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Definitions

• the present invention relates to a process for producing a purified synthesis gas stream from a feed synthesis gas stream comprising contaminants.
• Synthesis gas streams are gaseous streams mainly comprising carbon monoxide and hydrogen. Synthesis gas streams are generally produced via partial oxidation or steam reforming of hydrocarbons including natural gas, coal bed methane, distillate oils and residual oil, and by gasification of solid fossil fuels such as biomass or coal or coke.
• solid or very heavy (viscous) fossil fuels which may be used as feedstock for generating synthesis gas, including biomass, solid fuels such as anthracite, brown coal, bitumous coal, sub-bitumous coal, lignite, petroleum coke, peat and the like, and heavy residues, e.g. hydrocarbons extracted from tar sands, residues from refineries such as residual oil fractions boiling above 360 0 C, directly derived from crude oil, or from oil conversion processes such as thermal cracking, catalytic cracking, hydrocracking etc. All such types of fuels have different proportions of carbon and hydrogen, as well as different substances regarded as contaminants.
• solid fuels such as anthracite, brown coal, bitumous coal, sub-bitumous coal, lignite, petroleum coke, peat and the like
• heavy residues e.g. hydrocarbons extracted from tar sands, residues from refineries such as residual oil fractions boiling above 360 0 C, directly derived from crude oil, or from oil
• the synthesis gas will contain contaminants such as carbon dioxide, hydrogen sulphide, carbonyl sulphide and carbonyl disulphide while also nitrogen, nitrogen-containing components (e.g. HCN and NH3) , metals, metal carbonyls (especially nickel carbonyl and iron carbonyl), and in some cases mercaptans.
• Purified synthesis gas can be used in catalytical chemical conversions or to generate power.
• a substantial portion of the world's energy supply is provided by combustion of fuels, especially natural gas or synthesis gas, m a power plant.
• Synthesis gas is combusted with air in one or more gas turbines and the resulting gas is used to produce steam. The steam is then used to generate power .
• IGCC Integrated Gasification Combined Cycle
• IGCC systems were devised as a way to use coal as the source of fuel m a gas turbine plant.
• IGCC is a combination of two systems.
• the first system is coal gasification, which uses coal to create synthesis gas.
• the syngas is then purified to remove contaminants.
• the purified synthesis gas may be used m the combustion turbine to produce electricity.
• the second system in IGCC is a combined-cycle, or power cycle, which is an efficient method of producing electricity commercially.
• a combined cycle includes a combustion turbine/generator, a heat recovery steam generator (HRSG), and a steam turbine/generator.
• the exhaust heat from the combustion turbine may be recovered in the HRSG to produce steam. This steam then passes through a steam turbine to power another generator, which produces more electricity.
• a combined cycle is generally more efficient than conventional power generating systems because it re-uses waste heat to produce more electricity.
• IGCC systems are clean and generally more efficient than conventional coal
• Processes for producing a purified synthesis gas stream generally involve the use of expensive line-ups.
• cold methanol may be used to remove hydrogen sulphide and carbon dioxide by physical absorption.
• concentrations of these contaminants m the purified synthesis gas will still be in the ppmv range.
• contaminant concentrations m the ppmv range are still too high. Purifying the synthesis gas streams to a higher degree using a methanol-based process would be uneconomical due to the disproportionately large amounts of energy required to regenerate the methanol.
• H2S needs to be removed, usually by contacting the methanol comprising H2S with a stripping gas at elevated temperatures, resulting in a stripping gas comprising H2S. H2S m this stripping gas is then converted to elemental sulphur, requiring a considerable capital and operational expenditure.
• a process is disclosed wherein sulphur species are removed using low-temperature amine- based absorption processes, followed by a solvent regeneration Claus/SCOT process unit.
• the disadvantage of such a process is that it is limited to the feed gas composition suitable for a Claus process, which is rather high m hydrogen sulphide concentration.
