USH1539H - Method of reducing hydrogen chloride in synthesis gas - Google Patents

Method of reducing hydrogen chloride in synthesis gas Download PDF

Info

Publication number
USH1539H
USH1539H US08/153,591 US15359193A USH1539H US H1539 H USH1539 H US H1539H US 15359193 A US15359193 A US 15359193A US H1539 H USH1539 H US H1539H
Authority
US
United States
Prior art keywords
sodium
gas
hydrogen chloride
gas stream
candle filter
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.)
Abandoned
Application number
US08/153,591
Inventor
Uday Mahagaokar
Egon L. Doering
Phillip E. Unger
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.)
Shell USA Inc
Original Assignee
Shell Oil Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shell Oil Co filed Critical Shell Oil Co
Priority to US08/153,591 priority Critical patent/USH1539H/en
Assigned to SHELL OIL COMPANY reassignment SHELL OIL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: UNGER, PHILLIP EDWARD, DOERING, EGON LORENZ, MAHAGAOKAR, UDAY
Priority to KR1019960702546A priority patent/KR960705903A/en
Priority to PCT/EP1994/003699 priority patent/WO1995013340A1/en
Priority to CA002176354A priority patent/CA2176354A1/en
Priority to JP7513593A priority patent/JPH09504822A/en
Priority to EP95900688A priority patent/EP0728172A1/en
Priority to AU81414/94A priority patent/AU8141494A/en
Priority to CN94194120A priority patent/CN1135233A/en
Priority to ZA948905A priority patent/ZA948905B/en
Publication of USH1539H publication Critical patent/USH1539H/en
Application granted granted Critical
Abandoned legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/68Halogens or halogen compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/20Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses

Definitions

  • the invention relates to a method for reducing halide content, especially hydrogen chloride content, of a synthesis gas stream.
  • Fuel sources particularly coals, often have an undesirable halide content.
  • the halogens in halides such as chlorine in chlorides, form acids in the synthesis gas mixture which can cause severe corrosion in the downstream processing equipment.
  • the halides also pose environmental and safety hazards if emitted to the atmosphere.
  • a prior known method of removing HCl is by a wet absorption system.
  • the synthesis gas must be cooled and passed through an aqueous absorption column.
  • the HCl is absorbed in the water and neutralized with NaOH.
  • This method has drawbacks since cooling the gas to remove the HCl is inefficient and results in heat/energy loss.
  • additional equipment costs and maintenance costs result from the addition of an absorption column to the process.
  • Economic drawbacks also result from the need for a large water treatment plant due to a buildup of salts in the water from the absorption column.
  • the invention is a method for reducing the hydrogen chloride content of a synthesis gas stream including the steps of:
  • carbonaceous materials are suitable as feed sources for gasification. These include bituminous coal, sub-bituminous coal, anthracite coal, lignite, liquid hydrocarbons, petroleum coke, various organic scrap materials, municipal refuse, solid organic refuse contaminated with radioactive materials, paper industry refuse, and photographic scrap. Coal and petroleum coke are preferred feeds in this invention.
  • the metal compounds are alkali compounds. These include potassium oxide, potassium hydroxide, potassium bicarbonate, potassium carbonate, sodium oxide, sodium hydroxide, sodium bicarbonate, and sodium carbonate. Nahcolite, a naturally occurring form of sodium bicarbonate, is preferred for its economy and availability.
  • the metal compounds are optionally used individually or in combination.
  • the metal compounds are mixed with the synthesis gas after the synthesis gas leaves the gasifier.
  • the metal compound is injected, preferably dry, into the synthesis gas stream. It is transported pneumatically in nitrogen or carbon dioxide or in any other conventional dry feed manner.
  • at least a portion of the sensible heat of the synthesis gas is recovered prior to adding the metal compound. More preferably, the synthesis gas passes through a first heat recovery zone, a solids removal zone, then a second heat recovery zone, and then the metal compound is injected into the gas stream recovered from the second heat recovery zone.
  • the solids removal stage is preferably a cyclone or ceramic candle filter, used individually or in combination.
  • An electrostatic precipitator is optionally used where the system pressure is at or near atmospheric.
  • the maximum amount of sensible heat is recovered which does not reduce the temperature of the synthesis gas below the condensation point of any chloride compounds present in the synthesis gas. Such condensation results in equipment corrosion problems.
  • the metal compound After the metal compound is injected it will react with the chlorine in the hydrogen chloride to form a solid salt.
  • the metal compound either reacts directly with the hydrogen chloride or the metal compound may first thermally decompose prior to such reaction. Where the metal compound is a sodium compound, e.g., sodium bicarbonate, sodium chloride is formed. The resulting metal chloride is a solid.
  • the solid-salt-containing synthesis gas stream then passes to a ceramic candle filter. Additionally, much of the reaction between the metal compound and the hydrogen chloride occurs on the upstream surface of the ceramic candle filter. This is because the residence time between the point of metal compound injection and the filter will typically be too short for complete reaction. Extension of the pathway to increase the residence time would be uneconomical.
  • a cake of salt solids builds up on the surface of the ceramic candle filter.
  • the contact time between the hydrogen chloride and the alkali metal compounds or their thermal decomposition products is increased to provide a longer effective residence time without the uneconomical expense of lengthening the piping.
  • the synthesis gas recovered from the ceramic candle filter has reduced amounts of halides, e.g., hydrogen chloride, and is preferably substantially free of halides, e.g., hydrogen chloride.
  • the synthesis gas is then passed to a third heat recovery zone, to maximize sensible heat recovery before passing the synthesis gas to any wet cleanup units, such as a sulfur removal scrubbing unit.
  • chloride in the coal evolves into hydrogen chloride.
  • the initial concentrations of hydrogen chloride and other halides in the synthesis gas vary widely with the type and source of the feed to the gasifier. Chloride concentrations in coal range from about 0.01% by weight chlorine to about 0.35% by weight chlorine. Other halide concentrations in coal are typically much lower than chloride concentrations.
  • At least a stoichiometric amount of metal compounds must be mixed with the synthesis gas with respect to the halide concentration in the synthesis gas.
  • halides e.g., chlorides. This assures a high degree of removal of the chlorides. More than about three times the stoichiometric ratio is wasteful of metal compounds and makes the process uneconomical without any apparent benefit.
  • the synthesis gas will initially contain from about 10 ppm by volume (ppmv) to about 1000 ppmv chloride where the feed is coal. After gasification and reaction and solids removal of the metal halides, the concentration of chloride in the synthesis gas is from about 0.1 ppmv to about 5 ppmv.
  • the gasifier is operated at gasifying conditions. These conditions may vary from feed to feed.
  • the temperature is a temperature high enough to gasify a substantial portion of the carbonaceous feed and to prevent the formation of undesirable side-products, such as tars and phenols and other aromatics.
  • Typical temperatures in the gasifier are from about 1100° C. to about 2000° C.
  • the gasifier temperature is preferably from about 1450° C. to about 1575° C. More preferably, the temperature is from about 1425° C. to about 1510° C.
  • the pressure of the gasifier is from about 200 psig to about 600 psig. Preferably the pressure is from about 300 psig to about 450 psig.
  • the synthesis gas temperature is above the point at which any corrosive ammonium halide compounds, such as ammonium chlorides, will condense.
  • This temperature varies with the type and concentration of halide compound. This is typically at least about 300° F.
  • the temperature at the point of injection is preferably not above the condensation point of sodium chloride. This is typically below about 1200° F. This limitation is necessary since sodium chloride must be a solid to be removed by the ceramic candle filter. It is not essential, however, that the temperature at the point of injection be above the point of condensation of sodium chloride, so long as the mixture reaches this temperature prior to reaching the upstream surface of the ceramic candle filter.
  • the temperature of the synthesis gas stream at the point of metal compound injection is from about 350° F. to about 700° F., more preferably from about 450° F. to about 500° F.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Industrial Gases (AREA)

Abstract

The invention is a method for reducing the hydrogen chloride content of a synthesis gas stream by (a) gasifying a carbonaceous feed material in an entrained flow gasifier to produce a gas/solids mixture of hydrogen, carbon monoxide, hydrogen chloride gas, and flyslag particles; (b) passing the gas/solids mixture solids removal zone where at least a portion of the flyslag particles are removed, to produce a gas stream; (c) mixing with the gas stream an alkali metal oxide, hydroxide, bicarbonate, or carbonate to produce a metals/gas mixture; (d) passing the metals/gas mixture to a ceramic candle filter; (e) reacting on the surface of the ceramic candle filter the alkali metal compounds with the hydrogen chloride to produce solid alkali metal chloride; and (f) recovering a gas stream from the ceramic candle filter substantially free of hydrogen chloride and solids.

