WO1994016990A1 - Procede d'extraction de sulfure au moyen de carbone catalytique - Google Patents

Procede d'extraction de sulfure au moyen de carbone catalytique Download PDF

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Publication number
WO1994016990A1
WO1994016990A1 PCT/US1994/000884 US9400884W WO9416990A1 WO 1994016990 A1 WO1994016990 A1 WO 1994016990A1 US 9400884 W US9400884 W US 9400884W WO 9416990 A1 WO9416990 A1 WO 9416990A1
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WO
WIPO (PCT)
Prior art keywords
char
temperature
catalytically
nitrogen
carbonaceous
Prior art date
Application number
PCT/US1994/000884
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English (en)
Other versions
WO1994016990B1 (fr
Inventor
Richard A. Hayden
Original Assignee
Calgon Carbon Corporation
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 Calgon Carbon Corporation filed Critical Calgon Carbon Corporation
Priority to JP6517278A priority Critical patent/JP2572206B2/ja
Publication of WO1994016990A1 publication Critical patent/WO1994016990A1/fr
Publication of WO1994016990B1 publication Critical patent/WO1994016990B1/fr

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Classifications

    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8612—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • C01B17/046—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 without intermediate formation of sulfur dioxide
    • C01B17/0469—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 without intermediate formation of sulfur dioxide at least one catalyst bed operating below the dew-point of sulfur
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents

Definitions

  • the present invention relates to the use of a highly -catalytically-active carbonaceous char for the removal of sulfide from gas or liquid media in the presence of oxygen .and water.
  • extrinsic parameters can include particle size distribution, pore volume distribution, and contact time. It is further the object of the present invention to produce and employ such carbonaceous chars at minimal cost and hazard when compared to prior art
  • the present invention comprises the removal of sulfides and mercaptans from media containing oxygen and water by the catalytic action of carbonaceous chars.
  • These chars are prepared by the low-temperature carbonization and oxidation of a nitrogen-poor feedstock.
  • the oxidized low- temperature char is then subjected to a nitrogen-containing compound at high temperatures during the initial calcination or calcination/activation.
  • high-temperature carbonaceous chars are those produced by thermal treatment at temperatures greater than 700 C.
  • Low temperature carbonaceous chars are those that have not experienced temperatures greater than 700 C.
  • the preferred nitrogen-poor feedstock is a bituminous coal or a bituminous coal-like material such as those derived from higher or lower rank bitumens, coals, or lignocellulose materials by various chemical treatments.
  • higher rank coals include anthracite or semi-anthracite coals
  • lower rank coals include peat, lignite, and sub-bituminous coals.
  • chemical treatment of these feedstocks include alkali metal treatment of the high rank materials and zinc chloride or phosphoric acid treatment of the low rank materials. These types of treatments can also be applied to lignocellulose materials .
  • the feedstock material is pulverized, mixed if necessary with small amounts of a suitable binder such as pitch, briquetted or otherwise formed, and sized.
  • the sized material is then extensively oxidized at temperatures less than 700 C, preferably less than 400 C. The oxidation is continued until additional gains in the catalytic activity of the final product are no longer evident.
  • the oxidation is well beyond that typically required to remove the coking properties of bituminous coals and produces an optimally oxidized char.
  • Other convenient means of oxidation can also be used to effect the low-temperature oxidation and carbonization of the starting material.
  • the oxidized low-temperature carbonaceous char is then exposed to small amounts of an inexpensive, abundant, and relatively non-toxic nitrogen-containing compound such as urea during, not after, the initial calcination and condensation of the carbon structure.
  • the amounts of nitrogen-containing compounds used are typically small, preferably less than 5% by weight of the oxidized low-temperature carbonaceous char or such that additional gains in the catalytic activity of the final product are no longer evident.
  • the treatment is carried out by heating the oxidized low-temperature char to high temperatures, preferably between 850 C and 950 C, in the presence of the nitrogen-containing compound. This heating is preferably conducted under an atmosphere that is inert except for the gases and vapors attributable to the char and/or the nitrogen-containing compound.
  • the heating rate and temperatures are preferably selected such that additional gains in the catalytic activity of the final product are no longer evident.
  • the nitrogen-treated high-temperature carbonaceous char may then be activated to the desired density at temperatures above 700 C in steam and/or carbon dioxide, with or without the addition of other gasifying agents such as air.
  • the calcined or calcined/activated carbonaceous char is then cooled in an oxygen-free or otherwise inert atmosphere to temperatures less than 400 C, preferably less than 200 C. Additional gains in catalytic activity may be realized by repeating the oxidation/exposure to nitrogen- containing compounds/calcination or calcination/activation/inert cooling as many times as may be desired.
  • any other method known to generate catalytic activity in high temperature carbonaceous chars may be applied to the resultant product to further enhance its catalytic activity.
  • the catal tically-active carbonaceous char prepared according to the above method is then contacted with a sulflde-containing media in the presence of water and oxygen. Sulfide is removed from the media by catalytic oxidation to primarily sulfates and elemental sulfur.
  • the operating temperature is between about 0 C and 300 C and preferably between about 0 C and 100 C and more preferably between about 25 C and 90 C.
  • Example 1 demonstrates the H 2 S removal capacity of a specific mesh size fraction of a commercial activated carbon.
  • Example 2 demonstrates the H- ⁇ S removal capacity of the invention. Comparison of these two examples shows that the performance of the invention greatly exceeds that of a typical activated carbon.
  • a commercially available activated carbon, BPL manufactured by Calgon Carbon Corporation, Pittsburgh PA
  • BPL manufactured by Calgon Carbon Corporation, Pittsburgh PA
  • This carbon showed an Apparent Density ( Test Method TM-7, Calgon Carbon Corporation, Pittsburgh PA) of 0.504 grams per cc and a CC1 4 Number ( Test Method TM-6, Calgon Carbon Corporation, Pittsburgh PA ) of 55.1 %.
  • the sized carbon was loaded into a column having an inside diameter of approximately 0.73 inches to give a bed depth of 9 inches. Column loading was done in such a manner as to achieve a packing density equivalent to the Apparent Density.
  • a gas stream having a relative humidity of greater than 509c, an oxygen content of greater than 17 v/v%, and a known HjS concentration of approximately 1 v/v% was passed through this column at a flow rate of 1450 +/- 20 cc/minute under ambient conditions.
  • the effluent from this column was monitored and the elapsed time required to achieve a 50 ppm H_S breakthrough was measured. For this carbon sample the elapsed time period was equal to 9 minutes.
  • Bituminous coal was pulverized, mixed with about 4 to 6% coal tar pitch, and briquetted.
  • the resultant briquettes were crushed and sized to produce an approximately less than 4 mesh size and greater than 10 mesh size (U.S. Standard Series sieves) material.
  • this material was oxidized by heating from 100 C to 200 C at a rate of 200 C per hour, then from 200 C to
  • the resultant oxidized material was cooled to near ambient temperatures in a low oxygen content atmosphere, sized to produce an approximately less than 5 and greater than 6 mesh size (U.S. Standard Series sieves) material, and subsequently impregnated with an aqueous urea solution and dried.
  • the quantity of urea solution used was sufficient to produce a 4% urea loading on a dry weight basis. After impregnation, portions of the oxidized, impregnated low-temperature char were rapidly heated to 950 C under an inert gas atmosphere.
  • the resultant materials were activated with steam at 950 C for a sufficient period of time to achieve the desired yield. After activation, the materials were cooled to ambient temperature under an inert atmosphere.
  • the catalytically-active activated carbonaceous chars so produced when combined and sized to less than 5 mesh (U.S. Standard Series) and greater than 6 mesh (U.S. Standard Series) exhibited an Apparent Density (Test Method TM- 7, Calgon Carbon Corporation, Pittsburgh PA) of 0.495 grams per cc.
  • the CC Number of the sized, combined chars was 55.5%.
  • the H 2 S removal ability of the sized, catalytically-active, activated high-temperature carbonaceous char prepared as described above was determined using conditions identical to those described in Example 1. For this sample of catalytically-active activated carbonaceous char the elapsed time period required to achieve a 50 ppm H 2 S breakthrough was equal to 326 minutes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Catalysts (AREA)

