remaining steps will work with or without carbon dioxide in the gas stream. Any conventional method of separation will work, e.g. cryogenic separation, ethanol-amine solvent, or alkaline water wash.
  • the gas is then passed to the catalytic reactor 22, which in this embodiment is a Fischer- Tropsch reactor utilizing an iron-based catalyst.
  • the catalytic reactor 22 which in this embodiment is a Fischer- Tropsch reactor utilizing an iron-based catalyst.
  • Many different types of reactors can be used in the present invention, including fischer-tropsch reactors, water shift reactors, inverse water shift reactors, oxo synthesis reactors, and carbonylation reactors.
  • a few examples of Fischer- Tropsch reactors which are all possible to use in the present invention are described in U.S. Patents 5,504,118, 4,499,209, and 5,844,006.
  • the liquid and gaseous output of the reactor is passed to settling and aftertreatment, 22.
  • This process step consists of settling, hydrogenation, and distillation.
  • an oil phase mainly consisting of C5+ hydrocarbons and alcohols will separate from a water phase, mainly consisting of water, lower alcohols, ketons, and aldehydes.
  • the oil phase is hydrogenated and distilled into various fractions, e.g. wax, diesel, jet fuel, and naphtha.
  • olefins will be saturated to paraffins, and the distilled fuel will therefore have a very low content of olefins.
  • the water phase is also hydrogenated, in such a way that ketons and aldehydes are reacted to alcohols.
  • the water phase can then be used as a ion-free cleaning agent, or the alcohols can be distilled out, and sold separately.
  • Remaining reactive gases from the settling can be flared in the flare 28, or recycled to the gas storage tank 14.
  • inert gases mainly nitrogen
  • a large fraction of the nitrogen must be released through a flare or chimney.
  • the off-gases passed on from the basic oxygen furnace 10 will have a high content of carbon- bearing gases only during the blow of oxygen into the steel melt.
  • the valves 12 are adjusted so that only gas containing a pre-determined content of carbon-bearing gas is passed on to the gas storage tank 14.
  • This pre-determined content of carbon-bearing gas is optimized with regard to the overall economics of the process, depending on conditions such as market value of carbon dioxide.
  • the valve 12 will be set at minimum of approximately 40-60%. carbon-bearing gas.
  • the typical composition of the off-gas from a basic oxygen furnace gas will be around 65 vol.-% > carbon monoxide, around 15 vol.-%> carbon dioxide, around 18 vol.-% nitrogen gas, and less than 2 vol.-%> hydrogen gas.
  • the off-gas is essentially sulphur-free.
  • the off-gas contains 5-50 mg/Nm 3 dust, mainly ferrous oxides.
  • the amount of off- gas will be around 120 million Nm 3 per year.
  • the off-gas is produced during the oxygen blows in the basic oxygen furnace 10, usually around 15 minutes, and then no gas is produced before the next blow, which will usually be a time period of 20 to 30 minutes.
  • the size of the gas storage tank 14 is chosen to minimize the risk of production stops due to too low gas levels. Thus, the size should be at least as large as the amount of gas produced by one blow, and preferably two or three times the volume of off-gas produced in one blow. This will allow for a steady flow of gas from the gas storage tank 14 to the compressor 16.
  • the compressor 16 will compress the off-gas to approximately! 0 to 50 bars.
  • the gas is then passed to the shift reactor 18, in which steam is injected.
  • the steam reacts with the carbon monoxide of the gas, producing carbon dioxide and hydrogen.
  • carbon dioxide separation unit 20 some of the carbon dioxide may be separated for use in other applications, within or outside the plant.
  • the catalysis reactor 22 which in this embodiment is a Fischer-Tropsch reactor, will then use the carbon monoxide and hydrogen content of the gas to produce the following end products:
  • oxygenates e.g. alcohols, aldehydes, and ketons
  • a residual gas will contain carbon dioxide, hydrogen, and some light hydrocarbons.
  • the products from the reactor are passed on to settling and aftertreatment. From the settler, gases are flared or vented off via the flare 18. A small fraction of the gas may also be recycled to the gas storage tank 14.
  • the alkanes and alkenes from the settling are passed on to a hydrogenation step, where the alkenes are saturated using hydrogen and a suitable catalyst.
  • the product from the hydrogenation will consist essentially of alkanes. Lighter alkanes, up to about 20 carbon atoms, can easily be separated using ordinary distillation techniques, whereas heavier alkanes may need to be separated in vacuum distillation or solvent extraction. Since mainly non-cyclic alkanes are produced, no azeotrops will be present in the distillation.
  • Swedish diesel fuel environmental class 1 is currently the cleanest standard diesel fuel in the world.
