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WO2017031166A1 - Procédé d'activation de carbone faiblement expansible et dispositif de stockage d'énergie associé - Google Patents

Procédé d'activation de carbone faiblement expansible et dispositif de stockage d'énergie associé Download PDF

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Publication number
WO2017031166A1
WO2017031166A1 PCT/US2016/047281 US2016047281W WO2017031166A1 WO 2017031166 A1 WO2017031166 A1 WO 2017031166A1 US 2016047281 W US2016047281 W US 2016047281W WO 2017031166 A1 WO2017031166 A1 WO 2017031166A1
Authority
WO
WIPO (PCT)
Prior art keywords
heating
carbon
powder
alkali metal
metal hydroxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2016/047281
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English (en)
Inventor
Kishor Purushottam Gadkaree
Jia Liu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corning Inc
Original Assignee
Corning Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Corning Inc filed Critical Corning Inc
Priority to CN201680047038.1A priority Critical patent/CN107922195A/zh
Priority to KR1020187006962A priority patent/KR20180040625A/ko
Publication of WO2017031166A1 publication Critical patent/WO2017031166A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
    • 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
    • C01B32/342—Preparation characterised by non-gaseous activating agents

Definitions

  • the disclosure generally relates to the field of energy storage devices.
  • the disclosure provides a low foaming method of making activated carbon, which method provides improved efficiency and cost benefits.
  • Fig. 1 is a TGA-DSC of the dried green coke powder of Example 1. Detailed Description
  • the disclosed method of making and using provide one or more advantageous features or aspects, including for example as discussed below.
  • Features or aspects recited in any of the claims are generally applicable to all facets of the invention. Any recited single or multiple feature or aspect in any one claim can be combined or permuted with any other recited feature or aspect in any other claim or claims.
  • indefinite article “a” or “an” and its corresponding definite article “the” as used herein means at least one, or one or more, unless specified otherwise.
  • Abbreviations which are well known to one of ordinary skill in the art, may be used (e.g., “h” or “hrs” for hour or hours, “g” or “gm” for gram(s), “mL” for milliliters, and “rt” for room temperature, “nm” for nanometers, and like abbreviations).
  • Alkali activation offers the unique ability to control the pore size distribution of the activated carbon product in the micropore size range (i.e., pores smaller than 2 nm).
  • Such alkali activated carbon has significantly higher capacitance than steam activated carbons, which are dominant commercially.
  • the cost of alkali activation is traditionally much higher than that of steam activation for a number of reasons, including vaporization of alkali metal, corrosion to furnace and crucibles, safety, etc. Due to these concerns, the furnace needs to be designed to handle these factors and hence, is expensive. It is desirable to maximize the throughput in the activation furnace to lower process cost.
  • alkali activation involves: mixing a powder of a carbonaceous raw material and one or more alkali compounds (e.g., KOH, NaOH, K2CO 3 , Na2CC>3, etc.);
  • alkali compounds e.g., KOH, NaOH, K2CO 3 , Na2CC>3, etc.
  • the alkali compound(s) melt and react with carbon material to release gases, with water and hydrogen being the main species.
  • significant volume expansion and foaming can occur, to limiting the amount of material that can be loaded in the crucible and in turn the furnace throughput. For instance, only 20 to 30% of material can be loaded in a crucible by volume. If the amount of volume expansion and foaming can be reduced, then more material can be loaded in a given crucible and the furnace throughput can be improved.
  • the present disclosure provides a different method, where volume expansion and foaming are significantly reduced by controlling the composition of the carbon source material or carbon raw material, specifically, the content of volatile organic compounds (VOCs).
  • VOCs volatile organic compounds
  • a carbon raw material or carbon source material used for activation is typically prepared by heat-treating a carbon-containing material at an elevated temperature to
  • the carbonization temperature is not well controlled.
  • the present disclosure demonstrates that careful control of the carbonization temperature provides control over the VOC content in the carbonized material, which in turn has a significant impact on the amount of expansion/foaming. The resulting activated carbon properties are also greatly influenced.
  • the disclosure provides a method of making activated carbon comprising:
  • VOC volatile organic compound
  • the method can further comprise, for example, a first heating of the resulting milled powder at from 200 to 450 °C, for from 10 mins to 24 hours, in an inert atmosphere.
  • the method can further comprise, for example, making a mixture of the resulting first heated milled powder and an alkali metal hydroxide, and a second heating of the mixture at from 600 to 1,000 °C.
