WO2001085307A1 - Process for the purification of flue gas - Google Patents

Process for the purification of flue gas Download PDF

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Publication number
WO2001085307A1
WO2001085307A1 PCT/NL2001/000338 NL0100338W WO0185307A1 WO 2001085307 A1 WO2001085307 A1 WO 2001085307A1 NL 0100338 W NL0100338 W NL 0100338W WO 0185307 A1 WO0185307 A1 WO 0185307A1
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Prior art keywords
flue gas
carbonaceous material
process according
carbon
purification
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PCT/NL2001/000338
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French (fr)
Inventor
Dirk Van De Kleut
Robert Jan De Jonge
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Norit Nederland B.V.
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Publication date
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Priority to DK01928248T priority Critical patent/DK1280593T3/en
Priority to KR20027015030A priority patent/KR100637977B1/en
Priority to EP20010928248 priority patent/EP1280593B1/en
Priority to DE2001601222 priority patent/DE60101222T2/en
Priority to PT01928248T priority patent/PT1280593E/en
Priority to US10/275,675 priority patent/US6843831B2/en
Priority to AT01928248T priority patent/ATE253969T1/en
Priority to AU2001255106A priority patent/AU2001255106A1/en
Priority to JP2001581957A priority patent/JP4057296B2/en
Publication of WO2001085307A1 publication Critical patent/WO2001085307A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • 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
    • 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
    • B01D53/04—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 with stationary adsorbents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S95/00—Gas separation: processes
    • Y10S95/90—Solid sorbent
    • Y10S95/901—Activated carbon

