WO1993013184A1 - Procede de traitement des gaz obtenu par gazeification du charbon, gazeification des residus, gazeification des dechets ou gazeification de l'huile - Google Patents

Procede de traitement des gaz obtenu par gazeification du charbon, gazeification des residus, gazeification des dechets ou gazeification de l'huile Download PDF

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Publication number
WO1993013184A1
WO1993013184A1 PCT/NL1992/000240 NL9200240W WO9313184A1 WO 1993013184 A1 WO1993013184 A1 WO 1993013184A1 NL 9200240 W NL9200240 W NL 9200240W WO 9313184 A1 WO9313184 A1 WO 9313184A1
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Prior art keywords
gas
sulfur
gasification
sorbent
coal
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PCT/NL1992/000240
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English (en)
Inventor
Jan Adolf Lagas
Johannes Borsboom
Anton Scholten
John Wilhelm Geus
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Gastec N.V.
Comprimo, B.V.
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Application filed by Gastec N.V., Comprimo, B.V. filed Critical Gastec N.V.
Priority to EP93902571A priority Critical patent/EP0643757A1/fr
Publication of WO1993013184A1 publication Critical patent/WO1993013184A1/fr
Priority to FI943128A priority patent/FI943128A/fi

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    • 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
    • C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0408—Pretreatment of the hydrogen sulfide containing gases

