CA1335694C - Refining of raw gas - Google Patents
Refining of raw gasInfo
- Publication number
- CA1335694C CA1335694C CA000579047A CA579047A CA1335694C CA 1335694 C CA1335694 C CA 1335694C CA 000579047 A CA000579047 A CA 000579047A CA 579047 A CA579047 A CA 579047A CA 1335694 C CA1335694 C CA 1335694C
- Authority
- CA
- Canada
- Prior art keywords
- process according
- gas
- secondary stage
- raw gas
- gasifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/023—Reducing the tar content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Industrial Gases (AREA)
- Treating Waste Gases (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Gas Separation By Absorption (AREA)
- Artificial Filaments (AREA)
- Control And Other Processes For Unpacking Of Materials (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Fats And Perfumes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a process for the refining of a raw gas produced from a carbonaceous material by means of a gasification process, refining taking place in a secondary stage separated from the gasifier. In order to reduce the gas contents of tar in the form of organic compounds condensible at lower temperatures, such as ambient temperatures, and of ammonia, the refining is carried out in a secondary stage being a fast circulating fluidized bed, the bed material of which at least mainly being an active material in the form of a material that is catalytic for tar and ammonia conversion, whereby a catalytic conversion of tar and ammonia contained in the raw gas is obtained. In order to decrease the content of hydrogen chloride in the gas, an active material that can absorb chloride also is used. Fresh catalytic and absorbing material is supplied in an amount sufficient to have the hydrogen chloride present in the raw gas absorbed on the material, a corresponding amount of the material containing absorbed chloride being discharged from the secondary stage.
Description
~ 1 1 335694 R~FINING OF RAW GAS
This invention relates to a process for the refining of a raw gas produced from a carbonacQous material by means of a gasification process in which the refing takes place in a secondary stage separated from the gasifier of the gasifi-cation process.
A raw gas produced from different kinds of biofuels and used as a fuslgas is a valuable oil substitute for demanding applications in which the process dsmands make direct solid fuel fireing impossible, e.g. fireing of lime kilns or conversion of existing oil fired boilers.
For other types of applications, 8 .g. so-called coge-neration (of electrical power and heat) by ue of diesel en-gines, very high demands on the gas purity concerning prima-rily tars and dust are set. Moreover, environmental aspects often lead to demands on low concentrations of compounds which when combustsd form harmful emissions, ~uch as NOX, SOx and various chlorinated compounds. The last mentioned is valid especially for a gas produced from refuse derived fuel, RDF. These demands on the gas purity can be satisfied by the raw gas being refined by an appropriate method.
Gasification of RDF with subsequent refining of the raw gas means an environmentally favourable method for energy recovery from wastes by utilization of refined gas in exist-ing boilers or for cogeneration in diesel engines and/or boilers.
Besides, utilization of raw gas often is connected with other technical problems.
At temperatures below 1200C tar is always present in a raw gas produced by gasification of a carbonaceous mate-rial, e.g. coal, peat, bark, wood or RDF, which limits the utilization to combustion of hot gas in direct or close con-nection to the gasifier. Operational disturbances caused by tarcoating on apparatuses and armatures are a great problem 'S~
which limits the availability. During combustion of hot gas, nitrogen and in certain cases also sulphur ~e.g. from peat) bound in tars, as well as ammonia, H2S (peat) or HCl (from RDF), furthermore give rise to emissions which are harmful to the environment (N0x, Sx and HCl, respectively, and chlori-nated hydrocarbons, i.a. dioxines).
Despite extensive research concerning tar and ammonia conversion, 80 far no process which in an industrial scale can achieve sufficisntly far-reaching raw gas refining has been developed. The traditional way of reducing tar contents in a raw gas is by means of wet scrubbing, but aerosol for-mation in the scrubber makes the tar removal inefficient.
Furthermore, a proce~s water wit~h high contQnts of organic compounds and ammonia is obtained. Consequently, this water in its turn must be cleaned before being discharged to a sewerage. When gasifying RDF the process water also contains high concentrations of dissolved hydrochloric acid and/or ammonium chloride. When gasifying more sulphur rich fuels, e.g. peat or coal, the raw gas also has to be purified to remove hydrogen sulphide.
The object of the presented invention is to provide a raw gas refining process, by means of which the above men-tioned problems will be solved to a great extent.
This object is achieved by the process according to the invention having the features defined in the enclosed claims.
The invention thus concerns a process for the refining of a tar and ammonia containing raw gas, in special cases also containing considerable quantitiQs of hydrogen chloride, the gas being produced by means of an arbitrary gasification proc~ss from a carbonaceous material, e.g. bark, wood, psat or Refuse Derived Fuel, RDF, wherein in a secondary stage conversion takes place in contact with an appropriate activs (catalytic and possibly absorbing) mat~rial, e.g. dolomite, of the tar and ammonia presQnt in the raw gas, preferably to 1 33569~
such a level that the remaining contents are below 500 and 300 mg/Nm3 respectively. In special cases absorption of hy-drogen chloride to almost thermodynamic equilibrium simul-tanQously takes place. The secondary 8tage consists of a Cir-culating Fast Fluidized Bed (CFB~ with a bed material at least mainly in form of an active material, e.g. dolomite.
With this arrangement the secondary stage also could be in-tegrated with an arbitrary CFB-gasifiQr, only preceded by a primary particle separator, or another type of gasifier.
We have found that sufficient conversion of tars and ammonia and in special cases simultaneous absorption of hy-drogen chloride can be achiQvsd, by first separating the tar containing gas from pyrolysing larger fuel particles in the gasifying stage and then in a separate secondary stage in the form of a circulating fast fluidized bed contacting the gas with a suitable active material, such as dolomite, at suitable proces~ paramsters.
If the carbonaceous material also contains sulphur in considQrable amounts, which e.g. is the ca~e for peat, absorption of hydrogen sulphide on the catalytic and absorb-ing material will of course also take place.
The amount of active material which is required in relation to the raw gas amount is determined by the required space-velocity for catalytic conversion of tars and ammonia and depends on several parameters such as ths temperature, the residence time of the gas, the particle size of the ac-tive material, the partial pressure of reactants and the de-gree of deactivation of the active material. Too low tempera-turs and/or C02 partial pressure can result in the tar con-version causing carbon deposition on the active surface, which results in deactivation. If this occurs the material can be activated by treatment with an oxidizing gas, e.g. air and~or steam. Absorption of HCl (and/or H2S) takes place ~o rapidly at the temperatures of intersst that these reactions become almost determined by the equilibrium and result in a 4 1 33~9~
consumption of active material corresponding to the formed solid chloride Cand sulphide resp.).
