WO2005093018A1 - Produits particulaires lies insolubles - Google Patents

Produits particulaires lies insolubles Download PDF

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Publication number
WO2005093018A1
WO2005093018A1 PCT/US2004/005926 US2004005926W WO2005093018A1 WO 2005093018 A1 WO2005093018 A1 WO 2005093018A1 US 2004005926 W US2004005926 W US 2004005926W WO 2005093018 A1 WO2005093018 A1 WO 2005093018A1
Authority
WO
WIPO (PCT)
Prior art keywords
lubricant
product
mixture
binding agent
particulate
Prior art date
Application number
PCT/US2004/005926
Other languages
English (en)
Inventor
Arthur Ferretti (Deceased)
Original Assignee
WILT, Louise, C.
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 WILT, Louise, C. filed Critical WILT, Louise, C.
Priority to PCT/US2004/005926 priority Critical patent/WO2005093018A1/fr
Priority to CA2554582A priority patent/CA2554582C/fr
Publication of WO2005093018A1 publication Critical patent/WO2005093018A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/34—Other details of the shaped fuels, e.g. briquettes
    • C10L5/36—Shape
    • C10L5/361—Briquettes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
    • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
    • C10L5/105—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with a mixture of organic and inorganic binders

Definitions

  • This invention relates to a bio-based binding agent that is particularly effective when used in conjunction with a process disclosed herein for making impermeable agglomeratges from finely divided minerals, such as coal, and for making insoluble composite materials from particulated lignocellulosics. Many finely divided but otherwise useful materials are neglected or abandoned merely because they contain unwanted moistures; clearly, a low cost means for bonding such materials into durable products with a permanently reduced moisture content would enhance both their utility and value. Providing such a means is a principal objective of this invention. Earlier, attempts were made to adapt techniques disclosed in Applicant's US
  • Patent N° 5,371, 194 Biomass Derived Thermoset Resin
  • N° 5,582,682 Process for Making Celliilosic Composites
  • coalescing may include both direct and indirect transfer of heat generated by compressive friction to the incipient agglomerate.
  • Essential to the dewatering method utilized in this invention is the presence on particulate surfaces of a substance, defined herein as a wet-tack lubricant, in very dilute solution.
  • the preferred wet-tack lubricant is polyethylene oxide (PEO), a non- ironic water-soluble resin particularized by Union Carbide Corporation (UCI), Danbury, CT 06817, in brochure UC-876 5/95-5M.
  • Relevant properties of PEO mentioned in the brochure include: "Lubricity, Friction Reduction, Water
  • hydrophilic PEO in the process of present invention distinguishes it from US patent Ns 5,670,056 of Yoon et al, which utilizes a hydrophobic reagent - preferably, mono unsaturated fatty esters or polysiloxane polymers - to aid mechanical means for dewatering coal-fines. No treatment beyond the dewatering of fine materials, such as agglomeration or bonding, is mentioned or suggested.
  • the hydrophilicity, lubricity, thickening, shear-thinning, and fines affinity of PEO combine to facilitate particulate dewatering, densification and, unexpectedly, bonding during coalition.
  • agglomerates made from mineral particulate by the process of the present invention have no need for the interim strength provided by PEO or supplemental heat; they are inherently insoluble and impermeable and - because they have been subjected to factional heat of compressive coalition - strong and durable. But no appreciable heat is produced during disc pelletizing; therefore, although agglomerates made on these machines are impermeable and insoluble, supplemental heat is needed to obtain a peak strength product.
  • insoluble and impermeable refer to the behavior of a product or substance with respect to water.
  • White's US Patent Ns 4,865,691 exploits a unique property of normally insoluble but water swellable polyvinyl (PVOH) particles: Swollen particles are dispersed in a dilute aqueous suspension of cellulosic fiber which, as excess water is drained, acts as a sieve retaining the swollen PVOH particles within the web. When heated, the entrapped swollen residual free water diffuse into the web and, on cooling, solidify into a paper-reinforcing binder.
  • PVOH polyvinyl
  • PVOH is employed in a dissolved state as a coal-fines binder in the processes described in US patents Ns 4,787,913 of Goleczka, et al, and N2S 4,586,936 and 4,863,485 of Schaffer, et al, they are easily distinguished from the present invention, wherein PVOH is used in an undissolved state. Neither swelling or dissolving PVOH powder is necessary to the present invention.
  • the 'cook-out' (dissolution) temperature of PVOH is specified by the manufacturer, APCI, as below 205°F (93°C) for all grades.
  • the ostensibly-dry composite material must be heated to melt and diffuse the PVOH, preferably while contained in a mold or press.
  • Coalesced composite material with interim strength provided by PEO, may also be processed e.g., molded, rolled, and shaped, and later subjected to heat sufficient to melt and disperse the binding agent, and dry the product.
  • a small amount of PVOH will enhance composite tensile strength and flexibility.
  • small amounts of various lipids, such as paraffin, paraffin emulsions, and stearates and steric acids will enhance composite hydrophobicity.
  • substantially water-insoluble PVOH powder hydrolyzed to a super, fully, or intermediate, extent is deemed suitable for use in this invention, with the higher viscosities (22-72 cps) preferred.
  • the utility of undissolved PVOH powder is not mentioned in APCI's brochure, nor is it disclosed in any other prior art.
  • substantially water-insoluble means a substance that will not dissolve appreciably in water at room temperature, i.e., less that 25% w/w will dissolve in 30 minutes.
  • the use of soluble protein is old in the art of maker paper coatings and adhesives; the process of Krinski, et al, disclosed in US Patent Ns 5,766,331, for making a pigment binder exemplifies such use.
  • a cation binding agent is added to inhibit formation of the insoluble gel created by addition of calcium oxide, or hydroxide, to a protein solution.
  • This gel - termed herein a bio-based binding agent - is a basic and necessary element of the present invention, from which Krinski, et al. '331 is clearly distinguished by its teaching of the inhibition of gel formation - a contrary instruction.
  • US Patent Ns 5,543,164 of Krochta, et al a method for making edible protein-based insoluble film and coating for foods is described.
