WO2011102754A2 - Produit d'addition sulfoné de nano-amas de carbone, procédé de fabrication et d'utilisation - Google Patents

Produit d'addition sulfoné de nano-amas de carbone, procédé de fabrication et d'utilisation Download PDF

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Publication number
WO2011102754A2
WO2011102754A2 PCT/RU2011/000078 RU2011000078W WO2011102754A2 WO 2011102754 A2 WO2011102754 A2 WO 2011102754A2 RU 2011000078 W RU2011000078 W RU 2011000078W WO 2011102754 A2 WO2011102754 A2 WO 2011102754A2
Authority
WO
WIPO (PCT)
Prior art keywords
sulfoadduct
sulfuric acid
pitch
adduct
sulfo
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/RU2011/000078
Other languages
English (en)
Russian (ru)
Other versions
WO2011102754A3 (fr
Inventor
Андрей Николаевич ПОНОМАРЁВ
Михаил Евгеньевич ЮДОВИЧ
Александр Алексеевич КОЗЕЕВ
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Individual
Original Assignee
Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of WO2011102754A2 publication Critical patent/WO2011102754A2/fr
Publication of WO2011102754A3 publication Critical patent/WO2011102754A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
    • C10C3/023—Working-up pitch, asphalt, bitumen by chemical means reaction with inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12—Antivirals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • C04B35/62857—Coating fibres with non-oxide ceramics
    • C04B35/62873—Carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83—Carbon fibres in a carbon matrix
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5248—Carbon, e.g. graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/616—Liquid infiltration of green bodies or pre-forms