We have thus found that absorption of chloride Cand in certain casQs also of hydrogen sulphide) on an active mate-rial such as dolomite is a rapid reaction and rQquires pre-sence of a considerably less amount of active material in relation to the gas flow than catalytic conversion of tars and ammonia.
Utilization of a secondary stage in the form of a fast circulating fluidized bed (CFB) means considerable advan-tages.
Such a bed is able to handle dust entrained from the gasifier, gives very uniform temperatures in the reaction zone and also gives a homogeneous contact between gas and bed material, that is to say little risk for variations in con-version/absorption degree. Further, the particle size can be varied downward~ to a great extent, for those cases in which this is needed to give increased conversion at a given tempe-rature and space-velocity. Considerable erosion of the bed material also results in increased accessible active surface.
Also, a secondary stage designed as a CFB with advantage can be integrated with an arbitrary CFB gasifier, which merely has a primary particle separator, or another type of gasi-fier. One also achieves relatively small diameters when scaling up, since the gas velocities can be kept relatively high, up to about 10 m/s, preferably up to 6 m/s.
In case the gasifier consists of a CFB gasifier, a connection directly after primary dust separation can thus be made. If an active material is used as a bed material in the CFB gasifier, the secondary stage can in an advantageous manner be integrated with the gasifier, e.g. 80 that dust from a secondary particle separator after the secondary stage F
is totally or partly recycled to the gasifier. In this way, the total losses of bed material also become lower, and one ~ 5 ~ l 33569~
also obtains the advantage of using only one type of bed material.
Ths necessary amount of active material in the reactor shaft of the secondary stage for sufficient catalytic conver-sion of tar and ammonia is controlled by the totally added amound and by controlled recirculation of bed material. Re-quired conversion determines suitable combination of tempera-ture, particle ~ize and amount of active material. Because of abrasion, deactivation and/or absorption of HCl (and possibly H2S) consumed active material is replaced by adding corre-sponding amount3 of fresh active material and/or activated such material. The residence time of the gas can be controll-ed by the combination diameter~hei~ht abovs the ~as inlet.
In those special cases, when HCl is present in the raw gas in considerable amounts, the active material entrained by the outlet gas from the secondary stage means that the HCl absorption is improved, since thermodynamically it becomes more far-reaching at lower temperatures, undsr the condition that the refined gas is cooled down to an essentially lower temperature before final dust removal.
In the following the invention will be described by way of a non-limiting embodiment while referring to the en-closed drawing, which schematically shows a gasification and gas refining system which embodies the present invention.
In the system shown in the drawing carbonaceous mate-rial 1 is conveyed to a gasifier 3, which consists of a cir-culating fast fluidized bed (CFB). This comprises a reactor 51, a primary separator 52 and recirculation means 53 for bed material separated in the primary separator. The bed material consists of an active catalytic and absorbing material, pre-ferably in the form of dolomite, mixed with ungasified car-bonaceous material, char. The primary separator 52 is a mechanical separator of non-centrifugal type, suitably a U-beam separator, in accordance with what is described in our ~ 1 335694 European Patent EP 0 103 613, relating to a CFB boiler and hereby referred to.
The hot raw gas 2 produced in the gasifier 3 is with-drawn directly from the primary separator 52 and is fed di-~ 5 rectly to a gas cleaning secondary stage 25 without any addi-tional dust removal. The secondary stage 25 i8 designed as a circulating fast fluidized bed ~CFB) 26 and has the same kind of active bed material ~8 the gasifier 3.
The raw gas 2 is supplied to the secondary stage 25 8c that it constitutes a fluidizing gas.
The secondary stage 25 is designed with a long and narrow reactor shaft with arbitrary cross section (e.g. cir-cular or square). Bed material which follows with the gas stream out form tha top of ths reactor shaft is separated to a major part in a primary particle separator 27, preferably a U-beam separator of the same ~ind as the U-beam separator of the gasifier, followed by a secondary separator 28, preferab-ly a cyclone. The material 30 separated in the primary par-ticle separator i8 recycled to the lower part of the circu-lating bed 26 through a recirculation facility. ThG material 29 separated in the secondary particle separator 28 is added mainly to the lower part of the gasifier 3, stream 31. When needed, a part of the material stream 29 also can be supplied to the lower part of the circulating bed 26, stream 34, and/or be discharged out of the system, stream 43.
For feeding fresh catalytic and absorbing material 14 to the secondary stage 25 a side feeding device 15 located on a suitable height is used. Consumed andfor deactivated mate-rial 35 is discharged by means of a discharging device 36 3 located in connection with the bottom of the secondary stage 25.
The active material used in the secondary stage in this example consists of a calcium-magnesium carbonate con-taining material, preferably dolomite, with a particle size smaller than 2 mm, preferably smaller than 1 mm, which in ~ 7 combination with the passing gas forms the circulating fluidized bed 26.
The ga~ velocity in the upper section of the reactor shaft, calculated on the free cross section, is adjusted 80 that it is below 10 m/s, preferably not above 6 m/s.
The fluidizing gas of the fast circulating bed 26 con-sist~ of the raw gas 2 and added oxidizing gas 13, e.g. air.
When needed additional oxidizing gas 33 can be added to the secondary stage 25 on one or on several other suitable, higher located levels.
Conversion of tar and ammonia contained in the raw gas 2 and absorption of chloride containsd in the raw gas take place by means of contact with the catalytic and absorbing material in the circulating bed 26 within a tsmperature in-terval of 600-1000C, preferably 700-900C or most preferably 850-950C. The required temperature level is maintained by burning combustibls gas components insidQ the sQcondary stagQ
25, which is controlled by adjustment of the amount of added oxidizing gas, strQams 13 and 33.
The average suspension density in the reactor shaft of the seconday stage 25 is maintained within an interval of 20-300 kg/m3, preferably within an interval of 80-250 kg/m3, 80 that a neces~ary contact between the passing gas and the active material is obtained. This is achieved by adjusting the total amount of circulating material in combination with controlling the flow rate of recycled material 30 and 34.
