CN102378735A - Process for producing a purified synthesis gas stream - Google Patents

Process for producing a purified synthesis gas stream Download PDF

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CN102378735A
CN102378735A CN2010800152292A CN201080015229A CN102378735A CN 102378735 A CN102378735 A CN 102378735A CN 2010800152292 A CN2010800152292 A CN 2010800152292A CN 201080015229 A CN201080015229 A CN 201080015229A CN 102378735 A CN102378735 A CN 102378735A
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gas stream
synthesis gas
stream
cos
carbonic acid
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I·C·梵登鲍恩
G·J·范赫林根
C·J·史密特
A·F·沃尔德惠斯
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Shell Internationale Research Maatschappij BV
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Abstract

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/waterto react at least part of the carbon monoxide tocarbon 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 ulphide-oxidizing bacteria in the presence of oxygen in a bioreactor to obtain a sulphur slurry and a regenerated aqueous alkaline washing liquid; (d) removing carbon dioxide from the H2S-depleted synthesis gas stream, to obtain the purified synthesis gas stream and a gas stream enriched in CO2..

Description

Be used to produce the method for the synthesis gas stream of purifying
The present invention relates to a kind of method of producing the synthesis gas stream of purifying by the charging synthesis gas stream that contains pollutent.
Synthesis gas stream is the gas stream that mainly comprises carbon monoxide and hydrogen.Synthesis gas stream partially oxidation or the steam reformation of the hydrocarbon through comprising Sweet natural gas, coal bed methane, distillate and residual oil and the gasification through solid fossil fuel such as biomass or coal or coke usually prepares.
Exist and manyly can be used as the solid of the raw material that is used to produce synthetic gas or the fossil oil of very heavy (gluing); Comprise biomass; Solid fuel is hard coal, earthy browncoal (brown coal), bituminous coal, sub-bituminous coal, dark-coloured brown coal (lignite), refinery coke, mud coal etc. for example; With heavy residual oil; The hydrocarbon that for example extracts from Tar sands, from the residual oil of refinery as directly deriving from crude oil or deriving from oily conversion process such as the boiling point of thermo-cracking, catalytic pyrolysis, hydrocracking etc. is higher than 360 ℃ residue oil fraction.The fuel of all these types all has the carbon and the hydrogen of different ratios, and the different substances that is regarded as pollutent.
Depend on the raw material that is used to produce synthetic gas, synthetic gas will contain pollutent, and for example carbonic acid gas, hydrogen sulfide, carbonyl sulfide and carbonyl disulfide also contain nitrogen, nitrogen component (for example HCN and NH simultaneously 3), metal, metal carbonyls (particularly nickle carbonoxide and iron carbonyl) and also contain mercaptan in some cases.
The synthetic gas of purifying can be used for the catalytic chemistry conversion or is used for generating.The major part that world energy is supplied with is that the burning by fuel, particularly Sweet natural gas or synthetic gas in the power station provides.In one or more internal combustion turbine, make the synthetic gas burning, and the gas that is produced is used to produce steam with air.Use this steam to generate electricity then.
Using the specially suitable system of synthetic gas generating is Integrated gasification combined cycle (IGCC) system.The IGCC system designs by the mode of using coal as fuel source in the gas-turbine plant.IGCC is the combination of two systems.First system is a gasification, and it uses coal to produce synthetic gas.Then with the synthetic gas purifying to remove pollutent.The synthetic gas of purifying can be used for internal combustion turbine and generate electricity.
Second system among the IGCC is a combined cycle, or power cycle, and it is the effective ways of commercial generating.Combined cycle comprises internal combustion turbine/producer, heat recovery steam generator (HRSG) and steam turbine/producer.Can in HRSG, retrieve from the used heat of internal combustion turbine to produce steam.Make this steam pass steam turbine then and be provided with power to give another producer, this produces more.Combined cycle is more effective than conventional power generation usage system usually, and this is because it utilizes waste heat to produce more again.The IGCC system is cleaning and more effective than conventional coal-fired power plant usually.