Definitions

  • the invention relates to a process for the treatment of gases obtained by coal gasification, residue gasification, waste gasification or oil gasification.
  • Coal gasification plants are built for the production 5 of synthesis gas or fuel gas, which is used for generating electricity in generators which are driven by gas turbines. Coal gasification plants have advantages over directly fired coal-fired power plants, since such plants have more favorable properties with respect to emission and efficiency.
  • the synthesis or fuel gas originating from the A ' gasification of coal, oil or residues often contains COS, CS 2 .
  • the following process route is utilized.
  • the gas to be treated is purified, whereby sulfur- containing components are removed from the gas, followed by recovery of sulfur from these sulfur-containing components, followed by a residual gas sulfur purification step.
  • this last step it is attempted to recover the residual percentage of sulfur before emitting the residual gas via a flue into the atmosphere.
  • processes are utilized in which often aqueous solvents are used. These processes are subdivided into five main groups, viz., chemical solvent processes, physical solvent processes, physical/chemical solvent processes, redox processes, in which H2S is oxidixed directly to sulfur in aqueous solutions, and finally the group fixed bed processes, in which H 2 S is absorbed or adsorbed chemically or physically, or is selectively catalytically oxidized to sulfur.
  • the first three groups of processes mentioned are typically used in the industry for the removal of large amounts of sulfur from typically large quantities of gas.
  • the last two groups of processes mentioned, with the exception of fixed bed oxidation, are limited with regard to the amount of sulfur to be removed and the concentration of H 2 S in the gases to be purified and are therefore less suitable for use in large industrial gas purification plants.
  • the chemical solvent processes include the so-called amine processes, in which aqueous solutions of alkanolamines are used, and the so-called hot potassium carbonate processes, in which aqueous solutions or potassium carbonate are used.
  • amine processes in which aqueous solutions of alkanolamines are used
  • hot potassium carbonate processes in which aqueous solutions or potassium carbonate are used.
  • different types of chemicals are used, for instance dimethyl ether of polyethylene glycol (DMPEG) , known in this branch of the art under the name of Selexol, N-methyl-pyrrolidone (NMP) , known under the name of Purisol, or methanol, known under the name of Rectisol.
  • DMPEG polyethylene glycol
  • NMP N-methyl-pyrrolidone
  • Purisol or methanol
  • the Sulfinol process is very well known. This process uses a mixture of an alkanolamine with sulfolane, dissolved in a small amount of water.
  • an absorber and a regenerator are utilized.
  • the sulfur- containing components are chemically and/or physically attached to the solvent.
  • the sulfur-containing components are detached from the solvent, which can subsequently be reused.
  • the extent to which -E ⁇ S and other sulfur compounds, such as COS and CS2, but also, for instance, carbon dioxide (CO2) , are removed, is dependent on the solvent chosen and the pressure. The higher the pressure, the more sulfur compounds are removed. For instance, from a synthesis gas or fuel gas containing 1 vol.% H2S, approximately 99.5% of the sulfur compounds are removed at an absolute pressure of 5 bar, whereas from natural gas containing 1 vol.% H2S, approximately 99.95% of these compounds are removed at a pressure of 80 bar. The removal of sulfur compounds, however, is never complete and upon subsequent use of the gas, the compounds still present can give rise to some emission of SO2.
  • CO2 carbon dioxide
  • the solvents used in these methods are recycled from the absorber to the regenerator and subsequently back to the absorber.
  • Heat exchangers are typically used to save energy.
  • the sulfur compounds removed, together with the COzr are passed from the regenerator to a sulfur recovery plant, so as to recover sulfur from H 2 S and other sulfur compounds.
  • the Claus process consists of a thermal step followed by typically two or three reactor steps.
  • the thermal step one-third of the H 2 S is combusted to form SO 2 according to the reaction:
  • the efficiency of a Claus plant is between 90 and 98%, depending on the number of reactors. In view of the environmental requirements, this sulfur recovery efficiency is presently insufficient and industrial plants are equipped with residual gas sulfur cleaning plants, known in the process technology under the names of Tail Gas Treating Units (TGTU) or Tail Gas Clean-up Units (TGCU) .
  • TGTU Tail Gas Treating Units
  • TGCU Tail Gas Clean-up Units
  • Residual gas sulfur cleaning processes are described inter alia in U.H.F. Sander et al. , "Sulphur, Sulphur Dioxide and Sulphuric Acid", The British Sulphur Corporation Ltd, 59-95 (1984) .
  • the residual gases from a residual gas sulfur cleaning plant are after-burnt in an afterburner or incinerator before the residual gases are discharged.
  • the total SO2 emission is the sum of the efficiency loss in the gas purifications step and in the sulfur recovery step.
  • the total SO2 emission is 5.475%, which corresponds to a total sulfur recovery efficiency of 94.525%.
  • the gas purification plant having an efficiency of 99.95% and the Claus plant followed by a SCOT plant having an efficiency of 99.8%
  • the total SO2 emission is 0.25%, calculated on the sulfur initially present, which corresponds with a total sulfur recovery efficiency of 99.75%.
  • This gas purification by means of a selective oxidation catalyst whereby the H2S in the gas is oxidized to sulfur above the sulfur melting point of 120°C, as described, for instance, in European patent application 242,920 and in German patent application 39 03 294, has the drawback that the gas that leaves the gas purification, after condensation of the sulfur formed, still contains sulfur vapor, since, after condensation of the sulfur, the gas is still saturated with sulfur vapor. In the fuel gas line system, this sulfur vapor can give rise to serious obstruction. Another inevitable problem is that small amounts of SO2 are formed as well when the oxidation catalyst is used. SO2 and water vapor can, after condensation, give serious corrosion problems in the fuel gas system.