  • the selected optimized paraffinic fuel mixtures were further tested according to the 13 mode ECE R49 test cycle and were found to have lower emissions than MK1 fuel with regard to all measured emissions.
  • composition of the fuels were chosen so that they can be manufactured from industrial off-gases using a Fischer-Tropsch catalysis reactor in the production process described in figure 1 and in the above text. However, other manufacturing methods are also possible.
  • the fuels may also be manufactured from renewable raw materials, e.g. wood chips.
  • the production process in this case is first a partial oxidation of the wood chips, producing synthesis gas.
  • the synthesis gas is passed to a Fischer-Tropsch reactor, and the process thereafter is essentially the same as that described above.
  • Fischer-Tropsch reactor For further reference on the thereafter is essentially the same as that described above.
  • U.S. Pat. No. 4,678,860 Other raw materials used in a similar process could be natural gas, sewage sludge, or other types of waste.
  • the fuels could also be manufactured using traditional refinery technology, using crude oil as the raw material. However, a large number of de-sulphurization, distillation, and purification steps are needed in this case, making Fischer-Tropsch processes more economical in most cases.
  • F-T fuel Fischer-Tropsch fuel
  • the F-T fuel mixture 1 consist of 90%> straight-chain n-paraffins, CIO to CI 3 in length, which has a high cetane number and rather good lubricity properties but not so good cold flow properties. It was therefore mixed with 10%> n-heptane (C7H16).
  • the F-T fuel mixture 2 consist of 60%> straight-chain n-paraffins, CIO to CI 3 in length, 20% strongly branched-chain iso-paraffm, CIO to CI 5 in length, and 20% weakly branched-chain iso-paraffin. CIO to C13 in length.
  • the branched-chain iso-paraffins have slightly lower cetane number and less good lubricity properties but very good cold flow properties compared to straight-chain paraffin.
  • MKl diesel was used.
  • the test engine consists of a basic AVL Type 501 cylinder block and Volvo - 2 1 cylinder head.
  • the single cylinder research engine, equipped with C-3 Lucas unit - injector, has the following configuration:
  • Turbocharger performance of a six cylinder production engine was simulated by the AVL 5153 supercharging group according to the discrete parameters read from the Volvo test No FP01940865 - 867 - 874 - 876 - 878 - 880.
  • the engine would run at the same power- speed points and supercharging specifications as in the Volvo tests.
  • Such performance would help to compare the reference results, when the engine runs on conventional fuel MKl, with F-T fuel test results.
  • the engine cooling water temperature was set at constant value of 85 Celsius degree via the engine water cooling unit AVL 553, whereas the lube oil temperature was set at constant value of 90 Celsius degree via the oil cooling unit AVL 554.
  • the fuel conditioning system used during this investigation was AVL 753 M - 120.
  • the speed-torque engine operating range was controlled by an AVL PUMA engine test system.
  • a system includes measuring devices such as: Variable Sampling Smoke Meter AVL 415, Dynamic Fuel Meter AVL 733 S, and Exhaust Gas Analytical System CEB series equipped with a Bench Integration Computer BIC.
  • the emission test system was calibrated before the test procedure and it was controlled continuously during the long day test.
  • the regulated emission NOx and HC were measured in ppm at wet conditions, whereas CO and CO 2 were measured at dry conditions.
  • the soot formation was measured in FSN (Filter Smoke Number) units. According to the software program, and device arrangement for constant length of the sampling volume, FSN might be converted to mg/m 3 .
  • the air mass flow was measured by a thermal Air Mass Flow Meter (AFM), which is placed before the inlet of the air filter onto the compressor. After the compressor unit the compressed air is led tlirough a FD 160 Air Drier, where the moisture is removed by cooling the air to near freezing point.
  • AFM Thermal Air Mass Flow Meter
  • the by-pass Constant Pressure Regulator (CPR) maintains a constant supply pressure of about 5 bar for the boost pressure control group.
  • the Boost Pressure Control Group (BPCG) 5262 provides the requested charging air temperature and pressure for the engine.
  • An accurate Hygrotest 602 instrument with the probe of the humidity measuring transducer directly installed on the steady vessel of the BPCG 5262 was used to measure small quantities of the remaining humidity.
  • the remote injection program is design to give injection control for timing and duration of the main pulse via a PC.
  • This program is integrated into the existing fuelling strategies. Therefore, the Engine Control Unit (ECU) can be operated in a normal running mode with existing controls or via the remote program which will directly control the injection pulse.
  • ECU Engine Control Unit
  • a software for analysis of the combustion and thermodynamics through measurements of cylinder pressure and other fuel injection related variables has been developed under the name Dragon.