Definitions

  • the invention is directed to a process for the purification of flue gas, wherein flue gas is contacted with a carbonaceous material.
  • a well-known method to remove dioxins, furans and mercury compounds is to inject a powdered adsorbent in the ducts of a flue gas cleaning system, after which hazardous compounds adsorb onto the adsorbent.
  • the spent adsorbent is removed from the flue gas in a particle collection system.
  • the collection of the adsorbent is often performed in existing ESP, FF or wet scrubbers, which makes this technology especially suited for existing flue gas cleaning installations.
  • a vast amount of patents have been granted describing various flue gas cleaning installation modifications applying powdered adsorbents for flue gas cleaning.
  • flue gas In general, flue gas consists of fly ash and various gasses and volatile compounds, such as nitrogen, oxygen, carbon dioxide, nitrogen oxides, water, carbon monoxide, sulphur dioxide, and various acid gasses.
  • gasses and volatile compounds such as nitrogen, oxygen, carbon dioxide, nitrogen oxides, water, carbon monoxide, sulphur dioxide, and various acid gasses.
  • the precise composition of the flue gas is determined by the nature of the process generating the flue gas and can vary significantly in time. A suitable adsorbent must be able to withstand these variations of the flue gas composition.
  • the maximum temperature at which powdered adsorbents can be used is partly determined by the maximum operating temperature of the particle collection system.
  • the maximum operating temperatures are typically 450°C, respectively 300°C.
  • the maximum operating temperature is always below 100 °C.
  • the maximum application temperature is preferably kept below 250 °C to prevent the formation of additional dioxins due to the so-called de no ⁇ o synthesis route.
  • Various adsorbents are used for the cleanup of flue gas. Commonly reported adsorbents for this application are activated carbon and activated lignite cokes.
  • the adsorption capacities of activated carbon and activated lignite cokes for dioxins and furans can be extremely divers, depending amongst others on the nature of the raw material and on the method of production.
  • the carbon types used in flue gas cleaning are produced from raw materials like peat, coal, or lignite, produced by steam activation processes.
  • carbon adsorbents are produced by milling reactivated granular carbon or activated carbon waste.
  • the PAC types based on reactivated carbon or on activated carbon waste generally have a varying quality due to the varying quality of the raw material.
  • the main properties determining the quality of activated carbon for flue gas cleaning are the adsorption properties and the ignition properties.
  • the adsorption properties are mainly determined by the pore structure and by the particle size distribution of the powdered activated carbon.
  • the pore structure of the carbon is defined by the nature of the raw material and by the process conditions during activation.
  • a suitable activated carbon preferably contains a high micropore volume for a high adsorption capacity, next to a high mesopore volume for a rapid transport of the adsorbates to the adsorbing pores.
  • the particle size distribution is primarily determined by the quality of the milling equipment.
  • the temperature in the ESP or FF of the flue gas cleaning system ranges from 100 to 200°C. In some cases the temperatures are even higher.
  • the present invention is based on the surprising discovery of a material that meets these objects, when applied in flue gas purification.
  • a new carbonaceous adsorbent material was found having a pore structure that is likely superior to that of activated carbons commonly used for flue gas cleaning.
  • the new material is produced as a by-product in the synthetic rutile production industry and has excellent ignition properties. These combined properties make this new adsorbent especially suitable for flue gas cleaning.
  • the said solid carbonaceous material is produced as waste product during the production of synthetic rutile from titaniferous ores (ilmenite, leucoxene, or slag).
  • titaniferous ores inorganic ores
  • carbon is used for the chemical reduction of iron within the titanoferous minerals, possibly in combination with chlorine.
  • the reduced iron is subsequently removed from the minerals to obtain synthetic rutile.
  • a carbonaceous waste product After recovery of the synthetic rutile from the solid material a carbonaceous waste product remains, which has been found to have a pore structure corresponding to the pore structure of activated carbons that are suitable for adsorption of contaminants such as dioxins, furans and mercury compounds from flue gas. If necessary the material can be purified, sieved a ⁇ d/or ground to obtain the optimal properties. More in particular, the particle size may need to be regulated, depending on the type of system used. Generally the material is modified to have a particle size between 1 and 100 ⁇ m.
  • the said carbonaceous material can be used in the same manner as the presently used powdered carbons, by injecting them at a suitable location in the flue gas. This can be done in the dry form, as wetted material and/or in combination with alkaline materials, such as lime to remove acidic substances from the flue gas. After the material has adsorbed the contaminants, it is again removed from the gas, for example by ESP or FF.
  • the flue gas has generally been subjected to some treatment prior to the introduction of the carbonaceous material, such as cooling to recover some heat from it, removal of fly ash, and the like. More in particular, the flue gas may be cooled to a temperature between 0 and 500°C, before contacting it with the said solid carbonaceous material.
  • the pore structure of activated carbons is generally divided into three major size ranges: micropores (pore radius ⁇ 1 nm), mesopores (1 nm ⁇ pore radius ⁇ 25 nm), and macropores (pore radius > 25 nm).
  • the respective pore volumes are generally derived from adsorption experiments with standard adsorbates (micropores and mesopores), or from mercury porosimetry (macropores and larger mesopores).
  • the micropores and the mesopores are generally used for adsorption of adsorbates, whereas the macropores and larger mesopores (transporting pores) are used for transport of adsorbates from the surroundings to the adsorbing pores.
  • a suitable activated carbon for flue gas cleaning contains both adsorbing pores and transporting pores in sufficient amounts, to provide optimum adsorption capacity and fast adsorption kinetics.
  • the macropores have largely disappeared due to the milling process.
  • a commonly accepted analytical parameter for activated carbon is the so-called iodine number.
  • the iodine number is the amount of iodine adsorbed onto activated carbon (in g iodine/g carbon) in equilibrium with a 0.02 N iodine solution.
  • the test method has been described extensively in ASTM D 4607-86.
  • the iodine number of activated carbon is related to its micropore volume.
  • An alternative parameter indicating the micropore volume of activated carbon is the equilibrium butane adsorption capacity when the carbon is brought into contact with dry air containing 0.24 vol% butane. The iodine number is thus related to the volume of the adsorbing pores.
  • a parameter indicating the combined pore volume of larger mesopores and small macropores is the molasses number.
  • the molasses number is defined as the number of milligrams activated carbon required to achieve the same decolorizing effect as 350 mg of a standard carbon, determined using a standard molasses solution by a standard procedure. Due to the large size of the molasses molecules only large pores can be entered, therefore, the molasses number is an indication for the volume of the transporting pores. In this case, the molasses number decreases as the transporting pore volume increases.
  • Table 1 contains typical iodine numbers and the molasses numbers of several activated carbon types that are commonly used for flue gas cleaning, as well as those of the carbonaceous residue produced in the synthetic rutile production process. Based on these values, the adsorption properties and . adsorption kinetics of the carbonaceous residue are more favorable for flue gas cleaning compared to the currently applied carbon types, because both adsorption and transport pore volumes are higher.
  • the auto-ignition hazard of stationary activated carbon layers can be assessed by determining the so-called critical ignition temperature (CIT).
  • CIT critical ignition temperature
  • the CIT test method is in principal identical to the UN test method, only the temperature at which the sample is tested is made variable. Depending on the outcome of the first test at a pre-selected temperature, a new test temperature is chosen and a fresh carbon sample is tested. This is repeated until the highest temperature at which no ignition took place and the lowest temperature at which ignition did take place are about 10 °C apart. The 5 CIT is defined as the average of these temperatures.
  • Table 2 contains the CIT values of several activated carbon types that are commonly used for flue gas cleaning, as well as that of the carbonaceous residue produced in the synthetic rutile production process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Incineration Of Waste (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

The present invention is directed to a process for the purification of flue gas, wherein flue gas is contacted with a carbonaceous material, said carbonaceous material comprising the solid carbonaceous residue of synthetic rutile production from titaniferous ores.