  • the total sulfur recovery efficiency can be increased considerably, the efficiency loss being even negligibly small, for instance less than 0.1 %, so that, accordingly, no or substantially no sulfur components are discharged via the flue to the atmosphere anymore.
  • the process according to the invention is considerably cheaper than the processes known from the prior art.
  • the invention relates to a process for the treatment of synthesis gas or fuel gas obtained by coal gasification, residue gasification, waste gasification or oil gasification, in which the gas stream obtained by gasification, which contains reducing and possibly inert gases, is treated for the removal of sulfur, optionally after separation of the desired product synthesis or fuel gas, is subsequently hydrogenated, the sulfur compounds still present in the gas stream thereby being converted to hydrogen sulfide, the hydrogen sulfide is removed from the gas stream by adsorption or absorption on a solid or liquid adsorbent or absorbent and the loaded adsorption or absorption medium is supplied to the coal, residues, waste or oil to be gasified.
  • Suitable raw materials for gasification to form synthesis or fuel gas are the sulfur-containing raw materials conventional in the art, such as various types of coal (pit coal, brown coal and the like) , oil (fuel oil and other, typically heavy petroleum fractions) , waste (household waste, synthetic materials, waste treatment slurry and the like) and residues.
  • the synthesis or fuel gas is preferably obtained from the gasification of coal, fuel oil or residues of petroleum refinement.
  • the process according to the invention can be practiced in a number of ways.
  • the gas stream originating from the gasification is split into a synthesis or fuel gas stream and a gas stream which contains the sulfur compounds.
  • This last gas stream is subsequently purified in a known manner by oxidation of the oxidizable sulfur compounds to elemental sulfur, which is subsequently separated by condensation. Residual gaseous sulfur and sulfur compounds are hydrogenated to H 2 S. Then the sulfur compounds present, optionally after oxidation, are sorbed on a solid or liquid adsorbent or absorbent (hereinafter to be referred to as sorbent) .
  • sorbent solid or liquid adsorbent or absorbent
  • splitting the gas stream coming the gasification into a synthesis or fuel gas stream and a gas stream that contains the sulfur compounds can occur in a conventional manner, for instance in one of the manners discussed in the introduction.
  • the * total gas stream is subjected to a selective oxidation of the H2S, this oxidation being carried out in such a manner that the greater part of the hydrogen sulfide present is oxidized to elemental sulfur, which is subsequently separated.
  • the gas stream is treated in the manner described hereinabove: hydrogenation, sorption and supply of the loaded sorbent to the feed of the gasification.
  • the essence of the invention resides in the manner in ⁇ which the last residues of H2S are removed from the largely purified gas.
  • the solid or liquid sorbent may consist of any substance that does not have an adverse influence on the gasification process.
  • the sorbent may be solid or liquid. Liquid sorbents could for instance be oils such as
  • 'sponge oil* or exhausted oil but also mineral oil, vegetable oil, or an alkaline reactive aqueous solution, such as a solution of sodium, potassium and/or calcium hydroxide, or lime milk.
  • an alkaline reactive aqueous solution such as a solution of sodium, potassium and/or calcium hydroxide, or lime milk.
  • a solid sorbent advantageous use may be made of iron oxide, copper oxide, calcium oxide and/or manganese oxide, active carbon, iron oxide-impregnated active carbon, pit coal which may or may not be activated, or brown coal.
  • the process can be carried out in such a manner that the H2S obtained after the hydrogenation is oxidized with oxygen at a temperature of less than 120°C to form elemental sulfur, which is deposited on the sorbent, whereafter the loaded sorbent is supplied to the feed of the gasification.
  • the sorbent may, in addition to the medium to be gasified, advantageously contain active carbon, dolomite, lime, iron compounds and/or siderite.
  • the synthesis or fuel gas coming from the gasification will, in addition to CO, H 2 and H2S, often contain COS, CS2/* C0 2 * HCN and NH3. Such a gas is highly reducing.
  • the gas stream to be treated is split into a purified synthesis or fuel gas stream and a sulfur-containing gas stream.
  • the sulfur compounds are thus oxidized as much as possible to elemental sulfur, which is subsequently condensed.
  • the residual sulfur and sulfur compounds are catalytically hydrogenated and removed from the gas stream. This last occurs according to the invention by adsorption or absorption and supplying the thus obtained loaded sorbent to the feed of the gasification. If so desired, a part of the H 2 S can be removed directly after the hydrogenation, using a known method, for instance a SCOT process.
  • the greater part of the sulfur compounds that are present in the synthesis or fuel gas are converted by selective oxidation to elemental sulfur, which is subsequently condensed.
  • the residual sulfur and sulfur compounds are catalytically hydrogenated and removed from the gas stream.
  • the last occurs according to the invention by adsorption or absorption and supplying the thus obtained loaded sorbent to the feed of the gasification. If so desired, a part of the H 2 S can be removed directly after the hydrogenation, using a known method, for instance a SCOT process.
  • H 2 S is converted over a suitable selective oxidation catalyst to form elemental sulfur according to the reaction H 2 S + 1 /2 0 2 ⁇ S + H 2 0.
  • the selective oxidation catalysts are used as described in European patent applications 242,920 and 242,006 and in European patent application 409,353, . because these yield a conversion efficiency in excess of 80% geven. The contents of these patent applications is incorporated herein by reference. It is surprising that the conversion percentages attained are achieved with these catalysts during oxidation in the presence of highly reducing gases as in the present case.