As indicated above, when synthetic gas is used to generate electricity, often require to remove pollutent to avoid pollutant sediment to gas turbine component.
When synthetic gas is used for the catalytic chemistry conversion, need be with pollutant removal to low-level to prevent poisoning of catalyst.
The method that is used to produce the synthesis gas stream of purifying is usually directed to the high flow process of cost of use (line-up).For example, cold methanol can be used for removing hydrogen sulfide and carbonic acid gas through physical absorption.The concentration of these pollutents in the synthetic gas of purifying will be still in the ppmv scope.For the application that wherein will make the synthetic gas catalyzed conversion, the Pollutant levels in the ppmv scope are still too high.Owing to make the energy of required big the out-of-proportion amount of Mathanol regenerating, it is uneconomic using method based on methyl alcohol that synthesis gas stream is purified to higher degree.In addition, must remove the H of absorption 2S, this normally comprises H through making at elevated temperatures 2The methyl alcohol of S contacts with stripping gas, comprises H thereby produce 2The stripping gas of S.Then with the H in this stripping gas 2S is converted into elemental sulfur, thereby needs considerable fund and process cost.
In US 2007/0072949, disclose a kind of method, used based on the absorption technique of low temperature amine in the method, then be that solvent reclamation Claus/SCOT processing unit is removed sulfur material.The shortcoming of this method is that it is limited to the feed gas composition that is fit to the Claus method, and the concentration of hydrogen sulfide of this composition is quite high.
The purpose of this invention is to provide and be used for the optimization method that purifying derives from the synthesis gas stream of a series of carbonaceousfuels, make the synthetic gas of purifying be suitable for other application, especially for generating.
Have now found that through directly removing H from the charging synthesis gas stream 2S, this purpose can be achieved.
Therefore; The invention provides the method for producing the synthesis gas stream of purifying by the charging synthesis gas stream; Said charging synthesis gas stream also comprises hydrogen sulfide, HCN and/or COS except that comprising main ingredient carbon monoxide and hydrogen; This method may further comprise the steps: (a) remove HCN and/or COS through said charging synthesis gas stream is contacted with water gas converting catalyst; The part reaction of carbon monoxide is a carbonic acid gas thereby make at least, and obtains the synthesis gas stream of poor HCN of containing and/or COS; (b) pass through at H 2S removes in the district and makes the synthesis gas stream of poor HCN of containing and/or COS contact the hydrogen sulfide of removing in this gas stream with the aqueous alkaline washings, thereby obtains the poor H of containing 2The synthesis gas stream of S and the aqueous stream that comprises sulfide; (c) thus the aqueous stream that comprises sulfide is contacted with sulfur bacteria obtains sulphur slurry and regenerated aqueous alkaline washings; (d) from the poor H that contains 2The synthesis gas stream of S is removed carbonic acid gas, thereby obtains the synthesis gas stream of purifying and be rich in CO 2Gas stream.
This method makes it possible to be removed to hydrogen sulfide, carbonyl sulfide and/or prussic acid low-level.The synthetic gas of purifying is because its low pollutant level is suitable as fuel (aptly in internal combustion turbine) or is used for the catalytic chemistry conversion.The synthetic gas of purifying is particularly suitable for Integrated gasification combined cycle (IGCC).
In step (d), obtain in elevated pressure, the carbon dioxide under 4-12bara aptly.Can this carbon dioxide further be pressurizeed and is used for for example enhanced oil recovery.
Because through being converted into elemental sulfur with H 2S directly removes from synthesis gas stream, and this method is economical.The poor H that contains 2The synthesis gas stream of S has low-down H 2S concentration, thus make it possible to use cheap non-selective acid gas removal unit to remove residual H 2S and CO 2
Should be understood that the amount of pollutent and type can change and depend on the amount of these pollutents that the raw material that is used for producing the charging synthesis gas stream exists in the charging synthesis gas stream.
