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    • 专利摘要:
    method for washing hydrogen sulfide and carbon dioxide from a gas obtainable through the gasification of carbon biomass. the present invention relates to the field of hydrocarbon production through the gasification of carbonaceous material. it provides a two-step gas washing method as part of a gas refining process. more specifically, it reveals a method for removing hydrogen sulfide and carbon dioxide from the synthesis of gas produced through gasification. it introduces a use of a new combination of washing approaches for this application. as a specific application, this process is used as part of a net biomass (btl) process.
    公开号:BR112013019997B1
    申请号:R112013019997-0
    申请日:2012-02-08
    公开日:2020-12-15
    发明作者:Jan WAHLSTRÖM；Juhani Aittamaa；Isto Eilos
    申请人:Neste Oyj；
    IPC主号:
    专利说明:

    Technical Field
    [0001] The present invention relates to the field of hydrocarbon production through the gasification of carbonaceous material. It provides a two-step gas washing method as part of a syngas refining process. More specifically, it reveals a method for removing hydrogen sulfide and carbon dioxide from the synthesis of gas produced through gasification. It introduces the use of a new combination of washing approaches for this application, one of which involves a chemical reaction and the other is based on physical absorption. As a specific application, this process is used as part of a liquid biomass (BTL) process. Background
    [0002] Gasification of carbonaceous materials primarily produces carbon monoxide and hydrogen, a mixture known as "syngas" (synthesis gas). Carbon dioxide, water and various hydrocarbons are by-products abundant in the product of gasification. Depending on the source and composition of the raw coal material and the gasification conditions, the levels of by-products and derivatives typically present as impurities vary, influencing refining strategies.
    [0003] During gasification, sulfur and its derivatives that originate from biomass are mainly converted to hydrogen sulfide (H2S) and carbonyl sulfide (COS). Gasification of the raw material from biomass produces very low levels of sulphidic impurities, relatively low levels of nitric and low levels of ash. The level of carbon dioxide is typically higher than that of gasification of mineral coal. These levels of impurities are still harmful to the processing of other chemical materials and the gas has to be purified. The decrease in the concentration of hydrogen sulfide is mandatory with regard to the functioning of the catalysts later on in the refining of the synthesis gas. On the other hand, the role of carbon dioxide in future reactions is basically like an inert gas. The reason for the removal of CO2 is related to the optimization of the currents and the reduction of the volumes of recycling flows and equipment. The strategies known from the gasification of mineral coal are not easily applicable.
    [0004] Together carbon dioxide, hydrogen sulfide and carbonyl sulfide are referred to as acidic gas since they dissolve in water to form acids. One of the most common means for purifying gases is the absorption that has been used to remove acid gas from natural and synthesis gases. When purifying the synthesis gas from biomass, absorption with a liquid solvent has been shown to be more efficient than absorption with a solid. For physical absorption. organic solvents in cold temperatures and high pressure are common. Roughly speaking, the higher the pressure, the colder the temperature and the higher the purity of the absorbent, and the better the washing effect. For chemical absorption, solutions of arsenic salts, various amines and carbonates are known. In general, the absorbent is regenerated by increasing the temperature and / or releasing the pressure.
    [0005] The foregoing technique describes effective absorbents for the removal of acid gas using, for example, methanol. Methanol requires low temperatures to be efficient and to prevent the loss of the absorbent. A very well-known commercial process with the use of methanol is the desulfurization process marketed under the trade name Reclisol®. The Reclisol® desulfurization process does not require the hydrolysis of the COS to H2S and can reduce the contents of the sulfur compound to relatively low levels in the synthesis gas. Methanol has a high affinity for hydrocarbons as well as acid gas. It also exhibits capabilities for the removal of not only sulfur and CO2 compounds, but also many relevant trace components (carbonyls, HCN), which makes washing with Reclisol a useful process. The synthesis gas is then reheated to about 350 ° C and passed through a fixed bed of a sulfur compound solvent, such as a ZnO guard bed to further reduce the decomposed sulfur contents in the synthesis gas. . Large temperature differences between the phases of the process consume a large amount of energy and make processing very expensive.
    [0006] In the prior art, EP 2223889 discloses a device that provides for greater development of washing if multiple steps with methanol as an integrated part of a Combined Gasification Cycle, IGCC. With the device revealed, as a multi-step process, this version of the Reclisol process removes CO2 as well as gas. As a process related to the production of energy, the purity requirements, however, are different from those applied in the production of chemicals and fuels in which a higher purity is required.
    [0007] Another prior art document, US 2010163803 describes a process for the production of gas products from a crude synthesis gas that is obtained through the gasification of coal and / or heavy oil. The origin of the gas gives the process a characteristic component profile. The invention of the process reveals how the displaced and non-displaced gas streams are purified from the sulfur and CO2 components, in the washing of acid gas, more specifically a washing with oxygen methanol. A suitable apparatus for the process is also described. Both the sulfur and CO2 components are removed together, the washes do not provide for the separation of these components.
    [0008] In addition to the physical absorption described above, chemical absorption is known in the art. The gas containing large volumes of hydrogen sulfide can be released from the said hydrogen sulfide through, first by conducting the gas stream into aqueous solutions containing copper ions in water for the absorption of the hydrogen sulfide and then oxidizing the copper sulfide thus formed with air or oxygen gas to produce elemental sulfur. The prior art document DE 2304497 describes an aqueous absorption medium containing rather high concentrations of copper ions (28.9 g of Cu in 1,400 ml of water) and the absorption of hydrogen sulfide carried out by bubbling the gas into the aqueous medium.
    [0009] Another document that represents the preceding technique, EP0986432 B1, describes a method for the selective removal of hydrogen sulfide from gases that comprise both H2O and CO2. When these components are present in the gas in a H211 to CO2 ratio of 2:11 the method removes 99% of the H2S selectively. However, when the ratio was 200: 1, the removal of H2S was 95%.
    [00010] There is still a need for an alternative method for the removal of sulfur and carbon dioxide components from the synthesis gas obtained through the gasification of carbonaceous material, especially when biomass gasification. In addition, there is a need with regard to removing the sulfur and carbon dioxide components from the synthesis gas in an energy efficient manner. There is also a need for effective combined removal of the sulfur component and carbon dioxide. Still, there is a constant need with regard to simplification, increase in effective capacity and identification of possibilities regarding the synergy of the total BTL process. Summary of the Invention
    [00011] The present inventors have surprisingly discovered that a washing method that comprises two different absorption steps, one involving chemical absorption and the other physical absorption, provides a high purity product with an energy consumption lower than that of the prior art methods. As the first aspect, a method for washing hydrogen sulfide and carbon dioxide from the gas that can be obtained through the gasification of carbon dioxide is provided in this patent application, which comprises: (a) putting in contact with said gas with a first absorbent solution comprising transition metal ions, said transition metals selected from copper, zinc, iron and cobalt, and mixtures thereof in aqueous acidic solution; (b) connecting the sulfide ions to said absorbent solution; (c) recovering the gas from step (b); (d) contacting the gas recovered from step (c) with a second absorbent solution comprising an organic solvent; (e) linking the carbon dioxide to said absorbent solution; (f) recovering the washed gas from step (e).
    [00012] A method is also provided for washing hydrogen sulfide and carbon dioxide from a gas obtainable through the gasification of carbon biomass, which comprises: (a) contacting said gas with a first aborbent solution comprising transition metal ions, said transition metals selected from copper, zinc, iron and cobalt, and mixtures thereof in aqueous acidic solution; (b) attaching the hydrogen sulfide to said first absorbent solution; (c) recovering the gas from step (b); (d) contacting the gas recovered from step (c) with a second absorbent solution comprising an organic solvent; (e) attaching the carbon dioxide to said second absorbent solution; (f) recovering the washed gas from step (e). This method and its modalities provide advantages. One of the advantages is a process scheme, in which the need for thermal conditioning and the equipment for heat exchange, especially for cooling, is significantly reduced when compared to processes using only methanol washing . The two-stage washing arrangement is necessary because the high levels of both H2S and CO2, surprisingly, the H2S removed in the first absorption step affects the second absorption by releasing the requirements for the absorption conditions , for example, allowing a higher temperature for washing with the organic solvent. In addition, energy consumption is lower.