  • the catalyst according to European patent applications 242,920 and 242,006 contains a support, of which the surface that can come into contact with the gaseous phase exhibits no alkaline properties under the reaction conditions, whilst on this surface a catalytically active material has been provided. Further, the specific surface area of this catalyst is less than 20 m 2 /g, and less than 10% of the total pore volume in this catalyst has a pore radius of between 5 and 500 A.
  • the catalyst according to European patent application 409,353 has a specific surface area of more than 20 m 2 /g and an average pore radius of at least 25 A, whilst this catalyst exhibits substantially no activity for the Claus reaction under the reaction conditions .
  • the process according to the invention can also be carried out using other oxidation catalysts, such as for instance the Rhone Poulenc CRS-31-catalyst, a Ti ⁇ 2 catalyst described in European patent applications 38741 and 60741; the so-called Selectox catalyst, described in U.S. Patent Nos. 4,123,507, 4,243,647 and 4,311,683; the catalyst described in U.S. Patent No. 4,197,277; the catalyst described in U.S. Patent No. 4,519,992; the catalyst described in European patent application 91,551; and the catalyst described in European patent application 84200720.5.
  • Rhone Poulenc CRS-31-catalyst a Ti ⁇ 2 catalyst described in European patent applications 38741 and 60741
  • the so-called Selectox catalyst described in U.S. Patent Nos. 4,123,507, 4,243,647 and 4,311,683
  • the catalyst described in U.S. Patent No. 4,197,277 the catalyst described in
  • the SO 2 thus formed will, upon hydrogenation, use more H 2 , which is economically unattractive. Moreover, in the last step much more hydrogen sulfide must be removed, so that the required amount of sorbent increases and thus the process becomes more expensive.
  • the selective oxidation reaction occurs best in the temperature range of between 180°C and 300°C with a minor excess of air oxygen.
  • the molar ratio oxygen/hydrogen sulfide is preferably set between 0.5 and 2.0, and in particular between 0.5 and 1.0. It is practically inevitable that through side-reactions a small amount of SO 2 is formed, for instance by gaseous phase oxidation of sulfur vapor. Important is that the temperature in the selective oxidation bed is maintained above the dew point of sulfur so as to prevent the sulfur formed from condensing .in the catalyst bed.
  • the selective oxidation of hydrogen sulfide occurs with the aid of a catalyst suitable for that purpose.
  • the greater part of the hydrogen sulfide preferably more than 50%, which is present in the gas stream, is converted and recovered as elemental sulfur. Subsequently all sulfur compounds and oxygen residues formed by side- reactions in the extraction are converted to hydrogen sulfide and water through hydrogenation.
  • the selective oxidation of hydrogen sulfide is carried out with a slight stoichiometric excess of oxygen with regard to the hydrogen sulfide.
  • the gas mixture from the selective oxidation reactor is cooled to 125-160°C, the sulfur thereby being condensed.
  • the gas mixture consists of sulfur components in the form of H 2 S, S ⁇ 2 r sulfur vapor and sulfur mist and a small amount of oxygen.
  • these sulfur components are converted using a catalyst with hydrogenating properties .
  • the gas stream is heated from the condensation temperature of 125-160°C to a temperature level of approx. 200°C of higher, depending on the properties of the hydrogenation catalyst chosen.
  • the gas stream is heated to 250-300°C.
  • Catalysts which have the desired hydrogenating properties and moreover are sulfur- resistant, are known to the skilled worker and are typically catalysts having aluminium oxide as a support, which contain Co-Mo, as described in Catal. Rev.-Sci.Eng*. 2.1, (2), 275-318 (1980) .
  • the CO2 When the gas stream contains CO2 in addition to H2S, the CO2 will not interfere with the selective oxidation, hydrogenation and absorption or adsorption.
  • the gas stream also contains COS and/or CS2
  • the gas stream contains HCN and NH3
  • the gas is preferably washed or HCN and NH3 are reacted to remove these components completely. Removal through washing of the gas or conversion will preferably occur before the selective oxidation step.
  • the water content will have to be regulated so as to control the reaction
  • CO shift reaction in which CO reacts with water to form H 2 and CO2.
  • a cobalt-molybdenum on alumina catalyst is used. In practice, this will typically occur in at least two reactors with intermittent heat removal.
  • the gas stream is subsequently purified of the residual H2S by adsorbing or absorbing it preferably to the pit coal to-be gasified or to the oil residues and subsequently supplying it to the gasification in adsorbed or absorbed form.
  • the gas stream to be purified is the synthesis or fuel gas and has an increased pressure, for instance 20 bar, the solid or liquid sorbent must also be adjusted to that pressure.
  • lockhoppers are used. These are parallel lock vessels which operate discontinuously; when one vessel is unloaded, the other is filled.
  • the solid substance is fed into the lock vessel at atmospheric pressure, whereafter the vessel is closed.
  • the vessel is adjusted to a pressure of at least 20 bar with a suitable gas, for instance nitrogen.
  • the contents are introduced via a metering device, for instance a cell wheel lock, into a line for pneumatic transport, or directly into the adsorber or absorber.
  • the pneumatic transport can be effected with an inert gas, such as nitrogen, but also with the synthesis or fuel gas to be gasified.
  • an intensive contact between the gas to be purified and the sorbent is effected.
  • air is added to the gas so as to promote oxidative adsorption.
