EP0412587B1 - Procédé de purification d'un gaz combustible brut provenant de la gazéification de combustibles solides - Google Patents

Procédé de purification d'un gaz combustible brut provenant de la gazéification de combustibles solides Download PDF

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Publication number
EP0412587B1
EP0412587B1 EP90201697A EP90201697A EP0412587B1 EP 0412587 B1 EP0412587 B1 EP 0412587B1 EP 90201697 A EP90201697 A EP 90201697A EP 90201697 A EP90201697 A EP 90201697A EP 0412587 B1 EP0412587 B1 EP 0412587B1
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EP
European Patent Office
Prior art keywords
crude gas
water
filter
gas
zone
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 - Lifetime
Application number
EP90201697A
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German (de)
English (en)
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EP0412587A1 (fr
Inventor
Erhard Lath
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GEA Group AG
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Metallgesellschaft AG
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Publication date
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Publication of EP0412587A1 publication Critical patent/EP0412587A1/fr
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Expired - Lifetime legal-status Critical Current

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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
    • C10K1/02—Dust removal
    • C10K1/024—Dust removal by filtration
    • 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
    • C10K1/02—Dust removal
    • C10K1/026—Dust removal by centrifugal forces
    • 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
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
    • C10K1/06—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials combined with spraying with water
    • 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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • 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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • 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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
    • 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
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas

Definitions

  • the invention relates to a method for cleaning the raw gas from the gasification of solid fuels, in particular carbon-containing waste, with oxygen-containing gasification agent, wherein a carbon oxides, hydrogen and methane and as contaminants dust, NH3 and hydrogen halide containing raw gas with temperatures of about 500 to 1200 ° C generated becomes. Garbage can also be given to gasification.
  • the invention has for its object to remove from the raw gas NH3, HCl, HF and dust in a simple manner so that the amount of impurities to be removed is as small as possible.
  • this is achieved by cooling the raw gas to temperatures of 150 to 400 ° C, the cooled raw gas with an NH3 content of at least 0.1 vol .-% in a spray drying zone and in contact with sprayed return water brings, the return water is completely evaporated, that you pass the steam containing raw gas from the spray drying zone at temperatures of 80 to 250 ° C through a filter, in the filter at least 80 wt .-% of the solids contained in the raw gas in the filter inlet and at least 50 wt.
  • the raw gas is passed from the filter through a saturation zone in which the raw gas is brought into direct contact with sprayed water, the raw gas is saturated with water vapor and cooled to temperatures of 50 to 90 ° C.
  • the Saturation zone derives saline and solids-containing water with a pH of 7.5 to 9.5 and gives the spray drying zone as return water, and that the raw gas from the saturation zone is aftertreated to remove dust and saline liquid droplets.
  • the raw gas entering the spray drying zone has a considerable NH 3 content of at least 0.1% by volume up to about 1% by volume.
  • This NH3 content usually results in the raw gas without further notice that the fuels are not burned but gasified, the energy required for this being supplied by partial oxidation.
  • oxygen air or air enriched with oxygen, steam is also used as the gasifying agent, which can be partially replaced by CO2.
  • the calorific value of the gas produced during gasification can be in an incinerator and e.g. can also be used in a power plant. It is important that the raw fuel gas is cleaned in a cost-effective manner and yet with sufficient intensity. In the method of the invention, the cleaning of the raw gas does not lead to polluted wastewater that would have to be cleaned again.
  • the process can be carried out completely without the addition of chemicals, if only it is ensured that the NH3 content in the raw gas in the entrance to the spray drying zone is sufficiently high. In the gasification of waste and municipal waste, this is usually the case without the addition of external NH3.
  • Heavy metals or heavy metal compounds also desublimate, accumulate preferentially in the spray drying zone on the desublimated halogen particles and on the dust brought in with the raw gas and can thus also be removed from the gas to a sufficient extent.
  • the pH in the water is 7.5 to 9.5, so that cheap carbon steel can be used for the systems and pipes.
  • a cost reduction through energy savings is also given by the fact that one can manage with a relatively small amount of water both in the spray drying zone and in the saturation zone.
  • the gas from the saturation zone mainly contains dust and saline liquid droplets, so that an aftertreatment is necessary.
  • a wet electrostatic filter, a wet scrubber, a droplet separator are particularly suitable for this aftertreatment, the latter also being able to be connected downstream of a wet scrubber, or a condenser. It is important to remove the dust and the saline liquid droplets without adding chemicals.
  • the water that contains dust and salt is also fed into the spray drying zone.
  • solid fuels for example coal or biomass, or also carbon-containing wastes, which are introduced in line (2), are gasified with air from line (3).
  • the waste can be municipal waste, for example.
  • the reactor (1) can also be given water vapor coming from line (4).
  • the gasification air can be enriched with oxygen, you can only work with technically pure oxygen together with water vapor.
  • the process shown in the drawing shows that the fuel or waste is gasified in the circulating fluidized bed, but the gasification can also take place in the fluidized bed, in the entrained flow or in a fixed bed.
  • the deck furnace is also possible as a gasification reactor.
  • a mixture of raw gas and solids passes through the channel (6) to a cyclone (7), where the majority of the solids are separated from the gas. Instead of just one cyclone (7), you can also connect several cyclones in parallel or in series.
  • the solids are then partly fed back through lines (8) and (9) to the gasification reactor (1) and an excess can be drawn off in line (10). Ash is drawn off directly from the reactor (1) through line (5).
  • the dust-containing raw gas which contains combustible components and NH3, HCl and usually also in small quantities HF, leaves the cyclone (7) in line (12) at temperatures in the range of about 500 to 1200 ° C.
  • a first indirect cooling takes place in the heat exchanger (13). can be used to preheat the gasification air in line (3). For the sake of clarity, this possibility was not shown in the drawing. Further cooling can take place in the heat exchanger (14) if this is expedient.
  • the pre-cooled raw gas at temperatures of 150 to 400 ° C in the line (16) to a spray dryer (17). Care is taken to ensure that the NH3 content in the raw gas of line (16) is at least 0.1% by volume and is present in a sufficient amount for the reaction with the hydrogen halides in the raw gas. Usually the raw gas from the waste gasification contains enough NH3, but if the NH3 content is too low, foreign NH3 can be added.
  • Spray dryer (17) return water from line (18). This water carries halogen compounds, heavy metal compounds and dust with it, which have been washed out of the raw gas elsewhere. The pH value of the return water is therefore in the range from 7.5 to 9.5.
  • water is sprayed from the line (19) which contains hardly any impurities. Particular care is taken to ensure that no further chemicals are added to the spray dryer (17). Such an addition of chemicals would only lead to the need to dispose of large amounts of waste.
  • a mixture of raw gas and solids passes through the line (20) to a filter (21).
  • This filter in which the solids are separated from the gas dry, can be, for example, a bag filter, a candle filter, an electrostatic filter or one or more cyclones. It is important that at least 80% by weight of the solids introduced in the raw gas in line (20) and at least 50% by weight of the halogen compounds which are removed in line (22) are separated off in the filter (21). Usually at least 50% by weight of the heavy metals are also separated off in the filter (21).
  • the solids in the line (22), the amount of which has not been increased by avoiding the addition of foreign chemicals, must be removed and deposited.
  • the partially dedusted raw gas now flows in line (24) to a saturation zone (25), into which water is sprayed through line (23a).
  • a saturation zone 25
  • the raw gas is cooled further, saturated with water vapor and partially dedusted again.
  • Halogen and heavy metal compounds in particular are effectively removed by the sprayed water.
  • Salt and solids-containing water which has a pH in the range from 7.5 to 9.5 is drawn off from the sump (25a) of the saturation zone. This water is led through lines (18 a) and (18) back to the spray dryer (17).
  • the gas leaving the saturation zone (25) in line (26) has only a temperature in the range from 50 to 90 ° C.
  • a wet electrostatic filter (27) was provided in the drawing, which is acted upon with water from the line (28). Water containing dust and salt is drawn off in line (29) and added to the return water in line (18). Deviating from the drawing, the wet electrostatic filter (27) can be replaced by a wet scrubber and / or by a droplet separator.
  • Dust-free, water vapor-containing gas passes from the electrostatic filter (27) in line (30) to a condenser (31) in which the water vapor is partially condensed by indirect cooling and thus removed.
  • the condensate which is fairly clean water, is discharged in line (32) and distributed to lines (23) and (19), a partial stream can also be returned via line (33) and as rinsing water passed through the condenser.
  • the condenser (31) which can also be omitted behind a wet electrostatic precipitator, its calorific value can be regulated by adjusting the water vapor content in the gas.
  • purified fuel gas is available, which can be used, for example, in a Power plant can use.
  • the gas Before use, the gas can be heated by indirect heat exchange with the raw gas from line (12), for example in the heat exchanger (14).
  • the cleaning method of the invention it is readily possible to provide a fuel gas in line (35) which has maximum HCl values of 10 mg per Nm3 and dust, HF and heavy metals of at most 1 mg each.
  • This raw gas contains 10,000 mg of inert dust and 34 mg of heavy metals per Nm3.
  • the following temperatures occur in the different lines:
  • the spray dryer (17) has a height of 6 m and a diameter of 1.5 m, the downstream filter (21) is designed as a bag filter.
  • the line (22) 180 kg of filter dust accumulate per hour, which together with 1,200 kg / h of ash from the line (5) are to be disposed of from the gasification reactor (1).
  • the flowing out in the line (35), cleaned fuel gas contains less than 1 mg of dust, 5 mg of NH4Cl and 1 mg of heavy metals and 1.5 g of NH3 per Nm3.
  • the gas is heated to 500 ° C in the heat exchanger (14) and burned in a power plant boiler. In the boiler, which works on the principle of the circulating fluidized bed and is also fed with coal, the sulfur compounds are bound into the boiler ash in a known manner using limestone.