The residence time of the gas in the reactor shaft, calculated on an empty reactor shaft, is maintained within an interval of 0.2-20 8, preferably within an interval of 0.5_7 8.
When needed, activation of deactivated catalytic and absorbing material can be performed by adding oxidizing gas 32, e.g. air, to the material which is recycled to the lower part of the circulating bed, streams 30 and 34. The amount of added oxidizing gas 32 is controlled 80 that the activation takQs place within a tQmperature interval of 600-1000C, pre-ferably within an interval of 750-900C.
Before starting operation of the process heating of the secondary stage 25 including its bed material takes place by means of combustion of LP gas 24 therein.
The refined gas strQam 4 leaving the secondary separa-tor 28 of the secondary stage 25 is relieved from entrained finely divided bed material and stsam in the subsequent gas treatment stages.
The gas passes through two heat exchangers. In the first heat exchanger 37 heat exchange takes place with oxi-dizing gas, str~am 10, intended for both the ~Tasifier 3 and the secondary stage 25, 80 that preheated oxidizing gas 11 at the outlet from the heat exchanger 37 has a suitable tempera-ture, preferably about 400C. The preheatQd oxidizing gas 11 is used both in the gasifier 3 (among others as fluidizing gas~, stream 12, and in the sQcondary stagQ 25, streams 13, 32 and 33.
In the subsQquent second heat exchanger 38 the tempe-rature of the gas 5 is lowered to a level which permits the outlet gas 6 to be further cleaned by using e.g. standard textile filters or a cyclone for further dust removal, at 39, i.e. preferably down to 150-300C . The removQd dust 18 is withdrawn from the dust removal stage 39.
As mQntioned bQfore, the gas stream 4 contains en-trained finely divided active material which follows with the gas stream out of the secondary separator 28. In spQcial cases, e.g. in connection with gasification of RFD, the raw gas 2 from the gasifiQr contains considQrable amounts of HCl.
Since absorption of HCl on calcareous materials, such as do-lomite, is favoured by sinking temperature, thQ gas cooling in the heat exchangers 37 and 38 contributss to increase the degree of absorption of residual HCl on ths entrained mate-rial.
The almost dust-free gas 7, which leaves the dust rs-moval stage 39, is fed to a scrubber 40, in which it is re-lieved from moi~ture and other water soluble components. In the scrubber 40 both moistening of the gas stream 7 and con-densation of steam take place. At the current conditions also precipitation of almost all of the residual fines and absorp-tion of water soluble gas components, e.g. ~H3, HCl and/or NH4Cl, take place.
The water stream 20 leaving~the scrubber 40 i8 recir-culated by a pump 41, whereby it i8 cooled in a heat ex-changer 42, 80 that the temperature of the water 19 recycled to the scrubber 40 is kept within the interval 15-20C. Ex-cess water 21 i8 drained from the water circuit.
The gas 8 leaving the scrubber can for industrial app-lications be regarded as pure, i.e. it i8 almost free from tars, ammonia, dust, HCl and H2S. However, at the present outlet temperatures ~about 30C) it is uaturated with steam.
Depending on the application, in order to decrease the rela-tive humidity, the gasstream 8 can be preheated or passed through an additional drying stage in order to rsduce its moisture content. The pure gas satiesfies the requirements for engine operation, e.g. by means of turbocharged diesel engines, and can be burned without any subsequent exhaust gas cleaning.
For more simple applications, e.g. heat generation in boilers, the scrubber 40 can be omitted, 80 that the refined gas can be utilized either directly after the heat exchanger 37, stream 22, or after the dust separator 39, stream 23.
In the describQd example the secondary stage 25 has been integrated with a gasifier 3 based on CFB technology.
The gasifier 3 can produce the raw gas 2 from several dif-fsrent kinds of fusls, e.g. coarse bark, peat or refuse de-rived fuels ~DF. As bed material in the circulating bed of the gasifier 3 it is, as mentioned, convenient to use a cata-lytic and absorbing material of the same type as in the secondary stage 25.
The total pressure drop of the oxidizing gas supplied, e.g. air, at the passage through ths production loop, is slightly above 1 bar. This sets requirements on using a com-pressor 16, which increases the oxidizing gas pressure in stream 9 to the pressure level in stream 10 necessary in view of the purpose involved.
This invention relates to a process for the refining of a raw gas produced from a carbonacQous material by means of a gasification process in which the refing takes place in a secondary stage separated from the gasifier of the gasifi-cation process.
A raw gas produced from different kinds of biofuels and used as a fuslgas is a valuable oil substitute for demanding applications in which the process dsmands make direct solid fuel fireing impossible, e.g. fireing of lime kilns or conversion of existing oil fired boilers.
For other types of applications, 8 .g. so-called coge-neration (of electrical power and heat) by ue of diesel en-gines, very high demands on the gas purity concerning prima-rily tars and dust are set. Moreover, environmental aspects often lead to demands on low concentrations of compounds which when combustsd form harmful emissions, ~uch as NOX, SOx and various chlorinated compounds. The last mentioned is valid especially for a gas produced from refuse derived fuel, RDF. These demands on the gas purity can be satisfied by the raw gas being refined by an appropriate method.
Gasification of RDF with subsequent refining of the raw gas means an environmentally favourable method for energy recovery from wastes by utilization of refined gas in exist-ing boilers or for cogeneration in diesel engines and/or boilers.
Besides, utilization of raw gas often is connected with other technical problems.
At temperatures below 1200C tar is always present in a raw gas produced by gasification of a carbonaceous mate-rial, e.g. coal, peat, bark, wood or RDF, which limits the utilization to combustion of hot gas in direct or close con-nection to the gasifier. Operational disturbances caused by tarcoating on apparatuses and armatures are a great problem 'S~
which limits the availability. During combustion of hot gas, nitrogen and in certain cases also sulphur ~e.g. from peat) bound in tars, as well as ammonia, H2S (peat) or HCl (from RDF), furthermore give rise to emissions which are harmful to the environment (N0x, Sx and HCl, respectively, and chlori-nated hydrocarbons, i.a. dioxines).