  • the duration of contact between the gas to be purified and the sorbent is not critical, although, depending on the type of sorbent and the nature and the amount of hydrogen sulfide to be removed from the gas*, in principle for each sorbent an optimum contact time is given. This can be determined experimentally in a simple manner. Depending on the type of sorbent, in each case a different, but maximum load will apply, so that it loses its activity after a certain residence time. It is therefore preferred to pass the sorbent through the adsorber in such a manner that the spread in residence time is limited.
  • the absorber or adsorber comprises an activation section and an absorption or adsorption section.
  • the activation section the unactivated sorbent is contacted with the unpurified gas, whereafter, in the absorption or adsorption section, the gas that flows from the activation section is purified in countercurrent flow with activated sorbent to the desired level.
  • the absorber or adsorber is also possible to design the absorber or adsorber as a cascade of contact devices, so as to limit the spread of residence of the solids and to realize the desired contact pattern of gas and solids.
  • the choice of a suitable contact device is not critical. The optimal choice will be determined depending inter alia on the size of the sorbent particles .
  • the sorbent consists of a fine powder, for instance pulverized coal such as is supplied to the gasifier
  • a fluidized or circulating bed is most suitable. These beds are known per se, for instance in catalytic cracking and whirling bed combustion. On account of the spread in particle size, a part of the solids may be entrained with the gas stream. A gas—solids separator passes the solids back to the bed.
  • cyclones which may or may not be combined with a filter, have been found suitable.
  • the use of a tray column has been found to be suitable.
  • a stepped flow of the sorbent is obtained.
  • a packed bed can be conveniently used.
  • this bed is refreshed continuously (moving bed) , for instance by -using a transport lock in the bottom.
  • Such a principle is known in a so-called shelf furnace.
  • a packed bed with coarse sorbent has an advantage over the fluidized bed in that the gas velocity calculated on the diameter of the adsorber or absorber may be greater without the solids being blown away or too large a pressure drop arising.
  • the sorbent After the sorbent has been loaded, it is passed to the gasifier.
  • a suitable method for this purpose is to introduce the loaded sorbent, for instance using a cell wheel lock, into a pneumatic transport system and subsequently to pass it directly into the gasifier.
  • a coarse sorbent When a coarse sorbent is used, it is preferred to grind it first . In the case of coal gasification, it can then be mixed with the coals in the transport section to the lockhoppers which supply the gasifier.
  • liquid sorbents It is also possible to use liquid sorbents.
  • Well known is 'sponge oil 1 , whereby H2S is absorbed from the gas stream to be purified by absorption into the oil. Exhausted oil can be used for this purpose too.
  • the oil can be contacted with the oil in co-current or countercurrent flow in a column provided with gas/liquid contact trays or a with a packing material.
  • a solid sorbent such as active carbon, pulverized coal or brown coal can be added to the oil.
  • sorbents can be used, such as active carbon, dolomite or lime (CaO) , iron oxide, iron ore, siderite and the like. If H2S is absorbed to dolomite or iron oxide, respectively CaS and FeS are formed. Upon return to the gasification plant, during combustion, H 2 S, COS and CS2 are formed again, which, in the process according to the invention, are converted again to elemental sulfur. Because the amount of the sorbent is relatively small, this does not have any influence on the quality or any slag formed.
  • Figuur 1 gives a schematic overview of a process according to the invention.
  • An amount of pit coal or oil residue to be gasified is passed through line 1 to the gasification plant 2.
  • the synthesis or fuel gas produced is passed via line 3 to the selective oxidation reactor 5.
  • the slag formed is removed from the gasification plant via line 4.
  • the gas is brought to the desired temperature in the line 3.
  • the amount of oxygen or air needed for the oxidation is supplied via line 6.
  • the elemental sulfur produced in reactor 5 is removed, after condensation, via line 7.
  • the gas is brought to the desired hydrogenation temperature before being passed into the hydrogenation reactor 9. All SO 2 , residual O 2 , and sulfur vapor and drops of sulfur mist are converted to H2S and H2O.
  • the gas from the hydrogenation reactor 9 is passed, after cooling, via line 10 to an absorber or adsorber 11.
  • the H 2 S still present in the main stream 10 is absorbed or adsorbed in the adsorber or absorber 11.
  • the loaded sorbent is returned to the gasification plant 2 via line 12.
  • the desulfurized synthesis or fuel gas leaves the plant via line 13.
  • FIG. 2 gives a schematic view of another process according to the invention.
  • An amount of pit coal or oil residue to be gasified is passed via line 1 to the gasification plant 2.
  • the synthesis gas or fuel gas produced is passed via line 3 to a gas purification 14.
  • the slag formed is removed from the gasification plant via line 4.
  • the desulfurized synthesis or fuel gas leaves the plant via line 13.
  • the sulfur-containing inert gas stream is passed via line 15 to the Claus plant 16, in which the greater part of the sulfur compounds is converted to elemental sulfur, which is removed via line 17. Via line 18, the gas is supplied to a selective oxidation reactor 5.
  • the gas is brought to the desired temperature in line 18.
  • the amount of oxygen or air needed for the oxidation is supplied via line 6.
  • the elemental sulfur produced in reactor 5 is removed, after condensation, via line 7.
  • the gas is brought to the desired hydrogenation temperature before being passed into the hydrogenation reactor 9. All SO2, residual O2, and sulfur vapor and drops of sulfur mist are converted to H2S and H2O.
  • the gas from the hydrogenation reactor 9 is passed, after cooling, via line 10 to an absorber or adsorber 11.
  • the H 2 S still present in the main stream 10 is absorbed or adsorbed in the adsorber or absorber 11.
  • the loaded sorbent is supplied to the gasification plant 2 via line 12.