    [00013] As the present method is especially suitable for washing the synthesis gas derived from biomass, the washing combination, especially in a determined sequence provides an efficient treatment for gas that has a high concentration in moles of CO2 and H2S. This method proved to produce washed gas having an H2S level of less than 20 ppb, and even lower levels of less than 1 ppb.
    [00014] As a second aspect, when used as part of a biomass to liquid process, the washing method is applied among the other steps of the process providing an improved method for the production of hydrocarbons or derivatives thereof. The method below comprises the steps: i. gasifying the raw material from the biomass in the presence of oxygen and / or water vapor to produce a gas comprising carbon monoxide, carbon dioxide, hydrogen, water and hydrocarbons; ii. optionally a tar reform step; iii. optionally removing the tar component, such as naphthalenes; iv. optionally adjusting the ratio of hydrogen to carbon monoxide; v. washing according to claim 1; saw. converting in a synthesis reactor at least a significant part of the carbon monoxide and the hydrogen contained in the gas into a product selected from the composition of hydrocarbons and derivatives thereof; and vii. recovering the product.
    [00015] When the synthesis of step vi is the FischerTropsch (FT) synthesis, the washing protocol of step v reduces the acid gases viable in the FT synthesis process feed to levels as low as 20 ppb, satisfying the requirements regarding to FT catalysts, and the CO2 level is low enough to prevent it from accumulating in the process. Brief Invention of the Figures
    [00016] Figure 1 illustrates an experiment that comprises contacting the gas with a first absorbent solution, in this context, an aqueous solution of CuSO4, connecting the H2S to it and recovering the gas according to steps (a), ( b) and (c) of claim 1. The figure describes a mole ratio of the flow of H2S flowing to the outlet of the wash bottle / moles of H2S flowing into the inlet of the wash bottle as a function of time (h: min.) The experiment started at 9:33 and the last point was measured at 15:11.
    [00017] Figure 2 illustrates another experiment that comprises the contact of the gas with the first absorbent solution, in this context an aqueous solution of CuSO4, connecting the H2S to it and recovering the gas according to steps (a), (b ) and (c) of claim 1. The figure describes a mole ratio of the H2S flow flowing to the wash bottle outlet / moles of H2S flowing to the wash bottle inlet as a function of time (h: min .) The experiment started at 9:53 and the last point was measured at 15:16.
    [00018] Figure 3 illustrates an experiment that comprises the contact of the gas with the first absorbent solution, in this context an aqueous solution of CuSO4, connecting the H2S to it and recovering the gas according to steps (a), (b ) and (c) of claim 1. The figure describes a mole ratio of the H2S flow flowing to the wash bottle outlet / moles of H2S flowing to the wash bottle inlet as a function of time (h: min .) The experiment started at 10:43 and the last point was measured at 13:22.
    [00019] Figure 4 describes a simple flow diagram of an embodiment of the method of the present invention for the removal of H2S and CO2 through a two-step process. Detailed Invention of the Invention
    [00020] In this patent application a new method is provided for washing hydrogen sulfide (H2S) and carbon dioxide (CO2) from a gas that can be obtained by gasifying a carboniferous biomass. The characteristic with this method is that it involves two washes in a row, one of which involves a chemical reaction and the other is based on physical absorption. The first wash comprises: (a) contacting said gas with a first absorbent solution comprising ions of a transition metal, said transition metals selected from copper, zinc, iron and cobalt and mixtures of themselves, in acidic aqueous solution; (b) connecting the sulfide ions to said first absorbent solution; (c) recovering the gas from step (b).
    [00021] The first wash selectively removes the hydrogen sulfide from the gas. The removal efficiency is high. At least 90%, preferably at least 95% of the hydrogen sulfide present in the feed material can be removed at this stage.
    [00022] The second wash comprises: (d) contacting the gas recovered from step (c) with a second absorbent solution comprising an organic solvent; (e) linking the carbon dioxide to said absorbent solution; (f) recovering the washed gas from step (e).
    [00023] The second wash mainly removes carbon dioxide. As the concentration of hydrogen sulfide had already been considerably reduced in the first washing step, the absorption capacity of the second absorbent can be used mainly for the removal of carbon dioxide. The inventors have found that the hydrogen sulfide concentration is further lowered in the second wash providing a gas recovered to such a high purity, that in some cases, the guard beds that remove H2S before synthesis reactions can be omitted.
    [00024] When applying the method of the present invention, the selection of conditions with respect to the second wash may be less severe than when applying the corresponding wash with the separate organic solvent. Temperatures, pressure, recycling, etc., do not need to be taken to the extreme to obtain the desired levels of purity. Especially noteworthy is the temperature at which high purity was also acquired experimentally.
    [00025] Yet another advantage of the present invention is that when sequential removal of H2S first and CO2 thereafter is applied, these process units are essentially independent of each other. In particular, the second washing step can be directed to the level of purity required by the processing that follows without compromising the ultra clean character of the first absorption step. Thus, the independent control of the removal of acid gases is possible through the present method.
    [00026] In the form used here, in this patent application, "absorbent solution" refers to a washing liquid used for washing the gas. For processing purposes, such as fresh, it is preferably a true solution, so that all components are solubilized in the solvent. A person skilled in the art understands that, when used, especially when there has been a chemical reaction involved, said absorbent solution may contain solids or precipitates.
    [00027] With "connecting a gas to an absorbent solution", it basically means the absorption of said gas to said solution. This includes all phases of absorption, mass transfer from gas to a solvent gas interface, dissolution of the gas in the liquid phase, and in a case of chemical absorber, the chemical reaction in question.
    [00028] The two-step method preferably removes at least 99%, preferably at least 99.9% of the H2S present in the gas supply. Of the carbon dioxide, the removal is at least 90%, preferably at least 95% of the CO2 present in the gas supply.
    [00029] When the process is described, the measures and the results, the proportions given are in percentages of the total volume of dry gas gas, unless stated otherwise.
    [00030] An illustration of the method is given in Figure 4, which describes a simple flowchart of an embodiment of the method of the present invention for the removal of H2S and CO2 through a two-step process. In said figure 4, the crude synthesis gas is fed to an optional hydrolysis reactor, which converts HCN and COS, followed by an optional water washing reactor, from the outlet from which the aqueous HCl and NH3 are removed. The essence of the invention is inside the next two reactors. P first of which is a reactor named in figure 6 as the CuS precipitation unit. In the said reactor, the gas is brought into contact with the diluted aqueous solution of CuSO. With sulfides that originate from hydrogen sulfide gas, copper forms CuS, which is practically not soluble in water and precipitates out of solution.
    [00031] The gas recovered in this way is then taken to a washing unit with methanol to remove CO2. Methanol has a good ability to remove acid gases, however, as most of the hydrogen gas sulfide had already been removed in the previous step, the unit is designed only for the removal of CO2.
    [00032] According to the modality described in figure 4, the gas is fed to the absorption unit (CuS precipitation) from a gas washer (water wash). The first step of absorption in acidic aqueous solution can preferably be carried out at the same temperature as that of the said wash, cooling is only required before the second wash with methanol.
    [00033] Optionally a guard bed (Figure 4) or multiple guard beds can be added downstream of the units, with respect to safety and in the vessel of abnormal situations.
    [00034] The combination of the first and second absorbents according to claim 1 has surprisingly proven to allow for the desired purity and separate recovery of CO2 and H2S providing savings in energy consumption compared to washing with one-step methanol when removing H2S and CO2. Feed characteristics.