• the invention provides a process for producing a purified synthesis gas stream from a feed synthesis gas stream comprising besides the main constituents carbon monoxide and hydrogen also hydrogen sulphide, HCN and/or COS, the process comprising the steps of: (a) removing HCN and/or COS by contacting the feed synthesis gas stream with a water gas shift catalyst in a shift reactor in the presence of steam/water to react at least part of the carbon monoxide to carbon dioxide, and to obtain a synthesis gas stream depleted in HCN and/or in COS; (b) removing hydrogen sulphide in the synthesis gas stream depleted in HCN and/or in COS by contacting this gas stream in a H2S-removal zone with an aqueous alkaline washing liquid to obtain a H2S-depleted synthesis gas stream and a sulphide-comprising aqueous stream; (c) contacting the sulphide-comprising aqueous stream with sulphide-
• the process enables removal of hydrogen sulphide, carbonyl sulphide and/or hydrogen cyanide to low levels.
• the purified synthesis gas because of its low level of contaminants, is suitable for use as fuel, suitably in gas turbines, or for use in catalytical chemical conversions.
• the purified synthesis gas is especially suitable for use m an Integrated Gasification Combined Cycle (IGCC) .
• IGCC Integrated Gasification Combined Cycle
• step (d) a carbon dioxide stream at elevated pressure, suitably in the range of from 4 to 12 bara is obtained.
• This carbon dioxide stream can be further pressurised and used for example for enhanced oil recovery.
• the process is economical because H2S is removed directly from the synthesis gas stream via conversion into elemental sulphur.
• the synthesis gas stream depleted in H2S has very low concentrations of H2S, enabling the use of an inexpensive non-selective acid gas removal unit to remove remaining H2S as well as CO2 •
• the amount and type of contaminants m the feed synthesis gas stream can vary and depends on the amount of these contaminants present in the feedstock used to generate the feed synthesis gas stream.
• the feed synthesis gas stream is obtained by gasification of feedstock.
• the amount of H2S and COS m the synthesis gas stream leaving the gasifier is below 15 volume%, typically below 5 volume% based on the synthesis gas stream.
• the amount of H2S and COS in the synthesis gas stream leaving the gasifier will be below 20 volume%, typically below 10 volume% based on the synthesis gas stream.
• the synthesis gas stream generated from a feedstock may comprise particulate matter, for example fly-ash or soot particles. Therefore, m a preferred embodiment synthesis gas exiting a synthesis gas generation unit is contacted with scrubbing liquid in a soot scrubber to remove particulate matter, in particular soot, thereby obtaining the feed synthesis gas stream.
• the synthesis gas stream exiting the synthesis gas generating unit is generally at elevated temperature and/or elevated pressure. Especially m the event that the synthesis gas is generated m a gasifier, the synthesis gas stream exiting the gasifier will be at elevated temperature and at elevated pressure.
• the scrubbing step m the soot scrubber is preferably performed at elevated temperature and/or at elevated pressure.
• the temperature at which the synthesis gas is contacted with scrubbing liquid is in the range of from 40 to 160 °C, more preferably from 110 to 150 0 C.
• the pressure at which the synthesis gas stream is contacted with scrubbing liquid is in the range of from 20 to 80 bara, more preferably from 20 to 60 bara.
• the amount of HCN and/or COS in the feed synthesis gas stream depends on the composition of the feedstock from which the synthesis gas is derived and the technology applied for the production of synthesis gas.
• the amount of COS in a feed synthesis gas stream derived from solid fossil fuel feedstocks, especially coal is from about 100 to 3000 ppmv, based on the feed synthesis gas stream.
• the amount of COS is generally in the range of from 1 to 100 ppmv.
• HCN and/or COS is removed from the feed synthesis gas stream via catalytic conversion.
• Catalysts for the hydrolysis of HCN and/or COS are known to those skilled m the art and include for example Ti ⁇ 2-based catalysts or catalysts based on alumina and/or chromium-oxide .
• Preferred catalysts are Ti ⁇ 2 ⁇ based catalysts .
• the amount of water/steam is preferably between 5 v/v% and 80 v/v%, more preferably between 10 v/v% and 70 v/v%, still more preferably between 15 v/v% and 50 v/v%, based on steam.
• step (a) the feed synthesis gas stream is contacted with a water gas shift catalyst in a shift reactor to remove HCN and/or COS and to additionally react at least part of the carbon monoxide with water to form carbon dioxide and hydrogen.