  • the desulfurized synthesis or fuel gas leaves the plant via line 19.
  • the coal gas was cooled to 250°C by cooling with recirculation gas and a synthesis or fuel gas cooler, whereafter the gas was purified of dust by means of dry gas filters and a wet dust collector. Thus an acid slurry was formed, which was passed to a stripper. In the wet dust collector, the gas cooled further to 120°C. Subsequently, the gas was heated to 180°C and passed over a reactor filled with a titanium oxide catalyst for conversion of HCN to NH3 and CO2.
  • the gas was heated to 200°C with the aid of a heat exchanger. 1500 Nm 3 /h oxygen was supplied to the gas mixture. The molar oxygen/H2S ratio was set at 0.6. Then the gas mixture was passed through a selective oxidation reactor which contained a catalyst based on iron oxide, provided on silicon dioxide. More than 80% of the H 2 S present in the gas was converted to elemental sulfur. The outlet temperature of the selective oxidation reactor was 240°C. The gas was subsequently passed to the sulfur condensor, where 68.6 t/d sulfur was condensed at a temperature of 130°C.
  • the gas was then heated to 285°C to convert all sulfur components and residual O 2 to H 2 S and H2O in a hydrogenation reactor containing a Co-Mo on alumina catalyst, using the H 2 present in the gas.
  • the outlet temperature of the hydrogenation reactor was 325°C. Subsequently, the gas was cooled to 50°C.
  • the product gas contained 2 ppm volume H 2 S, so that the desulfurization efficiency was 99.97%.
  • an amount of 150 t/d fuel oil (Bunker C quality) containing 1.3 t/d sulfur was gasified in an oil gasification plant with 177 t/d O 2 and 69.1 t/d steam.
  • the fuel oil was mixed with 3 t/d carbon black from a carbon black separator and 9 t/d brown coal * loaded with 0.54 t/d sulfur. Carbon black and brown coal were ground fine and added to the fuel oil in dispersed form.
  • This mixture was passed to the burner of the gasifier and atomized. At 1550°C and an absolute pressure of 20 bar, this mixture was gasified. In a waste heat boiler, the gas was cooled to 300°C, generating 455 t/d high-pressure steam of an absolute pressure of 40 bar.
  • the partially cooled gas was passed through a carbon black separator, where the carbon black formed in the gasifier was separated with water.
  • the product gas was subsequently washed in a water washer to remove the last traces of carbon black.
  • the carbon black slurry was treated with naphtha, with water and carbon black separating.
  • the carbon black was, as specified, mixed with the fuel oil.
  • This gas was heated to 240°C using a gas-fired indirect heater.
  • 760 Nm 3 /d (1.08 t/d) O2 was supplied, which resulted in a molar oxygen/H2S ratio of 0.6.
  • the gas mixture was passed to a selective oxidation reactor, which contained a titanium-containing catalyst. More than 70% of the H2S present in the gas was converted to elemental sulfur. The outlet temperature of the reactor was 265°C. The gas was then passed to a sulfur condensor where 1.3 t/d sulfur was condensed at a temperature of 135°c.
  • the gas was then heated to 285°C to convert all sulfur components to H2S and H 2 O in a hydrogenation reactor, using the H 2 present in the gas .
  • the hydrogenation reactor contained a Co-Mo catalyst whose support material was alumina.
  • the product gas contained 1 ppm volume H 2 S, so that the desulfurization efficiency was 99.94%.
  • the amount of fuel gas which was available after cooling by means of steam generation, after dust removal and after hydrolysis of HCN and COS was 160,000 Nm 3 /h.
  • the gas had an 25 absolute pressure of 25 bar, a temperature of 0°C and had the following composition:
  • This gas was subsequently contacted in an absorber of a gas purification plant with a monodiethanolamine solution, the
  • the product gas contained 4 ppm H 2 S.
  • the acid H2S/CO2 gas mixture was passed to a sulfur recovery plant.
  • the sulfur recovery plant consisted of a thermal stage, two Claus reactor stages and a selective oxidation reactor stage.
  • the amount of acid gas was 2410 Nm 3 /h and had the following composition at 40°C and an absolute pressure of 1.8 bar
  • the molar oxygen/H 2 S ratio was set at 0.8.
  • the inlet temperature of the selective oxidation reactor was 210°C and the outlet temperature was 270°C.
  • the selective oxidation reactor was filled with an iron/chromium catalyst on ⁇ - alumina.
  • the sulfur formed in the sulfur recovery plant was condensed after each stage and removed. The amount was 935 kg/h. To the remaining inert gas, whose composition was as follows:
  • the temperature of the egressing gas was 325°C. At this temperature, the inert gas was subsequently passed directly over an absorber containing dehydrated bog ore. The residual 0.8 vol.% H 2 S was absorbed in the form of iron sulfide. The egressing inert gas contained less than 100 ppm volume H 2 S. Via an after-burning stage, the inert gas was passed to the flue.
  • the iron oxide was loaded with sulfur to 8%.
  • the amount of iron oxide needed was 425 kg/h.
  • the sorbent loaded with sulfur was ground and mixed with the pit coal and, together, introduced into the gasifier.
  • the synthesis gas obtained in the gasification had an absolute pressure of 15 bar and a temperature of 35°C.
  • the amount was 260,000 Nm 3 /d and had the following composition:
  • This gas was contacted in a gas purification plant with a physical solvent, the H2S, the COS being absorbed completely and the CO2 being absorbed partially.
  • the purified gas contained 10 ppm (vol) H2S.
  • the absorbed H2S, COS and CO2 gas were passed, after desorption, to a sulfur recovery plant (as described in Example 3) where H2S and COS were converted to elemental sulfur.
  • the temperature of the egressing gas was 320°C.
  • the inert gas was then cooled to 40°C, with condensation of 2.8 t/d water, which was removed from the system.
  • the active carbon loaded with sulfur was added to the feed of the gasifier.
  • the egressing amount of inert gas was 11190 Nm 3 /d and contained 3 ppm H 2 S and was subsequently passed to a flue.
  • the total desulfurization efficiency was 99.92 %.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Industrial Gases (AREA)