Despite extensive research concerning tar and ammonia conversion, 80 far no process which in an industrial scale can achieve sufficisntly far-reaching raw gas refining has been developed. The traditional way of reducing tar contents in a raw gas is by means of wet scrubbing, but aerosol for-mation in the scrubber makes the tar removal inefficient.
Furthermore, a proce~s water wit~h high contQnts of organic compounds and ammonia is obtained. Consequently, this water in its turn must be cleaned before being discharged to a sewerage. When gasifying RDF the process water also contains high concentrations of dissolved hydrochloric acid and/or ammonium chloride. When gasifying more sulphur rich fuels, e.g. peat or coal, the raw gas also has to be purified to remove hydrogen sulphide.
The object of the presented invention is to provide a raw gas refining process, by means of which the above men-tioned problems will be solved to a great extent.
This object is achieved by the process according to the invention having the features defined in the enclosed claims.
The invention thus concerns a process for the refining of a tar and ammonia containing raw gas, in special cases also containing considerable quantitiQs of hydrogen chloride, the gas being produced by means of an arbitrary gasification proc~ss from a carbonaceous material, e.g. bark, wood, psat or Refuse Derived Fuel, RDF, wherein in a secondary stage conversion takes place in contact with an appropriate activs (catalytic and possibly absorbing) mat~rial, e.g. dolomite, of the tar and ammonia presQnt in the raw gas, preferably to 1 33569~
such a level that the remaining contents are below 500 and 300 mg/Nm3 respectively. In special cases absorption of hy-drogen chloride to almost thermodynamic equilibrium simul-tanQously takes place. The secondary 8tage consists of a Cir-culating Fast Fluidized Bed (CFB~ with a bed material at least mainly in form of an active material, e.g. dolomite.
With this arrangement the secondary stage also could be in-tegrated with an arbitrary CFB-gasifiQr, only preceded by a primary particle separator, or another type of gasifier.
We have found that sufficient conversion of tars and ammonia and in special cases simultaneous absorption of hy-drogen chloride can be achiQvsd, by first separating the tar containing gas from pyrolysing larger fuel particles in the gasifying stage and then in a separate secondary stage in the form of a circulating fast fluidized bed contacting the gas with a suitable active material, such as dolomite, at suitable proces~ paramsters.
If the carbonaceous material also contains sulphur in considQrable amounts, which e.g. is the ca~e for peat, absorption of hydrogen sulphide on the catalytic and absorb-ing material will of course also take place.
The amount of active material which is required in relation to the raw gas amount is determined by the required space-velocity for catalytic conversion of tars and ammonia and depends on several parameters such as ths temperature, the residence time of the gas, the particle size of the ac-tive material, the partial pressure of reactants and the de-gree of deactivation of the active material. Too low tempera-turs and/or C02 partial pressure can result in the tar con-version causing carbon deposition on the active surface, which results in deactivation. If this occurs the material can be activated by treatment with an oxidizing gas, e.g. air and~or steam. Absorption of HCl (and/or H2S) takes place ~o rapidly at the temperatures of intersst that these reactions become almost determined by the equilibrium and result in a 4 1 33~9~
consumption of active material corresponding to the formed solid chloride Cand sulphide resp.).
We have thus found that absorption of chloride Cand in certain casQs also of hydrogen sulphide) on an active mate-rial such as dolomite is a rapid reaction and rQquires pre-sence of a considerably less amount of active material in relation to the gas flow than catalytic conversion of tars and ammonia.
Utilization of a secondary stage in the form of a fast circulating fluidized bed (CFB) means considerable advan-tages.
Such a bed is able to handle dust entrained from the gasifier, gives very uniform temperatures in the reaction zone and also gives a homogeneous contact between gas and bed material, that is to say little risk for variations in con-version/absorption degree. Further, the particle size can be varied downward~ to a great extent, for those cases in which this is needed to give increased conversion at a given tempe-rature and space-velocity. Considerable erosion of the bed material also results in increased accessible active surface.
Also, a secondary stage designed as a CFB with advantage can be integrated with an arbitrary CFB gasifier, which merely has a primary particle separator, or another type of gasi-fier. One also achieves relatively small diameters when scaling up, since the gas velocities can be kept relatively high, up to about 10 m/s, preferably up to 6 m/s.
In case the gasifier consists of a CFB gasifier, a connection directly after primary dust separation can thus be made. If an active material is used as a bed material in the CFB gasifier, the secondary stage can in an advantageous manner be integrated with the gasifier, e.g. 80 that dust from a secondary particle separator after the secondary stage F
is totally or partly recycled to the gasifier. In this way, the total losses of bed material also become lower, and one ~ 5 ~ l 33569~
also obtains the advantage of using only one type of bed material.
Ths necessary amount of active material in the reactor shaft of the secondary stage for sufficient catalytic conver-sion of tar and ammonia is controlled by the totally added amound and by controlled recirculation of bed material. Re-quired conversion determines suitable combination of tempera-ture, particle ~ize and amount of active material. Because of abrasion, deactivation and/or absorption of HCl (and possibly H2S) consumed active material is replaced by adding corre-sponding amount3 of fresh active material and/or activated such material. The residence time of the gas can be controll-ed by the combination diameter~hei~ht abovs the ~as inlet.
In those special cases, when HCl is present in the raw gas in considerable amounts, the active material entrained by the outlet gas from the secondary stage means that the HCl absorption is improved, since thermodynamically it becomes more far-reaching at lower temperatures, undsr the condition that the refined gas is cooled down to an essentially lower temperature before final dust removal.
In the following the invention will be described by way of a non-limiting embodiment while referring to the en-closed drawing, which schematically shows a gasification and gas refining system which embodies the present invention.
In the system shown in the drawing carbonaceous mate-rial 1 is conveyed to a gasifier 3, which consists of a cir-culating fast fluidized bed (CFB). This comprises a reactor 51, a primary separator 52 and recirculation means 53 for bed material separated in the primary separator. The bed material consists of an active catalytic and absorbing material, pre-ferably in the form of dolomite, mixed with ungasified car-bonaceous material, char. The primary separator 52 is a mechanical separator of non-centrifugal type, suitably a U-beam separator, in accordance with what is described in our ~ 1 335694 European Patent EP 0 103 613, relating to a CFB boiler and hereby referred to.