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  • 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)
  • Gasification And Melting Of Waste (AREA)
  • Treating Waste Gases (AREA)

Claims (3)

  1. Procédé d'épuration du gaz brut provenant de la gazéification de combustibles solides, notamment de déchets carbonés, par un agent de gazéification contenant de l'oxygène, avec production d'un gaz brut ayant des températures de 500 à 1200°C environ et contenant des oxydes de carbone, de l'hydrogène et du méthane ainsi que, comme impuretés, de la poussière, du NH₃ et des haloacides, caractérisé en ce qu'il consiste à refroidir le gaz brut à des températures de 150 à 400°C, à envoyer le gaz brut refroidi ayant une teneur en NH₃ d'au moins 0,1 % en volume dans une zone de séchage par pulvérisation et à le mettre en contact avec de l'eau recyclée qui y est pulvérisée, l'eau recyclée étant évaporée entièrement, à envoyer le gaz brut contenant de la vapeur provenant de la zone de séchage par pulvérisation et ayant des températures de 80 à 250°C dans un filtre, à séparer à l'état sec dans le filtre au moins 80 % en poids des matières solides contenues dans le gaz brut à l'entrée du filtre et au moins 50 % en poids de composés halogénés, à envoyer le gaz brut du filtre dans une zone de saturation dans laquelle on met le gaz brut en contact direct avec de l'eau pulvérisée, à saturer ainsi le gaz brut de vapeur d'eau et à le refroidir à des températures de 50 à 90°C, à évacuer de la zone de saturation de l'eau contenant du sel et des matières solides et ayant un pH de 7,5 à 9,5 et à la charger dans la zone de séchage par pulvérisation en tant qu'eau recyclée et à retraiter le gaz brut provenant de la zone de saturation pour en éliminer la poussière et les gouttes de liquide contenant du sel.
  2. Procédé suivant la revendication 1, caractérisé en ce qu'il consiste à effectuer le retraitement du gaz brut provenant de la zone de saturation dans un électrofiltre en voie humide, dans un laveur en voie humide, dans un séparateur de gouttelettes et/ou dans un condenseur et à envoyer l'eau qui s'y forme en tant qu'eau recyclée à la zone de séchage par pulvérisation.
  3. Procédé suivant la revendication 1 ou 2, caractérisé en ce qu'il consiste à refroidir le gaz retraité, à en éliminer de la vapeur d'eau par condensation et à envoyer au moins une partie du produit condensé à la zone de saturation.
EP90201697A 1989-08-11 1990-06-27 Procédé de purification d'un gaz combustible brut provenant de la gazéification de combustibles solides Expired - Lifetime EP0412587B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3926575A DE3926575A1 (de) 1989-08-11 1989-08-11 Verfahren zum reinigen von rohbrenngas aus der vergasung fester brennstoffe
DE3926575 1989-08-11