    [00035] When refining the synthesis gas that can be obtained from biomass gasification, the acid gases mainly consist of H2S, CO2 and COS. As an example of a typical composition, the gas composition fed for gas washing comprises as the main components (calculated from dry gas) from 20 to 40% by volume of H2, from 10 to 30% by volume CO, and as acid gas impurities from 50 to 400 ppm of H2S, from 20 to 40% by volume of CO2 and from 5 to 50 ppm of COS and other traces.
    [00036] The special characteristics for refining gas originating from biomass are high concentrations of H2S and CO2. If there is a need to recover these components separately, the references of the preceding technique suggest the use of physical absorption, as chemical absorbents tend to remove CO2 and H2S at the same time. Transition metal ions.
    [00037] In the method for washing hydrogen sulfide and carbon dioxide from a gas obtainable through the gasification of carbon biomass, the first step of this method comprises first contacting said gas with a first absorbent solution comprising transition metal ions in acidic aqueous solution.
    [00038] This step is efficient for the removal of 4 H2S. The present inventors have found that in acidic aqueous solutions, transition metals, for example, Cu2 + ions, react quickly with H2S in liquid even at very small concentrations of the metal ions. The results evidenced in Patent Application EP 11153704 (not yet published) describing a method for the purification of gasification gas (synthesis gas) by absorbing the impurities of the synthesis gas in a liquid absorption medium containing metal ions capable of to bind to sulfide ions in solid sulfides that have a low solubility in water and in aqueous solutions. Thus, said metal ions, preferably and predominantly ions of bivalent transition metals, have the effect of sulfide alloys, present as H2S in the gas phase, from the gas to said first absorbent solution. When reacted with this solution, the gas is recovered for further processing.
    [00039] Another document of the preceding technique, EP 0986432 B1, discusses the theory, especially the precipitation characteristics exhaustively from paragraph 27 to paragraph 43.
    [00040] However, now the inventors have further developed the idea and have proven that when the absorption of a transition metal ion for the removal of H2S, as the first wash, is combined with a wash with methanol for the removal of CO2 , said washes together provide an unexpected synergy.
    [00041] The first step is performed by contacting the gas with the first absorption solution, and thus an acidic aqueous washing solution containing metal ions capable of binding to the sulfide ions of the sulfide compounds present in the gas. The concentration of the transition metal cations is small, for example, the aqueous solution has a concentration in relation to the transition metal ions of about 0.00001 to 0.01 M. A significant part of the sulfide impurities present and contained in the gas it can be converted into transition metal sulfides. The sulfides formed in this way are preferably precipitated into the washing solution by half than the sulfide impurities are removed from the gas. The purified gas obtained in this way is recovered from the aqueous solution.
    [00042] The metal ions, that is, the cations, of the washing solution are derived from the transition metals selected from copper, zinc, iron and cobalt and mixtures thereof. Preferably, the washing solution comprises cations of divalent metals (Me2 +) of copper (Cu2 +), zinc (Zn2 +) or iron (Fe2 +) or mixtures thereof, as these cations react with the sulfides (S2-) forming salts with very low solubility in water. In practice, the most suitable salts used as the sources of the metal cations comprise traces of other metal derivatives, as well as, for example, the commercial CuSO4 salt also comprises some monovalent copper, such as Cu2SO4. Copper has proven to be economically efficient and has proved successful in experimental studies, especially when added as CuSO4.
    [00043] The transition metal ions are obtained from water-soluble metal salts by dissolving said salts in water. In one embodiment, the aqueous solution is prepared by dissolving about 1 to 10,000 parts, preferably about 50 to 5000 parts by weight of a metal salt within 1,000,000 parts by weight of water.
    [00044] When applied to remove H2S from the synthesis gas obtainable from biomass gasification, typically the concentration of the metal ion compound in the washing solution may be lower than about 1000 ppmw, preferably lower than 100 ppmw, calculated from the weight of the absorption liquid. This allows for a concept of a very effective and profitable integrated process for the removal of H2S and other impurities mentioned above from the synthesis gas.
    [00045] The concentration of Me2 + ions in the aqueous wash solution is typically about 0.00005 M to 0.005 mM per liter, preferably about 0.001 to 0.001 M.
    [00046] The aqueous wash solution is acidic or weakly acidic; preferably it has a pH of about 1 to 6.5, and specifically about 1 to 5. The pH will vary within the indicated range depending on the selection of the metal cations. For example, in the embodiment in which the source of the metal cations is CuSO4, the aqueous solution has a pH of at least about 3, preferably a pH from 4 to 5.
    [00047] In general, the gas is brought into contact with the washing solution at a temperature from 10 to 80 ° C and at a pressure from 0.1 to 5 MPa (1 to 50 bar) ( absolute pressure). Thus, washing can be carried out at ambient temperature and pressure (20 to 25 ° C and 0.1 MPa (1 bar (s))), although it is also possible to work with the present technology at lower temperatures (from 10 to < 20 ° C) and at high temperatures (> 25 to 80 ° C) it can be in excess of 0.1 MPa (1 bar (s)), for example, from about 0.15 to 5 MPa (1.5 to 50 bar (s)).
    [00048] Typically, the synthesis gas obtained from gasification is recovered at a higher temperature than that indicated in the preceding one. For this reason, in one embodiment, the gas gas is cooled to a temperature in the range indicated above (from 10 to 80 ° C) before being put in contact with the liquid to be washed. When the temperature is higher than 80 ° C the reaction is quick, but the precipitate is formed as very fine particles that are difficult to be recovered from the washing liquid. If the temperature is below 10 ° C, the need for cooling increases operating costs. It is possible to recover some heat contained in the gasification gas by contacting it with a cooling medium, for example, with water for cooling, in a heat exchanger.
    [00049] However, as the aqueous wash is first, the need for cooling exists only in relation to the second wash, providing energy efficiency for both the washing method according to the invention and for the complete production of gas and further refining.
    [00050] Under these conditions, also acidic compounds, such as hydrogen chloride, can be absorbed. Also, the aqueous solution containing the metal ions can be applied in an acidic form. That way, it will be able to absorb more impurities, such as ammonia (NH3) and hydrogen chloride (HCl) as well as other alkaline and acidic impurities. With regard to the total process, this is yet another advantage.
    [00051] The molar ratio of the metal cations to the sulfide compounds of the gas to be purified (i.e. the Me2 + / S2 ratio in the feed) is typically in excess of 1, preferably from about 1.4 to about 6. Surprisingly, the use of metal ions is efficient and no large excess is necessary, since the reaction continues to be irreversible as the precipitated month leaves the solution. Process equipment.
    [00052] Technically, said contact of the gas with a first absorbent solution comprising transition metal ions in an aqueous acidic solution can be implemented in a tray or densified column and / or applied through spraying or atomization. In a first preferred embodiment, the contact of the synthesis gas with the absorption medium takes place by spraying or atomizing the absorption medium within the gas. Preferably, the contact of the synthesis gas with the absorption medium takes place at the interface between the gas and droplets of the absorption medium. In a second preferred embodiment, the gas to be purified is bubbled into a stirred tank containing the absorption solution. In a third modality, absorption towers with plates and / or densification can be used in an operation against current. The type of detailed equipment depends on the concentration of the metal ions in the solution and the amount and content of impurities in the gas. One way to perform the chemical absorption process is to use the chemical spray absorption concept combined with a sieve tray or sieve trays above the spray chamber section (s) as described and shown in Figure 6 of the pa order - try EP 11153704.
    [00053] Thus, in a specific modality based on the spray chamber approach, the washing solution is brought into contact with the gas in a spray chamber that has an essentially vertical central axis, said gas being fed in. of the spray chamber from the bottom or from the top and removed from the opposite end in such a way as to advance in the direction of the central axis of the spray chamber. The washing solution is fed through spray nozzles arranged in at least two spray zones arranged in series along the central axis at different heights in the spray chamber. The gas is fed into the spray chamber, for example, of the preceding type, through gas distributors located below the lowest spray zone, and the metal sulphide is removed from the absorber together with the used washing liquid through an outlet at the bottom of the chamber.