Description

PROCESS FOR THE PURIFICATION OF FLUE GAS
The invention is directed to a process for the purification of flue gas, wherein flue gas is contacted with a carbonaceous material.
Various industrial processes produce vast amounts of flue gas streams containing environmentally hazardous substances, such as fly ash, acid gasses, NOx, dioxins, furans, and heavy metal compounds. Examples of such industries are waste incinerators burning various feeds (municipal waste, clinical waste, hazardous waste), the metallurgical industry, the metal recovery industry, power plants, cement plants and the like.
In order to reduce the emission of hazardous substances, many industries are obliged to clean up their flue gasses before ventilation in the environment. Depending on the nature of the pollutant, various techniques have been developed to clean up the flue gas. For example, fly ash can be removed with electrostatic precipitators (ESP), fabric filters (FF) or wet scrubbers. Acid gasses are mostly bound to alkaline compounds, either in a (semi-) dry system with spray dryer adsorbers (SDA), or in wet systems using scrubbers. Many flue gas cleaning installations have been build containing these basic components.
For the removal of dioxins, furans and mercury compounds from flue gas often additional measures have to be taken in order to comply with the current emission limits. Mostly, the flue gasses.are brought into contact with an adsorbent to bind these compounds.
A well-known method to remove dioxins, furans and mercury compounds is to inject a powdered adsorbent in the ducts of a flue gas cleaning system, after which hazardous compounds adsorb onto the adsorbent. In subsequent parts of the installation the spent adsorbent is removed from the flue gas in a particle collection system. The collection of the adsorbent is often performed in existing ESP, FF or wet scrubbers, which makes this technology especially suited for existing flue gas cleaning installations. A vast amount of patents have been granted describing various flue gas cleaning installation modifications applying powdered adsorbents for flue gas cleaning.
The conditions under which adsorbents are applied depend to a large extent on the nature of the industrial process generating the flue gasses and on the modification of the flue gas cleaning installation.
In general, flue gas consists of fly ash and various gasses and volatile compounds, such as nitrogen, oxygen, carbon dioxide, nitrogen oxides, water, carbon monoxide, sulphur dioxide, and various acid gasses. The precise composition of the flue gas is determined by the nature of the process generating the flue gas and can vary significantly in time. A suitable adsorbent must be able to withstand these variations of the flue gas composition.
The maximum temperature at which powdered adsorbents can be used is partly determined by the maximum operating temperature of the particle collection system. For ESP and FF the maximum operating temperatures are typically 450°C, respectively 300°C. In wet scrubbers the maximum operating temperature is always below 100 °C. The maximum application temperature is preferably kept below 250 °C to prevent the formation of additional dioxins due to the so-called de noυo synthesis route. Various adsorbents are used for the cleanup of flue gas. Commonly reported adsorbents for this application are activated carbon and activated lignite cokes.
The adsorption capacities of activated carbon and activated lignite cokes for dioxins and furans can be extremely divers, depending amongst others on the nature of the raw material and on the method of production. Usually, the carbon types used in flue gas cleaning are produced from raw materials like peat, coal, or lignite, produced by steam activation processes. Alternatively, carbon adsorbents are produced by milling reactivated granular carbon or activated carbon waste. The PAC types based on reactivated carbon or on activated carbon waste generally have a varying quality due to the varying quality of the raw material.
The main properties determining the quality of activated carbon for flue gas cleaning are the adsorption properties and the ignition properties. The adsorption properties are mainly determined by the pore structure and by the particle size distribution of the powdered activated carbon. The pore structure of the carbon is defined by the nature of the raw material and by the process conditions during activation. A suitable activated carbon preferably contains a high micropore volume for a high adsorption capacity, next to a high mesopore volume for a rapid transport of the adsorbates to the adsorbing pores. The particle size distribution is primarily determined by the quality of the milling equipment.
When applying powdered carbon under oxidising conditions at elevated temperatures as in flue gas, the possibility of ignition of the carbon has to be taken into account. Typically, the temperature in the ESP or FF of the flue gas cleaning system ranges from 100 to 200°C. In some cases the temperatures are even higher.
Ignition of carbon adsorbents is usually first observed in the dust collection sections of an ESP or a FF, since on these spots warmed up carbon can accumulate. Under sufficiently severe conditions in principle all carbon adsorbents can eventually ignite, resulting in undesired excessive temperature increases. Changes in the design of the installation can reduce the ignition hazard. Choosing the proper carbon adsorbent can reduce the ignition hazard as well. In general the ignition properties of an activated carbon or other material used in flue gas cleaning systems are determined using a standard ignition test. Such tests are defined in the Recommendations for the transport of dangerous goods, 9th revised edition, United Nations, 1995, parts 14.5.5 and 33.3.1.3.3. Next to the adsorption and ignition properties, secondary properties such as material availability and production costs also determine the suitability of an adsorbent for flue gas cleaning.
It is an object of the present invention to provide an alternative to the presently used powdered activated carbon, whereby the ignition characteristics of the material are improved.
It is also an object of the present invention to provide a carbonaceous material suitable for flue gas purification, wherein the material has an improved balance of properties in relation to adsorption characteristics and ignition behaviour.
The present invention is based on the surprising discovery of a material that meets these objects, when applied in flue gas purification. Surprisingly, a new carbonaceous adsorbent material was found having a pore structure that is likely superior to that of activated carbons commonly used for flue gas cleaning. The new material is produced as a by-product in the synthetic rutile production industry and has excellent ignition properties. These combined properties make this new adsorbent especially suitable for flue gas cleaning.