  • the first heating results in a carbon having a VOC content of from 10 to 20 wt%.
  • the first heating is accomplished in an container open to an external atmosphere
  • the second heating is accomplished in a container having a vent.
  • the alkali metal hydroxide can be, for example, powdered KOH
  • the carbon source can be, for example, powdered green coke.
  • the alkali metal hydroxide and the carbon source can be, for example, in a weight ratio of from 1 : 1 to 4: 1.
  • the milled powder has a d50 particle size of from 2 to 300 microns.
  • the drying, milling, and first heating substantially eliminates expansion and foaming of the mixture during the second heating.
  • the second heating can be accomplished, for example, in for 10 mins to 6 hrs in a forming gas, in an inert gas, or in a combination thereof.
  • the disclosure provides a method of making activated carbon, which method provides improved efficiency and cost benefits.
  • the disclosure provides a method for the economic preparation of alkali activated carbon.
  • the disclosed carbonization methods are advantaged for at least the following reasons:
  • the throughput in the activation process can be significantly increased for a given furnace, which can lower process cost.
  • the mixing process is further simplified by foregoing an additive, particularly compared to a liquid additive, which liquid additive present a challenge due to clumping when a liquid is mixed with a solid powder.
  • Cost of the optimized carbonization process can be lowered.
  • the disclosure provides a method for producing activated carbon via chemical activation.
  • a Rodeo green coke from Conoco Phillips was dried in a retort furnace under N 2 purge at 125°C for 16 hrs and then milled to a fine powder having a d50 of about 5 microns.
  • a sample of the powder was tested using TGA-DSC as shown in Fig. 1. Note that significant weight loss started to occur while the weight loss at 1000°C was 13.2%.
  • Portions of the green coke powder were heat treated for 2 hrs in a retort furnace under N 2 purge at 200°C, 400°C, 500°C, and 600°C, respectively. Based on the TGA data, the weight losses at these temperatures correspond to 0.3%, 1.9%, 3.8%, and 6.6%, respectively. Using the 1000°C data point as a reference, the volatile organic compound (VOC) content in these four samples was 12.9%, 11.3%, 9.4%, and 6.6%, respectively.
  • VOC volatile organic compound
  • Each of the four heat treated green coke samples and a dried and milled green coke sample (as control) were mixed with a KOH powder (Sigma- Aldrich catalog # 06103) at a ratio of 1 :2 by weight.
  • Each of the mixed samples was filled into a nickel crucible to about 40% of the volume.
  • Each crucible had a lid having a vent hole in the lid. All five crucibles were loaded in a retort furnace and activated under N 2 purge using the following thermal cycle: ramp at 300°C/hr to 850°C, soak at 850°C for 2 hours, furnace cool to ambient temperature. Photographic images were taken and the material bed depth in each crucible was measured before and after activation.
  • the control sample and the actual samples (images not shown) that were heat treated at 200°C and 400°C showed relatively low levels of volume expansion/foaming.
  • the 500°C sample showed elevated level of foaming and the material in the crucible actually rose through the vent hole on the lid.
  • the 600°C sample showed significantly more foaming and the material overflowed from the crucible. This trend can be attributed to the trend in the VOC content in the green coke samples.
  • Table 1 below shows the volume expansion of the five samples, where the "average normalized expanded volume after activation" is defined as the average material volume in the crucible after activation divided by the initial material mass before activation. The smaller the average normalized expanded volume, the more material that could be filled in the crucible. The data further supported the trend observed in the pictures.
  • Fig. 1 shows a TGA-DSC graph of the dried green coke powder of Example 1.
  • a char was prepared by carbonizing wheat flour at 800°C. The weight loss was
  • the char prepared at 800°C was milled to a fine powder having a dso of about 5 microns and used in the following experiment.
  • the char powder was mixed with a KOH powder (Sigma- Aldrich catalog # 06103) at a ratio of 1 : 1.8 by mass.
  • the mixed powder was filled in four different nickel crucibles (without lid) to different levels: A) about 24 vol%; B) about 33 vol%; C) about 41 vol%; and D) about 49 vol%.
  • the VOC content in the carbon raw material has a significant effect on volume expansion, foaming, or both, during alkali activation.
  • the amount volume expansion, foaming, or both can be significantly reduced so that more carbon material can be filled into a given crucible and furnace. This increases the throughput without new capital investment and lowers the cost of the activation process, which activation is the most expensive step in alkali activated carbon manufacture.
  • too much VOC content is disfavored because the VOCs tend to react with and consume a portion of the KOH so that the KOH ratio may need to be increased to achieve the same level of activation.