Usually, the charging synthesis gas stream obtains through the gasification of raw material.
When using solid fossil fuel biological example matter or coal, leave H in the synthesis gas stream of gasifier as raw material 2The amount of S and COS is usually less than 15 volume % based on this synthesis gas stream meter, typically is lower than 5 volume %.
When using oil residue, leave H in the synthesis gas stream of gasifier as raw material 2The amount of S and COS will be lower than 20 volume % usually based on this synthesis gas stream meter, typically be lower than 10 volume %.
The synthesis gas stream that is produced by raw material can comprise particulate matter, for example flying dust or soot particulates.Therefore, in preferred embodiments, the synthetic gas that leaves the synthetic gas generation unit is contacted to remove particulate matter with washings, cigarette ash particularly, thus obtain the charging synthesis gas stream.The synthesis gas stream that leaves the synthetic gas generation unit is under the temperature and/or elevated pressure of rising usually.Result under the situation of gasifier at synthetic gas especially, the synthesis gas stream that leaves gasifier will be under the temperature and elevated pressure of rising.For fear of additional cooling and/or depressurization step, in soot scrubber, preferably under temperature that raises and/or elevated pressure, implement washing step.Preferably, the temperature that synthetic gas contacts with washings is 40-160 ℃, more preferably 110-150 ℃.Preferably, the pressure that synthesis gas stream contacts with washings is 20-80bara, more preferably 20-60bara.
The amount of HCN and/or COS depends on the composition of the raw material that derives synthetic gas and produces the applied technology of synthetic gas in the charging synthesis gas stream.Usually, count about 100-3000ppmv derived from the amount of COS in the charging synthesis gas stream of solid fossil fuel raw material, particularly coal based on this charging synthesis gas stream.For biomass, the amount of COS is generally 1-100ppmv.
In step (a), HCN and/or COS are removed from the charging synthesis gas stream through catalyzed conversion.
The catalyzer that is used for HCN and/or COS hydrolysis is known to those skilled in the art and comprises for example based on TiO 2Catalyzer or based on the catalyzer of aluminum oxide and/or chromic oxide.Preferred catalyzer is based on TiO 2Catalyzer.
The amount of water/steam is preferably 5v/v%-80v/v% based on vaporimeter, more preferably 10v/v%-70v/v%, also more preferably 15v/v%-50v/v%.
In the preferred implementation of step (a), the charging synthesis gas stream is contacted to remove HCN and/or COS and to make part carbon monoxide and water reaction formation carbonic acid gas and hydrogen at least in addition with water gas converting catalyst.
Step (a) especially preferred embodiment in, as be present in the catalyzer in one or more fixed-bed reactor in the presence of to hang down the steam of measuring the carbon monoxide in the charging synthesis gas stream transformed.Can use a series of shift-converters, wherein in each reactor drum, carry out the water-gas shift conversion step.Supply to first or the charging synthesis gas stream of unique water-gas shift in the content of carbon monoxide be preferably 50vol.% at least, more preferably 55-70vol.% by butt.The charging synthesis gas stream preferably contains hydrogen sulfide and is sulfided state (sulphided) and activity to keep catalyzer.The minimum content of hydrogen sulfide will depend on the sulfur material that exists in working temperature, air speed (GHSV) and the charging synthesis gas stream of shift-converter.Preferably, there is 300ppm H at least in the charging synthesis gas stream 2S.See from the viewpoint of catalyst activity, to H 2The maximum of S is restriction not.
In the preferred implementation of step (a), the charging synthesis gas stream get into first or during unique water-gas shift wherein steam and the mol ratio of carbon monoxide be preferably 0.2: 1-0.9: 1.Charging synthesis gas stream its temperature when getting into shift-converter is preferably 190-230 ℃.In addition, temperature in is preferably than the high 10-60 of dew point ℃ of the charging of going to each water-gas shift conversion step.Air speed in the reactor drum is preferably 6000-9000h -1Pressure is preferably 2-5MPa, more preferably 3-4.5MPa.
