US20120172216A1 - High-performance adsorbents based on activated carbon having high meso- and macropososity - Google Patents

High-performance adsorbents based on activated carbon having high meso- and macropososity Download PDF

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US20120172216A1
US20120172216A1 US12/595,728 US59572808A US2012172216A1 US 20120172216 A1 US20120172216 A1 US 20120172216A1 US 59572808 A US59572808 A US 59572808A US 2012172216 A1 US2012172216 A1 US 2012172216A1
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performance adsorbents
activated carbon
performance
adsorbents
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Bertram Böhringer
Sven Fichtner
Jann-Michael Giebelhausen
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Bluecher GmbH
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/44—Elemental carbon, e.g. charcoal, carbon black
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
    • 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
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    • 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
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J20/28014—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 form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • B01J20/28078—Pore diameter
    • B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
    • 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
    • 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
    • C01B32/354—After-treatment
    • C01B32/382—Making shaped products, e.g. fibres, spheres, membranes or foam
    • 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
    • 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
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/306—Surface area, e.g. BET-specific surface
    • 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
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/311—Porosity, e.g. pore volume
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention concerns the adsorption arts. More particularly, the present invention concerns high-performance adsorbents based on activated carbon of high meso- and macroporosity and a process for production thereof and also the use of these high-performance adsorbents, particularly for adsorptive filtering materials, for the food industry (for example for preparing and/or decolorizing food products, for the adsorption of toxins, noxiants and odors, particularly from gas or air streams, for purifying or cleaning gases, particularly air, and liquids, particularly water, for application in medicine or to be more precise pharmacy, and also as sorptive storage media particularly for gases, liquids and the like.
  • Activated carbon has fairly unspecific adsorptive properties and therefore is the most widely used adsorbent. Legislation as well as the rising sense of responsibility for the environment lead to a rising demand for activated carbon.
  • Activated carbon is generally obtained by carbonization (also referred to by the synonyms of smoldering, pyrolysis, burn-out, etc) and subsequent activation of carbonaceous compounds, preferably such compounds as lead to economically reasonable yields. This is because the weight losses through detachment of volatile constituents in the course of carbonization and through the subsequent burn-out in the course of activation are appreciable.
  • carbonization also referred to by the synonyms of smoldering, pyrolysis, burn-out, etc
  • carbonaceous compounds preferably such compounds as lead to economically reasonable yields.
  • Customary starting materials are coconut shells, charcoal and wood (for example wood wastes), peat, bituminous coal, pitches, but also particular plastics which play a certain part in the production of woven activated carbon fabrics for example.
  • Activated carbon is used in various forms: pulverized carbon, splint coal carbon, granulocarbon, molded carbon and also, since the end of the 1970s, spherical activated carbon (“spherocarbon”).
  • Spherical activated carbon has a number of advantages over other forms of activated carbon such as pulverized carbon, splint coal carbon, granulocarbon, molded carbon and the like that make it useful or even indispensable for certain applications: it is free flowing, abrasion resistant or to be more precise dustless, and hard.
  • Spherocarbon is in great demand for particular applications, for example, because of its specific form, but also because of its high abrasion resistance.
  • Spherocarbon is mostly still being produced today by multistage and very costly and inconvenient processes.
  • the best known process consists in producing spherules from bituminous coal tar pitch and suitable asphaltic residues from the petrochemical industry, which are oxidized to render them unmeltable and then smoldered and activated.
  • spherocarbon can also be produced in a multistage process proceeding from bitumen. These multistage processes are very cost intensive and the associated high cost of this spherocarbon prevents many applications wherein spherocarbon ought to be preferable by virtue of its properties.
  • WO 98/07655 A1 describes a process for producing activated carbon spherules wherein a mixture comprising a diisocyanate production distillation residue, a carbonaceous processing aid and if appropriate one or more further additives is processed into free-flowing spherules and subsequently the spherules obtained in this way are carbonized and then activated.
  • the activated carbon known for this purpose from the prior art does have a certain degree of meso- and macroporosity, but that degree is not sufficient in all cases.
  • increasing porosity is often observed to be accompanied by an unwelcome, occasionally unacceptable decrease in mechanical stability or to be more precise abrasion resistance.
  • the fraction of the total pore volume which is ⁇ -counted for by meso- and macropores and the absolute pore volume always sufficient to ensure adequate performance capability and/or an adequate impregnatability (for example impregnation with metals or metal salts) for all applications.