  • the present invention is readily differentiated from the process of Krochta et al '164, in which: A solution of denatured protein is applied to the exterior of a food item or made into a food wrapping film - rather than incorporated as a necessary reagent in the composition of an industrial product; and, all means for denaturation, including heat, chemical or enzymatic treatment, may be employed - rather than the addition of calcium oxide or hydroxide, the only means found effective in the present invention.
  • alkali denaturation transforms the protein in situ into an insoluble gelatinous material - which during coalition, bonds the particulate and forms a moisture barrier - thereby yielding an insoluble and impermeable agglomerate.
  • Impermeability - which is vital to the ability of sym-fuel to regain a high BTU level and survive all-weather storage and transport - is verified with a simple water-soak test: No weight gain is observed after an agglomerate made by the process of this invention has been immersed in water for 24 hours.
  • the process of this invention is based on the discovery that a dewatered product with insoluble inter-particle bonds can be obtained when an alkali, such as lime, is admixed with a mixture of moist PEO-treated particulate and a soluble protein, and the resulting admixture is coalesced.
  • an alkali such as lime
  • a gelatinous insoluble substance - which acts as a binding agent and a permanent sealant - is formed in situ in the coalesced product.
  • this binding agent provides limited product integrity and strength.
  • coalesced particulate is an inert mineral, such as coal fines
  • the frictional heat that accompanies compressive coalition evaporates residual moisture from the agglomerate making it stronger and more durable - in addition to being insoluble and impermeable.
  • Use of this procedure with lignocellulosic particulate yields an analogous product; however, because only a negligible amount of frictional heat is generated during cellulosic coalition, supplemental heat is required to obtain a substantially dry composite.
  • the binding agent yields an insoluble but not impermeable composite, moisture can be re-absorbed into the lumens and pores of lignocellulosic - unless such penetration is precluded by the addition of a hydrophobizing ingredient to the feedstock mixture, or application of a water- repellant coating to the composite product.
  • a hopper to feed minerals fines ⁇ 1 cm x 0 at a measured rate to a conveyor;
  • a conveyor to transport the fines and hot coalesced product to a heat exchanger / conveyors;
  • An auger-type heat-exchanger-conveyor that effects fines heating and coalesced product transport;
  • a bucket elevator to transport the heated fines to a pug-mill type mixer; •
  • a dispenser that adds a controlled quantity of a solution of a wet-tack lubricant and protein;
  • a hopper to feed metered amounts of an alkali compound to the mixer; and
  • a compression-type dewatering and coalition apparatus such as the briquetting mill indicated.
  • an ostensibly-dry material is dry to the senses but may contain some free water; expressing 'essentially all free water' means expelling from the feedstock an amount of water that will achieve an ostensibly dry condition.
  • PRB Powder River Basin
  • the invention was found to embrace not only the agglomeration of particles of chemically-inert materials, such as coal, but the making of composite materials from particulated lignocellulosics. Distinction is made between agglomerates and composite based on how particles are bonded: in the former, particles are bound to each other with a binding agent; in a composite the particles are embedded, or held, within a binding agent matrix.
  • the lignocellulosic residues of field, forest, farm and paper-making often contain an amount of free water - naturally, or added during refining- that makes their use economically marginal or unacceptable.
  • particulate means either a finely-divided lignocellulosic fiber with an average length of less than about 3 A" with an L/D ratio of no less than about 20, or a particle of a chemically inert substance, i.e., an insoluble, non-reactive, normally infusible material that is no greater than about one cm across.
  • ANALYSIS The Market Value estimate assumes a 1,000 BTU syn-fuel product with a selling price of about $14.50/ton (mine) - based on a rail-delivery distance equal to coal with the same BTU content from Unita Basin-Colorado. At break-even, a liberal allowance of $8/ton total for binding agent and Wyodak coal fines allows a comfortable margin of $6.50/ ton of syn-fuel for other operating costs (labor, energy, repairs, etc,.), leaving the $25/ton tax credit (if available) intact.
  • PEO and binding agent depend on particulate characteristics, such as, particle size and surface area, absorbency and porosity.
  • PEO is a known coal-fines dewatering aid, it was never previously used in combination with a particulate binder - presumably because of its solubility and its purported tendency to resist and/or defeat adhesion.
  • Manufacturing syn-fuel from Wyhodak fines should be profitable enterprise (Table 1., Analysis).
  • a product with ⁇ 15.5% inherent moisture made from fines originally containing 26/4% water would justify an increase of « $l l/ton, from $3.50/ton to $14.50/ton - based on 8400 BTU/lb coal and syn-fuel at » 11,000 BTU/lb.
  • the fundamental objective of this invention is provision of a technically superior and less costly means for dewatering marginal value particulate materials, such as coal fines, and reconstituting such materials into more convenient and valuable forms, e.g., insoluble and impermeable agglomeratges of solid synthetic fuel.
  • Subservient objectives include provision of: • A novel biomass-based binding agent that is useful in the aforesaid reconstitution process and does not entail a heating or drying step per se; - A process of making a synthetic fuel product from coat-fines ordinarily abandoned; • A process for making composite materials from marginal value lignocellulosics.
  • this invention provides a novel and low-cost bio-based binding-agent and a new manufacturing process which - together with orthodox production equipment - comprise a unique system for making products from a variety of particulate feedstocks, including finely-divided lignocellulosic fiber and particles, or fines, of chemically-inert minerals.
  • COALESCED PRODUCT TRIALS (TABLE 3.): Excellent products were obtained with all mineral materials; a limitation (i.e., permeability) was observed in the lignocellulosic composites unless a hydrophobizing agent was added to the feedstock mixture, or a coating was applied to the product.
  • a limitation i.e., permeability
  • BTU syn-fuel briquettes from moist Wyodak (PRB) coal fines with a bio-based binding agent is the preferred embodiment of this invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