    [00054] In modalities in which regeneration is applied after the absorption of sulfides, crystals of month and other solids are separated from the circulating aqueous washing liquid.
    [00055] A transition ion washing unit can also consist of two Me2 + aqueous wash sections (named following the direction of the gas flow) in which the first section is operated with an aqueous wash diluted with Me2 + ions and the second section with another aqueous wash very concentrated with Me2 + ions. The required amount of Me2 + ions is fed in the form of an aqueous solution with Me2 + inside the second wash section and circulated. The synthesis gas from the first wash section will be fed into the second wash section in which almost all of the H2S in the synthesis gas will be removed by backwashing.
    [00056] The results of purification using transition metal ions in aqueous acidic washing liquids are very good. The present method is capable of removing a significant part of the hydrogen sulfide from the gas. At least 98% by volume, preferably at least 99.5% by volume of the hydrogen sulfide is removed from the gas. As a result, in a preferred embodiment, the concentration of hydrogen sulfide in the gas after the first washing step is less than about 100 ppb by volume, specifically less than about 50 ppb by volume. This is further reduced by the second washing step which mainly removes carbon dioxide, but by reducing the hydrogen sulfide content to less than 20 ppb, preferably to less than 10 ppb or even less than 1 ppb.
    [00057] The purified gas in the first absorption provides the food for the second absorption step in which a solution comprising an organic absorber is used. Washing with a second absorbent solution comprising an organic absorbent.
    [00058] After the step of contacting the gas with the first absorbent solution, the gas recovered from it is then brought into contact with a second absorbent solution comprising an organic absorbent.
    [00059] Different organic absorbers are available for this washing step. Alcohols are common organic absorbents, such as methanol and ethanol. Other commercially available reagents are the potassium salts of diethylamino-acetic acid and dimethylamino-acetic acid, sodium-2-amino propanic acid, sodium salt of amino-propionic acid and sodium phenolate. Tributyl phosphate has been considered a weak solvent for CO2, however, in combination with the first absorbent step of the present invention, performance is enhanced. Also applicable organic solvent is propylene carbonate, which is mentioned as being specifically suitable for processes in which a partial pressure for CO2 is high. Another suitable absorbent in this category is N-methyl pyrrolidone, which is a stable, non-corrosive and easily available solvent. To remove other impurities (such as COS), N-methyl pyrrolidone can be diluted with water. In general, said solvents comprise some water and if obtained from regeneration also some impurities.
    [00060] A second typical absorbent solution primarily comprises methanol. Washing with methanol as such is known in the art and a person skilled in the art has an ample supply of literature (such as, for example, Esteban, A., V. Hernandez, and K. Lunsford, "Exploit the Benefits of Methanol," Proceedings of the 79th Annual Convention, Gas Processors Association, Tulsa, Oklahoma, 2000.) to guide you through the selection and optimization of process conditions. In this context, it is used in combination with aqueous washing with transition metal ions, the combination of which provides good results for gases comprising H2S and abundant CO2 as impurities.
    [00061] The purpose of washing with methanol and to decrease the concentration of CO2 in the synthesis gas in order to decrease the total amount of inert in the Fischer-Tropsch feed. After removing the tar, the synthesis gas is cooled before washing with MeOH, and the condensed water is removed. Then, the synthesis gas is cooled to the absorption temperature and fed into the methanol wash column. The outlet of the synthesis gas from the methanol wash column has a CO2 concentration of about 15 mole%, preferably less than 4 mole%, and more preferably about 2 mole%. The gas recovered in this way is then carried through heating to the guard beds.
    [00062] When used for gas obtained from biomass gasification, the use of an organic solvent provides an additional advantage by removing selected aromatic impurities from benzene, toluene and naphthalene. If a low enough level is obtained through the absorption step, additional separation is not necessary or optionally only simple guard beds can be included.
    [00063] Within the context of the present invention, the combination of the first absorption step and the second absorption step provides advantages over the prior art solutions. As the first absorption step effectively removes H2S, the conditions with respect to the second absorption step need not be as severe as in the prior art processes. the present inventors have demonstrated that instead of the highly chilled conditions (-40 ° C or even -70 ° C) traditionally applied, for example, as washes with methanol, the second absorption was carried out at temperatures of -23 ° C and -13 ° C and simulated at temperatures of -10 ° C with excellent results. These results provide considerable advantages for the project model and for the selection of operating parameters.
    [00064] When the first and second absorption steps according to the invention are applied, the requirements regarding the conditions of the second absorption are relaxed. In general, in physical absorption, the higher the pressure, the colder the temperature and the higher the purity of the absorbent, lead to a better washing effect. However, the present inventors have concluded that to the extent that H2S had been removed from the gas, high CO2 removal can be achieved by regenerating the organic solvent and / or the higher absorption temperature and / or a higher pressure low stringent. CO2 recovery.
    [00065] The CO2 stream from methanol regeneration is cooled in two stages: hydrocarbons are condensed from the synthesis gas and the methanol emissions to the CO2 column are reduced by cooling. The cooled CO2 stream is heated to prevent unwanted additional air humidity from condensing near the column. Energy consumption.
    [00066] The method of the present invention as defined in claim 1, comprises two steps of chemical absorption. In the absorption processes, there are three stages that determine energy consumption. The preference parameters that contribute to low energy consumption are selected.
    [00067] The first is the conditioning of the gas (pre-heating or pre-cooling of the gas) to be flushed before feeding for the absorption stage. For chemical absorption, the temperature range that can be applied is much wider and the need for thermal conditioning at this stage is typically lower than for physical absorption. In many cases, no conditioning is necessary, as chemical washing can be carried out at the temperature of the preceding process step.
    [00068] The next energy intensive phase that follows consists of the absorption steps. There, depending on the selected reagents, conditions and purity level, the need for cooling or heating the reactor and / or reagents exists, specifically in physical absorption.
    [00069] The third point at which energy consumption must be considered is in the regeneration of the absorber. Absorber regeneration.
    [00070] As an embodiment of the invention, the method may further comprise regenerating the first or the second absorbent solution or optionally both.
    [00071] Depending on the absorbent and the level of purity required, three procedures regarding their regeneration are known to a person skilled in the art. The simplest and least expensive method for regeneration is flash regeneration, in which the pressure of the absorbent is, for example, gradually decreased. The concentration of the acid gas is determined by the last step, the pressure of which is usually slightly higher than the ambient pressure. By using a vacuum in the last step, the concentration of the acid gas in the absorbent can be further lowered.
    [00072] When higher purity is required, regeneration can be carried out by extracting the absorbent with an inert gas. In the extraction, the pressure of the absorber is lowered and then the partial pressures of the gases to be removed are reduced by feeding an inert gas to the reactor. A negative side of the regeneration system is the dilution of the acid gas flow with the inert gas used.
    [00073] Both methods of regeneration, scintillation and extraction still leave some acidic gas in the absorption solvent. For cases in which the level of hydrogen sulfide to be removed is very low, these methods are sufficient. However, with regard to the higher concentrations of hydrogen sulfide in regeneration based on the boiling of the solvent such as hot regeneration is necessary. This provides a very high degree of purity with respect to the gas to be flushed and in addition a high concentration of gas in the effluent gases. The underlying principle in this method is that the solubility of the gas within the absorbent solvent is reduced by raising the temperature. The solvent is heated to its boiling point, whereby the vaporized solvent extracts impurities. When the steam is then cooled and condensed, it can be reused for absorption. Hot regeneration required expensive heat exchangers and consumes enormously heat for the vaporization of the solvent. It is the most expensive of the aforementioned methods. However, hot regeneration is almost always necessary with respect to chemical absorbents as the acid gases are chemically linked to them.
    [00074] With regard to the physical absorbent, in this context the meta-nol, regeneration through the drop or gradual decrease in pressure is more appropriate due to the strong correlation between the solubility of the acid gas and the partial pressure. If high purity is required, regeneration of the physical absorbent can be carried out by extraction with an inert gas or by boiling or distilling the solvent.