Publications (2)

Publication Number Publication Date
EP0412587A1 EP0412587A1 (fr) 1991-02-13
EP0412587B1 true EP0412587B1 (fr) 1993-09-22

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US (1) US5041144A (fr)
EP (1) EP0412587B1 (fr)
DE (2) DE3926575A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8306665B2 (en) 2006-05-05 2012-11-06 Plasco Energy Group Inc. Control system for the conversion of carbonaceous feedstock into gas
US8435315B2 (en) 2006-05-05 2013-05-07 Plasco Energy Group Inc. Horizontally-oriented gasifier with lateral transfer system
US9109172B2 (en) 2006-05-05 2015-08-18 Plasco Energy Group Inc. Low temperature gasification facility with a horizontally oriented gasifier

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DE4206943A1 (de) * 1992-03-05 1993-09-09 Krupp Koppers Gmbh Verfahren zur reinigung eines durch vergasung von kohlenstoffhaltigem material gewonnenen gases
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JP5547659B2 (ja) 2007-02-27 2014-07-16 プラスコエナジー アイピー ホールディングス、エス．エル．、ビルバオ、シャフハウゼン ブランチ 加工原料／チャー変換とガス改質を伴うガス化方式
US8038746B2 (en) * 2007-05-04 2011-10-18 Clark Steve L Reduced-emission gasification and oxidation of hydrocarbon materials for liquid fuel production
AR066535A1 (es) * 2007-05-11 2009-08-26 Plasco Energy Group Inc Un sistema de reformulacion de gas inicial en un gas reformulado y procedimiento para dicha reformulacion.
US8377154B2 (en) * 2010-05-18 2013-02-19 Kellogg Brown & Root Llc Gasification system and process for maximizing production of syngas and syngas-derived products
US9321640B2 (en) 2010-10-29 2016-04-26 Plasco Energy Group Inc. Gasification system with processed feedstock/char conversion and gas reformulation
US10378970B2 (en) 2015-02-24 2019-08-13 Prasidiux, Llc Thermochromic liquid crystal temperature indicator
CN110105988A (zh) * 2019-04-22 2019-08-09 宝钢工程技术集团有限公司 荒煤气除尘装置及除尘方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8306665B2 (en) 2006-05-05 2012-11-06 Plasco Energy Group Inc. Control system for the conversion of carbonaceous feedstock into gas
US8435315B2 (en) 2006-05-05 2013-05-07 Plasco Energy Group Inc. Horizontally-oriented gasifier with lateral transfer system
US9109172B2 (en) 2006-05-05 2015-08-18 Plasco Energy Group Inc. Low temperature gasification facility with a horizontally oriented gasifier

Also Published As

Publication number Publication date
DE3926575A1 (de) 1991-02-14
US5041144A (en) 1991-08-20
DE59002819D1 (de) 1993-10-28
EP0412587A1 (fr) 1991-02-13

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