Definitions

  • the present invention relates to the field of carbon chemistry, and in particular to the preparation of new pitch-based products and their uses.
  • Peks (from gol. Rivers — tar) are the residues from the distillation of tar or tar. Depending on the feedstock, there are coal, peat, wood, oil pecks.
  • Coal tar pitch is obtained from the processing of coal tar.
  • the main components of the pitch are multicore condensed aromatic and heterocyclic compounds, the products of their polymerization and polycondensation.
  • Pitches are spatially-structured disperse systems, do not have specific melting and solidification temperatures, and melt in the range characterized by a softening temperature.
  • medium-temperature coal tar pitch is distinguished
  • Pitches are mainly used to produce electrode (ashless) coke, as a binder for briquetting solid fuels, as raw materials for producing fibers, or as a waterproofing material.
  • carbon nanoclusters are increasingly used in industry.
  • carbon nanoclusters one can mention soot, nanodiamonds, fullerenes, nanotubes, astralenes, graphenes. They were used, in particular, to correct the mobility of concrete mixtures.
  • clusters were used in the form of suspensions, which led to their delamination during storage and use, as well as to the dependence of their properties on temperature and acidity of the medium.
  • Fulleroids are a class of nanocarbon homologs having a frame curved spherical (fullerene) or frame curved non-spherical structure (astralen). Fulleroids are widely studied, but their production at the moment is mainly the result of the application of thin plasma technologies and a very expensive process.
  • the objective of the invention is to obtain alternative types of carbon nanoclusters, as well as the study of products that can be obtained by chemical treatment of the pitch, in particular, when it is treated with sulfuric acid, and their possible applications.
  • the dispersion of the pitch particles changes, resulting in the formation of particles of the submicron range having the structure of condensed aromatic rings with functional sulfonic acid groups.
  • coal tar pitch contains components that can form carbon nanoclusters in large quantities.
  • the inventors found that when treating coal tar pitch with sulfuric acid, two main products are formed, one of which is a mixture of low molecular weight aromatic sulfonic acids, and the other is a mixture of hyperaromatic nanocarbon sulfonic acids.
  • the alkali neutralization of the pitch treated with sulfuric acid leads to contamination of the target product with sodium or ammonium sulfates, which are difficult to dispose of, and which, when used, for example, as a plasticizer for concrete, can have an unpredictable, most often negative effect on the properties of the resulting concrete.
  • the authors also found that neutralization with calcium hydroxide precipitates the salts of the sulfo adduct of carbon nanoclusters, as a result of which the soluble fraction does not contain an active nanocarbon component.
  • aromatic nanocarbon sulfonic acids sulfoadducts of carbon nanoclusters
  • the aromatic nanocarbon sulfonic acids sulfoadducts of carbon nanoclusters discovered by the authors have properties that allow low-temperature carbonization when filling porous bodies and modifying carbon fibers and fabrics, can be used as modifiers for concrete plasticizers, improving their plasticizing properties, and also exhibit powerful antiviral properties being non-toxic in vivo.
  • the pitch of the HTP of the Nizhny Tagil production, the pitch of the HTP of the Cherepovets production and the STP of the Cherepovets production were used.
  • the pitch is ground in an impact mill to achieve a particle size of 0.15 to 1.5 mm, in particular 0.5 to 1.5 mm.
  • Sulfuric acid with a concentration of at least 60% can be used for processing.
  • the milled pitch with sulfuric acid is heated at a temperature of 60-90 ° C, for example at a temperature of 80 ° C, with vigorous stirring under a hood. In this case, a reaction occurs on the surface of the particles, which leads to the production of a powder of submicron dispersion.
  • the reaction is completed when the activity of hydrogen ions (pH) reaches a value of 4-5 units. Residues of sulfuric acid are removed by washing with water.
  • the resulting powder contains a component soluble in polar solvents. It can be separated, for example, in a Soxhlett apparatus.
  • the resulting soluble in polar solvents component can be divided into several fractions, in particular into fractions having different molecular weights, for example, into two fractions: with a higher specific gravity and lower specific gravity, or fractions having a higher and lower molecular weight .
  • the invention provides a single stage of chemical treatment, consisting only in treatment with sulfuric acid, and the acid is removed without the use of additional reagents, and in the process of washing with water.
  • the contribution of the present invention to the state of the art lies in the fact that a particular component or its target fractions for which unexpected useful properties are found are extracted from sulfonated pitch.
  • Example 1 Obtaining a product.
  • Example 1 The water-soluble portion obtained in Example 1 was diluted until the solid phase disappeared and placed on a centrifuge. In a centrifuge with a rotation frequency of more than 12 thousand revolutions per minute for at least 30 minutes, the product is separated by the molecular weight gradient. For example, two fractions are selected: high and low molecular weight. Both solutions are evaporated on a rotary evaporator to obtain dry aromatic fractions of sulfonic adduct carbon nanoclusters ("heavy” and "light”). Before evaporation, a finer additional chromatographic separation of the desired fractions by weight can be carried out.
  • the obtained target fractions retain the solubility properties in polar solvents (water, alcohols) when heated to 120 ° C, and for some fractions to 140 ° C and above. When heated to temperatures above 200 ° C, almost all fractions desulfurize and the solubility property is lost. Thus, the possibility of low-temperature carbonization is achieved when filling porous bodies and modifying ("healing") the surface of carbon fibers and tissues in order to increase their physicomechanical characteristics.
  • the introduction of the obtained target fractions in an amount from 0.1 to 10% of the mass in the composition of plasticizers of concrete mixtures increases the efficiency of their action.
  • the introduction of 3% of the mass of the obtained fraction in the Melflux 1641F hyperplasticizer allows us to switch from the workability index of concrete mix P1 to the index workability P5 with a water-cement ratio of 0.27 and an amount of plasticizer not exceeding 0.12% of the mass relative to the amount of binder.
  • the sulfo-adduct according to the invention can be used as a modifier of plasticizers for concrete, improving their plasticizing and water-reducing properties, and according to the invention also proposes a new modifier of plasticizers for concrete.
  • aqueous solution of the obtained fractions at concentrations from 15 ⁇ g / ml to 400 ⁇ g / ml ensures the suppression of the activity of a wide range of viruses, including the human immunodeficiency virus, without showing cytotoxicity, which allows us to consider the obtained fractions as the active principle of powerful antiviral drugs. Therefore, the sulfo-adduct of the invention can be used as an antiviral agent, and the invention also provides a new antiviral agent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Communicable Diseases (AREA)
  • Oncology (AREA)
  • Civil Engineering (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Virology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Composite Materials (AREA)
  • Inorganic Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Working-Up Tar And Pitch (AREA)