    [00075] Preferably, the regenerated absorption solution can be taken back to the washing process and reused after adjustment to the appropriate reaction conditions.
    [00076] In one embodiment, when the washes combination according to the invention is applied as a part of the biomass with respect to the gas process, the regeneration of the second absorbent solution comprising an organic solvent can be destined to serve for the total process. The methanol that comes out of the methanol wash column is taken, first into the CO scintillation drum, in which mainly the CO is recovered and recycled to the main stream. Then the methanol that is released is flared to obtain the CO2 to be used in the hoppers blocking the biomass feed. Finally, the outgoing methanol is flared to obtain a feed into the methanol wash column.
    [00077] A part of the scintillated methanol is taken to a regeneration column, in which the methanol is extracted with a mixture of air and nitrogen to obtain a very pure feed to the top of the methanol wash column. Nitrogen is added to the air for extraction to reduce the oxygen concentration below the explosion limit.
    [00078] A portion of the regenerated methanol is fed to another methanol drying column, in which water is removed from the methanol. The impurities are linked to accumulate within the methanol recirculation and in this way a part of the methanol is bled into the used MeOH tank.
    [00079] It should be noted that the requirements regarding regeneration for the present process are less stringent than for processes that use only methanol washing, inasmuch as the synergistic action of the two absorption processes provides purity taller. Recovery of metal sulphides.
    [00080] In addition, from the aqueous solution or slurry, metal sulfides that have poor solubility in the aqueous medium, can be removed by any liquid solid separation process. The separation of solids is simple and many separation techniques, such as filtration, decantation or hydro cyclones are available. This separation is attractive when compared to the prior art methods, in which the regeneration of the H2S-containing absorbent is typically conducted to a regeneration section. From said regeneration section of the preceding technique, the acid gases separated from the absorbent are taken to a sulfur plant that converts H2S into elemental sulfur (S). These investments can be avoided entirely.
    [00081] The precipitate of metal sulfides can also be treated for the separation of the metal and the sulfur derivatives and both consequently recovered. For example, when the metal sulfide is CuS, the separated solids can be used as a raw material in the copper industry, both for the preparation of metallic copper and other copper compounds, and the sulfur recovered from that process. it can be used as raw material for the production of sulfuric acid, typically integrated into the site. The use of purified gas.
    [00082] After the treatment according to claim 1, a purified gas is obtained. The H2S level in the gas recovered from step (e) is less than 20 ppb, preferably less than 10 ppb, and most preferably less than 2 ppb. Purified gas has several uses. It can be used for the production of hydrogen, methanol, ethanol, dimethyl ether or aldehyde, optionally via hydro formulation or directly used in engines for the production of, for example, electricity. Synthetic natural gas (SNG) can also be produced from synthesis gas.
    [00083] The purified gas can also be used for the production of hydrocarbon compositions containing C4-C90 hydrocarbons, optionally after purification. Specifically, the hydrocarbon composition can be produced using a Fisher-Tropsch (FT) process.
    [00084] As a specific modality of a total process, the removal of acid gas can be applied in a process for the production of hydrocarbons or derivatives thereof from a raw material from biomass. The method below comprises the steps: i. gasifying the raw material from the biomass in the presence of oxygen and / or water vapor to produce a gas comprising carbon monoxide, carbon dioxide, hydrogen, water and hydrocarbons; ii. optionally a tar reform step; iii. optionally removing the tar component, such as naphthalenes; iv. optionally adjusting the ratio of hydrogen to carbon monoxide; v. washing according to claim 1; saw. converting in a synthesis reactor at least a significant part of the carbon monoxide and the hydrogen contained in the gas into a product selected from the composition of hydrocarbons and derivatives thereof; and vii. recovering the product.
    [00085] According to a preferred mode, the steps are taken in the order from i to vii. Even though the washing according to claim 1 is referred to here, in this patent application, as the washing step v, it is understood to comprise all the characteristics of the claim as filed.
    [00086] H2S removal is necessary for the protection of the synthesis catalyst. In addition, when applying this method for the production of hydrocarbons using FT synthesis, although CO2 acts as an inert gas in the synthesis, it affects the selectivity of the synthesis guiding towards the C5 + products, whereby, at least partial CO2 removal is made desirable with respect to the total process. Contrary to the processes described in the documents of the preceding technique in relation to the purification of synthesis gas derived from mineral coal, the attention in the removal of the acid gas, when applied to the gas originating in biomass, is mainly paid for the removal of CO2.
    [00087] Another considerable value in favor of the present process is that the high pressure advances both absorption and the subsequent FT synthesis. If the pressure is increased before absorption or at least before the second wash of the present method, there is no need to change the pressure after washing. A person skilled in the art learns that increasing the absorption pressure above the level required to the level required for FT synthesis is not preferred, although it is possible. Typically the pressure used in the FT synthesis is from 2 to 6 MPa (20 to 60 bar), preferably from 2 to 3 MPa (20 to 30 bar), which practically sets the upper limit for the absorption process.
    [00088] In an embodiment of this method, the use of iron and co-balto as the metal ions in the first absorbent solution is antagonistic, since they are used in other parts of the general process, specifically as catalysts of synthesis FT. However, copper is the metal ion preferably used specifically as CuSO4.
    [00089] Optionally, the process may comprise a tar reform step, such as, for example, in accordance with patent application Fl 20105201. It discloses a method for the purification of gas gas from tar and impurities ammonia with the use of catalysts at high temperatures. The pre-catalytic zone comprises layers of zirconium / noble metal catalyst followed by the actual catalytic zone comprising a nickel or other layers of reforming catalysts. Oxygen or other oxidizer and optionally water vapor can be taken to the reforming zone to increase the temperature.
    [00090] For catalytic FT synthesis, the molar ratio of hydrogen to carbon monoxide is preferably from 1: 7 to 2: 2, advantageously about 2. To adjust the ratio, the person skilled in technician can select between different strategies. The said proportion can be adjusted through a water and gas displacement reaction (WGS) either as the displacement of the acid gas or after the appropriate sweetening of the gas, and thus the purification of the gas from the acid gases. Another approach is the addition of hydrogen obtained from another place in the process, or from another process to adjust the said proportion.
    [00091] To a certain extent, the COS can be hydrolyzed in the first absorption step of the present invention. However, separate hydrolysis is sometimes necessary. According to an embodiment of the method above for the production of hydrocarbons, step v is preceded by a COS hydrolysis step. Said hydrolysis produces H2S which is consequently removed in the first absorption step and CO2 is removed in the second absorption of the washing process of the present invention. This is advantageous in cases where the syngas contain disturbing amounts of COS. COS has poor solubility with respect to both chemical and physical absorbers, causing difficulties in purification.
    [00092] In addition, according to one modality, it is also advantageous to operate a water wash before the washing steps to minimize NH3 and HCl in the transition metal precipitation step. Said NH3 and HCl interfere in the metal precipitation stage and their removal contributes to a purer CuS precipitate.
    [00093] The following experiments were carried out to demonstrate the concept of the present invention. They are to be understood as illustrating certain examples of the invention and not by any means as a limitation. Experimental part.
    [00094] The method of the present invention is a two-step washing process.
    [00095] The first phase, absorption using an aqueous solution comprising transition metal ions, was described in applicants' previous patent application EP1 11153704. These experiments now described as examples 1 and 2, also apply for the first stage of the present invention. In the aforementioned first phase, the gas to be purified is brought into contact with a first absorbent solution comprising transition metal ions, said transition metals selected from copper, zinc, iron and cobalt and mixtures thereof, in acidic aqueous solution (in the CuSO4 aqueous solution experiments); hydrogen sulfide0 is attached to said first absorbent solution and the gas is recovered
    [00096] The second phase, absorption through cold methanol is widely described in the prior art. As the second stage of the present invention, washing with an absorbent comprising an organic solvent has a special feature of removing mainly carbon dioxide, in that the sulfur derivatives have already been removed. It can be described as first by contacting the gas recovered from the first wash with a second absorbent solution, which comprises an organic solvent, binding the carbon dioxide to said second absorbent solution and finally recovering the washed gas, preferably to a further processing.