Abstract

L'invention se rapporte à un procédé amélioré destiné à l'extraction sélective de sulfure de milieux gazeux ou liquides contenant de l'eau et de l'oxygène, et consistant à mettre lesdits milieux en contact avec un charbon de bois à activité catalytique. Le perfectionnement consiste à utiliser un charbon à activité catalytique obtenu par la carbonisation et l'oxydation d'une houille bitumineuse ou d'un matériau analogue après quoi le charbon est exposé à un composé contenant de l'azote à des températures élevées au cours de la calcination et/ou de l'activation initiales du matériau oxydé.
PCT/US1994/000884 1993-01-21 1994-01-21 Procede d'extraction de sulfure au moyen de carbone catalytique WO1994016990A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6517278A JP2572206B2 (ja) 1993-01-21 1994-01-21 触媒炭素による硫化物の除去法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US872393A 1993-01-21 1993-01-21
US08/008,723 1993-01-21

Publications (2)

Publication Number Publication Date
WO1994016990A1 true WO1994016990A1 (fr) 1994-08-04
WO1994016990B1 WO1994016990B1 (fr) 1994-09-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/000884 WO1994016990A1 (fr) 1993-01-21 1994-01-21 Procede d'extraction de sulfure au moyen de carbone catalytique

Country Status (3)

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JP (1) JP2572206B2 (fr)
CA (1) CA2131987A1 (fr)
WO (1) WO1994016990A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0795351A3 (fr) * 1996-03-11 1997-12-03 Calgon Carbon Corporation Procédé pour l'oxydation catalytique de fer ferreux dans des milieux liquides
KR101512562B1 (ko) 2013-08-20 2015-04-16 대전대학교 산학협력단 플라타너스낙엽을 활용한 바이오매스 흡착제의 제조방법
US10633307B2 (en) 2015-06-01 2020-04-28 Calgon Carbon Corporation Method for inerting activated carbon in biogas purification equipment

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101439504B1 (ko) 2012-10-09 2014-09-15 주식회사 포스코 황화수소 제거용 활성탄 제조방법 및 이에 의해 제조되는 활성탄

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US737579A (en) * 1902-12-06 1903-09-01 Ernst Burschell Process of purifying gas.
GB411918A (en) * 1932-01-04 1934-06-18 Franz Krczil Improvements in the methods and means for producing active charcoal or for re-activating spent charcoal
US3630959A (en) * 1969-06-04 1971-12-28 Standard Oil Co Ohio Carbonization of bituminous coals
JPS5220395A (en) * 1975-08-08 1977-02-16 Mitsubishi Petrochem Co Ltd Process for producing porous carbonaceous particles
US5256384A (en) * 1991-03-26 1993-10-26 Metallgesellschaft Aktiengesellschaft Activated carbon process for removing hydrogen sulfide from gases

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US737579A (en) * 1902-12-06 1903-09-01 Ernst Burschell Process of purifying gas.
GB411918A (en) * 1932-01-04 1934-06-18 Franz Krczil Improvements in the methods and means for producing active charcoal or for re-activating spent charcoal
US3630959A (en) * 1969-06-04 1971-12-28 Standard Oil Co Ohio Carbonization of bituminous coals
JPS5220395A (en) * 1975-08-08 1977-02-16 Mitsubishi Petrochem Co Ltd Process for producing porous carbonaceous particles
US5256384A (en) * 1991-03-26 1993-10-26 Metallgesellschaft Aktiengesellschaft Activated carbon process for removing hydrogen sulfide from gases

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Removal by Adsorption of Hydrogen Sulfide by a New Type of Activated Carbon Containing Nitrogen", BOKI et al., JAPANESE JOURNAL OF HYGIENE, Vol. 38, No. 5, December 1983, pgs. 877-882. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0795351A3 (fr) * 1996-03-11 1997-12-03 Calgon Carbon Corporation Procédé pour l'oxydation catalytique de fer ferreux dans des milieux liquides
KR101512562B1 (ko) 2013-08-20 2015-04-16 대전대학교 산학협력단 플라타너스낙엽을 활용한 바이오매스 흡착제의 제조방법
US10633307B2 (en) 2015-06-01 2020-04-28 Calgon Carbon Corporation Method for inerting activated carbon in biogas purification equipment
US11958803B2 (en) 2015-06-01 2024-04-16 Calgon Carbon Corporation Method for inerting activated carbon in biogas purification equipment

Also Published As

Publication number Publication date
JP2572206B2 (ja) 1997-01-16
CA2131987A1 (fr) 1994-08-04
JPH07505116A (ja) 1995-06-08

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