  • This invention relates to high-performance adsorbents based on activated carbon in the form of discrete grains of activated carbon having: (a) at least 70% of the total pore volume formed by pores having pore diameters of more than 20 ⁇ ; (b) a measure of central tendency pore diameter (mean pore diameter) of more than 25 ⁇ ; (c) a BET surface area of at least 1,250 m 2 /g; and (d) an iodine number of at least 1,250 mg/g.
  • Such adsorbents typically have a high meso- and macroporosity, (i.e. a high meso- and macroporous fraction relative to the total pore volume), a large total pore volume and yet retain high stability to abrasion and bursting.
  • Further aspects of the present invention relate to a process for producing the high-performance adsorbents based on activated carbon.
  • the process utilizes a carbonaceous starting material and involves initially carbonizing and subsequently activating the starting material.
  • the activation step is carried out in two stages.
  • the carbonized starting material is initially subjected, in a first activating step in an atmosphere of water vapor, followed by a second activation step in an atmosphere that includes CO 2 .
  • Still further aspects of the present invention relate to a piece of protective apparel that includes the high-performance adsorbents described above.
  • FIG. 1 is a graph illustrating a N 2 adsorption isotherm for a first high-performance adsorbent of the present invention.
  • FIG. 2 is a graph illustrating a N 2 adsorption isotherm for a second high-performance adsorbent of the present invention.
  • the adsorbent to be provided according to the present invention should have a high meso- and macroporosity, i.e., a high meso- and macroporous fraction in relation to the total pore volume and also a large total pore volume, yet at the same time also good mechanical stability, particularly a high stability to abrasion and bursting.
  • micropores refers to pores having pore diameters of up to 20 ⁇ inclusive
  • meopores refers to pores having pore diameters in the range of more than 20 ⁇ (i.e., >20 ⁇ ) to 500 ⁇ inclusive
  • macropores refers to pores having pore diameters of more than 500 ⁇ (i.e., >500 ⁇ ):
  • the present invention proposes—in accordance with a first aspect of the present invention—high-performance adsorbents based on activated carbon in the form of discrete grains of activated carbon, preferably in spherical form, according to claim 1 . Further, in particular advantageous embodiments of the high-performance adsorbents of the present invention are subject matter of the corresponding subclaims.
  • the present invention further provides—in accordance with a second aspect of the present invention—the present invention process for producing the high-performance adsorbents according to the present invention, as more particularly defined in the corresponding process claims.
  • the present invention yet further provides—in accordance with a third aspect of the present invention—the present invention use of the high-performance adsorbents according to the present invention, as more particularly defined in the corresponding use claims.
  • the present invention accordingly provides—in accordance with a first aspect of the present invention—high-performance adsorbents based on activated carbon in the form of discrete grains of activated carbon, preferably in spherical form, these high-performance adsorbents being characterized by the following parameters:
  • the present high-performance adsorbents or to be more precise activated carbons in addition to the aforementioned properties or to be more precise parameters, particularly a high meso- and macropore volume fraction (i.e., a high pore volume fraction due to pores having a pore diameter of more than 20 ⁇ ), are further notable in particular for a large total porosity and a simultaneously large BET surface area.
  • the mechanical strength, particularly the abrasion resistance and the bursting or to be more precise compressive strength, of the present high-performance adsorbents is despite the high total porosity extremely high—in contrast to comparable high-porosity activated carbons of the prior art—so that the present high-performance adsorbents or to be more precise activated carbons are also suitable for applications where they are exposed to large mechanical loads.
  • parameter data are determined using standardized or explicitly indicated methods of determination or using methods of determination familiar per se to one skilled in the art.
  • the parameter data concerning the characterization of the porosity, particularly of the above-specified meso- and macropore fraction i.e., the fraction of the total pore volume of the high-performance adsorbents which is contributed by pores having pore diameters of more than 20 ⁇ ) each follow from the nitrogen isotherm of the activated carbon measured.
  • the measure of central tendency pore diameter is similarly determined on the basis of the respective nitrogen isotherms.
  • the BET method of determining the specific surface area is in principle known as such to one skilled in the art, so that no further details need be furnished in this regard. All BET surface area data are based on the ASTM D6556-04 method of determination.
  • the present invention utilizes the MultiPoint BET (MP-BET) method of determination in a partial pressure range p/p 0 of 0.05 to 0.1.
  • MP-BET MultiPoint BET
  • one special feature of the high-performance adsorbents of the present invention is that they have a very large total pore volume as determined by the Gurvich method, to provide a very large adsorptive capacity in which the meso- and macropore volume fraction (i.e., that is, the pore volume fraction due to pores having pore diameters above 20 ⁇ ) is high, viz. at least 55% of the total pore volume.