The said solid carbonaceous material is produced as waste product during the production of synthetic rutile from titaniferous ores (ilmenite, leucoxene, or slag). During the production of synthetic rutile, carbon is used for the chemical reduction of iron within the titanoferous minerals, possibly in combination with chlorine. The reduced iron is subsequently removed from the minerals to obtain synthetic rutile. (See Ullmann's Encyclopedia of Industrial Chemistry, Sixth Ed, 199 Electronic Release, Wiley- VHC, Weinheim (DE) on Titanium Dioxide, § 2.1.2.2. Synthetic Raw Materials)
After recovery of the synthetic rutile from the solid material a carbonaceous waste product remains, which has been found to have a pore structure corresponding to the pore structure of activated carbons that are suitable for adsorption of contaminants such as dioxins, furans and mercury compounds from flue gas. If necessary the material can be purified, sieved aήd/or ground to obtain the optimal properties. More in particular, the particle size may need to be regulated, depending on the type of system used. Generally the material is modified to have a particle size between 1 and 100 μm.
It is possible to combine the said carbonaceous material also with other solid materials, such as activated carbon and the like. However, it is preferred that the amount of material added is subordinate in amount to the said solid carbonaceous material. The carbonaceous material can be used in the same manner as the presently used powdered carbons, by injecting them at a suitable location in the flue gas. This can be done in the dry form, as wetted material and/or in combination with alkaline materials, such as lime to remove acidic substances from the flue gas. After the material has adsorbed the contaminants, it is again removed from the gas, for example by ESP or FF.
The flue gas has generally been subjected to some treatment prior to the introduction of the carbonaceous material, such as cooling to recover some heat from it, removal of fly ash, and the like. More in particular, the flue gas may be cooled to a temperature between 0 and 500°C, before contacting it with the said solid carbonaceous material.
The invention is now elucidated on the basis of the following examples, which are not intended to limit the scope of the invention.
EXAMPLE 1
The pore structure of activated carbons is generally divided into three major size ranges: micropores (pore radius < 1 nm), mesopores (1 nm < pore radius < 25 nm), and macropores (pore radius > 25 nm). The respective pore volumes are generally derived from adsorption experiments with standard adsorbates (micropores and mesopores), or from mercury porosimetry (macropores and larger mesopores). With activated carbons used for the purification of gasses, the micropores and the mesopores (adsorbing pores) are generally used for adsorption of adsorbates, whereas the macropores and larger mesopores (transporting pores) are used for transport of adsorbates from the surroundings to the adsorbing pores. A suitable activated carbon for flue gas cleaning contains both adsorbing pores and transporting pores in sufficient amounts, to provide optimum adsorption capacity and fast adsorption kinetics. For powdered activated carbon types the macropores have largely disappeared due to the milling process.
A commonly accepted analytical parameter for activated carbon is the so-called iodine number. The iodine number is the amount of iodine adsorbed onto activated carbon (in g iodine/g carbon) in equilibrium with a 0.02 N iodine solution. The test method has been described extensively in ASTM D 4607-86. The iodine number of activated carbon is related to its micropore volume. An alternative parameter indicating the micropore volume of activated carbon is the equilibrium butane adsorption capacity when the carbon is brought into contact with dry air containing 0.24 vol% butane. The iodine number is thus related to the volume of the adsorbing pores.
A parameter indicating the combined pore volume of larger mesopores and small macropores is the molasses number. The molasses number is defined as the number of milligrams activated carbon required to achieve the same decolorizing effect as 350 mg of a standard carbon, determined using a standard molasses solution by a standard procedure. Due to the large size of the molasses molecules only large pores can be entered, therefore, the molasses number is an indication for the volume of the transporting pores. In this case, the molasses number decreases as the transporting pore volume increases. Table 1 contains typical iodine numbers and the molasses numbers of several activated carbon types that are commonly used for flue gas cleaning, as well as those of the carbonaceous residue produced in the synthetic rutile production process. Based on these values, the adsorption properties and . adsorption kinetics of the carbonaceous residue are more favorable for flue gas cleaning compared to the currently applied carbon types, because both adsorption and transport pore volumes are higher.
Table 1 Typical Iodine numbers and Molasses numbers of various
10 activated carbons used for flue gas cleaning, and of the carbonaceous residue material.
Figure imgf000008_0001
EXAMPLE 2
15
The auto-ignition hazard of stationary activated carbon layers can be assessed by determining the so-called critical ignition temperature (CIT). The test method for determining the CIT of powdered activated carbon is similar to a test mentioned in the "Recommendations on the transport of
20 dangerous goods, issued by the United Nations", section 14.5.5 (ST/SG/AC.10/l/Rev.9). This test is designed to establish whether or not self- heating substances can be transported in bulk. In the UN-test it is determined if a carbon sample in a 1 liter cube (10x10x10 cm) auto-ignites at a fixed temperature of 140±2 °C. An elaborate description of this test can be found in 5 the above-mentioned manual.
The CIT test method is in principal identical to the UN test method, only the temperature at which the sample is tested is made variable. Depending on the outcome of the first test at a pre-selected temperature, a new test temperature is chosen and a fresh carbon sample is tested. This is repeated until the highest temperature at which no ignition took place and the lowest temperature at which ignition did take place are about 10 °C apart. The 5 CIT is defined as the average of these temperatures.
Table 2 contains the CIT values of several activated carbon types that are commonly used for flue gas cleaning, as well as that of the carbonaceous residue produced in the synthetic rutile production process. The
10 data in table 2 clearly indicate that the CIT of the carbonaceous residue is significantly higher than that of the regular flue gas cleaning carbon types.
Table 2 Typical critical ignition temperatures (CIT) and average particle size of various activated carbons used for flue gas cleaning, and of
15 the carbonaceous residue material.
Figure imgf000009_0001