Landscapes

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

Abstract

L'invention concerne un procédé de fabrication de charbon actif comprenant : le séchage d'une source de carbone présentant une teneur en composés organiques volatiles (COV) de 10 à 30 % en poids, comme défini ici ; et le broyage de la source de carbone séchée résultante pour obtenir une poudre. Le procédé peut, en outre, comprendre un premier chauffage de la poudre broyée résultante à une température de 200 à 450 °C, pendant une durée de 10 minutes à 24 heures. Le procédé peut, en outre, comprendre la préparation d'un mélange associant la première poudre broyée chauffée résultante et un hydroxyde de métal alcalin, puis la mise en œuvre d'un second chauffage du mélange formé de la poudre broyée et de l'hydroxyde de métal alcalin, comme défini ici.
PCT/US2016/047281 2015-08-17 2016-08-17 Procédé d'activation de carbone faiblement expansible et dispositif de stockage d'énergie associé Ceased WO2017031166A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201680047038.1A CN107922195A (zh) 2015-08-17 2016-08-17 低发泡碳活化方法及其储能装置
KR1020187006962A KR20180040625A (ko) 2015-08-17 2016-08-17 저 발포 탄소 활성화 방법 및 이의 에너지 저장 장치

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562206052P 2015-08-17 2015-08-17
US62/206,052 2015-08-17

Publications (1)

Publication Number Publication Date
WO2017031166A1 true WO2017031166A1 (fr) 2017-02-23

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PCT/US2016/047281 Ceased WO2017031166A1 (fr) 2015-08-17 2016-08-17 Procédé d'activation de carbone faiblement expansible et dispositif de stockage d'énergie associé

Country Status (4)

Country Link
KR (1) KR20180040625A (fr)
CN (1) CN107922195A (fr)
TW (1) TW201708106A (fr)
WO (1) WO2017031166A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4149995A (en) * 1977-12-30 1979-04-17 The Carborundum Company Granular activated carbon manufacture from brown coal treated with concentrated inorganic acid without pitch
EP2325139A1 (fr) * 2008-09-16 2011-05-25 JX Nippon Oil & Energy Corporation Matériau carboné pour condensateur électrique à double couche et procédé de production du matériau carboné
EP2554516A1 (fr) * 2010-03-30 2013-02-06 JX Nippon Oil & Energy Corporation Charbon actif pour électrode de condensateur double couche et procédé de production associé
WO2015017200A1 (fr) 2013-07-31 2015-02-05 Corning Incorporated Activation chimique de carbone comportant au moins un additif
US9136064B2 (en) 2013-07-26 2015-09-15 Corning Incorporated Carbon for high voltage EDLCs

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4149995A (en) * 1977-12-30 1979-04-17 The Carborundum Company Granular activated carbon manufacture from brown coal treated with concentrated inorganic acid without pitch
EP2325139A1 (fr) * 2008-09-16 2011-05-25 JX Nippon Oil & Energy Corporation Matériau carboné pour condensateur électrique à double couche et procédé de production du matériau carboné
EP2554516A1 (fr) * 2010-03-30 2013-02-06 JX Nippon Oil & Energy Corporation Charbon actif pour électrode de condensateur double couche et procédé de production associé
US9136064B2 (en) 2013-07-26 2015-09-15 Corning Incorporated Carbon for high voltage EDLCs
WO2015017200A1 (fr) 2013-07-31 2015-02-05 Corning Incorporated Activation chimique de carbone comportant au moins un additif

Also Published As

Publication number Publication date
TW201708106A (zh) 2017-03-01
KR20180040625A (ko) 2018-04-20
CN107922195A (zh) 2018-04-17

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