Description

I. FIELD OF THE INVENTION
The invention relates to a method for reducing halide content, especially hydrogen chloride content, of a synthesis gas stream.
II. BACKGROUND OF THE INVENTION
The combustion of a carbonaceous material such as a solid carbonaceous fuel by reaction with a source of gaseous oxygen is well known. In such a reaction, an amount of air or oxygen equal to or greater than that required for complete combustion is used, whereby the gaseous effluent contains carbon dioxide with little, if any, carbon monoxide. It is also known to carry out the gasification or partial oxidation of solid carbonaceous materials or fuels employing a limited quantity of oxygen or air so as to produce primarily carbon monoxide and hydrogen.
Fuel sources, particularly coals, often have an undesirable halide content. The halogens in halides, such as chlorine in chlorides, form acids in the synthesis gas mixture which can cause severe corrosion in the downstream processing equipment. The halides also pose environmental and safety hazards if emitted to the atmosphere.
Another problem caused by the halides is reduced efficiency of the gasification process. Condensation of some salts in the synthesis gas during cooling limits the overall efficiency of the heat recovery from the synthesis gas. This limitation in heat recovery occurs because some moderate sublimation temperature salts, such as ammonium chloride, are very corrosive when permitted to condense. Thus, to avoid having the salts condense, the synthesis gas cannot be cooled below the sublimation temperature of various salts. Since the temperature to which the synthesis gas may be cooled is thus limited, the heat recovery from the gas is accordingly limited. Chlorine-containing salts are formed due to the presence of HCl. By removing HCl from the synthesis gas, formation of such salts in the gas stream is reduced or eliminated and the gas can be cooled further to permit more thermal recovery.
A prior known method of removing HCl is by a wet absorption system. In that method the synthesis gas must be cooled and passed through an aqueous absorption column. The HCl is absorbed in the water and neutralized with NaOH. This method has drawbacks since cooling the gas to remove the HCl is inefficient and results in heat/energy loss. Also, additional equipment costs and maintenance costs result from the addition of an absorption column to the process. Economic drawbacks also result from the need for a large water treatment plant due to a buildup of salts in the water from the absorption column.
It is known from U.S. Pat. No. 5,118,480 to add metal-containing compounds such as nahcolite to a synthesis gas downstream of the gasifier to remove HCl in conjunction with removing sulfur with a metal oxide sorbent. However, this process fails to address the problem of high expense associated with long piping necessary to have sufficient residence time for complete reaction.
It would be advantageous to have a practical and economical dry method of removing the halides, without the high expense of long piping.
III. SUMMARY OF THE INVENTION
The invention is a method for reducing the hydrogen chloride content of a synthesis gas stream including the steps of:
(a) gasifying a carbonaceous feed material in an entrained flow gasifier under gasifying conditions thereby producing a gas/solids mixture comprising hydrogen, carbon monoxide, hydrogen chloride gas, and flyslag particles;
(b) passing the gas/solids mixture to a solids removal zone wherein at least a portion of the flyslag particles are removed, thereby producing a gas stream;
(c) mixing with the gas stream an alkali metal compound including at least one oxide, hydroxide, bicarbonate, or carbonate, of sodium or potassium, thereby producing a metals/gas mixture;
(d) passing the metals/gas mixture to a ceramic candle filter;
(e) reacting on the surface of the ceramic candle filter the alkali metal compounds, or thermal decomposition products thereof, with the hydrogen chloride thereby producing solid alkali metal chloride, wherein a cake of solids builds up on the surface of the ceramic candle filter thereby increasing the contact time between the hydrogen chloride and the alkali metal compounds or their thermal decomposition products;
(f) periodically removing at least a portion of the cake of solids; and (g) recovering from the ceramic candle filter a gas stream substantially free of hydrogen chloride.
IV. DETAILED DESCRIPTION OF THE EMBODIMENTS
A. Feeds and Metal Compounds and Mixture Thereof
Several types of carbonaceous materials are suitable as feed sources for gasification. These include bituminous coal, sub-bituminous coal, anthracite coal, lignite, liquid hydrocarbons, petroleum coke, various organic scrap materials, municipal refuse, solid organic refuse contaminated with radioactive materials, paper industry refuse, and photographic scrap. Coal and petroleum coke are preferred feeds in this invention.
The metal compounds are alkali compounds. These include potassium oxide, potassium hydroxide, potassium bicarbonate, potassium carbonate, sodium oxide, sodium hydroxide, sodium bicarbonate, and sodium carbonate. Nahcolite, a naturally occurring form of sodium bicarbonate, is preferred for its economy and availability. The metal compounds are optionally used individually or in combination.
The metal compounds are mixed with the synthesis gas after the synthesis gas leaves the gasifier. The metal compound is injected, preferably dry, into the synthesis gas stream. It is transported pneumatically in nitrogen or carbon dioxide or in any other conventional dry feed manner. Preferably, at least a portion of the sensible heat of the synthesis gas is recovered prior to adding the metal compound. More preferably, the synthesis gas passes through a first heat recovery zone, a solids removal zone, then a second heat recovery zone, and then the metal compound is injected into the gas stream recovered from the second heat recovery zone.
