WO2021080098A1 - Mercury removal adsorbents and manufacturing method thereof - Google Patents

Mercury removal adsorbents and manufacturing method thereof Download PDF

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WO2021080098A1
WO2021080098A1 PCT/KR2020/004077 KR2020004077W WO2021080098A1 WO 2021080098 A1 WO2021080098 A1 WO 2021080098A1 KR 2020004077 W KR2020004077 W KR 2020004077W WO 2021080098 A1 WO2021080098 A1 WO 2021080098A1
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sulfur
activated carbon
activation
petcoke
mercury removal
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Yongkwon CHUNG
Daejin SUNG
Yonghwa YEOM
Haewon JUNG
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HD Hyundai Oilbank Co Ltd
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Hyundai Oilbank Co Ltd
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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0262—Compounds of O, S, Se, Te
    • B01J20/0266—Compounds of S
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • C01B32/306—Active carbon with molecular sieve properties
    • 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
    • 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
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials

Definitions

  • the present invention relates to a mercury removal absorbent and a manufacturing method thereof, and more particularly to a mercury removal absorbent comprising a sulfur-containing activated carbon prepared from a petroleum coke, abbreviated petcoke, which is a final carbon-rich solid material that derives from oil refining and can either be fuel grade (high in sulfur and metals) or anode grade (low in sulfur and metals), and a manufacturing method for the mercury removal absorbent.
  • Mercury emitted into the air is very harmful to plants and animals including human. It is contained in exhaust emission mostly produced from the applications using fossil fuels and emitted into the air. In the petrochemical industries, hydrocarbon substances containing mercury cause corrosion of equipment and consequently enormous economic damages.
  • Activated carbon materials are utilized to remove mercury in the industrial processes of electricity generating station or the like using fossil fuels. Powder of activated carbon is sprayed into the flow of exhaust emission to adsorb mercury. In the adsorption of mercury in exhaust emission with activated carbon, the contact time for the activated carbon to adsorb mercury is so short that the activated carbon is separated and removed in the downstream process before using up its inherent adsorption capacity.
  • Halogen like chloride, bromine, iodine, etc. deposited as the second substance onto the activated carbon reacts with mercury according to a chemical adsorption reaction of the following formula (i):
  • Chemical adsorption, also known as chemisorption, on the activated carbon can accelerate the mercury removal efficiency of the activated carbon.
  • the mercury removal performance depends on halogen elements deposited on the activated carbon: iodine (I 2 ) > bromine (Br 2 ) > chlorine (Cl 2 ).
  • Iodine deposited as the secondary substance contributes to high performance, yet it is susceptible to stripping under temperature conditions for the release of exhaust emission, slowing down the activities of the iodine-deposited activated carbon.
  • the chemical deposition method is adopted to deposit iodine onto the activated carbon, albeit the iodine has a low affinity for the activated carbon and accordingly contributes to extremely low deposition efficiency. For this reason, it is necessary to consume iodine in a relatively large quantity and conduct an additional separation/regeneration process, resulting in a rise of the process cost.
  • Another technology suggests using a relatively inexpensive non-halogen substance like sulfur to deposit on the activated carbon for removal of mercury.
  • sulfur is a common measure taken in the case of exposure to mercury.
  • sulfur deposited on the activated carbon reacts with mercury according to the chemical adsorption reaction of the following formula (ii) so that the mercury is chemically adsorbed onto the activated carbon.
  • the chemical adsorption reaction of the Formula (ii) occurs under general adsorption conditions.
  • the reaction between mercury and sulfur is occurred even at room temperature.
  • the chemical adsorption efficiency by sulfur deposited onto activated carbon depends on the condition and quantity of the sulfur. Physical adsorption by activated carbon (i.e., adsorption onto the surface of pores) may also be involved in the removal of mercury by adsorption.
  • the procedures for preparing the sulfur-deposited activated carbon may include mixing activated carbon with powdered sulfur and conducting a heat treatment with high temperatures; or brining the activated carbon in contact with gaseous mercaptans or other sulfide-containing gas at high temperatures.
  • the resulting sulfur-deposited activated carbon has a problem that sulfur tends to be stripped due to its low affinity with the activated carbon.
  • the activated carbon is made from coconut, charcoal, or other biomasses through a complicated process including the steps of carbonization, pulverization, size classification, molding, activation, another pulverization and size classification. Furthermore, the production of the activated carbon from such raw materials highly costs with extremely inefficiency as it results in no more than about 10 % of production yield and requires an additional process of depositing the second substance onto the activated carbon.