The transformation efficiency of carbon monoxide can not be 100% usually, and this is because the steam that exists in the reactor feed is the substoichiometric amount.In preferred embodiments; When being the charging synthesis gas stream of 0.2-0.3 when beginning from comprise 55-70vol.% carbon monoxide and steam/CO mol ratio by butt, when using fixed-bed reactor in the shift-converter elute content of carbon monoxide by butt with being 35-50vol.%.Carbon monoxide is further transformed, then preferably make the shift-converter elute stand next water-gas shift conversion step.
For so follow-up water-gas shift conversion step, preferred steam/water and carbon monoxide mol ratio, temperature in and air speed are according to describing with regard to the first water-gas shift conversion step.As indicated above, the charging synthesis gas stream is obtained by gasification process aptly and stands water wash step aptly.Water will evaporate also finally in syngas mixture in this step.Gained steam and CO mol ratio will be aptly in aforesaid preferable range in the synthetic gas of this washing.This can cause not need steam or water being given at synthetic gas and add wherein when entering the first water-gas shift conversion step.For subsequent step, in order to obtain required steam and CO molar range, need steam or boiler feed water be joined each formerly in the elute of step.
Can repeat the water-gas shift step so that carbon monoxide content in the shift-converter elute of each next shift-converter progressively is reduced to the CO content that is lower than 5vol.% by butt.Found in 4 to 5 steps, or, in 4 to 5 reactor drums, can obtain such CO transformation efficiency with other mode.
The temperature rising of having found to control in each shift-converter is important.Each shift-converter of preferred operations makes the maximum temperature in the single catalyst in reactor bed be no more than 440 ℃, more preferably no more than 400 ℃.Under higher temperature the heat release methanation reaction can take place, thereby cause uncontrollable temperature to rise.
Used catalyzer water gas converting catalyst preferably in the shift-converter, it has activity and under low relatively temperature in, has activity and do not promote for example methanation of side reaction under preferred low steam and CO mol ratio.Aptly, catalyzer comprises the oxide compound or the sulfide of carrier and molybdenum (Mo), more preferably molybdenum (Mo) and the oxide compound of cobalt (Co) or the mixture of sulfide, even more preferably also comprise copper (Cu), tungsten (W) and/or nickel (Ni).Catalyzer also comprises one or more promotor/suppressor factor for example potassium (K), lanthanum (La), manganese (Mn), cerium (Ce) and/or zirconium (Zr) aptly.Carrier can be for example aluminum oxide, MgAl of high temperature material 2O 4Or MgO-Al 2O 3-TiO 2
The instance of suitable catalyst comprises active γ-Al 2O 3Carrier and 1-8wt%CoO and 6-10wt%MoO 3Catalyzer preferably exists with extrudate.
In the preferred implementation of step (a); The charging synthesis gas stream comprises 50vol.% carbon monoxide at least; Charging synthesis gas stream wherein steam and carbon monoxide mol ratio when getting into one or more reactor drums or reactor drum is preferably 0.2: 1-0.9: 1, and charging synthesis gas stream its temperature when one or more reactor drums of entering or reactor drum is 190-230 ℃.
Relate in the situation of transformationreation as indicated above in step (a), preferably, partly " conversion " synthesis gas stream is chosen wantonly after removing pollutent, is used for the hydrogen manufacturing, for example is in transformation absorption (PSA) step.The ratio that is used for the conversion synthesis gas stream of hydrogen manufacturing can be usually less than 15 volume %, preferably about 1-10 volume %.The hydrogen of making by this way can be used as hydrogen source then in the hydrogen cracking of hydrocarbon synthesis reaction product.This configuration reduce or even eliminated for example from the needs of the independent hydrogen source of outside supply source, said in other cases independent hydrogen source uses under obtainable situation usually.Therefore, said carbonaceous fuel feedstock can be provided at biomass or coal needed other reactant in the whole process of liquid products conversion, has increased the self-sufficiency of entire method.