The hot raw gas 2 produced in the gasifier 3 is with-drawn directly from the primary separator 52 and is fed di-~ 5 rectly to a gas cleaning secondary stage 25 without any addi-tional dust removal. The secondary stage 25 i8 designed as a circulating fast fluidized bed ~CFB) 26 and has the same kind of active bed material ~8 the gasifier 3.
The raw gas 2 is supplied to the secondary stage 25 8c that it constitutes a fluidizing gas.
The secondary stage 25 is designed with a long and narrow reactor shaft with arbitrary cross section (e.g. cir-cular or square). Bed material which follows with the gas stream out form tha top of ths reactor shaft is separated to a major part in a primary particle separator 27, preferably a U-beam separator of the same ~ind as the U-beam separator of the gasifier, followed by a secondary separator 28, preferab-ly a cyclone. The material 30 separated in the primary par-ticle separator i8 recycled to the lower part of the circu-lating bed 26 through a recirculation facility. ThG material 29 separated in the secondary particle separator 28 is added mainly to the lower part of the gasifier 3, stream 31. When needed, a part of the material stream 29 also can be supplied to the lower part of the circulating bed 26, stream 34, and/or be discharged out of the system, stream 43.
For feeding fresh catalytic and absorbing material 14 to the secondary stage 25 a side feeding device 15 located on a suitable height is used. Consumed andfor deactivated mate-rial 35 is discharged by means of a discharging device 36 3 located in connection with the bottom of the secondary stage 25.
The active material used in the secondary stage in this example consists of a calcium-magnesium carbonate con-taining material, preferably dolomite, with a particle size smaller than 2 mm, preferably smaller than 1 mm, which in ~ 7 combination with the passing gas forms the circulating fluidized bed 26.
The ga~ velocity in the upper section of the reactor shaft, calculated on the free cross section, is adjusted 80 that it is below 10 m/s, preferably not above 6 m/s.
The fluidizing gas of the fast circulating bed 26 con-sist~ of the raw gas 2 and added oxidizing gas 13, e.g. air.
When needed additional oxidizing gas 33 can be added to the secondary stage 25 on one or on several other suitable, higher located levels.
Conversion of tar and ammonia contained in the raw gas 2 and absorption of chloride containsd in the raw gas take place by means of contact with the catalytic and absorbing material in the circulating bed 26 within a tsmperature in-terval of 600-1000C, preferably 700-900C or most preferably 850-950C. The required temperature level is maintained by burning combustibls gas components insidQ the sQcondary stagQ
25, which is controlled by adjustment of the amount of added oxidizing gas, strQams 13 and 33.
The average suspension density in the reactor shaft of the seconday stage 25 is maintained within an interval of 20-300 kg/m3, preferably within an interval of 80-250 kg/m3, 80 that a neces~ary contact between the passing gas and the active material is obtained. This is achieved by adjusting the total amount of circulating material in combination with controlling the flow rate of recycled material 30 and 34.
The residence time of the gas in the reactor shaft, calculated on an empty reactor shaft, is maintained within an interval of 0.2-20 8, preferably within an interval of 0.5_7 8.
When needed, activation of deactivated catalytic and absorbing material can be performed by adding oxidizing gas 32, e.g. air, to the material which is recycled to the lower part of the circulating bed, streams 30 and 34. The amount of added oxidizing gas 32 is controlled 80 that the activation takQs place within a tQmperature interval of 600-1000C, pre-ferably within an interval of 750-900C.
Before starting operation of the process heating of the secondary stage 25 including its bed material takes place by means of combustion of LP gas 24 therein.
The refined gas strQam 4 leaving the secondary separa-tor 28 of the secondary stage 25 is relieved from entrained finely divided bed material and stsam in the subsequent gas treatment stages.
The gas passes through two heat exchangers. In the first heat exchanger 37 heat exchange takes place with oxi-dizing gas, str~am 10, intended for both the ~Tasifier 3 and the secondary stage 25, 80 that preheated oxidizing gas 11 at the outlet from the heat exchanger 37 has a suitable tempera-ture, preferably about 400C. The preheatQd oxidizing gas 11 is used both in the gasifier 3 (among others as fluidizing gas~, stream 12, and in the sQcondary stagQ 25, streams 13, 32 and 33.
In the subsQquent second heat exchanger 38 the tempe-rature of the gas 5 is lowered to a level which permits the outlet gas 6 to be further cleaned by using e.g. standard textile filters or a cyclone for further dust removal, at 39, i.e. preferably down to 150-300C . The removQd dust 18 is withdrawn from the dust removal stage 39.
As mQntioned bQfore, the gas stream 4 contains en-trained finely divided active material which follows with the gas stream out of the secondary separator 28. In spQcial cases, e.g. in connection with gasification of RFD, the raw gas 2 from the gasifiQr contains considQrable amounts of HCl.
Since absorption of HCl on calcareous materials, such as do-lomite, is favoured by sinking temperature, thQ gas cooling in the heat exchangers 37 and 38 contributss to increase the degree of absorption of residual HCl on ths entrained mate-rial.
The almost dust-free gas 7, which leaves the dust rs-moval stage 39, is fed to a scrubber 40, in which it is re-lieved from moi~ture and other water soluble components. In the scrubber 40 both moistening of the gas stream 7 and con-densation of steam take place. At the current conditions also precipitation of almost all of the residual fines and absorp-tion of water soluble gas components, e.g. ~H3, HCl and/or NH4Cl, take place.
The water stream 20 leaving~the scrubber 40 i8 recir-culated by a pump 41, whereby it i8 cooled in a heat ex-changer 42, 80 that the temperature of the water 19 recycled to the scrubber 40 is kept within the interval 15-20C. Ex-cess water 21 i8 drained from the water circuit.
The gas 8 leaving the scrubber can for industrial app-lications be regarded as pure, i.e. it i8 almost free from tars, ammonia, dust, HCl and H2S. However, at the present outlet temperatures ~about 30C) it is uaturated with steam.
Depending on the application, in order to decrease the rela-tive humidity, the gasstream 8 can be preheated or passed through an additional drying stage in order to rsduce its moisture content. The pure gas satiesfies the requirements for engine operation, e.g. by means of turbocharged diesel engines, and can be burned without any subsequent exhaust gas cleaning.
For more simple applications, e.g. heat generation in boilers, the scrubber 40 can be omitted, 80 that the refined gas can be utilized either directly after the heat exchanger 37, stream 22, or after the dust separator 39, stream 23.