  • a mercury removal absorbent comprising a sulfur-containing activated carbon prepared from a sulfur-containing petcoke through activation.
  • the sulfur-containing activated carbon may have an average particle size of 1 to 1,000 ⁇ m.
  • the sulfur-containing activated carbon may have a specific surface area (BET specific surface area) of 100 to 2,000 m 2 /g.
  • the sulfur-containing activated carbon may contain 1 to 20 weight percent of sulfur based on the total weight of the activated carbon.
  • the form of sulfur contained in activated carbon may be organic sulfur, sulfur oxide, element sulfur, sulfide or a combination of two or more thereof.
  • a method for manufacturing a mercury removal absorbent that comprises the steps of: introducing a sulfur-containing petcoke into a reactor; and activating the sulfur-containing petcoke in the reactor to obtain a sulfur-containing activated carbon.
  • the manufacturing method may further comprise pulverizing the sulfur-containing petcoke to have an average particle size of 1 to 1,000 ⁇ m prior to the introduction step.
  • the pulverization step may be followed by size classification to have an average particle size of 1 to 1,000 ⁇ m.
  • the activation may be selected from a group consisting of water vapor activation, supercritical CO 2 activation, peroxide activation, or a combination of two or more thereof.
  • the activation is water vapor activation.
  • the water vapor activation may include activating the sulfur-containing petcoke with a water vapor injection rate of 0.1 to 100 ml/min per gram (g) of the sulfur-containing petcoke at a temperature ranging from 500 °C to 900 °C for 0.5 to 20 hours.
  • the sulfur-containing activated carbon may contain 1 to 20 weight percent of sulfur based on the total weight of the activated carbon.
  • the reactor may be a tube type electric furnace or a rotary kiln.
  • the reactor may be maintained at its internal pressure in the range of 1 to 10 bar during the activation step.
  • a sulfur-containing petcoke is used to prepare a sulfur-containing activated carbon capable of eliminating mercury or the like contained in exhaust emission, thereby enabling the production of a sulfur-containing activated carbon without a sulfur deposition process to dramatically reduce the production cost.
  • FIG. 1 is a graph showing the mercury adsorption efficiency.
  • the present invention features the use of a petcoke (petroleum coke), especially sulfur-containing petcoke, as the raw material for the activated carbon.
  • the petcoke refers to a final carbon-rich solid material that derives from oil refining.
  • Petcoke is the coke that, in particular, derives from a final cracking process ⁇ a thermo-based chemical engineering process that splits long chain hydrocarbons of petroleum into shorter chains ⁇ that takes place in units termed coker units.
  • crude oil may be separated into LPG, naphtha, kerosene, diesel, atmospheric residue, etc. by distillation in the atmospheric distillation column.
  • the atmospheric residue is separated into oil fractions such as LPG, naphtha, kerosene, diesel, etc. and vacuum residue by distillation in a vacuum distillation column.
  • the vacuum residue is pyrolyzed into LPG, naphtha, kerosene, diesel, etc., and the unpyrolyzed residue becomes petcoke by solidification.
  • Petcoke is a carbon-rich solid material having about 10 % of the volatile content, partly with impurities such as metals, nitrogen, sulfur, oxygen, or the like as derived from the crude oil.
  • the sulfur-containing petcoke as used in the present invention contains a sulfur component derived from the crude oil in an amount of about 1 to 20 weight percent based on the total weight of the petcoke.
  • sulfur contained in the petcoke is present in the form of heterocyclic compound having sulfur and carbon such as thiophene.
  • the heterocyclic compound reacts with steam to decompose the carbon-sulfur (C-S) bond, and sulfur remains in elemental sulfur form while carbon is removed with CO gas.
  • C-S carbon-sulfur
  • the elemental sulfur contained in petcoke through the activation acts as a chemical adsorption site for removal of mercury. It is therefore unnecessary in the present invention to adopt the process of sulfur deposition of the prior art.
  • Sulfur is found in different allotropic forms: an S 8 ring allotrope with eight sulfur atoms arranged in a ring structure; an S 8 chain allotrope with eight sulfur atoms in a chain structure; an S 6 chain allotrope with six sulfur atoms in a chain structure; and an S 2 chain allotrope with two sulfur atoms in a chain structure.
  • the S 6 and S 2 chain allotropes produced at high temperatures are so highly reactive to play a major role in adsorbing mercury.
  • sulfur is found mainly in the S 8 ring or chain allotropic form at the room temperature.