• step (a) carbon monoxide in the feed synthesis gas stream is converted with a low amount of steam m the presence of a catalyst as present m one or more fixed bed reactors.
• a series of shift reactors may be used wherein m each reactor a water gas shift conversion step is performed.
• the content of carbon monoxide, on a dry basis, in the feed synthesis gas stream as supplied to the first or only water gas shift reactor is preferably at least 50 vol.%, more preferably between 55 and 70 vol.%.
• the feed synthesis gas stream preferably contains hydrogen sulphide m order to keep the catalyst sulphided and active.
• the minimum content of hydrogen sulphide will depend on the operating temperature of the shift reactor, on the space velocity (GHSV) and on the sulphur species present in the feed synthesis gas stream.
• GHSV space velocity
• the steam/water to carbon monoxide molar ratio in the feed synthesis gas stream as it enters the first or only water gas shift reactor is preferably between 0.2:1 and 0.9:1.
• the temperature of the feed synthesis gas stream as it enters the shift reactor is preferably between 190 and 230 °C.
• the inlet temperature is between 10 and 60 0 C above the dewpomt of the feed to each water gas shift conversion step.
• the space velocity in the reactor is preferably between
• the pressure is preferably between 2 and 5 MPa and more preferably between 3 and 4.5 MPa.
• the conversion of carbon monoxide may generally not be 100% because of the sub-stoichiomet ⁇ c amount of steam present in the feed of the reactor.
• the content of carbon monoxide in the shift reactor effluent, using a fixed bed reactor will be between 35 and 50 vol.% on a dry basis, when starting from a feed synthesis gas stream comprising between 55 and 70 vol.% carbon monoxide, on a dry basis, and a steam / CO ratio of 0.2 to 0.3 molar. If a further conversion of carbon monoxide is desired it is preferred to subject the shift reactor effluent to a next water gas shift conversion step.
• the preferred steam/water to carbon monoxide molar ratio, inlet temperature and space velocity for such subsequent water gas shift conversion steps is as described for the first water gas shift conversion step.
• the feed synthesis gas stream is suitably obtained from a gasification process and is suitably subjected to a water scrubbing step.
• water will evaporate and end up in the syngas mixture.
• the resultant steam to CO molar ratio in such a scrubbed syngas will suitably be within the preferred ranges as described above. This will result in that no steam or water needs to be added to the syngas as it is fed to the first water gas shift conversion step.
• steam or boiler feed water will have to be added to the effluent of each previous step.
• the water gas shift step may be repeated to stepwise lower the carbon monoxide content in the shift reactor effluent of each next shift reactor to a CO content, on a dry basis, of below 5 vol.%. It has been found that in 4 to 5 steps, or said otherwise, in 4 to 5 reactors such a CO conversion can be achieved.
• each shift reactor it is important to control the temperature rise m each shift reactor. It is preferred to operate each shift reactor such that the maximum temperature in the catalyst bed in a single reactor does not exceed 440 °C and more preferably does not exceed 400 0 C. At higher temperatures the exothermal methanation reaction can take place, resulting in an uncontrolled temperature rise.
• the catalyst used in the shift reactor is preferably a water gas shift catalyst, which is active at the preferred low steam to CO molar ratio and active at the relatively low inlet temperature without favouring side reactions such as methanation.
• the catalyst comprises a carrier and the oxides or sulphides of molybdenum (Mo) , more preferably a mixture of the oxides or sulphides of molybdenum (Mo) and cobalt (Co) and even more preferably also comprising copper (Cu) tungsten (W) and/or nickel (Ni) .
• the catalyst suitably also comprises one or more promoters/inhibitors such as potassium (K) , lanthanum (La) , manganese (Mn) , cerium (Ce) and/or zirconium (Zr) .
• the carrier may be a refractory material such as for example alumina, MgAl2U4 or MgO-Al2 ⁇ 3-Ti ⁇ 2 •
• An example of a suitable catalyst comprises an active Y-AI2O3 carrier and between 1-8 wt% CoO and between 6-10 wt% M0O3.
• the catalyst is preferably present as an extrudate.