In the describQd example the secondary stage 25 has been integrated with a gasifier 3 based on CFB technology.
The gasifier 3 can produce the raw gas 2 from several dif-fsrent kinds of fusls, e.g. coarse bark, peat or refuse de-rived fuels ~DF. As bed material in the circulating bed of the gasifier 3 it is, as mentioned, convenient to use a cata-lytic and absorbing material of the same type as in the secondary stage 25.
The total pressure drop of the oxidizing gas supplied, e.g. air, at the passage through ths production loop, is slightly above 1 bar. This sets requirements on using a com-pressor 16, which increases the oxidizing gas pressure in stream 9 to the pressure level in stream 10 necessary in view of the purpose involved.
Claims (51)
1. A process for the refining of a raw gas produced from a carbonaceous material by means of gasification, the raw gas containing tar and ammonia as impurities, the improvement comprising:
(a) contacting the raw gas in a secondary stage separate from the gasification, the secondary stage comprising a fast circulating fluidized bed containing active material which acts as a catalyst for conversion of tar and ammonia in said raw gas;
(b) maintaining the average suspension density of the catalytic material in said fluidized bed at a level between about 80 and about 250 kg/m/SUP 3/;
(c) converting said tar and ammonia in said raw gas by catalytic reaction in said fluidized bed to thereby result in a refined gas having a tar concentration of less than about 500 mg/NM/SUP 3/ and an ammonia concentration of less than about 300 mg/Nm/SUP 3/, said tar being converted by catalytic cracking, wherein the catalytic material is selected from the group consisting of magnesium-calcium carbonate, operating temperature of the secondary stage is maintained at between about 600 DEG.
C. and about 1,000 DEG. G.; and, (d) separating the refined gas from the active material by means of particle separation.
(a) contacting the raw gas in a secondary stage separate from the gasification, the secondary stage comprising a fast circulating fluidized bed containing active material which acts as a catalyst for conversion of tar and ammonia in said raw gas;
(b) maintaining the average suspension density of the catalytic material in said fluidized bed at a level between about 80 and about 250 kg/m/SUP 3/;
(c) converting said tar and ammonia in said raw gas by catalytic reaction in said fluidized bed to thereby result in a refined gas having a tar concentration of less than about 500 mg/NM/SUP 3/ and an ammonia concentration of less than about 300 mg/Nm/SUP 3/, said tar being converted by catalytic cracking, wherein the catalytic material is selected from the group consisting of magnesium-calcium carbonate, operating temperature of the secondary stage is maintained at between about 600 DEG.
C. and about 1,000 DEG. G.; and, (d) separating the refined gas from the active material by means of particle separation.
2. A process according to claim 1 comprising utilizing in order also to decrease the content of hydrogen chloride in the gas, an active material which also can absorb chloride, the operating temperature also being adjusted and intermittent or continuous feeding of fresh catalytic and absorbing material in sufficient amounts taking place so that hydrogen chloride present in the raw gas will be absorbed on the material sufficiently far-reaching so that the concentrations of hydrogen chloride in the refined gas will correspond to an almost thermodynamic equilibrium, while at the same time a sufficient amount of constantly present material active for catalytic conversion is maintained, a corresponding amount of the material containing absorbed chloride being discharged from the secondary stage intermittently or continuously.
3. A process according to claim 1 characterized in that the operating temperature of the secondary stage is adjusted within the interval of 600-1000°C.
4. A process according to claim 3 characterized in that the operating temperature of the secondary stage is controlled by added amounts of oxygen containing gas.
5. A process according to claim 1 characterized in that the active material consists of a magnesium-calcium carbonate containing material and the corresponding calcined (burnt) product on magnesium-calcium carbonate containing material or the corresponding calcined (burnt) product.
6. A process according to claim 5 characterized in that active material deactivated as a result of carbon deposition or by any other reason intermittently or continuously is discharged from the secondary stage and is replaced by equivalent amounts of fresh and/or activated material or fresh material or activated material.
7. A process according to claim 6 characterized in that deactivated active material discharged from the secondary stage is activated by treatment with an oxidizing gas in a separate activating stage, thus activated material being returned to the secondary stage.
8. A process according to claim 5 characterized in that active material deactivated as a result of carbon deposition or by any other reason is activated by treatment with an oxidizing gas in the system recirculating separated bed material of the secondary stage.
9. A process according to claim 8 characterized in that the activation takes place at an operating temperature within the interval of 600-1000°C.
10. A process according to claim 9 characterized in that the operating temperature of the activation is controlled by means of added amounts of gas containing oxygen.
11. A process according to claim 1 characterized in that the raw gas is supplied to the secondary stage directly from the gasifier without any intermediate dust removal.
12. A process according to claim 2 characterized in that the raw gas is supplied to the secondary stage directly from the gasifier without any intermediate dust removal.
13. A process according to claim 3 characterized in that the raw gas is supplied to the secondary stage directly from the gasifier without any intermediate dust removal.
14. A process according to claim 4 characterized in that the raw gas is supplied to the secondary stage directly from the gasifier without any intermediate dust removal.
15. A process according to claim 5 characterized in that the raw gas is supplied to the secondary stage directly from the gasifier without any intermediate dust removal.
16. A process according to claim 6 characterized in that the raw gas is supplied to the secondary stage directly from the gasifier without any intermediate dust removal.
17. A process according to claim 7 characterized in that the raw gas is supplied to the secondary stage directly from the gasifier without any intermediate dust removal.
18. A process according to claim 8 characterized in that the raw gas is supplied to the secondary stage directly from the gasifier without any intermediate dust removal.
19. A process according to claim 9 characterized in that the raw gas is supplied to the secondary stage directly from the gasifier without any intermediate dust removal.
20. A process according to claim 10 characterized in that the raw gas is supplied to the secondary stage directly from the gasifier without any intermediate dust removal.
21. A processing according to claim 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 wherein the gasifier comprises a fast fluidized bed, characterized in that the raw gas is supplied to the secondary stage directly from the primary separator of the gasifier without any additional dust separation.
22. A process according to claim 11 characterized in that the fluidizing gas of the secondary stage comprises the raw gas and possibly an oxidizing gas.