The solids removal stage is preferably a cyclone or ceramic candle filter, used individually or in combination. An electrostatic precipitator is optionally used where the system pressure is at or near atmospheric. Preferably, the maximum amount of sensible heat is recovered which does not reduce the temperature of the synthesis gas below the condensation point of any chloride compounds present in the synthesis gas. Such condensation results in equipment corrosion problems.
B. Reaction, Cooling, and Solids Removal
After the metal compound is injected it will react with the chlorine in the hydrogen chloride to form a solid salt. The metal compound either reacts directly with the hydrogen chloride or the metal compound may first thermally decompose prior to such reaction. Where the metal compound is a sodium compound, e.g., sodium bicarbonate, sodium chloride is formed. The resulting metal chloride is a solid.
The solid-salt-containing synthesis gas stream then passes to a ceramic candle filter. Additionally, much of the reaction between the metal compound and the hydrogen chloride occurs on the upstream surface of the ceramic candle filter. This is because the residence time between the point of metal compound injection and the filter will typically be too short for complete reaction. Extension of the pathway to increase the residence time would be uneconomical.
A cake of salt solids builds up on the surface of the ceramic candle filter. For the synthesis gas to get through the cake to exit the filter, it must travel a convoluted pathway through the solids cake. Thus, the contact time between the hydrogen chloride and the alkali metal compounds or their thermal decomposition products is increased to provide a longer effective residence time without the uneconomical expense of lengthening the piping.
The synthesis gas recovered from the ceramic candle filter has reduced amounts of halides, e.g., hydrogen chloride, and is preferably substantially free of halides, e.g., hydrogen chloride. Preferably, the synthesis gas is then passed to a third heat recovery zone, to maximize sensible heat recovery before passing the synthesis gas to any wet cleanup units, such as a sulfur removal scrubbing unit.
C. Concentrations of Halides, Ratios, and Percent Removal
In the reducing atmosphere and elevated temperatures of the gasifier, the chloride in the coal evolves into hydrogen chloride. The initial concentrations of hydrogen chloride and other halides in the synthesis gas vary widely with the type and source of the feed to the gasifier. Chloride concentrations in coal range from about 0.01% by weight chlorine to about 0.35% by weight chlorine. Other halide concentrations in coal are typically much lower than chloride concentrations.
At least a stoichiometric amount of metal compounds must be mixed with the synthesis gas with respect to the halide concentration in the synthesis gas. Preferably, one to three times the stoichiometric ratio is used of metal compounds to halides, e.g., chlorides. This assures a high degree of removal of the chlorides. More than about three times the stoichiometric ratio is wasteful of metal compounds and makes the process uneconomical without any apparent benefit.
From about 95% by weight to about 99% by weight of the halides, e.g., chlorides, are removed in the practice of this method. For example, the synthesis gas will initially contain from about 10 ppm by volume (ppmv) to about 1000 ppmv chloride where the feed is coal. After gasification and reaction and solids removal of the metal halides, the concentration of chloride in the synthesis gas is from about 0.1 ppmv to about 5 ppmv.
D. Operating Conditions
The gasifier is operated at gasifying conditions. These conditions may vary from feed to feed. The temperature is a temperature high enough to gasify a substantial portion of the carbonaceous feed and to prevent the formation of undesirable side-products, such as tars and phenols and other aromatics. Typical temperatures in the gasifier are from about 1100° C. to about 2000° C. Where the feed is coal, the gasifier temperature is preferably from about 1450° C. to about 1575° C. More preferably, the temperature is from about 1425° C. to about 1510° C. The pressure of the gasifier is from about 200 psig to about 600 psig. Preferably the pressure is from about 300 psig to about 450 psig.
At the point of injection of the alkali metal compound the synthesis gas temperature is above the point at which any corrosive ammonium halide compounds, such as ammonium chlorides, will condense. This temperature varies with the type and concentration of halide compound. This is typically at least about 300° F. The temperature at the point of injection, however, is preferably not above the condensation point of sodium chloride. This is typically below about 1200° F. This limitation is necessary since sodium chloride must be a solid to be removed by the ceramic candle filter. It is not essential, however, that the temperature at the point of injection be above the point of condensation of sodium chloride, so long as the mixture reaches this temperature prior to reaching the upstream surface of the ceramic candle filter. Preferably the temperature of the synthesis gas stream at the point of metal compound injection is from about 350° F. to about 700° F., more preferably from about 450° F. to about 500° F.