Claims

Claims
1. Process for the purification of flue gas, wherein flue gas is contacted with a carbonaceous material, said carbonaceous material comprising the solid carbonaceous residue of synthetic rutile production from titaniferous ores.
2. Process according to claim 1, wherein said carbonaceous material is injected into the flue gas to be purified.
3. Process according to claim 2, wherein the said carbonaceous material is removed from the flue gas after sufficient contact time for adsorbing contaminants from the flue gas.
4. Process according to claim 1-3, wherein the flue gas is cooled to a temperature between 0 and 500°C, before contacting it with the said solid carbonaceous material.
5. Process according to claim 1-4, wherein flue gas originating from waste incinerators, the metallurgical industry, the metal recovery industry, power plants or cement plants is treated.
6. Process according to claim 1-6, wherein dioxins, furans and mercury compounds are removed from the flue gas.
7. Process according to claim 1-6, wherein the said solid carbonaceous material is contacted with the flue gas in dry state, wet state and/or in combination with lime.
8. Process according to claim 1-7, wherein the said carbonaceous material is sieved, purified and/or ground, prior to use.
9. Use of a solid carbonaceous material comprising the solid carbonaceous residue of synthetic rutile production from titaniferous ores, in the purification of flue gas.
PCT/NL2001/000338 2000-05-08 2001-05-03 Process for the purification of flue gas WO2001085307A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
DK01928248T DK1280593T3 (en) 2000-05-08 2001-05-03 Flue gas purification process
KR20027015030A KR100637977B1 (en) 2000-05-08 2001-05-03 Process for the purification of flue gas
EP20010928248 EP1280593B1 (en) 2000-05-08 2001-05-03 Process for the purification of flue gas
DE2001601222 DE60101222T2 (en) 2000-05-08 2001-05-03 METHOD FOR PURIFYING EXHAUST GASES
PT01928248T PT1280593E (en) 2000-05-08 2001-05-03 PROCESS FOR THE PURIFICATION OF COMBUSTION GASES
US10/275,675 US6843831B2 (en) 2000-05-08 2001-05-03 Process for the purification of flue gas
AT01928248T ATE253969T1 (en) 2000-05-08 2001-05-03 METHOD FOR CLEANING EXHAUST GASES
AU2001255106A AU2001255106A1 (en) 2000-05-08 2001-05-03 Process for the purification of flue gas
JP2001581957A JP4057296B2 (en) 2000-05-08 2001-05-03 Exhaust gas purification method