23. A process according to claim 12 characterized in that the fluidizing gas of the secondary stage comprises the raw gas and possibly an oxidizing gas.
24. A process according to claim 13 characterized in that the fluidizing gas of the secondary stage comprises the raw gas and possibly an oxidizing gas.
25. A process according to claim 14 characterized in that the fluidizing gas of the secondary stage comprises the raw gas and possibly an oxidizing gas.
26. A process according to claim 15 characterized in that the fluidizing gas of the secondary stage comprises the raw gas and possibly an oxidizing gas.
27. A process according to claim 16 characterized in that the fluidizing gas of the secondary stage comprises the raw gas and possibly an oxidizing gas.
28. A process according to claim 17 characterized in that the fluidizing gas of the secondary stage comprises the raw gas and possibly an oxidizing gas.
29. A process according to claim 18 characterized in that the fluidizing gas of the secondary stage comprises the raw gas and possibly an oxidizing gas.
30. A process according to claim 19 characterized in that the fluidizing gas of the secondary stage comprises the raw gas and possibly an oxidizing gas.
31. A process according to claim 20 characterized in that the fluidizing gas of the secondary stage comprises the raw gas and possibly an oxidizing gas.
32. A process according to claim 22, 23, 24, 25, 26, 27, 28, 29, 30 or 31 characterized in that oxidizing gas which does not constitute a fluidizing gas, is added to the reactor of the secondary stage at one or several levels above the fluidizing gas supply.
33. A process according to claim 1 characterized by choosing the total amount of active material present in the secondary stage and controlling the recirculation flow of bed material for providing a suspension density of the circulating fast fluidized bed such that the desirable contact between the passing gas and the active material, for the catalytic conversion, is accomplished.
34. A process according to claim 1 characterized in that the gas velocity in the secondary stage calculated on an empty reactor shaft is maintained below 10 m/s.
35. A process according to claim 1 characterized in that the particle size of the catalytic and absorbing material is smaller than 2 mm.
36. A process according to claim 1 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
37. A process according to claim 2 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
38. A process according to claim 3 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
39. A process according to claim 4 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
40. A process according to claim 5 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
41. A process according to claim 6 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
42. A process according to claim 7 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
43. A process according to claim 8 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
44. A process according to claim 9 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
45. A process according to claim 10 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
46. A process according to claim 33 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
47. A process according to claim 34 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
48. A process according to claim 35 characterized in that the average suspension density in the reactor shaft is maintained within the interval of 20-300 kg/m3.
49. A process according to claim 36, 37, 38, 39, 40, 41, 42, 43, 45, 46, 47 or 48 characterized in that the residence time of the gas calculated on an empty reactor shaft, is kept within the interval of 0.2-20 s.
50. A process according to claim 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47 or 48 characterized in that the hydrogen chloride content in the refined gas, which leaves the secondary stage, is lowered further by means of absorption on the catalytic and absorbing material remaining in the gas after the particle separation of the secondary stage, wherein the gas after the secondary stage first is cooled to a temperature between 150 and 300°C and then is subject to additional dust separation.
51. A process according to claim 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 characterized in that the raw gas feeding of the secondary stage is connected directly to the primary particle separator of a gasifier having a fast circulating fluidized bed, in which the circulating bed material consists of an active material of the same type as in the secondary stage, in that dust separated in the secondary stage at least partly is recycled to the lower part of the gasifying reactor, and in that bed material entrained with the raw gas from the gasifier and material possibly discharged from the bottom of the gasifier are replaced by the material recycled to the gasifying reactor from the secondary stage in combination with fresh catalytic and absorbing material which is added to the gasifier intermittently or continuously.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8703816-2 | 1987-10-02 | ||
| SE8703816A SE459584B (en) | 1987-10-02 | 1987-10-02 | PROCEDURES FOR PROCESSING OF RAAGAS MANUFACTURED FROM COAL CONTENTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1335694C true CA1335694C (en) | 1995-05-30 |
Family
ID=20369746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000579047A Expired - Fee Related CA1335694C (en) | 1987-10-02 | 1988-09-30 | Refining of raw gas |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0310584B1 (en) |
| JP (1) | JP2573681B2 (en) |
| AT (1) | ATE88210T1 (en) |
| AU (1) | AU612199B2 (en) |
| CA (1) | CA1335694C (en) |
| DE (1) | DE3880253T2 (en) |
| DK (1) | DK175009B1 (en) |
| ES (1) | ES2039698T3 (en) |
| FI (1) | FI95924C (en) |
| GE (1) | GEP19980893B (en) |
| LT (1) | LT3842B (en) |
| LV (1) | LV11188B (en) |
| NO (1) | NO302422B1 (en) |
| SE (1) | SE459584B (en) |