L'invention concerne un procédé qui fait intervenir un mélange contenant un agent de liaison et une solution aqueuse d'un lubrifiant de pégosité humide pour fabriquer un produit insoluble à partir d'une matière particulaire. Ce procédé consiste à: ajouter la matière particulaire audit mélange pour obtenir un agent de liaison aqueux libre, un lubrifiant et un additif particulaire; puis entraîner la coalescence de l'additif pour obtenir le produit insoluble. Le produit peut être fabriqué au moyen d'une machine de coalescence telle qu'une machine de briquetage. L'oxyde de polyéthylène est, par exemple, un lubrifiant à pégosité humide. La matière particulaire peut être finement divisée. Le minéral chimiquement inerte, les métaux, les matières carbonifères et lignocellulosiques conjointement avec l'agent de liaison forment ensemble une composition d'origine biologique dotée d'un degré approprié d'alcool polyvinylique. La matière riche en protéines peut être un produit laitier ou du soja, du gluten, un concentré d'isolat de légumineuses, ou de la farine.
PCT/US2004/005926 2004-02-27 2004-02-27 Produits particulaires lies insolubles WO2005093018A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US2004/005926 WO2005093018A1 (fr) 2004-02-27 2004-02-27 Produits particulaires lies insolubles
CA2554582A CA2554582C (fr) 2004-02-27 2004-02-27 Produits particulaires lies insolubles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2004/005926 WO2005093018A1 (fr) 2004-02-27 2004-02-27 Produits particulaires lies insolubles