  • the sulfur-deposited activated carbon chiefly contains S 8 ring or chain allotrope, which contributes to the reduction of the mercury adsorption efficiency.
  • the pores of the petcoke is developed into more fine pores, and the C-S bond of the heterocyclic compound present on the surface of the pores is decomposed, so the occurred sulfur is trapped into the fine pores. Due to the steric hindrance of the fine pores and the low absolute content of the carbon-sulfur bond in the fine pores, it is ready to form the S 2 and S 6 chain allotropes rather than S 8 ring and chain allotropes.
  • sulfur may present in the form of sulfur compounds such as organic sulfur, sulfur oxides, sulfide, or the like as well as the elemental sulfur (i.e., S 2 and S 6 chain allotropes) as mentioned above.
  • sulfur compounds such as organic sulfur, sulfur oxides, sulfide, or the like as well as the elemental sulfur (i.e., S 2 and S 6 chain allotropes) as mentioned above.
  • S 2 and S 6 chain allotropes elemental sulfur
  • a porous activated carbon may be prepared through activation of the petcoke with a steam at 500 °C or above.
  • the pores of the activated carbon is difficult to develop when using the petcoke in the manufacture of the activated carbon rather than using the conventional raw materials such as coconuts, charcoal, or other biomass. Pulverizing the petcoke into fine powder before the activation helps to develop pores in the activated carbon. Also, increasing the pressure in activation process may increase the reaction rate and promote the activation reaction and hence helps the formation of the fine pores.
  • the sulfur-containing activated carbon may have an average particle size of 1 to 1,000 ⁇ m. Such an average particle size can be acquired through pulverization and/or size classfication of the petcoke before the activation of the petcoke, or pulverization and/or size classfication of the sulfur-containing activated carbon obtained after the activation of the petcoke. It is preferable to pulverize and/or classify the petcoke to an average particle size of 1 to 1,000 ⁇ m before the activation of the petcoke for the sake of increasing the specific surface area through the activation.
  • the sulfur-containing activated carbon particularly for removal of mercury, is used in the form of particles in order to enhance the adsorption efficiency for the mercury.
  • the particle size of the sulfur-containing activated carbon less than 1 ⁇ m renders particles blown off during the activation process and discharged together with the off-gas to cause a loss of the activated carbon.
  • the particle size of the sulfur-containing activated carbon greater than 1,000 ⁇ m incurs the problem with spraying particles during the use of the activated carbon for the removal of mercury.
  • the sulfur-containing activated carbon produced through the activation, preferably water vapor activation, of the sulfur-containing petcoke according to the present invention may have a specific surface area (BET specific surface area) of 100 to 2,000 m 2 /g.
  • the sulfur-containing activated carbon produced through the activation of the sulfur-containing petcoke according to the present invention may contain 1 to 20 weight percent of sulfur based on the total weight of the activated carbon.
  • the sulfur contained in the sulfur-containing activated carbon produced through the activation of the sulfur-containing petcoke according to the present invention may be present in the form of element sulfur, organic sulfur, sulfur oxide, sulfide, or a combination of two or more thereof.
  • a method for manufacturing a mercury removal absorbent comprises steps of: introducing a sulfur-containing petcoke into a reactor; and activating the sulfur-containing petcoke in the reactor to obtain a sulfur-containing activated carbon.
  • the manufacturing method may further comprise pulverizing the sulfur-containing petcoke to have an average particle size of 1 to 1,000 ⁇ m prior to the introduction step.
  • the pulverization step may be followed by size classification to have an average particle size of 1 to 1,000 ⁇ m.
  • the activation may be selected from the water vapor activation, supercritical CO 2 activation, peroxide activation, or a combination of two or more thereof.
  • the activation is water vapor activation.
  • the water vapor activation includes activating the sulfur-containing petcoke with a water vapor injection rate of 0.1 to 100 ml/min per gram of the sulfur-containing petcoke at a temperature ranging from 500 °C to 900 °C for 0.5 to 20 hours.
  • the sulfur-containing activated carbon contains 1 to 20 weight percent of sulfur based on the total weight of the activated carbon.
  • the reactor as used herein may be a tube type electric furnace or a rotary kiln.
  • the reactor is preferably a rotary kiln.
  • the steam inlet may be positioned to charge the steam towards the top or bottom of the rotary kiln.
  • the reactor may be maintained at the internal pressure in the range of 1 to 10 bar during the activation step.
  • the crude oil was distilled in the atmospheric distillation column and separated into LPG, naphtha, kerosene, and diesel, atmospheric residue, etc.