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EP00201649.1 2000-05-08
EP00201649 2000-05-08

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AT (1) ATE253969T1 (en)
AU (1) AU2001255106A1 (en)
DE (1) DE60101222T2 (en)
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* Cited by examiner, † Cited by third party
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US7575629B2 (en) 2005-11-30 2009-08-18 Basf Catalysts Llc Pollutant emission control sorbents and methods of manufacture
US7578869B2 (en) 2005-11-30 2009-08-25 Basf Catalysts Llc Methods of manufacturing bentonite pollution control sorbents
US7704920B2 (en) 2005-11-30 2010-04-27 Basf Catalysts Llc Pollutant emission control sorbents and methods of manufacture
US7753992B2 (en) 2006-06-19 2010-07-13 Basf Corporation Methods of manufacturing mercury sorbents and removing mercury from a gas stream
US7879305B2 (en) * 2006-01-03 2011-02-01 University Of Wyoming Apparatus and method for sequestering flue gas CO2
US8506918B2 (en) 2006-01-03 2013-08-13 University Of Wyoming Apparatus and method to sequester contaminants
US8673257B2 (en) 2006-01-03 2014-03-18 University Of Wyoming Apparatus and method to sequester contaminants
US8685351B2 (en) 2007-09-24 2014-04-01 Basf Corporation Pollutant emission control sorbents and methods of manufacture and use
US8728974B2 (en) 2007-09-24 2014-05-20 Basf Corporation Pollutant emission control sorbents and methods of manufacture and use
US10220369B2 (en) 2015-08-11 2019-03-05 Calgon Carbon Corporation Enhanced sorbent formulation for removal of mercury from flue gas
EP2858747B1 (en) * 2012-06-11 2019-12-04 Calgon Carbon Corporation Sorbents for removal of mercury