In step (a), obtain the poor synthesis gas stream that contains prussic acid and/or COS.
In step (b), the poor synthesis gas stream that contains prussic acid and/or COS is contacted so that hydrogen sulfide is transferred to the aqueous alkaline washings from the poor synthesis gas stream that contains prussic acid and/or COS with the aqueous alkaline washings.
Suitable aqueous alkaline washings comprises hydroxide aqueous solution, for example the solution of sodium hydroxide or oxyhydroxide potassium and carbonic acid (hydrogen) salt brine solution in the water.
Aptly, step (b) is more preferably implemented under 10-50 ℃ the temperature at 5-70 ℃.Aptly, step (c) is at 1-100bar (g), and more preferably the pressure of 1.5-80bar (g) is implemented down.
Randomly, washings is a buffered.Preferred buffer compounds is carbonate, supercarbonate, phosphoric acid salt and their mixture, particularly yellow soda ash and/or sodium hydrogencarbonate.
The concentration of buffer compounds depends on the composition of gas stream especially and usually regulates by making washings remain in the preferred pH scope such mode.
Preferably, the pH of washings is 4.5-10, more preferably 5.5-9.0.
In step (c), in bio-reactor, in the presence of oxygen, use sulfur bacteria that the hydrogen sulfide in the washing medium is converted into elemental sulfur.
The sulfur bacteria of mentioning among this paper is to be the bacterium of elemental sulfur with sulfide oxidation.Suitable sulfur bacteria can for example be selected from known Thiobacillus and sulphur Microspira (genera Thiobacillus and Thiomicrospira) the aerobic culture of autotrophy.
The principal reaction that can in bio-reactor, take place is that the microbiology of sulphur and vitriol forms:
(1a) the generation HS of sulphur -+ 1/2O 2→ 1/8S 8+ OH -
(1b) the generation HS of sulphur 5 -+ 1/2O 2→ 5/8S 8+ OH -
(2) the generation HS of sulfate radical -+ 2O 2+ OH-→ SO 4 2-+ H 2O
The sulphur slurry can comprise one or more products of principal reaction, comprises elemental sulfur and sulfate radical.
Regenerated aqueous alkaline washings can comprise sulfur granules.
The sulfur bacteria of mentioning among this paper is to be the bacterium of elemental sulfur with sulfide oxidation.Suitable sulfur bacteria can for example be selected from known Thiobacillus and the aerobic culture of sulphur Microspira autotrophy.
Preferably, the reaction medium in the bio-reactor is a buffered.The selection mode of buffer compounds makes the bacterium that exists in the oxidation reactor can tolerate them.Preferred buffer compounds is carbonate, supercarbonate, phosphoric acid salt and their mixture, particularly yellow soda ash and/or sodium hydrogencarbonate.The concentration of buffer compounds depends on the composition of gas stream and especially usually by making that the pH of reaction medium is 6.0-12.0 in the oxidation reactor, preferred 7.0-11.0, and more preferably the such mode of 8.0-10.0 is regulated.
Typical pressure in the bio-reactor is 0.5-2bar (g).
Preferably, at least a portion of the moisture sulphur slurry that obtains in the step (c) is separated with regenerated aqueous alkaline washings.Aptly, in solid/liquid separator, carry out this separating step.Suitable solid/liquid separator is described in Chemical Engineers ' Handbook of Perry, and the 7th edition, in the 22nd chapters and sections (1997).
The sulphur content of isolating moisture sulphur slurry is suitably 5w/w%-50w/w% based on this slurry meter.Typically, the water with the sulphur slurry is removed to the degree that acquisition has the sulphur cake of the dried solids content of 55-70%.Aptly, the sulphur purity of sulphur cake is counted 90-98w/w% based on the dry weight of this sulphur cake.Randomly, be 95wt% sulphur at least, preferably the sulphur cream of 99wt% sulphur at least thereby can the pulp once more of sulphur slurry, filtration and dry be obtained purity.Thereby the sulphur cream generation dry weight content that can randomly dryly so obtain is at least 85%, preferred at least 90% powder.This powder can be used as mycocide, fertilizer or miticide aptly.