  • the atmospheric residue obtained in the atmospheric distillation column was distilled under vacuum in the vacuum distillation column and separated into LPG, naphtha, kerosene, diesel, and a vacuum residue.
  • the vacuum residue thus obtained was pyrolyzed into LPG, naphtha, kerosene, diesel, etc., and the unpyrolyzed residue became a sulfur-containing petcoke.
  • the activated carbon prepared using the petcoke was evaluated in terms of the mercury adsorption performance.
  • a gas simulating the exhaust gas composed of 12 weight percent of CO 2 , 7 weight percent of H 2 O, 5 weight percent of O 2 , 500 ppm of SO 2 , 200 ppm of NO, 65 to 75 ppm of Hg with respect to the total weight of the simulation gas was fed into a fixed bed reactor containing an activated carbon sample.
  • the temperature of the fixed bed reactor was maintained at 140 °C.
  • the 40-minute adsorption performance was evaluated.
  • the evaluation results are presented in FIG. 1, where PetcokeAC shows the mercury adsorption performance of the sulfur-containing activated carbon obtained in Example 5.
  • a comparison of the mercury adsorption performance was made between the sulfur-containing activated carbons of the present invention and commercial adsorbents as comparative examples, which were GL50 (CABOT), Hg-LH (DARCO), and RBHG3 (CABOT).
  • Example 1 Div. Surface area (m 2 /g) C (wt.%) S (wt.%) Example 1 138 89 10 Example 2 157 91 8 Example 3 216 92 7 Example 4 105 91 8 Example 5 612 92 7
  • the sulfur-containing activated carbon of Example 5 exhibited the mercury removal efficiency of 94 %.
  • Such a high level of the mercury removal efficiency was shown at the beginning of the adsorption and maintained in a steady and stable manner throughout the use of the sulfur-containing activated carbon.

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Abstract

Disclosed is a mercury removal absorbent and a manufacturing method thereof that uses a sulfur-containing petcoke to eliminate the necessity of the sulfur deposition process, yet enables the production of a sulfur-containing activated carbon and accordingly provides a dramatic reduction of the production cost.

Description

MERCURY REMOVAL ADSORBENTS AND MANUFACTURING METHOD THEREOF
The present invention relates to a mercury removal absorbent and a manufacturing method thereof, and more particularly to a mercury removal absorbent comprising a sulfur-containing activated carbon prepared from a petroleum coke, abbreviated petcoke, which is a final carbon-rich solid material that derives from oil refining and can either be fuel grade (high in sulfur and metals) or anode grade (low in sulfur and metals), and a manufacturing method for the mercury removal absorbent.
Mercury emitted into the air is very harmful to plants and animals including human. It is contained in exhaust emission mostly produced from the applications using fossil fuels and emitted into the air. In the petrochemical industries, hydrocarbon substances containing mercury cause corrosion of equipment and consequently enormous economic damages.
Activated carbon materials are utilized to remove mercury in the industrial processes of electricity generating station or the like using fossil fuels. Powder of activated carbon is sprayed into the flow of exhaust emission to adsorb mercury. In the adsorption of mercury in exhaust emission with activated carbon, the contact time for the activated carbon to adsorb mercury is so short that the activated carbon is separated and removed in the downstream process before using up its inherent adsorption capacity.
For more effective removal of mercury in a short contact time, technologies for removal of mercury have been developed to deposit a second substance onto the activated carbon.
Halogen like chloride, bromine, iodine, etc. deposited as the second substance onto the activated carbon reacts with mercury according to a chemical adsorption reaction of the following formula (i):
X 2 + Hg -> HgX 2 (X = Cl, Br, I) (i).
Chemical adsorption, also known as chemisorption, on the activated carbon can accelerate the mercury removal efficiency of the activated carbon.
The mercury removal performance depends on halogen elements deposited on the activated carbon: iodine (I 2) > bromine (Br 2) > chlorine (Cl 2).
Iodine deposited as the secondary substance contributes to high performance, yet it is susceptible to stripping under temperature conditions for the release of exhaust emission, slowing down the activities of the iodine-deposited activated carbon. Besides, the chemical deposition method is adopted to deposit iodine onto the activated carbon, albeit the iodine has a low affinity for the activated carbon and accordingly contributes to extremely low deposition efficiency. For this reason, it is necessary to consume iodine in a relatively large quantity and conduct an additional separation/regeneration process, resulting in a rise of the process cost.