Publications (1)

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WO2005093018A1 true WO2005093018A1 (fr) 2005-10-06

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010122271A1 (fr) * 2009-04-24 2010-10-28 Gurdebeke Sa Installation et procédé de fabrication de combustible solide de récupération
CN102585955A (zh) * 2011-12-31 2012-07-18 冯恩福 优质圆条式聚化燃料型煤的制备方法
CN108753405A (zh) * 2018-08-21 2018-11-06 芜湖聚焰生物质能源科技有限公司 秸秆生物质燃料的制备方法
CN109135862A (zh) * 2018-07-09 2019-01-04 安徽大地节能科技有限公司 一种生物质燃料粘结剂及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013116A (en) * 1998-02-02 2000-01-11 Major; Billy Joseph Briquette binder composition
US6344078B1 (en) * 1999-05-27 2002-02-05 Corning Incorporated Binder system for honeycomb ceramic bodies and a method for producing said honeycomb bodies

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013116A (en) * 1998-02-02 2000-01-11 Major; Billy Joseph Briquette binder composition
US6344078B1 (en) * 1999-05-27 2002-02-05 Corning Incorporated Binder system for honeycomb ceramic bodies and a method for producing said honeycomb bodies

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010122271A1 (fr) * 2009-04-24 2010-10-28 Gurdebeke Sa Installation et procédé de fabrication de combustible solide de récupération
FR2944803A1 (fr) * 2009-04-24 2010-10-29 Gurdebeke Sa Installation et procede de fabrication de combustible solide de recuperation
CN102585955A (zh) * 2011-12-31 2012-07-18 冯恩福 优质圆条式聚化燃料型煤的制备方法
CN109135862A (zh) * 2018-07-09 2019-01-04 安徽大地节能科技有限公司 一种生物质燃料粘结剂及其制备方法
CN108753405A (zh) * 2018-08-21 2018-11-06 芜湖聚焰生物质能源科技有限公司 秸秆生物质燃料的制备方法

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Publication number Publication date
CA2554582C (fr) 2013-02-05
CA2554582A1 (fr) 2005-10-06

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