  • Thermodynamic analysis also gives a number of parameters that characterizes the combustion processes, such as heat release rate, ignition delay, injection duration and fractions of the premixed-diffusion combustion.
  • a NOx formation model is also implemented, but since the accurate measuring instrumentation is used, this model was not activated.
  • Burst to File sampling code sampled the high frequency signals, such as cylinder pressure, fuel pressure, needle lift, and solenoid valve signal. High frequency signals were further processed by the Dragon program giving the real values for needle lift and heat release history.
  • THERMODYNAMIC ANALYSIS Cylinder pressure was further processed for heat release analysis according to the Dragon software.
  • This program uses an algorithm with the aim of permitting a quick assessment of the combustion process i.e. the heat release and the temperature per degree crank angle and total heat released immediately after the measurement. In order to calculate such parameters, the indicated diagram must range at least from intake valve closed to exhaust valve opened.
  • thermodynamic calculation principle compares the measured pressure response with a computed pressure curve making use of the fact that a different pressure rise is observed in the compression phase and in the expansion phase depending on the time when combustion starts and develops.
  • the heat release rate is defined as the effective portion of combustion energy that is available for heating up the gas in the combustion chamber. Obviously, the computation of surface losses requires a computer algorithm, which has been developed for thermal simulation. Mathematical formulas for changes in volume, rate of heat release, total heat release, and gas temperature according to the different steps of calculations are not shown here, as they have been described in other publications [Atkinson et al, Heywood].
  • thermodynamic information when running on different fuels is the engine efficiency. This parameter is evaluated using a lower heat value for the fuels of 42.8 MJ/kg.
  • the only parameter, considered to vary in our investigation, has been the equivalent ratio, which differs for MKl and F-T fuels. Such difference is compensated during the tests, where the engine was run at the same equivalent ratio.
  • Table 5 shows the engine efficiencies values at different speed and load for conventional fuel MKl and F-T fuels.
  • Peak pressure and its location for MKl and F-T fuels 1200 rpm.
  • the peak pressure for MKl is slightly higher than those for F-T fuels.
  • the peak pressure location is also slightly later for MKl.
  • Higher peak pressure and its later location related to the piston position for MKl fuel points out the different properties in the combustion characteristics for F-T fuels.
  • Such a trend is hardly observed at rated speed as the peak pressure is located at the compression line (stroke) and not at the combustion line (expansion stroke).
  • thermodynamic analysis shows that F-T fuels exhibit better performance in comparison with conventional MKl .
  • the ECE R49 13 mode evaluation of specific weighted values have shown a general NOx reduction by 6%o, HC reduction by 11%, CO reduction by 10%) and Soot reduction by 19%>. Insignificant BSFC reduction was observed as well, but not as much as to be stated. At some loads (from light load 10%> to medium load 50%) the emission reductions were higher. Hence, NOx reduction reached 25%>, HC 50% and CO 30%o. Soot formation was observed to be reduced only at loads higher than 50%, and achieved the maximum reduction by 20%>.
  • F-T fuels are shown to be effective over the operating range of the engine, and particularly at light loads. From this viewpoint both F-T mixtures show the same trend.
  • the general index of ECE R49 test cycles evaluations for NOx and CO emissions is slightly different for F-Tl and F-T2 fuels. F-Tl forms less NOx and more CO in comparison with those emissions obtained when the engine runs on F-T2.
  • F-T fuels have shorter ignition delay and longer combustion duration when compared with those obtained when the engine runs on MKl fuel at the same operating point. Also the fraction of premixed combustion is much stronger for conventional fuel (MKl) than for F-T fuels as shown by the evaluated rate of heat release in the premixed zone. This is an indication of smooth engine running, lower combustion rate, and lower NOx formation. As a complement to this, the cylinder pressure characteristic is more favourable when the engine runs on F-T fuel, with lower peak and earlier location.
  • F-T fuels can be used in unmodified compression ignition engines with significant reduction of regulated emission and smoother thermodynamic characteristics. Also substantial qualitative reductions, e.g. reduction of the number of hazardous chemicals and reduction of the concentration of hazardous chemicals in the exhausts has been realised. Further optimisation of parameters such as injection timing and its CAD position or F-T fuel composition might lead to still lower exhaust emissions. It can be noted that both F-T fuels have very low densities, 744 and 761 kg/m 3 respectively. Several vehicle manufacturers have earlier stated that a fuel with a density below 800 kg/ m 3 would give functional problems with the engine.