Another technology suggests using a relatively inexpensive non-halogen substance like sulfur to deposit on the activated carbon for removal of mercury. Using sulfur is a common measure taken in the case of exposure to mercury. Similarly to halogen, sulfur deposited on the activated carbon reacts with mercury according to the chemical adsorption reaction of the following formula (ii) so that the mercury is chemically adsorbed onto the activated carbon.
S + Hg -> HgS (ii)
The chemical adsorption reaction of the Formula (ii) occurs under general adsorption conditions. The reaction between mercury and sulfur is occurred even at room temperature. The chemical adsorption efficiency by sulfur deposited onto activated carbon depends on the condition and quantity of the sulfur. Physical adsorption by activated carbon (i.e., adsorption onto the surface of pores) may also be involved in the removal of mercury by adsorption.
The procedures for preparing the sulfur-deposited activated carbon may include mixing activated carbon with powdered sulfur and conducting a heat treatment with high temperatures; or brining the activated carbon in contact with gaseous mercaptans or other sulfide-containing gas at high temperatures. Unfavorably, the resulting sulfur-deposited activated carbon has a problem that sulfur tends to be stripped due to its low affinity with the activated carbon.
These related arts involve the deposition of a second substance onto the activated carbon and consequently results in a considerably high production cost. The activated carbon is made from coconut, charcoal, or other biomasses through a complicated process including the steps of carbonization, pulverization, size classification, molding, activation, another pulverization and size classification. Furthermore, the production of the activated carbon from such raw materials highly costs with extremely inefficiency as it results in no more than about 10 % of production yield and requires an additional process of depositing the second substance onto the activated carbon.
For solving the problems with the prior art, it is an object of the present invention to provide a mercury removal absorbent and a manufacturing method thereof that can provide sulfur-containing activated carbon without the need for the sulfur deposition and accordingly a dramatic reduction of the production cost.
To achieve the object of the present invention, there is provided a mercury removal absorbent comprising a sulfur-containing activated carbon prepared from a sulfur-containing petcoke through activation.
The sulfur-containing activated carbon may have an average particle size of 1 to 1,000 μm.
The sulfur-containing activated carbon may have a specific surface area (BET specific surface area) of 100 to 2,000 m 2/g.
The sulfur-containing activated carbon may contain 1 to 20 weight percent of sulfur based on the total weight of the activated carbon.
The form of sulfur contained in activated carbon may be organic sulfur, sulfur oxide, element sulfur, sulfide or a combination of two or more thereof.
In another aspect of the present invention, there is also provided a method for manufacturing a mercury removal absorbent that comprises the steps of: introducing a sulfur-containing petcoke into a reactor; and activating the sulfur-containing petcoke in the reactor to obtain a sulfur-containing activated carbon.
The manufacturing method may further comprise pulverizing the sulfur-containing petcoke to have an average particle size of 1 to 1,000 μm prior to the introduction step.
The pulverization step may be followed by size classification to have an average particle size of 1 to 1,000 μm.
The activation may be selected from a group consisting of water vapor activation, supercritical CO 2 activation, peroxide activation, or a combination of two or more thereof.
Preferably, the activation is water vapor activation.
The water vapor activation may include activating the sulfur-containing petcoke with a water vapor injection rate of 0.1 to 100 ml/min per gram (g) of the sulfur-containing petcoke at a temperature ranging from 500 ℃ to 900 ℃ for 0.5 to 20 hours.
The sulfur-containing activated carbon may contain 1 to 20 weight percent of sulfur based on the total weight of the activated carbon.
The reactor may be a tube type electric furnace or a rotary kiln.
The reactor may be maintained at its internal pressure in the range of 1 to 10 bar during the activation step.
According to the present invention, a sulfur-containing petcoke is used to prepare a sulfur-containing activated carbon capable of eliminating mercury or the like contained in exhaust emission, thereby enabling the production of a sulfur-containing activated carbon without a sulfur deposition process to dramatically reduce the production cost.
FIG. 1 is a graph showing the mercury adsorption efficiency.
Hereinafter, a detailed description will be given as to the preferred embodiments of the present invention with reference to the accompanying drawing.
The present invention features the use of a petcoke (petroleum coke), especially sulfur-containing petcoke, as the raw material for the activated carbon. The petcoke refers to a final carbon-rich solid material that derives from oil refining. Petcoke is the coke that, in particular, derives from a final cracking process―a thermo-based chemical engineering process that splits long chain hydrocarbons of petroleum into shorter chains―that takes place in units termed coker units. For example, crude oil may be separated into LPG, naphtha, kerosene, diesel, atmospheric residue, etc. by distillation in the atmospheric distillation column. The atmospheric residue is separated into oil fractions such as LPG, naphtha, kerosene, diesel, etc. and vacuum residue by distillation in a vacuum distillation column. The vacuum residue is pyrolyzed into LPG, naphtha, kerosene, diesel, etc., and the unpyrolyzed residue becomes petcoke by solidification.