Claims (15)

What is claimed is:
1. A method for reducing the hydrogen chloride content of a synthesis gas stream comprising:
(a) gasifying a carbonaceous feed material in an entrained flow gasifier under gasifying conditions thereby producing a gas/solids mixture comprising hydrogen, carbon monoxide, hydrogen chloride gas, and flyslag particles;
(b) passing said gas/solids mixture to a solids removal zone wherein at least a portion of said flyslag particles are removed, thereby producing a gas stream;
(c) admixing with said gas stream an alkali metal compound comprising at least one oxide, hydroxide, bicarbonate, or carbonate, of sodium or potassium, thereby producing a metals/gas mixture;
(d) passing said metals/gas mixture to a ceramic candle filter;
(e) reacting on the surface of said ceramic candle filter said alkali metal compounds, or thermal decomposition products thereof, with said hydrogen chloride thereby producing solid alkali metal chloride, wherein a cake of solids builds up on the surface of said ceramic candle filter thereby increasing the contact time between said hydrogen chloride and said alkali metal compounds or their thermal decomposition products;
(f) periodically removing at least a portion of said cake of solids; and
(g) recovering from said ceramic candle filter a gas stream substantially free of hydrogen chloride.
2. The method according to claim 1 wherein the carbonaceous feed material is coal.
3. The method according to claim 2 wherein the amount of alkali metal compounds admixed with the effluent of said solids removal zone is at least a stoichiometric amount of alkali metal compounds with respect to the hydrogen chloride content of the synthesis gas.
4. The method according to claim 3 wherein the amount of alkali metal compounds admixed with the effluent of said solids removal zone is not more than about 3 times the stoichiometric amount of alkali metal compounds with respect to the hydrogen chloride content of the synthesis gas.
5. The method according to claim 2 wherein said coal is a bituminous coal and wherein said admixing step (c) consists essentially of injecting said alkali metal compound into said effluent of said solids removal zone.
6. The method according to claim 3 wherein said coal is a sub-bituminous coal and wherein said alkali metal compound is sodium bicarbonate and wherein in admixing step (c) said sodium bicarbonate is dry at the point of admixture.
7. A method for reducing the hydrogen chloride content of a synthesis gas stream comprising:
(a) gasifying a carbonaceous feed material in an entrained flow gasifier under gasifying conditions thereby producing a gas/solids mixture comprising hydrogen, carbon monoxide, hydrogen chloride gas, and flyslag particles;
(b) passing said gas/solids mixture to a first heat recovery zone wherein a portion of the sensible heat of the gas/solids mixture is recovered;
(c) passing said gas/solids mixture to a solids removal zone wherein substantially all of said flyslag particles are removed, thereby producing a gas stream;
(d) passing said gas stream to a second heat recovery zone wherein a portion of the sensible heat of the gas stream is recovered;
(e) admixing with the effluent of said second heat recovery zone a sodium compound comprising at least one oxide, hydroxide, bicarbonate, or carbonate of sodium, thereby producing a sodium/gas mixture;
(f) passing said sodium/gas mixture to a ceramic candle filter;
(g) reacting on the upstream surface of said ceramic candle filter said sodium compounds, or thermal decomposition products thereof, with said hydrogen chloride thereby producing solid sodium chloride, wherein a cake of sodium chloride builds up on the upstream surface of said ceramic candle filter thereby increasing the contract time between hydrogen chloride and said sodium compounds or thermal decomposition products thereof;
(h) periodically removing at least a portion of said cake of sodium chloride;
(i) recovering a gas stream effluent from said ceramic candle filter substantially free of hydrogen chloride; and
(j) passing said substantially-hydrogen-chloride-free gas stream to a third heat recovery zone wherein a portion of the sensible heat of the gas stream substantially free of hydrogen chloride is recovered.
8. The method according to claim 7 wherein the temperature in the gasifier is from about 1100° C. to about 2000° C.
9. The method according to claim 8 wherein the temperature in the gasifier is from about 1450° C. to about 1575° C.