  • Gurvich determination of total pore volume is a method of measurement/determination known per se in this field to a person skilled in the art.
  • Gurvich determination of total pore volume reference may be made for example to L. Gurvich (1915), J. Phys. Chem. Soc. Russ. 47, 805, and also to S. Lowell et al., Characterization of Porous Solids and Powders: Surface Area Pore Size and Density, Kluwer Academic Publishers, Article Technology Series, pages 111 et seq.
  • the Gurvich total pore volume of the high-performance adsorbents of the present invention is at least 0.8 cm 3 /g, particularly at least 1.0 cm 3 /g, preferably at least 1.2 cm 3 /g, and can generally attain values of up to 2.0 cm 3 /g, particularly up to 2.5 cm 3 /g, preferably up to 3.0 cm 3 /g, more preferably up to 3.5 cm 3 /g.
  • Gurvich total pore volume of the high-performance adsorbents of the present invention is generally in the range from 0.8 to 3.5 cm 3 /g, particularly 1.0 to 3.5 cm 3 /g, preferably 1.2 to 3.2 cm 3 /g.
  • the meso- and macropore volume of the high-performance adsorbents of the present invention is relatively high in that in general the carbon black method pore volume of the high-performance adsorbents of the present invention which is formed by pores having pore diameters of more than 20 ⁇ (i.e., that is, the meso- and macropore volume) is in the range from 0.4 to 3.3 cm 3 /g, particularly 0.8 to 3.2 cm 3 /g, preferably 1.0 to 3.1 cm 3 /g, more preferably 1.2 to 3.0 cm 3 /g, most preferably 1.2 to 2.8 cm 3 /g.
  • the pore volume formed by pores having pore diameters of more than 20 ⁇ is interchangeably also referred to as “external pore volume”.
  • At least 60%, particularly at least 65%, preferably at least 70%, more preferably at least 75%, most preferably at least 80% of the total pore volume of the high-performance adsorbents of the present invention is formed by the pore volume of pores having pore diameters of more than 20 ⁇ (i.e., that is, in other words, by the meso- and macropore volume).
  • the total pore volume of the high-performance adsorbents of the present invention is formed by the pore volume of pores having pore diameters of more than 20 ⁇ .
  • the aforementioned percentages thus identify that proportion of the total pore volume of the high-performance adsorbents of the present invention which is attributable to the fraction of the so-called external pore volume (i.e., the pore volume formed by pores having pore diameters of more than 20 ⁇ ).
  • the carbon black method of determination is known per se to one skilled in the art (as is the corresponding analysis, including plotting and fixing of the p/p o range), so that no further details are needed in this regard.
  • further details of the carbon black method of determining the pore surface area and the pore volume reference may be made for example to R. W. Magee, Evaluation of the External Surface Area of Carbon Black by Nitrogen Adsorption, Presented at the Meeting of the Rubber Division of the American Chem. Soc., October 1994, for example cited in: Quantachrome Instruments, AUTOSORB-1, AS1 WinVersion 1.50, Operating Manual, OM, 05061, Quantachrome Instruments 2004, Florida, USA, pages 71 ff.
  • the measure of central tendency pore diameter is relatively high in that in general it is at least 30 ⁇ , particularly at least 35 ⁇ , preferably at least 40 ⁇ .
  • the measure of central tendency pore diameter of the high-performance adsorbents of the present invention is in the range from 25 to 75 ⁇ , particularly 30 to 75 ⁇ , preferably 35 to 70 ⁇ , more preferably 40 to 65 ⁇ .
  • BET surface area is relatively large and that it is at least 1250 m 2 /g, preferably at least 1400 m 2 /g, more preferably at least 1500 m 2 /g, most preferably at least 1600 m 2 /g.
  • the BET surface area of the high-performance adsorbents of the present invention is in the range from 1250 m 2 /g to 2800 m 2 /g, particularly 1400 to 2500 m 2 /g, preferably 1500 to 2300 m 2 /g, more preferably 1600 to 2100 m 2 /g.
  • the carbon black method external pore surface area of the high-performance adsorbents of the present invention (i.e., that is, the pore surface area formed by pores having pore diameters of more than 20 ⁇ ) is relatively large, because of the high meso- and macropore fraction, and is generally in the range from 200 to 1000 m 2 /g, particularly 250 to 950 m 2 /g, preferably 350 to 900 m 2 /g, more preferably 400 to 850 m 2 /g.
  • the carbon black method external pore surface area of the high-performance adsorbents of the present invention forms up to 30%, particularly up to 40%, preferably up to 50% of the total pore surface area of the high-performance adsorbents of the present invention.