Abstract

L'invention se rapporte à un procédé de traitement du gaz de synthèse ou du gaz combustible obtenu par gazéification du charbon, gazéification des résidus, gazéification des déchets ou gazéification de l'huile. Le courant gazeux obtenu par gazéification, qui contient des gaz réducteurs et éventuellement inertes, est traité pour enlever le soufre, éventuellement après séparation du produit de synthèse ou du gaz combustible désiré, et est par la suite hydrogéné, les composés de soufre toujours ainsi présents dans le courant gazeux, étant convertis en sulfure d'hydrogène. Le sulfure d'hydrogène est retiré du courant gazeux par adsorption ou absorption sur un sorbant solide ou liquide et le sorbant chargé est amené vers le charbon, les résidus, les déchets ou l'huile à gazéifier.
PCT/NL1992/000240 1991-12-30 1992-12-29 Procede de traitement des gaz obtenu par gazeification du charbon, gazeification des residus, gazeification des dechets ou gazeification de l'huile WO1993013184A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP93902571A EP0643757A1 (fr) 1991-12-30 1992-12-29 Procede de traitement des gaz obtenu par gazeification du charbon, gazeification des residus, gazeification des dechets ou gazeification de l'huile
FI943128A FI943128A (fi) 1991-12-30 1994-06-29 Menetelmä hiilen, jätteen tai öljyn kaasutuksessa saatujen kaasujen käsittelemiseksi

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL9102195A NL9102195A (nl) 1991-12-30 1991-12-30 Werkwijze voor het behandelen van, door kolenvergassing, residuvergassing, afvalvergassing of olievergassing verkregen gassen.
NL9102195 1991-12-30