  • both F-T fuels have a higher energy content per litre than MKl fuel. This is due to a high hydrogen-content in saturated non-cyclic compounds, such as those used in the F-T fuels. This is contrary to the common assumption in the vehicle industry that the energy content per litre of fuel is approximately proportional to the density.
  • RME has a clearly oily-olefmic smell, and a brown to yellow colouring, whereas paraffins are usually colourless and have a neutral to stale smell.
  • the mixture surprisingly, has a fresh but discrete lemony smell, and a slightly green colouring.
  • Rape-seed oil is an essentially poly-unsaturated vegetable oil, whereas olive oil is an essentially mono-unsaturated vegetable oil, and cocoanut oil is essentially a saturated vegetable oil. These three biological fats were therefore added, 2% each, to a FT fuel. Without additives, the FT fuel had a HFRR wear scar of 642 micro-meters, a viscosity of 2,73 mm 2 /s, and a cold filter plugging point (CFPP) of -36°C.
  • CFPP cold filter plugging point
  • a drop of a substance was introduced into a combustion chamber with a temperature between 500 and 800 degrees C.
  • the exhausts from the chamber were analysed using a GC-MS instrument.
  • n-paraffins will not give any cyclic substances when combusted. Thus, the emissions will be free from cyclic substances, which are often toxic, such as cyclohexane, benzene, polyaromatics, etc.
  • n-paraffins have better lubrication properties than iso-paraffins, minimizing the need for lubrication additives.
  • n-paraffins with more than 7 carbon atoms are essentially non-toxic.
  • the chemical structure is similar to natural substances, such as natural fats.
  • the n-paraffin does not have the carboxylic group, the biological reactivity will be lower.
  • n-paraffms will be broken down to non-toxic karboxylic acids.
  • Karboxylic acids are used as energy storage in mammals.
  • n-paraffins are very good fuels in compression engines, with high cetane number, and will thereby also give efficient and low-emission combustion. Hexadecane, or cetane, has a cetane number of 100 by definition, and other n-paraffins will also have high cetane numbers.
  • n-paraffins are often less costly to manufacture than iso-paraffins. However, since n-hexane (C6H14) is known to be toxic, it should be avoided as far as possible in any fuel formulation.
  • (b) add slightly branched iso-paraffins, some of which have a much lower melting point than n-paraffms with the same number of carbon atoms.
  • the effect of branching on the melting point can be demonstrated by the following compounds: hexane (C6H14) melts at -95 degrees C, 2-methyl-pentane (C6H14) melts at -153,67 degrees C, whereas 3-methyl-pentane (C6H14) melts at -118 degrees C.
  • cold flow improvers mainly act as anti-crystallization compounds, and will thus fail to work at consistently low temperatures, such as arctic climates.
  • the preferred method would be to use as short C7+ n-paraffins as possible, and then add iso-paraffins with a low melting point as required to attain good cold flow properties. Adjust lubrication properties by adding as much biological fat or an ester of a biological fat as necessary
  • n-paraffins usually have better lubrication properties than iso-paraffins, the lubrication properties are usually not sufficient for use in modern compression engines.
  • the conventional method of attacking this problem is by addition of a commercial lubrication improving agent.
  • a methylated ester of rape-seed oil was found to give a number of advantages over the conventional method:
  • a fat of biological origin or a methylated ester of a fat of biological origin is added to the fuel, to attain the above attractive properties.
  • a fat of biological origin or a methylated ester of a fat of biological origin is added to the fuel, to attain the above attractive properties.
  • additives such as bactericides and fungicides, may be needed, based on the market needs in the country in question. These additives are usually only added in a few ppm to the fuel, and will have a negligible effect on the overall combustion and lubrication properties of the fuel.
  • a fuel with the following components will be arrived at: a) a main n-paraffinic component, constituting at least 60% of the total volume of the fuel, b) an addition of up to 40 vol.-%> iso-paraffins, in order to adjust cold-flow properties, c) 0-20% linear-chain oxygenates, chosen to be miscible with the main n-paraffinic component, and with at least five carbon and oxygen atoms in the longest linear chain, d) 0-20%o lubricants chosen from the group consisting of fats of biological origin, and methylated esters of fats of biological origin. e) optionally other minor additives, such as fungicides or bactericides, according to market needs.
  • catalytic carbon capture of the present invention will provide for a high energy efficiency and a high carbon capture ratio, thereby greatly decreasing net emissions of greenhouse gases to the atmosphere.
  • compression engine fuels that can be produced according to the present invention have particularly attractive qualities, such as:
  • Another set of variations include other catalytic processes in the catalytic reactor 24.
  • a third set of variations include that elements of the plant may switch places, e.g. carbon dioxide removal may in some cases be done before shift, or the off-gas holder 14 may be placed after the compression 16.