  • the carbon black method external pore surface area of the high-performance adsorbents of the present invention i.e., that is, the pore surface area formed by pores having pore diameters of more than 20 ⁇
  • the high-performance adsorbents of the present invention have an extremely high butane adsorption and simultaneously an extremely high iodine number, which fact characterizes their property of having excellent adsorption properties with regard to a wide variety of materials to be adsorbed.
  • the ASTM D5742-95/00 butane adsorption of the high-performance adsorbents of the present invention is generally at least 30%, particularly at least 35%, preferably at least 40%.
  • the high-performance adsorbents of the present invention have an ASTM D5742-95/00 butane adsorption in the range from 30% to 80%, particularly 35 to 75% preferably 40 to 70%.
  • the ASTM D4607-94/99 iodine number of the high-performance adsorbents of the present invention is generally at least 1250 mg/g, particularly at least 1300 mg/g, preferably at least 1350 mg/g.
  • the high-performance adsorbents of the present invention preferably have an ASTM D4607-94/99 iodine number in the range from 1250 to 2100 mg/g, particularly 1300 to 2000 mg/g, preferably 1350 to 1900 mg/g.
  • the iodine number can be taken as a measure for available surface area provided by predominantly larger micropores; the aforementioned values of the iodine number of the high-performance adsorbents of the present invention show that the high-performance adsorbents of the present invention simultaneously also have a high microporosity.
  • the high-performance adsorbents of the present invention similarly have high methylene blue and molasses adsorption numbers which together can be taken as a measure of available surface area provided predominantly by meso- and macropores.
  • the methylene blue number or to be more precise the methylene blue adsorption which indicates the amount of methylene blue adsorbed per defined amount of adsorbents, under defined conditions (i.e., the number of ml of a methylene blue standard solution decolorized by a defined amount of dry and pulverized adsorbents), relates to larger micropores and predominantly smaller mesopores and gives an indication of the adsorptive capacity of the high-performance adsorbents of the present invention in relation to molecules comparable in size to methylene blue.
  • the molasses number must be considered a measure of the meso- and macroporosity and indicates the amount of adsorbents which is required to decolorize a standard molasses solution, so that the molasses number gives an indication of the adsorptive capacity of the high-performance adsorbents of the present invention in relation to molecules that are comparable in size to molasses (generally sugar beet molasses).
  • the methylene blue and molasses numbers can be considered a measure of the meso- and macroporosity of the high-performance adsorbents of the present invention.
  • the methylene blue value of the high-performance adsorbents of the present invention which is determined by following the method of CEFIC (Conseil Eurodollaren des Féderations des Industries Chimiques, Avenue Louise 250, Bte 71, B—1050 Brussels, November 1986, European Council of Chemical Manufacturers' Federations, Test Methods for Activated Carbons, Item 2.4 “Methylene blue value”, pages 27/28) is at least 15 ml, particularly at least 17 ml, preferably at least 19 ml, and is generally in the range from 15 to 60 ml, particularly 17 to 50 ml, preferably 19 to 45 ml.
  • the methylene blue value according to the aforementioned CEFIC method is thus defined as the number of ml of a methylene blue standard solution which are decolorized by 0.1 g of dry and pulverized activated carbon. Performing this method requires a glass vessel with ground stopper, a filter and also a methylene blue standard solution prepared as follows: 1200 mg of pure methylene blue dye (corresponding to about 1.5 g of methylene blue to DAB VI [German Pharmacopeia, 6th edition] or equivalent product) are dissolved in water in a 1000 ml volumetric flask, and the solution is allowed to stand for several hours or overnight; to check its strength, 5.0 ml of the solution are diluted with 0.25% (volume fractions) acetic acid to 1.0 l in a volumetric flask and thereafter the absorbance is measured at 620 nm and 1 cm path length, and it has to be 0.840 ⁇ 0.010.
  • the absorbance is higher, it has to be diluted with the computed amount of water; if it is lower, the solution is discarded and made up fresh.
  • the high-performance adsorbents in the form of granular activated carbon are pulverized ( ⁇ 0.1 mm) and then dried to a constant weight at 150° C.
  • Precisely 0.1 g of the spherocarbon is then combined with 25 ml (5 ml) of the methylene blue standard solution in a ground glass flask (A preliminary test has to be carried out to see whether an initial addition of 25 ml of methylene blue standard solution with 5 ml additions or an initial addition of 5 ml of methylene blue standard solution with 1 ml additions can be used.).