• the feed synthesis gas stream comprises at least 50 vol.% of carbon monoxide
• the steam to carbon monoxide molar ratio in the feed synthesis gas stream as it enters the shift reactor or reactors is preferably between 0.2:1 and 0.9:1 and the temperature of the feed synthesis gas stream as it enters the shift reactor or reactors is between 190 and 230 0 C.
• step (a) involves the shift reaction as described heremabove
• a portion of the "shifted" synthesis gas stream, optionally after removal of contaminants, is used for hydrogen manufacture, such as in a Pressure Swing Adsorption (PSA) step.
• PSA Pressure Swing Adsorption
• the proportion of the shifted synthesis gas stream used for hydrogen manufacture will generally be less than 15% by volume, preferably approximately 1-10% by volume.
• the hydrogen manufactured in this way can then be used as the hydrogen source in hydrocrackmg of the products of the hydrocarbon synthesis reaction.
• This arrangement reduces or even eliminates the need for a separate source of hydrogen, e.g. from an external supply, which is otherwise commonly used where available.
• the carbonaceous fuel feedstock is able to provide a further reactant required in the overall process of biomass or coal to liquid products conversion, increasing the self-sufficiency of the overall process.
• step (a) a synthesis gas stream depleted in hydrogen cyanide and/or in COS is obtained.
• step (b) the synthesis gas stream depleted in hydrogen cyanrde and/or m COS rs contacted with aqueous alkaline washing liquid to transfer hydrogen sulphide from the synthesis gas stream depleted in hydrogen cyanide and/or in COS to the aqueous alkaline washing liquid.
• Suitable aqueous alkaline washing liquids include aqueous hydroxide solutions, e.g. sodium hydroxide or potassium hydroxide solutions in water and aqueous (bi) carbonate solutions.
• step (b) is performed at a temperature in the range of from 5 to 70 °C, more preferably from 10 to 50 0 C.
• step (c) is performed at a pressure in the range of from 1 to 100 bar (g) , more preferably from 1.5 to 80 bar (g) .
• the washing liquid is buffered.
• Preferred buffering compounds are carbonates, bicarbonates phosphates and mixtures thereof, especially sodium carbonate and/or sodium bicarbonate.
• concentration of the buffering compounds depends inter alia on the composition of the gas flow and is generally adjusted m such a way, that the washing liquid is kept within the preferred pH range.
• the pH of the washing liquid is in the range of from 4.5 to 10, more preferably from 5.5 to 9.0.
• step (c) hydrogen sulphide in the scrubbing medium is converted to elemental sulphur using sulphide- oxidising bacteria m the presence of oxygen m a bioreactor .
• sulphide-oxidising bacteria is to bacteria which can oxidise sulphide to elemental sulphur.
• Suitable sulphide-oxidising bacteria can be selected for instance from the known autotropic aerobic cultures of the genera Thiobacillus and Thiomicrospira.
• the main reactions that can take place in the bioreactor are the microbiological formation of sulphur and sulphate:
• the sulphur slurry may comprise one or more products of the main reactions, including elemental sulphur and sulphates.
• the regenerated aqueous alkaline washing liquid may comprise sulphur particles.
• sulphide-oxidising bacteria is to bacteria which can oxidise sulphide to elemental sulphur.
• Suitable sulphide-oxidising bacteria can be selected for instance from the known autotropic aerobic cultures of the genera Thiobacillus and Thiomicrospira.
• the reaction medium in the bioreactor is buffered.
• the buffering compounds are chosen in such a way that they are tolerated by the bacteria present in the oxidation reactor.
• Preferred buffering compounds are carbonates, bicarbonates phosphates and mixtures thereof, especially sodium carbonate and/or sodium bicarbonate.
• the concentration of the buffering compounds depends inter alia on the composition of the gas flow and is generally adjusted m such a way, that the pH of the reaction medium in the oxidation reactor is between 6.0 and 12.0, preferably between 7.0 and 11.0, more preferably between 8.0 and 10.0.
• Typical pressures in the bioreactor are between 0.5 and 2 bar (g) .
• at least part of the aqueous sulphur slurry obtained in step (c) is separated from the regenerated aqueous alkaline washing liquid.
• the separating step takes place in a solid/liquid separator. Suitable solid/liquid separators are described in Perry's Chemical Engineers' Handbook, 7*-h edition, section 22 (1997) .