Petcoke is a carbon-rich solid material having about 10 % of the volatile content, partly with impurities such as metals, nitrogen, sulfur, oxygen, or the like as derived from the crude oil.
Preferably, the sulfur-containing petcoke as used in the present invention contains a sulfur component derived from the crude oil in an amount of about 1 to 20 weight percent based on the total weight of the petcoke.
Preferably, sulfur contained in the petcoke is present in the form of heterocyclic compound having sulfur and carbon such as thiophene. For example, during the activation of petcoke with steam, the heterocyclic compound reacts with steam to decompose the carbon-sulfur (C-S) bond, and sulfur remains in elemental sulfur form while carbon is removed with CO gas. The elemental sulfur contained in petcoke through the activation acts as a chemical adsorption site for removal of mercury. It is therefore unnecessary in the present invention to adopt the process of sulfur deposition of the prior art.
Sulfur is found in different allotropic forms: an S 8 ring allotrope with eight sulfur atoms arranged in a ring structure; an S 8 chain allotrope with eight sulfur atoms in a chain structure; an S 6 chain allotrope with six sulfur atoms in a chain structure; and an S 2 chain allotrope with two sulfur atoms in a chain structure. The S 6 and S 2 chain allotropes produced at high temperatures are so highly reactive to play a major role in adsorbing mercury. Yet, sulfur is found mainly in the S 8 ring or chain allotropic form at the room temperature. Thus, the sulfur-deposited activated carbon chiefly contains S 8 ring or chain allotrope, which contributes to the reduction of the mercury adsorption efficiency.
But, upon activation of petcoke according the present invention, the pores of the petcoke is developed into more fine pores, and the C-S bond of the heterocyclic compound present on the surface of the pores is decomposed, so the occurred sulfur is trapped into the fine pores. Due to the steric hindrance of the fine pores and the low absolute content of the carbon-sulfur bond in the fine pores, it is ready to form the S 2 and S 6 chain allotropes rather than S 8 ring and chain allotropes.
In the preparation of a sulfur-contained activated carbon using a petcoke, sulfur may present in the form of sulfur compounds such as organic sulfur, sulfur oxides, sulfide, or the like as well as the elemental sulfur (i.e., S 2 and S 6 chain allotropes) as mentioned above. The presence of sulfur in the form of various sulfur compounds may contributes to a remarkable performance in the mercury removal.
A porous activated carbon may be prepared through activation of the petcoke with a steam at 500 °C or above. The pores of the activated carbon is difficult to develop when using the petcoke in the manufacture of the activated carbon rather than using the conventional raw materials such as coconuts, charcoal, or other biomass. Pulverizing the petcoke into fine powder before the activation helps to develop pores in the activated carbon. Also, increasing the pressure in activation process may increase the reaction rate and promote the activation reaction and hence helps the formation of the fine pores.
The sulfur-containing activated carbon may have an average particle size of 1 to 1,000 μm. Such an average particle size can be acquired through pulverization and/or size classfication of the petcoke before the activation of the petcoke, or pulverization and/or size classfication of the sulfur-containing activated carbon obtained after the activation of the petcoke. It is preferable to pulverize and/or classify the petcoke to an average particle size of 1 to 1,000 μm before the activation of the petcoke for the sake of increasing the specific surface area through the activation. Preferably, the sulfur-containing activated carbon, particularly for removal of mercury, is used in the form of particles in order to enhance the adsorption efficiency for the mercury. The particle size of the sulfur-containing activated carbon less than 1 μm renders particles blown off during the activation process and discharged together with the off-gas to cause a loss of the activated carbon. The particle size of the sulfur-containing activated carbon greater than 1,000 μm incurs the problem with spraying particles during the use of the activated carbon for the removal of mercury.
The sulfur-containing activated carbon produced through the activation, preferably water vapor activation, of the sulfur-containing petcoke according to the present invention may have a specific surface area (BET specific surface area) of 100 to 2,000 m 2/g.
The sulfur-containing activated carbon produced through the activation of the sulfur-containing petcoke according to the present invention may contain 1 to 20 weight percent of sulfur based on the total weight of the activated carbon.