10. The method according to claim 8 wherein the pressure in the gasifier is from about 200 psig to about 600 psig.
11. The method according to claim 9 wherein the pressure in the gasifier is from about 300 psig to about 450 psig.
12. The method according to claim 7 wherein the carbonaceous material is a bituminous or sub-bituminous coal, the alkali metal compound is sodium bicarbonate, and wherein prior to gasification the coal contains from about 0.01% by weight chlorine to about 0.35% by weight chlorine based on the coal as received and from about 95% by weight to about 99% by weight of the chlorine is removed in the ceramic candle filter in the form of sodium chloride.
13. The method according to claim 12 wherein prior to the reaction of the sodium carbonate or sodium oxide with the hydrogen chloride the gas stream contains from about 10 ppmv to about 1000 ppmv chlorine based on the gas volume and after the gas stream is recovered from said ceramic candle filter the gas contains from about 0.1 ppmv to about 5 ppmv of chlorine based on the gas stream.
14. The method of claim 7 wherein the carbonaceous feed is petroleum coke.
15. A method for reducing the hydrogen chloride content of a synthesis gas stream comprising:
(a) gasifying a bituminous or sub-bituminous coal in an entrained flow gasifier at a temperature from about 1450° C. to about 1575° C. and wherein the pressure in the gasifier is from about 300 psig to about 450 psig, thereby producing a synthesis gas mixture comprising hydrogen, carbon monoxide, hydrogen chloride gas, and flyslag particles;
(b) passing said synthesis gas mixture to a first heat recovery zone wherein a portion of the sensible heat of the synthesis gas mixture is recovered;
(c) passing said synthesis gas mixture to a first solids removal zone wherein substantially all of said flyslag particles are removed and recovering the synthesis gas from said solids removal zone, thereby producing a gas stream;
(d) passing said gas stream to a second heat recovery zone wherein a portion of the sensible heat of the gas stream is recovered;
(e) injecting nahcolite into said gas stream for admixture therewith;
(f) substantially decomposing said nahcolite to sodium carbonate and sodium oxide, thereby producing a sodium/gas mixture comprising hydrogen, carbon monoxide, hydrogen chloride, sodium carbonate, and sodium oxide;
(g) passing said sodium/gas mixture to a ceramic candle filter;
(h) reacting on the upstream surface of said ceramic candle filter said sodium carbonates and sodium oxides with said hydrogen chloride thereby producing solid sodium chloride, wherein a cake of solid sodium chloride builds up on the upstream surface of said ceramic candle filter thereby increasing the contact time between hydrogen chloride and said sodium carbonates or sodium oxides;
(i) periodically removing at least a portion of said cake of sodium chloride;
(j) recovering from said ceramic candle filter a gas stream substantially free of hydrogen chloride; and
(k) passing said gas stream substantially free of hydrogen chloride to a third heat recovery zone wherein a portion of the sensible heat of the substantially-hydrogen-chloride-free gas stream is recovered.
US08/153,591 1993-11-12 1993-11-12 Method of reducing hydrogen chloride in synthesis gas Abandoned USH1539H (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US08/153,591 USH1539H (en) 1993-11-12 1993-11-12 Method of reducing hydrogen chloride in synthesis gas
JP7513593A JPH09504822A (en) 1993-11-12 1994-11-08 Method for reducing hydrogen halide content in synthesis gas
PCT/EP1994/003699 WO1995013340A1 (en) 1993-11-12 1994-11-08 A method of reducing hydrogen halide(s) content in synthesis gas
CA002176354A CA2176354A1 (en) 1993-11-12 1994-11-08 A method of reducing hydrogen halide(s) content in synthesis gas
KR1019960702546A KR960705903A (en) 1993-11-12 1994-11-08 A METHOD OF REDUCING HYDROGEN HALIDE (S) CONTENT IN SYNTHESIS GAS
EP95900688A EP0728172A1 (en) 1993-11-12 1994-11-08 A method of reducing hydrogen halide(s) content in synthesis gas
AU81414/94A AU8141494A (en) 1993-11-12 1994-11-08 A method of reducing hydrogen halide(s) content in synthesis gas
CN94194120A CN1135233A (en) 1993-11-12 1994-11-08 Method for reducing hydrogen halide content in synthesis gas
ZA948905A ZA948905B (en) 1993-11-12 1994-11-10 A method of reducing hydrogen halide(s) content in synthesis gas