    [00097] The experiments carried out to provide evidence regarding the combination of the aforementioned phases, include the results from a pilot scale round (Examples 3 and 4) and simulation of the total process (Example 3). 1. Example 1. H2S removal semi-batch absorption test, using aqueous copper sulfate (CUSO4) as a model absorbent of the first absorbent solution. 1.1 Materials and methods.
    [00098] The absorption experiments were carried out with the use of a micro reactor equipment for the WGS reaction. The semi-batch absorption tests for the removal of H2S, using the aqueous copper sulfate solution (CuSO4) as the absorbent, were performed in a simple 0.5 liter gas washing bottle with magnetic stirring, placed on the production line of a micro reactor before the online mass spectrometer.
    [00099] The absorption tests were carried out at room temperature and atmospheric pressure. The total flow of the gas supply was 12 dm3 / hour to the WGS reactor. The basic composition of the gas supply is shown in Table 1. Table 1.

    [000100] The impurity components were purchased from AGA, as a mixture of H2S / H2, COS / H2 and NH3 / H2 gases, diluted in hydrogen. In the feed, the H2S concentration was 500 ppm (volume) in all experiments. In some tests also 85 ppm of COS and 800 ppm of NH3 were used in the diet. However, almost all of the COS had already been hydrolyzed before the absorption bottle, since it was not possible to bypass the catalytic reactor, in which the hydrolysis of the COS took place as a side reaction of the gas-water exchange reaction.
    [000101] The gas product was analyzed online with the use of a mass spectrometer (GC-MD, however, with the separation of GC not in use). The limit of quantification is dependent on the component, and in these MS measurements the limit of quantification was about 1 ppm.
    [000102] In the absorption experiments carried out in the laboratory using the bubbled gas washing bottle described above, the following test program was carried out as follows:. The concentration of CuSO4 varied in different experiments from a dilution of 50 ppm to 500 ppm. Mass transfer in the bubbled gas washing bottle was enhanced with stirring. . The absorption rate of H2S in the CuSO4 solution and water was measured at different CuSO4 concentrations. . The identification / quantification of the crystallized Cu solid components and the particle size distribution of the crystallized particles. 1.2 Results
    [000103] The feed speeds of the different impurity components in the synthesis gas that entered the WGS reactor in the experiments were: * Test 1 CuSθ4 conc. at 0.01%, H2S concentration in the 500 ppm feed gas, * Test 2 CuSθ4 conc. 0.01%, H2S concentration in the feed gas of 500 ppm, NH3 800 ppm, COS 85 ppm, * Test 3 CuSo4 conc. at 0.0051%, H2S concentration in the feed gas of 500 ppm, NH3 800 ppm, COS 85 ppm,
    [000104] Flow in moles at the outlet of the washing bottle / flow in moles of H2S at the entrance of the washing bottle in different experiments is shown as a function of time in Figures 1 3. 1.3 Conclusions
    [000105] CuSO4 was able to remove 500 ppm of H2S (molefaction) completely from the feed gas in both 0.01 and 0.0051% by weight aqueous solutions. The product is a solid CuS deposit. * the very high pH resulted in the deposition of, for example, hydroxides or metal carbonates, in which case none or less hydrogen sulfide was removed. Carbonate formation was also dependent on the partial pressure of CO2. * the very low pH resulted in no de-position formation in which case no hydrogen sulfide was removed (results not shown). * NH3 in the diet did not influence the H2S removed by copper sulfate.
    [000106] Regarding the results described in figures 1 to 3, it should be noted that the experimental arrangement was as follows: the bottle of the aqueous copper sulfate washing solution was placed between two coolers of the reactor product and one volumetric drum type gas flow meter. Through the opening of the valves the gas can be sent to the volumetric flow of the drum type through the aqueous solution of CuSO4 and after that to the GC-MS and then the gas was conducted to the volumetric gas meter of the drum type to exhaustion. The first point shown graphically is from the time point just before the gas is conveyed to the CuSO4 bottle. At that point in time, CuS precipitation is not yet detectable. Then, a series of 4 samples was taken within 7 minutes, after a short stop, a new series of 4 samples was taken within 7 minutes, etc.
    [000107] The points in the figures at which the H2S concentration is 0 indicate points at which all of the H2S is removed from the gas. Suddenly after that, all copper is depleted and the concentration of H2S increases again.
    [000108] Some of the tests had the COS contained in the food. Having passed the transfer reactor, it is practically completely hydrolyzed since the feed also contains water. COS + H2O <-> H2S + CO2
    [000109] Next, there is more H2S in the CuSO4 wash feed than the amount of H2S fed into the system. This effect can be seen in the analysis in the amount of effluent of 0 3 ppmv COS. 2. Example 2. Absorption test for the removal of H2S from the synthesis gas in the packed bed absorption column.
    [000110] The absorption tests for the removal of H2S from the synthesis gas in the packed bed absorption column were performed in a pilot scale test unit. Absorption performance was tested at a syngas preparation facility in Varkaus, Finland.
    [000111] The details of the absorber and data sheets are shown below: Absorber: * packed bed absorber, packing metal in 2in or 50mm, surface area of 100 m2 / m3, * height: 9 m, diameter 0.1 m. Feed gas: * feed speed: 50 60 kg / hour. * 3MPa pressure (30 bar), temperature 25 ° C * composition / mol%: CO 21, CO2 30, H2 31, CH4 3, N2 15, H2S 140 ppm, naphthalene 100 ppm, benzene 1200 ppm and traces of NH3 and of COS. Absorbent feeding: * CuSO4 water, concentration 0.15% by weight. * feeding speed was varied, equivalent to Cu2 + molar ratio of feeding to H2S 1.5 6.
    [000112] The mol% of H2S in the effluent gas was measured using an online hydrogen sulfite gas analyzer. The fraction and moles of H2S measured in affluents of the synthesis gas was at least d 70 ppb in a spring equivalent proportion of CU2 + to the H2S value of 6.
    [000113] As a result, the correlation between the concentration of S in the gas produced and the stoichiometric proportion of Cu / S in the feed was determined. Regarding stoichiometric proportions from 1 to 5, an almost linear correlation was observed, in which the stoichiometric ratio of 1.5 to Cu / S leads to less than 3 ppm. H2S and proportion and leads to 90 ppb, H2S in the gas product. 3. Example 3. Two-step washing protocol on a pilot scale. 3.1 Experiment equipment.
    [000114] The absorption experiments were carried out as beats on a pilot scale device. The feed was supplied from a synthetic gas preparation facility in Varkaus, Finland. A packaged absorption column was used for the two washes with aqueous solution, thus the first phase.
    [000115] The results were measured with standard analyzers: CH4, CO and CO2 with gas chromatography, H2 with FID and sulfur contents with a Hobre Novasulf HG400 analyzer. 3.2 Materials.
    [000116] The feed gas, the gas to be purified, originated from the biomass gasification. For this reason, there are some minor fluctuations in the feed composition. The composition of the feed gas is compiled in Table 5. Table 5.
    [000117] Composition of the feed gas.
    3.3 Conduct of experiments.
    [000118] The total gas supply was 50 kg / hour.
    [000119] At the beginning of the first absorption stage, the CuSO4 feed was zero. As far as the experiment was started, the aqueous solution was fed at a speed of 300 kg / hour. Both fresh and recycling feed were applied. In the aqueous feed, the concentration of CuSO4 was 0.210 g / liter. Considering the feed speeds. this gives a stoichiometric ratio of 1.10. The reaction temperature was adjusted to 29 ° C.
    [000120] The washing with methanol was carried out at a temperature of -23 ° C and the feeding of methanol to the washing column was 500 kg / hour.