  • the flask is shaken until decolorization occurs.
  • a further 5 ml (1 ml) of the methylene blue standard solution are added, and the flask is shaken to the point of decolorization.
  • methylene blue standard solution is repeated in 5 ml amounts (1 ml amounts) as long as decolorization still occurs within 5 minutes.
  • the entire volume of the test solution decolorized by the sample is recorded.
  • the test is repeated to confirm the results obtained.
  • the volume of the methylene blue standard solution in ml which are just decolorized is the methylene blue value of the high-performance adsorbents. It is to be noted in this connection that the methylene blue dye must not be dried, since it is heat sensitive; rather, the water content must be corrected for purely arithmetically.
  • the PACS method molasses number of the high-performance adsorbents of the present invention is at least 300, particularly at least 350, preferably at least 400, and is generally in the range from 300 to 1400, particularly 350 to 1300, preferably 400 to 1250, most preferably 700 to 1200.
  • the molasses number is determined by determining the amount of pulverized high-performance adsorbents based on activated carbon that is needed to decolorize a standard molasses solution. Determination is effected photometrically, and the standard molasses solution is standardized against a standardized activated carbon having a molasses number of 245 and/or 350. For further details in this regard, reference can be made to the two aforementioned prescriptive methods.
  • the high-performance adsorbents of the present invention have a high compressive or bursting strength (resistance to weight loading) and also an extremely high abrasion resistance.
  • the compressive or bursting strength (resistance to weight loading) per grain of activated carbon, in particular per spherule of activated carbon is thus at least 5 newtons, in particular at least 10 newtons and preferably at least 15 newtons.
  • the compressive or bursting strength (resistance to weight loading) per grain of activated carbon, particularly per spherule of activated carbon ranges from 5 to 50 newtons, in particular from 10 to 45 newtons and preferably from 15 to 40 newtons.
  • the abrasion hardness of the high-performance adsorbents of the present invention is also extremely high in that the abrasion resistance when measured by the method of CEFIC (Conseil Europeen des Féderations des Industries Chimiques, Avenue Louise 250, Bte 71, B—1050 Brussels, November 1986, European Council of Chemical Manufacturers' Federations, Test Methods for Activated Carbons, Item 1.6 “Mechanical Hardness”, pages 18/19) is always 100% or virtually 100%. Similarly, when measured according to ASTM D3802 abrasion resistances of the high-performance adsorbents of the present invention of 100% or virtually 100% are always obtained.
  • CEFIC Conseil Europeen des Féderations des Industries Chimiques, Avenue Louise 250, Bte 71, B—1050 Brussels, November 1986, European Council of Chemical Manufacturers' Federations, Test Methods for Activated Carbons, Item 1.6 “Mechanical Hardness”, pages 18/19
  • the applicant company has developed a modified test method on the lines of this CEFIC method in order that more meaningful values may be obtained.
  • the modified method of determination provides a better simulation of the resistance of the sample or to be more precise of the high-performance adsorbents to abrasion or attrition under near actual service conditions.
  • the sample is exposed to standardized conditions for a defined time in a horizontally swinging grinding cup charged with a tungsten carbide ball.
  • the procedure adopted for this purpose is as follows: 200 g of a sample are dried for one hour at (120 ⁇ 2)° C.
  • a circulating air drying cabinet type: Heraeus UT 6060 from Kendro GmbH, Hanau
  • a desiccator over drying agent to room temperature.
  • 50 g of the dried sample are removed and sieved off by means of a sieving machine equipped with an analytical sieve (for example, type: AS 200 control from Retsch GmbH, Hanau) at a swing amplitude of 1.2 mm for ten minutes through an analytical sieve, the analytical sieve being selected depending on the grain distribution of the sample to be measured (for example, analytical sieve of mesh size: 0.315 mm, diameter: 200 mm, height: 50 mm); the subsize grain is discarded.
  • an analytical sieve for example, type: AS 200 control from Retsch GmbH, Hanau
  • the analytical sieve being selected depending on the grain distribution of the sample to be measured (for example, analytical sieve of mesh size: 0.315 mm, diameter: 200 mm, height: 50 mm); the subsize grain is discarded.
  • the abrasion resistance of the high-performance adsorbents of the present invention is at least 75%, particularly at least 80%, preferably at least 85%, more preferably at least 90%, most preferably at least 95%.
  • the high-performance adsorbents of the present invention also have a certain degree of microporosity and thus also a certain micropore surface area (i.e. surface area which is formed by pores having pore diameters of ⁇ 20 ⁇ .