• the sulphur content of the separated aqueous sulphur slurry is suitably between 5 w/w% and 50 w/w%, based on the slurry.
• the water of the sulphur slurry is removed to an extent that a sulphur cake with a dry solids content of between 55 and 70% is obtained.
• the sulphur purity of the sulphur cake is between 90 and 98 w/w%, based on the dry weight of the sulphur cake.
• the sulphur slurry can be re- slurried, filtered and dried to obtain a sulphur paste with a purity of at least 95 wt% sulphur, preferably at least 99 wt% sulphur.
• the sulphur paste thus-obtained can optionally be dried to produce a powder with a dry weight content of at least 85%, preferably at least 90%.
• This powder can suitably be applied as a fungicide, a fertilizer or as a miticide.
• step (d) carbon dioxide is removed from the synthesis gas stream depleted in hydrogen sulphide.
• step (d) carbon dioxide is removed by contacting the synthesis gas stream depleted m H2S with absorbing liquid to remove carbon dioxide and remaining hydrogen sulphide.
• Suitable absorbing liquids may comprise chemical solvents or physical solvents or mixtures thereof.
• a preferred absorbing liquid comprises a chemical solvent and/or a physical solvent, suitably as an aqueous solution.
• Suitable chemical solvents are primary, secondary and/or tertiary amines, including sterically hindered amines .
• a preferred chemical solvent comprises a secondary or tertiary amine, preferably an amine compound derived from ethanolamme, more especially DIPA, DEA, MMEA (monomethyl-ethanolamine) , MDEA (methyldiethanolamme) TEA (triethanolamme) , or DEMEA (diethyl- monoethanolamme) , preferably DIPA or MDEA. It is believed that these chemical solvents react with acidic compounds such as H2S.
• step (d) carbon dioxide is removed using a membrane.
• the selectivity is defined as the ratio of the carbon dioxide permeability over the permeability of carbon monoxide and hydrogen as measured in single gas experiments.
• the selectivity of the membrane is between 10 and 200, preferably between 20 and 150.
• the membrane material is chosen from the group of polyethylene oxide based materials, preferably polyethylene oxide based material comprising block- copolymers, especially PEO 600/5000 T6T6T or a cross linked PEO, polyimide or polyaramide based materials, cellulose acetate based materials, zeolite based materials, preferably silica-alumina phosphate based materials, more preferably SAPO-34, micro-porous silica materials and carbon molecular sieves materials.
• polyethylene oxide based materials preferably polyethylene oxide based material comprising block- copolymers, especially PEO 600/5000 T6T6T or a cross linked PEO, polyimide or polyaramide based materials, cellulose acetate based materials, zeolite based materials, preferably silica-alumina phosphate based materials, more preferably SAPO-34, micro-porous silica materials and carbon molecular sieves materials.
• step (d) carbon dioxide is removed by cooling the gas stream to a temperature at which carbon dioxide will separate from the gas stream.
• the gas stream is cooled to a temperature at which carbon dioxide becomes a liquid or a solid so it can be separated from the gas stream.
• the purified synthesis gas obtained in step (d) has low levels of contaminants, suitably m the ppmv or even in the ppbv range.
• the gas stream enriched in CO2 obtained in step (d) is at a pressure m the range of from 3 to 15 bara, preferably from 5 to 15 bara.
• This pressurised gas stream enriched in CO2 can advantageously be used for enhanced oil recovery, with less compression equipment needed.
• the CC>2-enriched gas stream is further pressurised and used for enhanced oil recovery, suitably by injecting it into an oil reservoir where it tends to dissolve into the oil m place, thereby reducing its viscosity and thus making it more mobile for movement towards the producing well.
• the C ⁇ 2-en ⁇ ched gas stream is further pressurised and pumped into an aquifer reservoir for storage.
• the pressurised C ⁇ 2 ⁇ en ⁇ ched gas stream is further pressurised and pumped into an empty oil reservoir for storage.
• the purified synthesis gas is used for power generation, especially m an IGCC system.
• fuel and an oxygen- containmg gas are introduced into a combustion section of a gas turbine.
• the fuel is combusted to generate a hot combustion gas.