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002316020A (en) * 2001-04-23 2002-10-29 Kurita Water Ind Ltd Method for removing dioxins in exhaust gas of high humidity and removing agent
US7381387B2 (en) * 2003-08-14 2008-06-03 General Electric Company Mercury reduction system and method in combustion flue gas using coal blending
US7374736B2 (en) 2003-11-13 2008-05-20 General Electric Company Method to reduce flue gas NOx
US6895875B1 (en) * 2003-11-18 2005-05-24 General Electric Company Mercury reduction system and method in combustion flue gas using staging
US7514052B2 (en) * 2004-01-06 2009-04-07 General Electric Company Method for removal of mercury emissions from coal combustion
US7185494B2 (en) 2004-04-12 2007-03-06 General Electric Company Reduced center burner in multi-burner combustor and method for operating the combustor
US7249564B2 (en) * 2004-06-14 2007-07-31 General Electric Company Method and apparatus for utilization of partially gasified coal for mercury removal
DE102005003138A1 (en) * 2005-01-21 2006-07-27 Rwe Power Ag Sorbent, useful for e.g. purification of dry exhaust gas, comprises powdery carbon material that is reduced without addition of further inert components in its reactivity
US20070092418A1 (en) * 2005-10-17 2007-04-26 Chemical Products Corporation Sorbents for Removal of Mercury from Flue Gas
US7833315B2 (en) * 2008-02-26 2010-11-16 General Electric Company Method and system for reducing mercury emissions in flue gas
DE102009001230A1 (en) 2009-02-27 2010-09-02 Evonik Oxeno Gmbh Process for the separation and partial recycling of transition metals or their catalytically active complex compounds from process streams
UA109399C2 (en) 2009-04-01 2015-08-25 THERMALLY ACTIVATED COAL RESISTANT TO SELF-IGNITION
PE20131042A1 (en) 2010-08-30 2013-09-28 Albemarle Corp IMPROVED ABSORBERS TO REMOVE MERCURY FROM EMISSIONS PRODUCED DURING FUEL COMBUSTION
RU2013114265A (en) 2010-08-30 2014-10-10 Альбемарл Корпорейшн IMPROVED BROWNED SORBENTS FOR REMOVING MERCURY FROM EMISSIONS FROM FUEL COMBUSTION
US8491704B2 (en) 2011-01-11 2013-07-23 Praxair Technology, Inc. Six bed pressure swing adsorption process operating in normal and turndown modes
US8435328B2 (en) 2011-01-11 2013-05-07 Praxair Technology, Inc. Ten bed pressure swing adsorption process operating in normal and turndown modes
US8551217B2 (en) 2011-01-11 2013-10-08 Praxair Technology, Inc. Six bed pressure swing adsorption process operating in normal and turndown modes
US8496733B2 (en) 2011-01-11 2013-07-30 Praxair Technology, Inc. Large scale pressure swing adsorption systems having process cycles operating in normal and turndown modes
CA3085848C (en) 2011-04-15 2022-08-30 Carbon Technology Holdings, LLC Methods and apparatus for enhancing the energy content of carbonaceous materials from pyrolysis
LU91900B1 (en) * 2011-11-14 2013-05-15 Carbon Process & Plant Engineering S A Process for the catalytic removal of carbon dioxide NOx from exhaust gases
JP2015520726A (en) 2012-05-07 2015-07-23 バイオジェニック レゲント ベンチャーズ エルエルシー Biogenic activated carbon and methods of making and using it
WO2015061701A1 (en) 2013-10-24 2015-04-30 Biogenic Reagent Ventures, Llc Methods and apparatus for producing activated carbon from biomass through carbonized ash intermediates
SI3094593T1 (en) 2014-01-16 2022-05-31 Carbon Technology Holdings, LLC Carbon micro-plant
US20150239743A1 (en) * 2014-02-24 2015-08-27 Biogenic Reagent Ventures, Llc Highly mesoporous activated carbon
JP6417157B2 (en) * 2014-09-03 2018-10-31 太平洋セメント株式会社 Cement kiln exhaust gas treatment method
US9895659B2 (en) * 2014-09-24 2018-02-20 Linde Aktiengesellschaft Methods for removing contaminants from exhaust gases
WO2016065357A1 (en) 2014-10-24 2016-04-28 Biogenic Reagent Ventures, Llc Halogenated activated carbon compositions and methods of making and using same
US10589214B2 (en) * 2016-02-02 2020-03-17 University Of Kentucky Research Foundation CO2 mass transfer enhancement of aqueous amine solvents by particle additives
US11753698B2 (en) 2020-09-25 2023-09-12 Carbon Technology Holdings, LLC Bio-reduction of metal ores integrated with biomass pyrolysis
BR112023016400A2 (en) 2021-02-18 2023-10-31 Carbon Tech Holdings Llc METALLURGICAL PRODUCTS WITH NEGATIVE CARBON
WO2022232316A1 (en) 2021-04-27 2022-11-03 Carbon Technology Holdings, LLC Biocarbon compositions with optimized fixed carbon and processes for producing the same
EP4367070A1 (en) 2021-07-09 2024-05-15 Carbon Technology Holdings, LLC Processes for producing biocarbon pellets with high fixed-carbon content and optimized reactivity, and biocarbon pellets obtained therefrom
CA3237226A1 (en) 2021-11-12 2023-05-19 Carbon Technology Holdings, LLC Biocarbon compositions with optimized compositional parameters, and processes for producing the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB725555A (en) * 1953-01-02 1955-03-09 Dow Chemical Co Treatment of titaniferous material
GB756497A (en) * 1954-04-27 1956-09-05 Du Pont Recovery of titanium tetrachloride by adsorption
US4442076A (en) * 1982-11-17 1984-04-10 Scm Corporation Entrained downflow chlorination of fine titaniferous material
US5073355A (en) * 1989-07-05 1991-12-17 Kronos (U.S.A.), Inc. Process for the removal of chlorine from off-gases
US5403379A (en) * 1992-05-15 1995-04-04 Rgc Mineral Sands Limited Reduction of titaniferous ores and apparatus