  • the carbon black method micropore surface area of the high-performance adsorbents of the present invention which is formed by pores having pore diameters of ⁇ 20 ⁇ is at least 1000 m 2 /g, particularly at least 1100 m 2 /g, preferably at least 1200 m 2 /g, and is generally in the range from 1000 to 1800 m 2 /g, particularly 1100 to 1600 m 2 /g, preferably 1200 to 1500 m 2 /g.
  • the carbon black method micropore surface area of the high-performance adsorbents of the present invention which is formed by pores having pore diameters of ⁇ 20 ⁇ is at least 30%, particularly at least 40%, preferably at least 50% of the total pore surface area of the high-performance adsorbents of the present invention. More particularly, the carbon black method micropore surface area of the high-performance adsorbents of the invention which is formed by pores having pore diameters of ⁇ 20 ⁇ is in the range from 50 to 90%, particularly 55 to 85%, preferably 60 to 80% of the total pore surface area of the high-performance adsorbents of the present invention.
  • the weight-based adsorbed N 2 volume V ads(wt) of the high-performance adsorbents of the present invention is at least 300 cm 3 /g, particularly at least 350 cm 3 /g, preferably at least 375 cm 3 /g, and is particularly in the range from 300 to 800 cm 3 /g, preferably 350 to 700 cm 3 /g, more preferably 375 to 650 cm 3 /g.
  • the volume-based adsorbed N 2 volume V ads(vol) of the high-performance adsorbents of the present invention determined at a partial pressure p/p 0 of 0.25, is at least 75 cm 3 /cm 3 , particularly at least 100 cm 3 /cm 3 , and is particularly in the range from 75 to 300 cm 3 /cm 3 , preferably 80 to 275 cm 3 /cm 3 , more preferably 90 to 250 cm 3 /cm 3 .
  • the weight-based adsorbed N 2 volume V ads(wt) of the high-performance adsorbents of the present invention determined at a partial pressure p/p 0 of 0.995, is at least 400 cm 3 /g, particularly at least 450 cm 3 /g, and is particularly in the range from 400 to 2300 cm 3 /g, preferably 450 to 2200 cm 3 /g, more preferably 750 to 2100 cm 3 /g.
  • the volume-based adsorbed N 2 volume V ads(vol) of the high-performance adsorbents of the present invention determined at a partial pressure p/p 0 of 0.995, is at least 200 cm 3 /cm 3 , particularly at least 250 cm 3 /cm 3 , and is particularly in the range from 200 to 500 cm 3 /cm 3 , preferably 250 to 400 cm 3 /cm 3 , more preferably 275 to 380 cm 3 /cm 3 .
  • the high-performance adsorbents of the present invention are based on granular, in particular spherical, activated carbon whose measure of central tendency particle diameter, determined to ASTM D2862-97/04, is generally in the range from 0.01 to 2.0 mm, particularly 0.01 to 1.0 mm, preferably 0.05 to 0.09 mm, more preferably 0.1 to 0.8 mm, most preferably 0.15 to 0.7 mm.
  • the ash content of the high-performance adsorbents of the present invention is at most 1%, particularly at most 0.8%, preferably at most 0.6%, more preferably at most 0.5%.
  • the ASTM D2867-04/04 moisture content of the high-performance adsorbents of the present invention is at most 1%, particularly at most 0.5%, preferably at most 0.2%.
  • the high-performance adsorbents of the present invention generally have a bulk density, determined to ASTM B527-93/00, in the range from 150 to 750 g/l, particularly 175 to 650 g/l, preferably 200 to 600 g/l.
  • the present invention provides high-performance adsorbents based on activated carbon in the form of discrete grains of activated carbon, preferably in spherical form, particularly as described above, characterized by the following parameters:
  • the present invention further provides—in accordance with a second aspect of the present invention—the present invention process for producing the high-performance adsorbents according to the present invention.
  • the present invention accordingly provides a process for producing the above-described high-performance adsorbents based on activated carbon, which process comprises a carbonaceous starting material being initially carbonized and subsequently activated, wherein the activation is carried out in two stages, wherein the carbonized starting material is initially subjected, in a first activating step, to an activation in an atmosphere comprising water vapor, followed by a second activating step of activation in an atmosphere comprising CO 2 .
  • the high-performance adsorbents of the present invention are produced using carbonaceous starting materials, in particular sulfonated styrene-divinylbenzene copolymers, particularly sulfonated divinylbenzene-crosslinked polystyrenes, preferably in grain form, more preferably in spherical form.