| WO (1) | WO1989002909A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5139756A (en) * | 1989-10-05 | 1992-08-18 | Nkk Corporation | Catalytic oxidation of ammonia |
| JPH03122010A (en) * | 1989-10-05 | 1991-05-24 | Nkk Corp | Catalytic oxidative degradation of ammonia |
| US5827819A (en) * | 1990-11-01 | 1998-10-27 | Oregon Health Sciences University | Covalent polar lipid conjugates with neurologically active compounds for targeting |
| US5543390A (en) | 1990-11-01 | 1996-08-06 | State Of Oregon, Acting By And Through The Oregon State Board Of Higher Education, Acting For And On Behalf Of The Oregon Health Sciences University | Covalent microparticle-drug conjugates for biological targeting |
| DE4210003A1 (en) * | 1992-03-27 | 1993-09-30 | Ruhrkohle Ag | Combined process for the production of metallurgical coke and sponge iron |
| FI96321C (en) * | 1993-06-11 | 1996-06-10 | Enviropower Oy | Method and reactor for treating process gas |
| US5403366A (en) * | 1993-06-17 | 1995-04-04 | Texaco Inc. | Partial oxidation process for producing a stream of hot purified gas |
| US5401282A (en) * | 1993-06-17 | 1995-03-28 | Texaco Inc. | Partial oxidation process for producing a stream of hot purified gas |
| NL1001555C2 (en) * | 1995-10-27 | 1997-05-02 | Biomass Technology Group B V | Catalytically producing combustible gases, e.g., for generating energy |
| DE19907901C2 (en) * | 1999-02-24 | 2001-11-29 | Mg Technologies Ag | Process for the catalytic cracking of volatile higher hydrocarbons |
| RU111024U1 (en) * | 2008-09-26 | 2011-12-10 | Сименс Фаи Металз Текнолоджиз Гмбх | SYSTEM FOR DRY DUST DEPOSITION AND DRY CLEANING OF A GAS CONTAMINATED BY DUST AND HAZARDOUS SUBSTANCES FORMED IN IRON PRODUCTION UNITS IN THE CAST IRON PRODUCTION OR IN THE DEVICE FOR A DISASTER |
| DE102008049579A1 (en) * | 2008-09-30 | 2010-04-01 | Uhde Gmbh | Hot gas cleaning |
| DE102010024429A1 (en) * | 2010-06-21 | 2011-12-22 | Technische Universität München | Operating integrated gasification combined cycle power plant, comprises converting fuels in gasifier using adjuvants including oxygen, vapor, carbon dioxide and water, and cleaning raw gas from gasifier and treating gas in shift reactor |
| EP2606105B1 (en) | 2010-08-16 | 2022-10-26 | Singularity Energy Technologies, LLC | Sandwich gasification process for high-efficiency conversion of carbonaceous fuels to clean syngas with zero residual carbon discharge |
| DE102013008422A1 (en) * | 2013-05-16 | 2014-11-20 | Ecoloop Gmbh | Process for the purification of synthesis gases |
| CN103820170B (en) * | 2014-02-21 | 2015-09-02 | 陕西延长石油（集团）有限责任公司碳氢高效利用技术研究中心 | The conversion system of the coal-tar middle oil component of a kind of raw gas and carbonaceous particles and method |
| JP6345139B2 (en) * | 2015-03-13 | 2018-06-20 | 三菱日立パワーシステムズ株式会社 | Gas engine system |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3807090A (en) * | 1970-12-02 | 1974-04-30 | Exxon Research Engineering Co | Purifications of fuels |
| US4273749A (en) * | 1977-06-03 | 1981-06-16 | Hitachi, Ltd. | Refining process of hot gas containing hydrogen sulfide and ammonia |
| DE3017998C2 (en) * | 1980-05-10 | 1994-05-26 | Krupp Koppers Gmbh | Process for the catalytic treatment of partial oxidation raw gas |
| DE3404483A1 (en) * | 1984-02-08 | 1985-08-08 | Environment Protecting Engineers, Inc., Southfield, Mich. | Process for purifying pyrolysis gases and apparatus for carrying out this process |
| SE457355B (en) * | 1985-09-25 | 1988-12-19 | Skf Steel Eng Ab | MAKE SURE TO PREPARE A CLEAN, CARBON OXIDE AND GAS GAS INCLUDING GAS |
| SE8600639L (en) * | 1986-02-13 | 1987-08-14 | Goetaverken Energy Syst Ab | PROCEDURES AND DEVICES FOR SUBSTANCE PURPOSES ON GENERATION OF GAS FOR MESA OVEN OPERATIONS |
| DE3716199A1 (en) | 1987-05-14 | 1988-11-24 | Linde Ag | METHOD AND DEVICE FOR PURIFYING RAW GAS WITH SIMULTANEOUS RECOVERY OF SYNTHESIS AND FUEL GAS |
-
1987
- 1987-10-02 SE SE8703816A patent/SE459584B/en not_active Application Discontinuation
-
1988
- 1988-09-28 DE DE8888850323T patent/DE3880253T2/en not_active Expired - Fee Related
- 1988-09-28 WO PCT/SE1988/000502 patent/WO1989002909A1/en active IP Right Grant
- 1988-09-28 ES ES198888850323T patent/ES2039698T3/en not_active Expired - Lifetime
- 1988-09-28 AU AU25297/88A patent/AU612199B2/en not_active Ceased
- 1988-09-28 GE GEAP19881491A patent/GEP19980893B/en unknown
- 1988-09-28 EP EP88850323A patent/EP0310584B1/en not_active Expired - Lifetime
- 1988-09-28 AT AT88850323T patent/ATE88210T1/en not_active IP Right Cessation
- 1988-09-28 JP JP63508056A patent/JP2573681B2/en not_active Expired - Fee Related
- 1988-09-30 CA CA000579047A patent/CA1335694C/en not_active Expired - Fee Related
-
1990
- 1990-03-27 NO NO901393A patent/NO302422B1/en not_active IP Right Cessation
- 1990-03-30 DK DK199000810A patent/DK175009B1/en not_active IP Right Cessation
- 1990-03-30 FI FI901613A patent/FI95924C/en not_active IP Right Cessation
-
1993
- 1993-10-25 LV LVP-93-1170A patent/LV11188B/en unknown
- 1993-12-15 LT LTIP1598A patent/LT3842B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ES2039698T3 (en) | 1993-10-01 |
| GEP19980893B (en) | 1998-04-10 |
| AU2529788A (en) | 1989-04-18 |
| DK81090A (en) | 1990-05-28 |
| DK81090D0 (en) | 1990-03-30 |
| FI901613A0 (en) | 1990-03-30 |
| DE3880253T2 (en) | 1993-07-29 |
| NO302422B1 (en) | 1998-03-02 |
| NO901393D0 (en) | 1990-03-27 |
| WO1989002909A1 (en) | 1989-04-06 |
| EP0310584A3 (en) | 1990-03-14 |
| JP2573681B2 (en) | 1997-01-22 |
| ATE88210T1 (en) | 1993-04-15 |
| LT3842B (en) | 1996-04-25 |
| AU612199B2 (en) | 1991-07-04 |
| DK175009B1 (en) | 2004-04-19 |
| NO901393L (en) | 1990-03-27 |
| SE8703816D0 (en) | 1987-10-02 |
| FI95924C (en) | 1996-04-10 |
| JPH03500420A (en) | 1991-01-31 |
| FI95924B (en) | 1995-12-29 |
| LTIP1598A (en) | 1995-08-25 |
| LV11188B (en) | 1996-10-20 |
| EP0310584A2 (en) | 1989-04-05 |
| LV11188A (en) | 1996-04-20 |
| SE8703816L (en) | 1989-04-03 |
| EP0310584B1 (en) | 1993-04-14 |
| DE3880253D1 (en) | 1993-05-19 |
| SE459584B (en) | 1989-07-17 |
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