In step (d), carbonic acid gas is removed from the synthesis gas stream of depleted of hydrogen sulphide.
In first embodiment of step (d), through making the poor H of containing 2The synthesis gas stream of S with absorb liquid and contact to remove carbonic acid gas and residual hydrogen sulfide is removed carbonic acid gas.
Suitable absorption liquid can comprise chemical solvents or physical solvent or their mixture.
The preferred liquid that absorbs comprises chemical solvents and/or physical solvent, and these solvents are aptly as the aqueous solution.
Suitable chemical solvents is primary amine, secondary amine and/or tertiary amine, comprises sterically hindered amines.
Preferred chemical solvents comprises secondary amine or tertiary amine; Preferably, be more especially DIPA, DEA, MMEA (monomethyl-thanomin), MDEA (methyldiethanolamine) derived from the amine compound of thanomin; TEA (trolamine) or DEMEA (diethylammonium-monoethanolamine), preferred DIPA or MDEA.Think for example H of these chemical solventss and acidic cpd 2The S reaction.
In second embodiment of step (d), use film to remove carbonic acid gas.
Advantageously use the film that carbonic acid gas is had highly selective.But but the selectivity definition is the ratio by carbonic acid gas transmitance with the transmitance of carbon monoxide and hydrogen measured in the pure gas experiment.Preferably, the selectivity of film is 10-200, preferred 20-150.
Aptly; Mould material is selected from the material based on polyethylene oxide; The preferred package block copolymer containing based on the material of polyethylene oxide, particularly PEO 600/5000 T6T6T or crosslinked PEO, based on the material of polyimide or polyaramide, based on the material of rhodia; Based on the material of zeolite, be preferably based on the material of aluminosilicophosphate (silica-alumina phosphate), more preferably SAPO-34, little porous silica material and carbon molecular sieve material.
In the 3rd embodiment of step (d), can remove carbonic acid gas from the isolated temperature of this gas stream through gas stream being cooled to carbonic acid gas.Aptly, gas stream is cooled to the temperature that carbonic acid gas becomes liquid or solid, thereby it is isolated from gas stream.
The synthetic gas of the purifying that obtains in the step (d) has low pollutant level, aptly at ppmv or even in the ppbv scope.
What obtain in the step (d) aptly, is rich in CO 2Gas stream be in 3-15bara, under the pressure of preferred 5-15bara.This pressurization be rich in CO 2Gas stream can be advantageously used in enhanced oil recovery, wherein need less gas booster compressor.
Be rich in CO therein 2Gas stream need be in during highly compressed uses, for example when using it for when injecting subsurface formations, advantage is to be rich in CO 2Gas stream be under the elevated pressure.
In one embodiment, will be rich in CO 2Gas stream further pressurize and be used for enhanced oil recovery; Aptly through being injected in the oily reservoir; It tends to be dissolved in the oil of appropriate location in this oil reservoir, thereby reduces its viscosity and therefore make it have more large fluidity for moving towards recovery well.
In another embodiment, will be rich in CO 2Gas stream further pressurize and be pumped into be used in the retaining reservoir storage.
In another embodiment, with the CO that is rich in of pressurization 2Gas stream further pressurize and be pumped into and be used for storage in the empty oily reservoir.
For all above-mentioned selections, need a series of compressors will be rich in CO 2Gas stream be pressurized to required high pressure.To be rich in CO 2Gas stream usually need big and expensive compressor from the pressure that normal atmosphere is pressurized to about 10bara.Be in elevated pressure because this method produces, preferably be higher than the CO that is rich in of 10bara 2Gas stream, do not need a lot of compressors.
In preferred embodiments, the synthetic gas of purifying is used for generating, particularly in the IGCC system.