• the hot combustion gas is expanded m the gas turbine, usually via a sequence of expander blades arranged in rows, and used to generate power via a generator.
• Suitable fuels to be combusted in the gas turbine include natural gas and synthesis gas.
• Hot exhaust gas exiting the gas turbine is introduced into to a heat recovery steam generator unit, where heat contained m the hot exhaust gas is used to produce a first amount of steam.
• the hot exhaust gas has a temperature in the range of from 350 to 700 0 C, more preferably from 400 to 650 °C.
• the composition of the hot exhaust gas can vary, depending on the fuel gas combusted in the gas turbine and on the conditions in the gas turbine.
• the heat recovery steam generator unit is any unit providing means for recovering heat from the hot exhaust gas and converting this heat to steam.
• the heat recovery steam generator unit can comprise a plurality of tubes mounted stackwise. Water is pumped and circulated through the tubes and can be held under high pressure at high temperatures. The hot exhaust gas heats up the tubes and is used to produce steam.
• the heat recovery steam generator unit can be designed to produce three types of steam: high pressure steam, intermediate pressure steam and low pressure steam.
• the steam generator is designed to produce at least a certain amount of high pressure steam, because high pressure steam can be used to generate power.
• high-pressure steam has a pressure in the range of from 90 to 150 bara, preferably from 90 to 125 bara, more preferably from 100 to 115 bara.
• low-pressure steam is also produced, the low-pressure steam preferably having a pressure m the range of from 2 to 10 bara, more preferably from to 8 bara, still more preferably from 4 to 6 bara.
• high pressure steam is produced in a steam turbine, which high pressure steam is converted to power, for example via a generator coupled to the steam turbine.
• the purified synthesis gas because of its low level of contaminants, is also suitable for use in catalytic processes, preferably selected from the group of Fischer-Tropsch synthesis, methanol synthesis, dimethyl ether synthesis, acetic acid synthesis, ammonia synthesis, methanation to make substitute natural gas (SNG) and processes involving carbonylation or hydroformylation reactions.
• catalytic processes preferably selected from the group of Fischer-Tropsch synthesis, methanol synthesis, dimethyl ether synthesis, acetic acid synthesis, ammonia synthesis, methanation to make substitute natural gas (SNG) and processes involving carbonylation or hydroformylation reactions.
• FIG. 1 there is shown a process for producing a purified synthesis gas stream.
• This starts with the gasification of biomass or coal with oxygen in a gasification unit 1 to form a feed synthesis gas stream comprising hydrogen sulphide, HCN and/or COS.
• a feed synthesis gas stream comprising hydrogen sulphide, HCN and/or COS.
• removal of solids such as slag, soot and the like is done in a solids removal unit (not shown) .
• the resulting feed synthesis gas stream is led to a shift unit 2, where it is contacted with a shift catalysis, converting CO to CO2 and hydrolysmg HCN and COS.
• the resulting synthesis gas stream depleted in HCN and COS emanating from unit 2 is led to H2S-removal zone 3 where H2S is removed by contacting the synthesis gas stream with an aqueous alkaline washing liquid.
• the resulting synthesis gas stream depleted in H2S is led from H2S-removal zone 3 to acid gas removal unit 4, where it is contacted with absorbing liquid to remove CO2 and remaining H2S.
• Aqueous alkaline washing liquid comprising H2S is led from the H2S removal zone to bioreactor 5, where H2S is converted to elemental sulphur .
• a preferred embodiment is depicted, wherein the purified synthesis gas is used for power production.
• a purified synthesis gas stream as produced in a process according to Figure 1 is led to a power plant comprising a gas turbine (1) and a heat recovery steam generator unit (2).
• an oxygen-containing gas is supplied via line 4 to compressor 5.
• Purified synthesis gas as produced in a process described in Figure 1 is supplied via line 6 to combuster 7 and combusted in the presence of the compressed oxygen-containing gas.
• the resulting combustion gas is expanded in expander 8 and used to generate power in generator 9.
• Remaining exhaust gas comprising CO2 and oxygen is led via line 10 to a heat recovery steam generator unit 2.
• water is heated against the hot exhaust gas in in heating section 11 to generate steam.
• the steam is led via line 12 into a steam turbine 13 to produce additional power in generator 14.

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