Publications (1)

Publication Number Publication Date
WO1993013184A1 true WO1993013184A1 (fr) 1993-07-08

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EP (1) EP0643757A1 (fr)
FI (1) FI943128A (fr)
NL (1) NL9102195A (fr)
WO (1) WO1993013184A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995001217A1 (fr) * 1993-06-29 1995-01-12 Bfi Entsorgungstechnologie Gmbh Procede d'extraction separee de composes sulfures et de co2 contenus dans des gaz
EP1166848A1 (fr) * 2000-06-29 2002-01-02 The BOC Group plc Traitement de courants gazeux contenant du sulfure d'hydrogène
US6942842B2 (en) 2003-01-16 2005-09-13 Bayer Aktiengesellschaft Process for the desulfurization of CO gas
WO2007066810A1 (fr) 2005-12-08 2007-06-14 Sumitomo Chemical Company, Limited Procede de fabrication de chlore
DE102008032957A1 (de) * 2008-07-12 2010-01-14 Dinano Ecotechnology Llc Verfahren zur Gewinnung von synthetischem Diesel
WO2014108423A1 (fr) * 2013-01-09 2014-07-17 Thyssenkrupp Uhde Gmbh Procédé de production de gaz de synthèse à partir de charbon
CN107970754A (zh) * 2018-01-15 2018-05-01 青海盐湖工业股份有限公司 一种电石炉尾气的再利用装置及再利用方法
CN113864776A (zh) * 2021-11-03 2021-12-31 西南科技大学 一种建材工业燃料替代碳中和的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE562928A (fr) *
FR2300126A1 (fr) * 1975-02-06 1976-09-03 Hoelter H Procede de purification du gaz se formant au cours de la gazeification du charbon sous pression
US4085199A (en) * 1976-06-08 1978-04-18 Bethlehem Steel Corporation Method for removing hydrogen sulfide from sulfur-bearing industrial gases with claus-type reactors
US4206186A (en) * 1975-02-06 1980-06-03 Holter Gesellschaft Fur Patentverwertungsverfahren Mbh Refuse pyrolysis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE562928A (fr) *
FR2300126A1 (fr) * 1975-02-06 1976-09-03 Hoelter H Procede de purification du gaz se formant au cours de la gazeification du charbon sous pression
US4206186A (en) * 1975-02-06 1980-06-03 Holter Gesellschaft Fur Patentverwertungsverfahren Mbh Refuse pyrolysis
US4085199A (en) * 1976-06-08 1978-04-18 Bethlehem Steel Corporation Method for removing hydrogen sulfide from sulfur-bearing industrial gases with claus-type reactors

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995001217A1 (fr) * 1993-06-29 1995-01-12 Bfi Entsorgungstechnologie Gmbh Procede d'extraction separee de composes sulfures et de co2 contenus dans des gaz
EP1166848A1 (fr) * 2000-06-29 2002-01-02 The BOC Group plc Traitement de courants gazeux contenant du sulfure d'hydrogène
US6942842B2 (en) 2003-01-16 2005-09-13 Bayer Aktiengesellschaft Process for the desulfurization of CO gas
WO2007066810A1 (fr) 2005-12-08 2007-06-14 Sumitomo Chemical Company, Limited Procede de fabrication de chlore
DE102008032957A1 (de) * 2008-07-12 2010-01-14 Dinano Ecotechnology Llc Verfahren zur Gewinnung von synthetischem Diesel
WO2014108423A1 (fr) * 2013-01-09 2014-07-17 Thyssenkrupp Uhde Gmbh Procédé de production de gaz de synthèse à partir de charbon
CN104903428A (zh) * 2013-01-09 2015-09-09 蒂森克虏伯工业解决方案股份公司 由无烟煤生产合成气的工艺方法
CN104903428B (zh) * 2013-01-09 2019-01-18 蒂森克虏伯工业解决方案股份公司 由无烟煤生产合成气的工艺方法
CN107970754A (zh) * 2018-01-15 2018-05-01 青海盐湖工业股份有限公司 一种电石炉尾气的再利用装置及再利用方法
CN113864776A (zh) * 2021-11-03 2021-12-31 西南科技大学 一种建材工业燃料替代碳中和的方法

Also Published As

Publication number Publication date
NL9102195A (nl) 1993-07-16
FI943128A (fi) 1994-08-29
EP0643757A1 (fr) 1995-03-22
FI943128A0 (fi) 1994-06-29

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