In the IGCC system, typically, fuel and oxygen-containing gas are incorporated in the burning zone of internal combustion turbine.In the burning zone of internal combustion turbine, make fuel combustion produce the combustion gases of heat.Usually the expander blade sequence through setting in a row expands the combustion gases of heat in internal combustion turbine, and is used for generating electricity through generator.Treat in the internal combustion turbine that the incendiary suitable fuel comprises Sweet natural gas and synthetic gas.
The hot waste gas that leaves internal combustion turbine is incorporated in the heat recovery steam generator unit, use is included in the steam that heat in the hot waste gas produces first amount in this.
Aptly, hot waste gas has 350-700 ℃, more preferably 400-650 ℃ temperature.The composition of hot waste gas can change, and this depends on the condition in the burnt fuel gas and internal combustion turbine in the internal combustion turbine.
The heat recovery steam generator unit provides and is used for reclaiming heat and being any unit of the measure of steam with this thermal transition from hot waste gas.For example, the heat recovery steam generator unit can comprise a plurality of pipes that pile up installation.Water is carried out pumping and cycles through said pipe, it is remained under the high pressure-temperature.Hot waste gas heats said pipe and is used for producing steam.
The heat recovery steam generator unit can be designed to produce three types steam: HP steam, MP steam and LP steam.
Preferably, vapour generator is designed to produce at least one quantitative HP steam, and this is because HP steam can be used to generating.Aptly, HP steam has 90-150bara, preferred 90-125bara, the more preferably pressure of 100-115bara.Aptly, also produce LP steam, LP steam preferably has 2-10bara, is more preferably up to 8bara, also the more preferably pressure of 4-6bara.
In the heat recovery steam generator unit, preferably in steam turbine, produce HP steam, for example the generator through being connected with steam turbine is converted into power with said HP steam.
The synthetic gas of purifying; Because the pollutant level that it is low; Also be suitable for Catalytic processes, Catalytic processes is preferably selected from that fischer-tropsch is synthetic, methyl alcohol synthetic, dimethyl ether is synthetic, acetate is synthetic, the methanation of ammonia synthesis, preparation substitute natural gas (SNG) and relate to carbonylation or the technology of hydroformylation reaction.
Do not hope to receive the restriction of particular, description is described the present invention in further detail.In Fig. 1, shown the technology of the synthesis gas stream that is used to produce purifying.This technology is beginning in gasification unit 1, to use oxygen to make biomass or gasification form the charging synthesis gas stream that comprises hydrogen sulfide, HCN and/or COS.Preferably, solid for example the removal of slag, cigarette ash etc. remove in the unit (not shown) at solid and carry out.The charging synthesis gas stream that is produced is led to converter unit 2, make itself and conversion catalytic Contact in this, thereby CO is converted into CO 2And make HCN and COS hydrolysis.Lead to H with sending from the unit 2 poor HCN of containing of gained and the synthesis gas stream of COS 2S removes district 3, contacts H with the aqueous alkaline washings through making this synthesis gas stream in this 2S removes.With the poor H that contains of gained 2The synthesis gas stream of S is from H 2S removes district 3 and leads to acid gas removal unit 4, in this it is contacted to remove CO with absorption liquid 2With residual H 2S.This produces the synthesis gas stream of purifying and is rich in CO 2Gas stream.To comprise H 2The aqueous alkaline washings of S is from H 2S removes the district and leads to bio-reactor 5, in this with H 2S is converted into elemental sulfur.
In Fig. 2, embodiment preferred has been described, wherein the synthetic gas of purifying is used for generating.In Fig. 2, the synthesis gas stream of the purifying that produces in will the technology according to Fig. 1 leads to the power station that comprises internal combustion turbine (1) and heat recovery steam generator unit (2).In internal combustion turbine, oxygen-containing gas is supplied to compressor 5 through pipeline 4.To supply to burner 7 by the synthetic gas of the purifying that produces in the technology described in Fig. 1 and burning in the presence of the oxygen-containing gas of compression through pipeline 6.In expander 8, make the combustion gases expansion that is produced and in generator 9, be used for generating.To comprise CO through pipeline 10 2Lead to heat recovery steam generator unit 2 with the residual gas of oxygen.In the heat recovery steam generator unit, thereby water is heated generation steam once more by hot waste gas in heating zone 11.Through pipeline 12 steam is led to steam turbine 13 in generator 14, to produce other power.