    [000121] The experiment was run for 12.5 hours. 3.4 Results.
    [000122] The results revealed that of the 160 ppm of H2S present in the feed, only 160 ppm remained in the gas after washing with CuSO4. This gives 99.0% H2S removal efficiency compared to the first phase. The concentration of H2S was further reduced when washing with methanol, in which of the 160 ppb present in the gas before the methanol absorption phase, only 0.1 ppb remained after the absorption. The gas composition after washing with methanol was H2 48% by volume, CO 30% by volume, CO2 4% by volume CH4 4% by volume. and the rest of NH3. Thus, methanol reduced the concentration of CO2 from 29% in original volume to 4% in volume. 3.5 Conclusions.
    [000123] It can be concluded that the two-stage washing process combining a chemical washing step with a methanol wash removes H2S with a very high efficiency (from 16ppm to 1 ppb) and CO2 with sufficient efficiency. 4. Example 4. Two-step washing protocol on a pilot scale, high H2S purity. 4.1 Experiment conditions
    [000124] The conditions were the same as in Example 5, except for the gas supply which was 65 kg / hour, the aqueous CuSO4 supply was 200 kg / hour, and the concentration was 0.56 / liter giving a stoichiometric Cu / S ratio of 2.42. The experimental conditions and results that describe the recovered gas are given in Table 6.
    [000125] The reaction temperature was adjusted to 34 ° C.
    [000126] The methanol wash was performed at a temperature of -13 ° C. Table 6 Example 4 Aqueous feed Kg / h CuSO4 g / l Feed gas Kg / h H2S
    5. Example 5. A simulation of a method for washing hydrogen sulfide and carbon dioxide according to the present invention, combining a washing with CuSO4 and a washing with methanol.
    [000127] In this example, a two-step wash according to one embodiment of the invention was simulated. In the gas simulation, in the first stage it is fed to the CuSO4 precipitation column to remove H2S and some trace components, followed by washing with methanol to remove CO2. The simulation was performed by the Aspen Plus sheet flow program with the following process parameters: * The absorber models are speed-based models performed by Radfrac * The physical property and ELECNRTL VLE method * All reactions, except the reaction for Cu, Henry components, parameters etc., are set as defaults for Aspen Plus and performed using Electrolyte Wisard.
    [000128] The results from the simulation are compiled in Tables 7 and 8. Table 7.
    [000129] Results of the simulation: fractions in moles selected from the components when the method of the present invention is applied with the methanol temperature of -10 ° C.
    Table 8.
    [000130] From these results, it can be concluded that said combinations of washing with aqueous CuSO4 and washing with amine removes H2S and CO2 effectively.
    [000131] From equivalent simulations and first using only methanol (MeOH in table 8) as an absorbent and then using the combination of the first and second absorbent solutions (CuSO4 + MeOH in table 8) according to the present invention, consumption of energy such as water vapor and energy consumed, were calculated. The results are given in Table 8. Table 8.
    [000132] Energy consumption such as water vapor and electricity used for the absorption stages.

    [000133] These results confirm the effect of the present method with respect to the consumption of both water vapor and electricity. They check the energy efficiency of removing the sulfur and carbon dioxide components from the synthesis gas.
    权利要求:
    Claims (16)
    [0001]
    1. Method for washing hydrogen sulfide and carbon dioxide from a gas obtainable through the gasification of carboniferous biomass, characterized by the fact that it comprises: (a) contacting said gas with a first aborbent solution that comprises transition metal ions, said transition metals selected from copper, zinc, iron and cobalt, and mixtures thereof in aqueous acidic solution; (b) attaching the hydrogen sulfide to said first absorbent solution; (c) recovering the gas from step (b); (d) contacting the gas recovered from step (c) with a second absorbent solution comprising an organic solvent; (e) attaching the carbon dioxide to said second absorbent solution; (f) recovering the washed gas from step (e).
    [0002]
    2. Method according to claim 1, characterized in that the concentration of the transition metal ion in the washing solution is less than 1,000 ppm by weight, calculated from the weight of the first absorbent solution.
    [0003]
    Method according to claim 2, characterized in that the concentration of the transition metal ion in the washing solution is less than 100 ppm by weight, calculated from the weight of the first absorbent solution.
    [0004]
    Method according to claim 1 or 2, characterized in that said transition metal ions comprise copper.
    [0005]
    Method according to claim 4, characterized in that said transition metal ions comprise CuSO4.
    [0006]
    6. Method according to claim 1, characterized in that the contact of said gas with the first absorbent solution occurs at a temperature from 10 to 80 ° C and at a pressure from 0.1 to 4 MPa (1 to 40 bar).
    [0007]
    7. Method according to claim 1, characterized by the fact that the contact of said gas with the second solution occurs at a temperature of -40 to 50 ° C.
    [0008]
    8. Method according to claim 7, characterized in that the contact of said gas with the second solution occurs at a temperature of -30 to -10 ° C.
    [0009]
    Method according to any one of claims 1 to 8, characterized in that the H2S level of the gas recovered from step (f) is less than 20 ppb.
    [0010]
    10. Method according to claim 9, characterized by the fact that the H2S level of the gas recovered from step (f) is less than 1 ppb.
    [0011]
    Method according to claim 1, characterized by the fact that said first and second absorbent solutions are regenerated after gas recovery.
    [0012]
    12. Method for the production of hydrocarbons or derivatives thereof from the raw material of biomass, characterized by the fact that it comprises the steps of: (i) gasifying the raw material of the biomass in the presence of oxygen to produce a gas comprising carbon monoxide, carbon dioxide, hydrogen and hydrocarbons; (ii) optionally a tar reform step; (iii) optionally removing the tar component, such as naphthalenes, from the gas; (iv) optionally adjust the ratio of hydrogen to carbon monoxide; (v) washing as defined in claim 1; (vi) convert at least a significant part of the carbon monoxide and the hydrogen contained in the gas into a synthesis reactor into a product selected from the composition of hydrocarbons and derivatives thereof; and (vii) recovering the hydrocarbon or derivative thereof as the product.
    [0013]
    13. Method according to claim 12, characterized by the fact that step (v) is preceded by a COS hydrolysis step.
    [0014]
    Method according to any one of claims 1 to 13, characterized in that the second absorbent solution comprises an organic solvent selected from methanol, ethanol, potassium salts of diethylamino-acetic acid and dimethylamino-acid acetic, sodium-2-aminopropanic acid, hateful salts of amino propionic acid and sodium phenolate; tributyl phosphate, propylene carbonate, N-methyl pyrrolidone or mixtures thereof.
    [0015]
    Method according to any one of claims 1 to 14, characterized in that the second absorbent solution comprising an organic solvent, comprises methanol.