Abstract

L'invention concerne un produit d'addition sulfoné de nano-amas de carbone qui se présente comme un composant soluble dans des solvants polaires d'un produit d'interaction entre le brai de houille et l'acide sulfurique ou sa fraction. Il peut s'utiliser dans la carbonisation à basse température lors du remplissage de corps poreux et la modification de fibres et de tissus de carbone, en tant que modificateur de plastifiants pour bétons améliorant leur qualités plastifiantes et réductrices d'humidité et manifeste également de puissantes propriétés antivirales.
PCT/RU2011/000078 2010-02-08 2011-02-07 Produit d'addition sulfoné de nano-amas de carbone, procédé de fabrication et d'utilisation Ceased WO2011102754A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2010105074 2010-02-08
RU2010105074/04A RU2478117C2 (ru) 2010-02-08 2010-02-08 Сульфоаддукт нанокластеров углерода и способ его получения

Publications (2)

Publication Number Publication Date
WO2011102754A2 true WO2011102754A2 (fr) 2011-08-25
WO2011102754A3 WO2011102754A3 (fr) 2011-12-01

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PCT/RU2011/000078 Ceased WO2011102754A2 (fr) 2010-02-08 2011-02-07 Produit d'addition sulfoné de nano-amas de carbone, procédé de fabrication et d'utilisation

Country Status (2)

Country Link
RU (1) RU2478117C2 (fr)
WO (1) WO2011102754A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2657595C1 (ru) * 2017-08-15 2018-06-14 Андрей Николаевич Пономарев Коллоидный раствор серебряного углерона

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2576432C2 (ru) * 2013-12-17 2016-03-10 Александр Алексеевич Козеев Способ получения фуллеренполисульфокислоты сульфированием асфальтенов
RU2771546C1 (ru) * 2021-11-09 2022-05-05 Мокроусов Юрий Борисович Сульфоаддукт углерода

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3970690A (en) * 1971-08-02 1976-07-20 Kureha Kagaku Kogyo Kabushiki Kaisha Method for preparing dispersing agent
SU415889A3 (fr) * 1971-08-10 1974-02-15
SU859417A1 (ru) * 1974-05-17 1981-08-30 Восточный научно-исследовательский углехимический институт Способ получени электродного пека
SU1129221A1 (ru) * 1982-09-07 1984-12-15 Архангельский Ордена Трудового Красного Знамени Лесотехнический Институт Им.В.В.Куйбышева Способ получени в жущего дл дорожного строительства
RU1779598C (ru) * 1988-07-21 1992-12-07 Институт Химии Ан Узсср Смазка дл металлических форм
RU2114906C1 (ru) * 1997-06-10 1998-07-10 Тюменский научно-исследовательский и проектный институт природного газа и газовых технологий Уплотнительная смазка для резьбовых соединений
RU2145947C1 (ru) * 1998-08-31 2000-02-27 ОАО Всероссийский научно-исследовательский институт органического синтеза Способ получения пластификатора бетонных смесей
RU2233253C1 (ru) * 2002-10-15 2004-07-27 Урьев Наум Борисович Способ получения пластификатора бетонных смесей

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2657595C1 (ru) * 2017-08-15 2018-06-14 Андрей Николаевич Пономарев Коллоидный раствор серебряного углерона

Also Published As

Publication number Publication date
WO2011102754A3 (fr) 2011-12-01
RU2478117C2 (ru) 2013-03-27
RU2010105074A (ru) 2011-08-20

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