  • the divinylbenzene content of the sulfonated styrene-divinylbenzene copolymers used as starting materials to produce the high-performance adsorbents of the present invention should particularly be in the range from 1 to 20% by weight, particularly 1 to 15% by weight, preferably 2 to 10% by weight, based on the styrene-divinylbenzene copolymers.
  • the starting copolymers can in principle be selected from the gel type or else from the macroporous type.
  • the sulfonation can be carried out in situ (in particular before and/or during the carbonization), particularly using methods known per se to one skilled in the art, preferably by means of sulfuric acid and/or oleum and/or SO 3 ; this is familiar per se to one skilled in the art (cf. also the prior art described at the beginning).
  • Starting materials which have proven particularly advantageous are the gel-form or macroporous types of the corresponding ion exchange resins or of the corresponding unsulfonated precursors of ion exchange resins which still have to be sulfonated.
  • the carbonization (also known by the synonyms of pyrolysis, burn-out or smoldering) converts the carbonaceous starting polymers to carbon; that is, in other words, the carbonaceous starting material is carbonized.
  • the carbonization is carried out under an inert atmosphere (for example nitrogen) or an at most slightly oxidizing atmosphere.
  • the inert atmosphere of the carbonization in particular if it is carried out at comparatively high temperatures (for example in the range from about 500 to 650° C.) to be admixed with a minor amount of oxygen, in particular in the form of air (for example 1 to 5%) in order that an oxidation of the carbonized polymeric skeleton may be effected and the subsequent activation may thereby be facilitated.
  • the carbonization is carried out at temperatures of 100 to 950° C., particularly 150 to 900° C., preferably 300 to 850° C.
  • the total duration of the carbonization is approximately 30 minutes to approximately 10 hours, particularly approximately 1 hour to approximately 6 hours.
  • the carbonized intermediate product is subjected to an activation resulting, at the end of which, in the present invention's high-performance adsorbents based on activated carbon in grain form, in particular spherical form.
  • the basic principle of the activation is to degrade a portion of the carbon generated during the carbonization, selectively and specifically under suitable conditions. This gives rise to numerous pores, fissures and cracks, and the surface area per unit mass increases appreciably.
  • Activation thus involves a specific burn-out of the carbon. Since carbon is degraded in the course of activation, this operation goes hand in hand with a loss of substance which—under optimal conditions—is equivalent to an increase in the porosity and in the internal surface area and in the pore volume. Activation is therefore carried out under selective or to be more precise policed oxidizing conditions.
  • the special feature of how the high-performance adsorbents of the present invention are produced, as well as the selection of the starting material described above, resides in the specific management of the activation process, in particular in the twostageness of the activation process, wherein the carbonized starting material is initially subjected, in a first activating step, to an activation in an atmosphere comprising water vapor, followed by a second activating step in an atmosphere comprising CO 2 .
  • the studies carried out by the applicant have determined it is surprisingly only the separate performance of these activating steps in the aforementioned order that leads to the desired products.
  • the general procedure is for the first activating step to be carried out at temperatures of 700 to 1300° C., particularly 800 to 1200° C., preferably 850 to 950° C., and/or for a duration of 5 to 24 hours, preferably 5 to 15 hours, particularly 6 to 12 hours.
  • the duration of the first activation stage can be controlled as a function of the attainment of a predetermined iodine number; for example, the first activation stage can be carried out to attainment of an iodine number of at least 1000 mg/g, particularly at least 1250 mg/g.
  • the atmosphere of the first activation stage comprises water vapor, particularly a mixture of water vapor/inert gas, preferably a mixture of water vapor/nitrogen, or consists thereof.
  • the presence of activating gases other than water vapor must be foreclosed in the context of the first activation stage.
  • the amount used of water vapor is 25 to 350 l/h, particularly 50 to 300 l/h, reckoned as water (i.e., liquid water at 25° C. and under atmospheric pressure).
  • the amount used or the mass-based throughput of water vapor should advantageously be 0.01 to 50 l/(h ⁇ kg), particularly 0.02 to 25 l/(h ⁇ kg), preferably 0.02 to 5 l/(h ⁇ kg), reckoned as water (i.e., liquid water at 25° C. and under atmospheric pressure) and based on starting material to be activated with water vapor.
  • the general procedure for the second activating step is for the second activating step to be carried out at temperatures of 700 to 1300° C., particularly 800 to 1200° C., preferably 850 to 950° C., and/or for a duration of 1 to 10 hours, particularly 3 to 8 hours.
  • the atmosphere of the second activation stage comprises CO 2 , particularly pure CO 2 or a mixture of CO 2 /inert gas, particularly a mixture of CO 2 /nitrogen, or consists thereof, and pure carbon dioxide is particularly preferred.