    [0016]
    16. Method according to any one of claims 1 to 14, characterized in that the second absorbent solution, comprising an organic solvent, consists of methanol.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE350591C|1919-10-26|1922-03-23|Kohlentechnik M B H Ges|Process for removing hydrogen sulfide from gases|
    GB497255A|1937-03-06|1938-12-15|Standard Oil Dev Co|An improved process for refining petroleum distillates|
    US2889197A|1955-05-17|1959-06-02|Baumann Friedrich|Method of removing carbon dioxide and hydrogen sulphide from gases|
    US3435590A|1967-09-01|1969-04-01|Chevron Res|Co2 and h2s removal|
    US3761569A|1971-01-28|1973-09-25|Mobil Oil Corp|Method of removing hydrogen sulfide from gases|
    DE2304497A1|1973-01-31|1974-08-08|Norddeutsche Affinerie|Hydrogen sulphide removal from gases - by absorption in wash liq. contg. copper ions,and oxidn. in acid medium contg. halide|
    DE2433078C3|1974-07-10|1979-12-06|Metallgesellschaft Ag, 6000 Frankfurt|Process for the purification of gases produced by gasifying solid fossil fuels using water vapor and oxygen under pressure|
    US4252548A|1979-01-02|1981-02-24|Kryos Energy Inc.|Carbon dioxide removal from methane-containing gases|
    US4298584A|1980-06-05|1981-11-03|Eic Corporation|Removing carbon oxysulfide from gas streams|
    US4749555A|1986-10-02|1988-06-07|Shell Oil Company|Process for the selective removal of hydrogen sulphide and carbonyl sulfide from light hydrocarbon gases containing carbon dioxide|
    GB9116267D0|1991-07-27|1991-09-11|Tioxide Chemicals Limited|Aqueous compositions|
    FR2724161B1|1994-09-02|1996-11-15|Inst Francais Du Petrole|PROCESS FOR THE EXTRACTION OF HYDROGEN SULFIDE CONTAINED IN A GAS MIXTURE|
    NL1006200C2|1997-06-02|1998-12-03|Procede Twente B V|Method and system for the selective removal of contaminants from gas flows.|
    US6550751B1|1997-11-26|2003-04-22|Marsulex Environmental Technologies Corp.|Gas-liquid contactor with liquid redistribution device|
    WO2002004098A1|2000-07-11|2002-01-17|Nurmia, Wendie|Process for separating carbon dioxide, co2, from combustion gas|
    DE10036173A1|2000-07-25|2002-02-07|Basf Ag|Process for deacidifying a fluid stream and wash liquid for use in such a process|
    CA2366470A1|2001-12-28|2003-06-28|William Dale Storey|Solution and method for scavenging hydrogen sulphide|
    FI20030241A|2003-02-17|2004-08-18|Fortum Oyj|A method for producing a synthesis gas|
    NO326645B1|2005-06-28|2009-01-26|Ntnu Technology Transfer As|Process and apparatus for removing and recovering acid gases, CO2 and / or H2S.|
    CN101227964A|2005-07-22|2008-07-23|国际壳牌研究有限公司|Process for producing a gas stream depleted of hydrogen sulphide and of mercaptans|
    DE102007008690A1|2007-02-20|2008-08-21|Linde Ag|Production of gas products from synthesis gas|
    WO2008113766A2|2007-03-16|2008-09-25|Shell Internationale Research Maatschappij B.V.|Process to prepare a hydrocarbon|
    FI122786B|2007-07-20|2012-06-29|Upm Kymmene Oyj|Use of carbon dioxide from synthetic hydrocarbon chains|
    ES2603281T3|2007-07-20|2017-02-24|Upm-Kymmene Oyj|Procedure and apparatus for producing liquid biofuel from solid biomass|
    US8765086B2|2007-08-30|2014-07-01|Shell Oil Company|Process for removal of hydrogen sulphide and carbon dioxide from an acid gas stream|
    FI20075794A|2007-11-09|2009-05-10|Upm Kymmene Oyj|An integrated process for the production of diesel fuel from biological materials and products, uses and devices in connection with the process|
    FI20085400A0|2007-11-09|2008-04-30|Upm Kymmene Oyj|Method for integrated waste water treatment|
    US20090220406A1|2008-02-29|2009-09-03|Greatpoint Energy, Inc.|Selective Removal and Recovery of Acid Gases from Gasification Products|
    AU2009223177B2|2008-03-12|2013-10-03|Sasol Technology Limited|Hydrocarbon synthesis|
    CN102227250A|2008-11-28|2011-10-26|国际壳牌研究有限公司|Method of treating syngas stream and apparatus therefor|
    KR100948334B1|2009-02-09|2010-03-17|이상범|Ammonia and hydrogen sulfide removing aparatus contained in biogas|
    EP2223889A3|2009-02-25|2011-06-22|Linde Aktiengesellschaft|Device for converting solid or liquid fuels into a gaseous fuel|
    FI123686B|2010-03-03|2013-09-30|Neste Oil Oyj|A method for reforming gasification gas|
    US8945496B2|2010-11-30|2015-02-03|General Electric Company|Carbon capture systems and methods with selective sulfur removal|
    EP2484427B1|2011-02-08|2017-07-19|Neste Oyj|A two-stage gas washing method|
    ES2666417T3|2011-08-31|2018-05-04|Neste Oyj|Two-stage gas washing method applying sulfide precipitation and alkaline absorption|US8303676B1|2008-02-19|2012-11-06|Proton Power, Inc.|Conversion of C-O-H compounds into hydrogen for power or heat generation|
    US9698439B2|2008-02-19|2017-07-04|Proton Power, Inc.|Cellulosic biomass processing for hydrogen extraction|
    EP2484427B1|2011-02-08|2017-07-19|Neste Oyj|A two-stage gas washing method|
    ES2666417T3|2011-08-31|2018-05-04|Neste Oyj|Two-stage gas washing method applying sulfide precipitation and alkaline absorption|
    AU2013282904B2|2012-06-27|2016-11-03|Grannus, Llc|Polygeneration production of power and fertilizer through emissions capture|
    US9023243B2|2012-08-27|2015-05-05|Proton Power, Inc.|Methods, systems, and devices for synthesis gas recapture|
    US10005961B2|2012-08-28|2018-06-26|Proton Power, Inc.|Methods, systems, and devices for continuous liquid fuel production from biomass|
    DE102012110520B4|2012-11-02|2019-01-31|L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude|Process for the production of dry synthetic natural gas |
    FI20126265A|2012-12-04|2014-06-05|Vapo Oy|A process for enhancing the carbon footprint of fuel produced in a BtL plant|
    CN105228724B|2013-03-14|2018-06-12|代表Mt创新中心的斯塔米卡邦有限公司|Reduce COS and CS2Method|
    US10144875B2|2014-01-10|2018-12-04|Proton Power, Inc.|Systems, and devices for liquid hydrocarbon fuel production, hydrocarbon chemical production, and aerosol capture|
    CN103977671A|2014-06-06|2014-08-13|湖州强马分子筛有限公司|Waste-gas purifying treatment method and device of carbon molecular sieve|
    DE102014118345A1|2014-12-10|2016-06-16|L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude|Process and installation for the purification of raw synthesis gas|
    EP3271046B1|2015-05-12|2020-02-12|Siemens Aktiengesellschaft|Method and device for the desulphurisation of a gas flow|
    CN106310893A|2015-06-17|2017-01-11|中国石油化工股份有限公司|Absorption liquid with high hydrogen sulfide removal rate|
    GB201519139D0|2015-10-29|2015-12-16|Johnson Matthey Plc|Process|
    GB201519133D0|2015-10-29|2015-12-16|Johnson Matthey Plc|Process|
    BR112018008318A2|2015-10-29|2018-10-30|Johnson Matthey Public Limited Company|catalyst precursor, methods for preparing catalyst precursor and for producing a catalyst, water-gas displacement catalyst, and process for increasing hydrogen content|
    BR112018011232A2|2015-12-04|2018-11-21|Grannus Llc|hydrogen polygeneration production for use in various industrial processes|
    WO2018001991A1|2016-06-28|2018-01-04|Shell Internationale Research Maatschappij B.V.|Apparatus and process for purifying syngas|
    RU2020124715A|2017-12-27|2022-01-27|Шелл Интернэшнл Рисерч Маатсхаппий Б.В.|SYNTHESIS GAS PURIFICATION METHOD|
    CN108636061A|2018-04-17|2018-10-12|南安市创培电子科技有限公司|A kind of high effective desulphurization device of boiler waste gas|
    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-16| B06T| Formal requirements before examination|
    2020-06-02| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-09-24| B09A| Decision: intention to grant|
    2020-10-27| B25D| Requested change of name of applicant approved|Owner name: NESTE OYJ (FI) |
    2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11153704.9|2011-02-08|
    EP11153704|2011-02-08|
    EP11179451.7A|EP2484427B1|2011-02-08|2011-08-31|A two-stage gas washing method|
    EP11179451.7|2011-08-31|
    PCT/FI2012/050112|WO2012107640A2|2011-02-08|2012-02-08|A two-stage gas washing method|
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