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US08/153,591 USH1539H (en) 1993-11-12 1993-11-12 Method of reducing hydrogen chloride in synthesis gas

Publications (1)

Publication Number Publication Date
USH1539H true USH1539H (en) 1996-06-04

Family

ID=22547849

Family Applications (1)

Application Number Title Priority Date Filing Date
US08/153,591 Abandoned USH1539H (en) 1993-11-12 1993-11-12 Method of reducing hydrogen chloride in synthesis gas

Country Status (9)

Country Link
US (1) USH1539H (en)
EP (1) EP0728172A1 (en)
JP (1) JPH09504822A (en)
KR (1) KR960705903A (en)
CN (1) CN1135233A (en)
AU (1) AU8141494A (en)
CA (1) CA2176354A1 (en)
WO (1) WO1995013340A1 (en)
ZA (1) ZA948905B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040247509A1 (en) * 2003-06-06 2004-12-09 Siemens Westinghouse Power Corporation Gas cleaning system and method
US20100096594A1 (en) * 2008-10-22 2010-04-22 Dahlin Robert S Process for decontaminating syngas

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3615878B2 (en) * 1996-09-20 2005-02-02 三菱重工業株式会社 Gasification combined power generation facility
US6080301A (en) 1998-09-04 2000-06-27 Exxonmobil Research And Engineering Company Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins
US6475960B1 (en) 1998-09-04 2002-11-05 Exxonmobil Research And Engineering Co. Premium synthetic lubricants
CN101932678A (en) * 2008-02-05 2010-12-29 财团法人电力中央研究所 Fuel gas purification apparatus, power generation system, and fuel synthesis system
CN110075823B (en) * 2019-05-30 2022-04-12 新奥科技发展有限公司 Preparation method, preparation device and application method of catalyst for DEC synthesis

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4018868A (en) * 1975-03-19 1977-04-19 The Superior Oil Company Thermal crushing of alkali compounds in the removal of sulfur dioxides from a flue gas
US4062926A (en) * 1975-03-19 1977-12-13 The Superior Oil Company Sulfur dioxide removal using thermally crushed nahcolite
US4343631A (en) * 1981-01-30 1982-08-10 Westinghouse Electric Corp. Hot gas particulate removal
GB2106532A (en) * 1981-09-23 1983-04-13 Westfael Elekt Werke Process for the separation of chlorine fluorine and sulphur from fuel gas and flue or exhaust gas
US4468376A (en) * 1982-05-03 1984-08-28 Texaco Development Corporation Disposal process for halogenated organic material
US4681045A (en) * 1986-07-21 1987-07-21 William F. Cosulich Associates, P.C. Treatment of flue gas containing noxious gases
US4767605A (en) * 1984-11-30 1988-08-30 Waagner-Biro Aktiengesellschaft Method for separation of acid pollution gas
EP0314253A1 (en) * 1987-10-30 1989-05-03 Shell Internationale Researchmaatschappij B.V. Method and apparatus for separating fine particulates from a mixture of fine particulates and gas
US4839147A (en) * 1985-04-05 1989-06-13 Waagner-Biro Aktiengesellschaft Method of purifying combustion product gases contaminated with dust and noxious gases
US4857285A (en) * 1987-06-04 1989-08-15 General Electric Environmental Services, Inc. Method and system for removal of sulfur compounds from gases and for regenerating spent sorbents
US4908195A (en) * 1986-12-23 1990-03-13 Metallgesellschaft Aktiengesellschaft Process of purifying exhaust gas
EP0463367A1 (en) * 1990-06-25 1992-01-02 General Electric Environmental Services, Inc. Method for removing HCL and HF from coal derived fuel gas
EP0468540A1 (en) * 1986-11-19 1992-01-29 The Babcock & Wilcox Company Controlling emission of pollutants from coal-fired boiler systems
EP0573209A1 (en) * 1992-05-30 1993-12-08 Foseco International Limited Filtration of gases