  • the presence of activating gases other than CO 2 in particular the presence of water vapor, must be foreclosed in the context of the second activation stage.
  • the throughput or the amount used of CO 2 is 10 to 250 m 3 /h, particularly 20 to 200 m 3 /h (based on pure CO 2 ).
  • the amount used or the mass-based throughput of CO 2 should advantageously be 0.001 to 100 m 3 /(h ⁇ kg), particularly 0.01 to 50 m 3 /(h ⁇ kg), preferably 0.05 to 10 m 3 /(h ⁇ kg), reckoned as pure gaseous CO 2 under activating conditions, particularly at the respective pressure and the respective temperature, which are selected for the activation, and based on starting material to be activated with CO 2 .
  • the process is typically carried out such that the first and second activation stages merge into each other (for example by changing the activating atmosphere within the same apparatus).
  • Porosity can be adjusted or controlled to specific values by varying the previously specified activating conditions.
  • the high-performance adsorbents of the present invention can thus be custom tailored so to speak.
  • High-performance adsorbents based on activated carbon which combine high meso- and macroporosity with good microporosity and also high stability and abrasion resistance are not known from the prior art.
  • Another welcome aspect is the excellent adsorption behavior to molecules of virtually any desired molecular size due to the presence of all kinds of pores in relatively large amounts or fractions.
  • welcome is the excellent impregnatability of the products of the present invention with catalysts or to be more precise metals or metal salts.
  • the graphs in FIG. 1 and FIG. 2 show N 2 adsorption isotherms for two different high-performance adsorbents of the present invention, which were produced under different activating conditions.
  • the physical-chemical properties of the two high-performance adsorbents of the present invention are also summarized in Table 1 below.
  • a commercially available activated carbon from Kureha is also listed therein with the physical-chemical properties in question.
  • inventive high-performance adsorbents “activated carbon I” and “activated carbon II” recited in Table 1 are each produced as follows: commercially available dried ion exchanger precursors based on divinylbenzene-crosslinked polystyrene copolymers having a divinylbenzene content of about 4% are sulfonated in a conventional manner at temperatures of 100° C. to 150° C. using a sulfuric acid/oleum mixture. This is followed in a conventional manner by carbonization at temperatures up to 850° C. for four hours under nitrogen and subsequently the induction of activation.
  • Inventive activated carbon I was produced by performing the first activation stage (“water vapor activation”) for a duration of about 8.5 hours at about 900° C. with a water vapor throughput of about 100 m 3 /h and the second activation stage (“carbon dioxide activation”) for a duration of about 8.0 hours at about 900° C. with a carbon dioxide throughput of about 35 m 3 /h; in contrast, inventive activated carbon II was produced by performing the first activation stage (“water vapor activation”) for a duration of about 10.5 hours at about 925° C. with a water vapor throughput of about 125 m 3 /h and the second activation stage (“carbon dioxide activation”) for a duration of about 8 hours at about 925° C. with a carbon dioxide throughput of about 40 m 3 /h. After cooling down to room temperature, the inventive products recited in Table 1 are obtained.
  • the present invention further provides—in accordance with a third aspect of the present invention—the present invention use of the high-performance adsorbents according to the present invention.
  • the high-performance adsorbents of the present invention are particularly useful for the adsorption of toxins, noxiants and odors, for example from gas or to be more precise air streams.
  • the high-performance adsorbents of the present invention are further useful for purifying and cleaning gases, particularly for purifying air, and also liquids, such as, in particular, water (for example drinking water treatment). More particularly, the high-performance adsorbents of the present invention are useful for impregnation (for example with catalysts or to be more precise metals or metal salts).
  • the high-performance adsorbents of the present invention are also useful for example for or in the food industry, particularly for preparing and/or decolorizing food products.
  • the high-performance adsorbents of the present invention can further be used in adsorptive filtering materials or to be more precise in the manufacture of adsorptive filtering materials.
  • adsorptive filtering materials are useful in the manufacture of protective apparel in particular, for example protective suits, protective gloves, protective underwear, protective footwear, etc., in particular for the civilian or military sector (for example NBC protection).
  • the high-performance adsorbents of the present invention are further useful in the sector of medicine or pharmacy, particularly as a medicament or medicament constituent.
  • the high-performance adsorbents of the present invention can finally also be used as sorptive storage media for gases and liquids.
  • the high-performance adsorbents of the present invention are distinctly superior to comparable adsorbents of the prior art.

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US10532071B2 (en) 2020-01-14
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