The sulfur contained in the sulfur-containing activated carbon produced through the activation of the sulfur-containing petcoke according to the present invention may be present in the form of element sulfur, organic sulfur, sulfur oxide, sulfide, or a combination of two or more thereof.
In accordance with the present invention, a method for manufacturing a mercury removal absorbent comprises steps of: introducing a sulfur-containing petcoke into a reactor; and activating the sulfur-containing petcoke in the reactor to obtain a sulfur-containing activated carbon.
The manufacturing method may further comprise pulverizing the sulfur-containing petcoke to have an average particle size of 1 to 1,000 μm prior to the introduction step.
The pulverization step may be followed by size classification to have an average particle size of 1 to 1,000 μm.
The activation may be selected from the water vapor activation, supercritical CO 2 activation, peroxide activation, or a combination of two or more thereof.
Preferably, the activation is water vapor activation.
The water vapor activation includes activating the sulfur-containing petcoke with a water vapor injection rate of 0.1 to 100 ml/min per gram of the sulfur-containing petcoke at a temperature ranging from 500 ℃ to 900 ℃ for 0.5 to 20 hours.
The sulfur-containing activated carbon contains 1 to 20 weight percent of sulfur based on the total weight of the activated carbon.
The reactor as used herein may be a tube type electric furnace or a rotary kiln. For continuous production, the reactor is preferably a rotary kiln. The steam inlet may be positioned to charge the steam towards the top or bottom of the rotary kiln.
The reactor may be maintained at the internal pressure in the range of 1 to 10 bar during the activation step.
[Example 1]
The crude oil was distilled in the atmospheric distillation column and separated into LPG, naphtha, kerosene, and diesel, atmospheric residue, etc. The atmospheric residue obtained in the atmospheric distillation column was distilled under vacuum in the vacuum distillation column and separated into LPG, naphtha, kerosene, diesel, and a vacuum residue. The vacuum residue thus obtained was pyrolyzed into LPG, naphtha, kerosene, diesel, etc., and the unpyrolyzed residue became a sulfur-containing petcoke.
1.5 g of the sulfur-containing petcoke was charged into a tube type electric furnace and subjected to activation at 800 °C under the internal pressure of 5 bar for 6 hours.
In this regard, the steam was fed into the furnace at a rate of 2 ml/min. The sulfur-containing activated carbon obtained after the completion of the activation was measured in regards to the physical and chemical properties. The measurement results are presented in Table 1.
[Example 2]
The procedures were performed in the same manner as described in Example 1, excepting that the activation was carried out in the electric furnace under the internal pressure of 3 bar with the steam fed into the furnace at a rate of 4 ml/min.
[Example 3]
The procedures were performed in the same manner as described in Example 1, excepting that the activation was carried out in the electric furnace under the internal pressure of 2 bar for 9 hours.
[Example 4]
The procedures were performed in the same manner as described in Example 1, excepting that the activation was carried out in the electric furnace at a temperature of 850 °C under the internal pressure of 4 bar.
[Example 5]
The procedures were performed in the same manner as described in Example 1, excepting that the sulfur-containing petcoke was pulverized and size-classified to have an average particle size of 25 to 300 μm prior to the activation and that the activation was carried out in the electric furnace at a temperature of 550 °C under the internal pressure of 7 bar.
[Experimental Example 1]
The activated carbon prepared using the petcoke was evaluated in terms of the mercury adsorption performance. A gas simulating the exhaust gas composed of 12 weight percent of CO 2, 7 weight percent of H 2O, 5 weight percent of O 2, 500 ppm of SO 2, 200 ppm of NO, 65 to 75 ppm of Hg with respect to the total weight of the simulation gas was fed into a fixed bed reactor containing an activated carbon sample. The temperature of the fixed bed reactor was maintained at 140 °C. The 40-minute adsorption performance was evaluated. The evaluation results are presented in FIG. 1, where PetcokeAC shows the mercury adsorption performance of the sulfur-containing activated carbon obtained in Example 5.
A comparison of the mercury adsorption performance was made between the sulfur-containing activated carbons of the present invention and commercial adsorbents as comparative examples, which were GL50 (CABOT), Hg-LH (DARCO), and RBHG3 (CABOT).
Div. Surface area (m 2/g) C (wt.%) S (wt.%)
Example 1 138 89 10
Example 2 157 91 8
Example 3 216 92 7
Example 4 105 91 8
Example 5 612 92 7
As can be seen from the measurements of the mercury removal efficiency for the sulfur-containing activated carbons according to the present invention in FIG. 1, the sulfur-containing activated carbon of Example 5 exhibited the mercury removal efficiency of 94 %. Such a high level of the mercury removal efficiency was shown at the beginning of the adsorption and maintained in a steady and stable manner throughout the use of the sulfur-containing activated carbon.While the present invention has been particularly illustrated and described with reference to exemplary embodiments thereof, various modifications or changes can be made without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the disclosed embodiment, and it should be defined by the scope of the following claims and equivalents thereof.