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4018868A (en) * 1975-03-19 1977-04-19 The Superior Oil Company Thermal crushing of alkali compounds in the removal of sulfur dioxides from a flue gas
US4062926A (en) * 1975-03-19 1977-12-13 The Superior Oil Company Sulfur dioxide removal using thermally crushed nahcolite
US4343631A (en) * 1981-01-30 1982-08-10 Westinghouse Electric Corp. Hot gas particulate removal
GB2106532A (en) * 1981-09-23 1983-04-13 Westfael Elekt Werke Process for the separation of chlorine fluorine and sulphur from fuel gas and flue or exhaust gas
US4468376A (en) * 1982-05-03 1984-08-28 Texaco Development Corporation Disposal process for halogenated organic material
US4859438A (en) * 1984-11-30 1989-08-22 Waagner-Biro Aktiengesellschaft Method for separation of impurities from flowing gas
US4767605A (en) * 1984-11-30 1988-08-30 Waagner-Biro Aktiengesellschaft Method for separation of acid pollution gas
US4839147A (en) * 1985-04-05 1989-06-13 Waagner-Biro Aktiengesellschaft Method of purifying combustion product gases contaminated with dust and noxious gases
US4681045A (en) * 1986-07-21 1987-07-21 William F. Cosulich Associates, P.C. Treatment of flue gas containing noxious gases
EP0468540A1 (en) * 1986-11-19 1992-01-29 The Babcock & Wilcox Company Controlling emission of pollutants from coal-fired boiler systems
US4908195A (en) * 1986-12-23 1990-03-13 Metallgesellschaft Aktiengesellschaft Process of purifying exhaust gas
US4857285A (en) * 1987-06-04 1989-08-15 General Electric Environmental Services, Inc. Method and system for removal of sulfur compounds from gases and for regenerating spent sorbents
EP0314253A1 (en) * 1987-10-30 1989-05-03 Shell Internationale Researchmaatschappij B.V. Method and apparatus for separating fine particulates from a mixture of fine particulates and gas
EP0463367A1 (en) * 1990-06-25 1992-01-02 General Electric Environmental Services, Inc. Method for removing HCL and HF from coal derived fuel gas
US5118480A (en) * 1990-06-25 1992-06-02 General Electric Environmental Services, Incorporated Method for removing hcl and hf from coal derived fuel gas
EP0573209A1 (en) * 1992-05-30 1993-12-08 Foseco International Limited Filtration of gases

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Search Report of Feb. 7, 1995. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040247509A1 (en) * 2003-06-06 2004-12-09 Siemens Westinghouse Power Corporation Gas cleaning system and method
US7056487B2 (en) 2003-06-06 2006-06-06 Siemens Power Generation, Inc. Gas cleaning system and method
US20100096594A1 (en) * 2008-10-22 2010-04-22 Dahlin Robert S Process for decontaminating syngas
US8007688B2 (en) * 2008-10-22 2011-08-30 Southern Research Institute Process for decontaminating syngas

Also Published As

Publication number Publication date
ZA948905B (en) 1995-06-13
EP0728172A1 (en) 1996-08-28
CN1135233A (en) 1996-11-06
AU8141494A (en) 1995-05-29
KR960705903A (en) 1996-11-08
WO1995013340A1 (en) 1995-05-18
CA2176354A1 (en) 1995-05-18
JPH09504822A (en) 1997-05-13

Similar Documents

Publication Publication Date Title
US5720785A (en) Method of reducing hydrogen cyanide and ammonia in synthesis gas
US5435940A (en) Gasification process
US4344486A (en) Method for enhanced oil recovery
US3574530A (en) Method of removing sulfur dioxide from waste gases
US4468376A (en) Disposal process for halogenated organic material
US4148613A (en) Process for preparing sulfur-containing coal or lignite for combustion
US4442080A (en) Fluid bed SOX/NOX process--"hydrated calcine absorption"
US20100224835A1 (en) Production of synthesis gas through controlled oxidation of biomass
USH1539H (en) Method of reducing hydrogen chloride in synthesis gas
US4175929A (en) Process for control of pollutants generated during coal gasification
US4073862A (en) Process for removing ammonia, hydrogen sulfide and hydrocyanic acid from gases
US5866091A (en) Method for minimizing hydrogen halide corrosion in a partial oxidation process
US4790945A (en) Removal of hydrogen selenide
US5611963A (en) Method of reducing halides in synthesis gas
EP0272748B1 (en) Flyslag treatment
EP0438822B1 (en) A process for inhibition of sulphide inclusion in slag
WO1994022563A1 (en) Volatile metals capture from gazeous streams
US4693883A (en) Ammonia utilization process
US4755372A (en) Catalytic sulfur degassing
US4275044A (en) Sulfur dioxide disposal system
EP0487158B1 (en) Spent catalyst disposal
US4792405A (en) Removal of hydrogen selenide liquids
AU705393B2 (en) Method for minimizing hydrogen halide corrosion in a partial oxidation process
US4786291A (en) Method for increasing steam decomposition in a coal gasification process
US4969932A (en) Flyslag treatment utilizing a solids-containing concentrated aqueous stream and a cementitious material

Legal Events

Date Code Title Description
AS Assignment

Owner name: SHELL OIL COMPANY, TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MAHAGAOKAR, UDAY;DOERING, EGON LORENZ;UNGER, PHILLIP EDWARD;REEL/FRAME:007067/0830;SIGNING DATES FROM 19931101 TO 19931102

STCF Information on status: patent grant

Free format text: PATENTED CASE