Claims (11)

1. method of producing the synthesis gas stream of purifying by the charging synthesis gas stream, said charging synthesis gas stream also comprises hydrogen sulfide, HCN and/or COS except that comprising main ingredient carbon monoxide and hydrogen, and this method may further comprise the steps:
(a) through being contacted with water gas converting catalyst, said charging synthesis gas stream removes HCN and/or COS; The part reaction of carbon monoxide is a carbonic acid gas thereby make at least, and obtains the synthesis gas stream of poor HCN of containing and/or COS;
(b) pass through at H 2S removes in the district and makes the synthesis gas stream of poor HCN of containing and/or COS contact the hydrogen sulfide of removing in this gas stream with the aqueous alkaline washings, thereby obtains the poor H of containing 2The synthesis gas stream of S and the aqueous stream that comprises sulfide;
(c) thus the aqueous stream that comprises sulfide is contacted with sulfur bacteria obtains sulphur slurry and regenerated aqueous alkaline washings;
(d) from the poor H that contains 2The synthesis gas stream of S is removed carbonic acid gas, thereby obtains the synthesis gas stream of purifying and be rich in CO 2Gas stream.
2. according to the process of claim 1 wherein that said sulfur bacteria is selected from the aerobic culture of autotrophy of Thiobacillus and sulphur Microspira.
3. according to the method for claim 1; Wherein charging synthesis gas stream wherein steam/water and mol ratio of carbon monoxide when getting into shift-converter is preferably 0.2: 1-0.9: 1; Wherein charging synthesis gas stream its temperature when getting into shift-converter is 190-230 ℃, and wherein said charging synthesis gas stream comprises the carbon monoxide by butt at least 50 volume %.
4. according to each method in the aforementioned claim; Wherein in step (c); Synthesis gas stream through making depleted of hydrogen sulphide under low temperature and elevated pressure contacts and removes carbonic acid gas with absorbing liquid, thereby carbonic acid gas is transferred to absorption liquid and the purified gas stream that absorbs liquid and obtain to be rich in carbonic acid gas from said gas stream.
5. according to each method among the claim 1-3, wherein in step (c), use film to remove carbonic acid gas.
6. according to each method among the claim 1-3, wherein in step (c), be cooled to carbonic acid gas and can remove carbonic acid gas from the isolated temperature of this gas stream through synthesis gas stream with depleted of hydrogen sulphide.
7. according to each method in the aforementioned claim, wherein in internal combustion turbine, use the synthesis gas stream of said purifying to generate electricity.
8. according to the method for claim 7, wherein hot waste gas is emitted from internal combustion turbine, and this hot waste gas is incorporated in the heat recovery steam generator unit producing steam, this steam is used to produce other.
9. according to each method among the claim 1-6; Wherein the synthetic gas that is further purified is used for Catalytic processes, said Catalytic processes is preferably selected from that fischer-tropsch is synthetic, methyl alcohol synthetic, dimethyl ether is synthetic, acetate is synthetic, the methanation of ammonia synthesis, preparation substitute natural gas (SNG) and relate to carbonylation or the technology of hydroformylation reaction.
10. according to each method among the claim 1-9, the wherein said CO that is rich in 2Gas stream be in 5-50bara, preferred 10-50bara is more preferably under the pressure of 20-50bara.
11. according to the method for claim 10, wherein with the said CO that is rich in 2Further pressurization and inject subsurface formations of gas stream, be preferred for enhanced oil recovery or be used for storing into the retaining reservoir or be used for storing into empty oily reservoir.
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