Claims (14)

  1. A mercury removal absorbent, comprising a sulfur-containing activated carbon prepared by activation of a sulfur-containing petcoke.
  2. The mercury removal absorbent as claimed in claim 1, wherein the sulfur-containing activated carbon has an average particle size of 1 to 1,000 μm.
  3. The mercury removal absorbent as claimed in claim 1, wherein the sulfur-containing activated carbon has a BET specific surface area of 100 to 2,000 m 2/g.
  4. The mercury removal absorbent as claimed in claim 1, wherein the sulfur-containing activated carbon contains 1 to 20 weight percent of sulfur based on to the total weight of the activated carbon.
  5. The mercury removal absorbent as claimed in claim 1, wherein the sulfur contained in the activated carbon is present in the form of organic sulfur, sulfur oxide, element sulfur, sulfide or a combination of two or more thereof.
  6. A method for manufacturing a mercury removal absorbent, comprising:
    (1) introducing a sulfur-containing petcoke into a reactor; and
    (2) activating the sulfur-containing petcoke in the reactor to obtain a sulfur-containing activated carbon.
  7. The method as claimed in claim 6, further comprising:
    pulverizing the sulfur-containing petcoke to have an average particle size of 1 to 1,000 μm prior to the introduction step.
  8. The method as claimed in claim 7, wherein the pulverization step is followed by size classification.
  9. The method as claimed in claim 6, wherein the activation is selected from a group consisting of water vapor activation, supercritical CO 2 activation, peroxide activation, or a combination of two or more thereof.
  10. The method as claimed in claim 9, wherein the activation is water vapor activation.
  11. The method as claimed in claim 10, wherein the water vapor activation includes activating the sulfur-containing petcoke at a temperature ranging from 500 ℃ to 900 ℃ with a water vapor injection rate of 0.1 to 100 ml/min per gram of the sulfur-containing petcoke for 0.5 to 20 hours.
  12. The method as claimed in any one of 6, 7 and 8, wherein the sulfur-containing activated carbon contains 1 to 20 weight percent of sulfur based on the total weight of the activated carbon.
  13. The method as claimed in claim 6, wherein the reactor is a tube type electric furnace or a rotary kiln.
  14. The method as claimed in claim 6, wherein the reactor is maintained at an internal pressure in the range of 1 to 10 bar during the activation step.
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CN116730338A (en) * 2022-03-03 2023-09-12 国家能源投资集团有限责任公司 Activated carbon, preparation method and application thereof, mercury removal activated carbon, and preparation method and application thereof

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WO2008143831A2 (en) * 2007-05-14 2008-11-27 Corning Incorporated Sorbent bodies comprising activated carbon, processes for making them, and their use
US8696931B2 (en) * 2010-10-22 2014-04-15 Futamura Kagaku Kabushiki Kaisha Method of production of activated carbon for removal of mercury gas
WO2014105062A1 (en) * 2012-12-28 2014-07-03 Suncoke Technology And Development Llc. Systems and methods for removing mercury from emissions
CN110252255A (en) * 2019-06-28 2019-09-20 江西理工大学 A kind of preparation method and application of gaseous mercury adsorbent

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Publication number Priority date Publication date Assignee Title
WO2000010914A1 (en) * 1998-08-20 2000-03-02 Roger Etter Production and use of a premium fuel grade petroleum coke
WO2008143831A2 (en) * 2007-05-14 2008-11-27 Corning Incorporated Sorbent bodies comprising activated carbon, processes for making them, and their use
US8696931B2 (en) * 2010-10-22 2014-04-15 Futamura Kagaku Kabushiki Kaisha Method of production of activated carbon for removal of mercury gas
WO2014105062A1 (en) * 2012-12-28 2014-07-03 Suncoke Technology And Development Llc. Systems and methods for removing mercury from emissions
CN110252255A (en) * 2019-06-28 2019-09-20 江西理工大学 A kind of preparation method and application of gaseous mercury adsorbent

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116730338A (en) * 2022-03-03 2023-09-12 国家能源投资集团有限责任公司 Activated carbon, preparation method and application thereof, mercury removal activated carbon, and preparation method and application thereof

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