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4708853A (en) * 1983-11-03 1987-11-24 Calgon Carbon Corporation Mercury adsorbent carbon molecular sieves and process for removing mercury vapor from gas streams
DK158376C (en) * 1986-07-16 1990-10-08 Niro Atomizer As METHOD OF REDUCING THE CONTENT OF MERCURY Vapor AND / OR VAPORS OF Harmful Organic Compounds And / Or Nitrogen Oxides In Combustion Plant
EP0271618A1 (en) * 1986-12-15 1988-06-22 Calgon Carbon Corporation Mercury absorbent carbon molecular sieves
JPH04219308A (en) * 1990-12-17 1992-08-10 Mitsui Mining Co Ltd Production of formed active coke for desulfurization and denitration having high denitration performance
US5254521A (en) * 1992-08-03 1993-10-19 University Of North Dakota Energy And Environment Research Center Foundation Leonardite char adsorbents
US5700436A (en) * 1993-01-21 1997-12-23 Calgon Carbon Corporation Purification of air in enclosed spaces
US5733515A (en) * 1993-01-21 1998-03-31 Calgon Carbon Corporation Purification of air in enclosed spaces
US6439138B1 (en) * 1998-05-29 2002-08-27 Hamon Research-Cottrell, Inc. Char for contaminant removal in resource recovery unit
US6027551A (en) * 1998-10-07 2000-02-22 Board Of Control For Michigan Technological University Control of mercury emissions using unburned carbon from combustion by-products
FR2804042B1 (en) * 2000-01-25 2002-07-12 Air Liquide PROCESS FOR THE PURIFICATION OF A GAS BY ADSORPTION OF IMPURITIES ON SEVERAL ACTIVE COAL
US6582497B1 (en) * 2000-06-09 2003-06-24 Merck & Co., Inc. Adsorption power for removing mercury from high temperature high moisture gas streams
US6511527B2 (en) * 2001-02-06 2003-01-28 Ngk Insulators, Ltd. Method of treating exhaust gas
US6521021B1 (en) * 2002-01-09 2003-02-18 The United States Of America As Represented By The United States Department Of Energy Thief process for the removal of mercury from flue gas

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB725555A (en) * 1953-01-02 1955-03-09 Dow Chemical Co Treatment of titaniferous material
GB756497A (en) * 1954-04-27 1956-09-05 Du Pont Recovery of titanium tetrachloride by adsorption
US4442076A (en) * 1982-11-17 1984-04-10 Scm Corporation Entrained downflow chlorination of fine titaniferous material
US5073355A (en) * 1989-07-05 1991-12-17 Kronos (U.S.A.), Inc. Process for the removal of chlorine from off-gases
US5403379A (en) * 1992-05-15 1995-04-04 Rgc Mineral Sands Limited Reduction of titaniferous ores and apparatus

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US7578869B2 (en) 2005-11-30 2009-08-25 Basf Catalysts Llc Methods of manufacturing bentonite pollution control sorbents
US7704920B2 (en) 2005-11-30 2010-04-27 Basf Catalysts Llc Pollutant emission control sorbents and methods of manufacture
US7879305B2 (en) * 2006-01-03 2011-02-01 University Of Wyoming Apparatus and method for sequestering flue gas CO2
US8506918B2 (en) 2006-01-03 2013-08-13 University Of Wyoming Apparatus and method to sequester contaminants
US8673257B2 (en) 2006-01-03 2014-03-18 University Of Wyoming Apparatus and method to sequester contaminants
US7753992B2 (en) 2006-06-19 2010-07-13 Basf Corporation Methods of manufacturing mercury sorbents and removing mercury from a gas stream
US8480791B2 (en) 2006-06-19 2013-07-09 Basf Corporation Methods of manufacturing mercury sorbents and removing mercury from a gas stream
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US9067192B2 (en) 2007-09-24 2015-06-30 Basf Corporation Pollutant emission control sorbents and methods of manufacture and use
EP2858747B1 (en) * 2012-06-11 2019-12-04 Calgon Carbon Corporation Sorbents for removal of mercury
US11857942B2 (en) 2012-06-11 2024-01-02 Calgon Carbon Corporation Sorbents for removal of mercury
US10220369B2 (en) 2015-08-11 2019-03-05 Calgon Carbon Corporation Enhanced sorbent formulation for removal of mercury from flue gas
US10967357B2 (en) 2015-08-11 2021-04-06 Calgon Carbon Corporation Enhanced sorbent formulation for removal of mercury from flue gas

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