  • a fourth set of variations comprise elements that are omitted.
  • the shift reactor 18 may be omitted, if the carbon monoxide to hydrogen ratio is already adjusted to a ratio acceptable to the reactor 24.
  • the off-gas holder 14 may be omitted if the flow of off-gas is continuous.
  • a fifth set of variations include that any of the industrial off-gases mentioned above may be mixed with other types of off-gases or waste gases from incineration.
  • a sixth set of limitations includes variations in the paraffinic composition of the fuel, as well as the use of other oxygenates as combustion improvers, and the use of other esters of triglycerides to achieve sufficient lubricity properties. Accordingly, the scope of the invention should be determined not by the embodiment illustrated, but by the appended claims and their legal equivalents.

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Abstract

Les gaz de dégagement de l"industrie métallurgique contribuent à entre 10 et 15 % de toutes les émissions de dioxyde de carbone dans le monde. La réduction des émissions de ces gaz représente, par conséquent, un élément clef dans une stratégie quelconque visant à réduire les émissions de gaz à effet de serre nationales ou internationales. L"invention concerne un procédé permettant de réduire les émissions nettes de gaz à effet de serre provenant de gaz de dégagement industriels, au moyen de procédés catalytiques, tels qu"une catalyse de Fischer-Tropsch. Le procédé permet de réduire, de manière économique, les émissions nettes de gaz à effet de serre provenant de gaz de dégagement industriels carbonés jusqu"à une valeur comprise entre 80-95 %. L"invention concerne également un nouveau type de combustible à faible émission destiné à des moteurs à compression, le composant paraffinique principal de ce combustible pouvant être fabriqué sans mettre en oeuvre lesdits procédés catalytiques.
PCT/SE2001/002211 2000-10-13 2001-10-11 Procede de reduction d"emissions nettes de gaz a effet de serre provenant de gaz de degagement industriels carbones et combustible de moteur a compression produit a partir desdits gaz de degagement WO2002030553A2 (fr)

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WO2010057767A1 (fr) * 2008-11-21 2010-05-27 Siemens Vai Metals Technologies Gmbh & Co Procédé et dispositif de production d'un gaz brut de synthèse
US9721220B2 (en) 2013-10-04 2017-08-01 Baker Hughes Incorporated Environmental performance estimation

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US5689031A (en) * 1995-10-17 1997-11-18 Exxon Research & Engineering Company Synthetic diesel fuel and process for its production
WO1998005740A1 (fr) * 1996-08-02 1998-02-12 Exxon Research And Engineering Company Carburant diesel synthetique a emissions de particules reduites
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US6056793A (en) * 1997-10-28 2000-05-02 University Of Kansas Center For Research, Inc. Blended compression-ignition fuel containing light synthetic crude and blending stock
WO2000041799A1 (fr) * 1999-01-14 2000-07-20 Ge Energy And Environmental Research Corporation Procedes et appareil d'oxydation selective limitee thermiquement

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US3872025A (en) * 1969-10-31 1975-03-18 Bethlehem Steel Corp Production and utilization of synthesis gas
US4013454A (en) * 1975-03-04 1977-03-22 Robert Kenneth Jordan Coproduction of iron with methanol and ammonia
US4499209A (en) * 1982-11-22 1985-02-12 Shell Oil Company Process for the preparation of a Fischer-Tropsch catalyst and preparation of hydrocarbons from syngas
US5689031A (en) * 1995-10-17 1997-11-18 Exxon Research & Engineering Company Synthetic diesel fuel and process for its production
WO1998005740A1 (fr) * 1996-08-02 1998-02-12 Exxon Research And Engineering Company Carburant diesel synthetique a emissions de particules reduites
US6056793A (en) * 1997-10-28 2000-05-02 University Of Kansas Center For Research, Inc. Blended compression-ignition fuel containing light synthetic crude and blending stock
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WO2000041799A1 (fr) * 1999-01-14 2000-07-20 Ge Energy And Environmental Research Corporation Procedes et appareil d'oxydation selective limitee thermiquement

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WO2010057767A1 (fr) * 2008-11-21 2010-05-27 Siemens Vai Metals Technologies Gmbh & Co Procédé et dispositif de production d'un gaz brut de synthèse
JP2012509456A (ja) * 2008-11-21 2012-04-19 シーメンス・ファオアーイー・メタルズ・テクノロジーズ・ゲーエムベーハー 合成生ガス製造方法並びに装置
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US9721220B2 (en) 2013-10-04 2017-08-01 Baker Hughes Incorporated Environmental performance estimation

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WO2002030553A3 (fr) 2002-06-20

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