WO2006022599A1 - Procede et equipement de production de graphite exfolie et moyen de l'utiliser - Google Patents

Procede et equipement de production de graphite exfolie et moyen de l'utiliser Download PDF

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Publication number
WO2006022599A1
WO2006022599A1 PCT/SK2005/000016 SK2005000016W WO2006022599A1 WO 2006022599 A1 WO2006022599 A1 WO 2006022599A1 SK 2005000016 W SK2005000016 W SK 2005000016W WO 2006022599 A1 WO2006022599 A1 WO 2006022599A1
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WIPO (PCT)
Prior art keywords
exfoliated graphite
heater
till
graphite
exfoliated
Prior art date
Application number
PCT/SK2005/000016
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English (en)
Other versions
WO2006022599B1 (fr
Inventor
Marian Metke
Galina Metkeova
Peter Ostromecky
Original Assignee
Marian Metke
Galina Metkeova
Peter Ostromecky
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
Priority claimed from SK332-2004A external-priority patent/SK3322004A3/sk
Application filed by Marian Metke, Galina Metkeova, Peter Ostromecky filed Critical Marian Metke
Publication of WO2006022599A1 publication Critical patent/WO2006022599A1/fr
Publication of WO2006022599B1 publication Critical patent/WO2006022599B1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B17/00—Furnaces of a kind not covered by any preceding group
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation
    • C01B32/225—Expansion; Exfoliation
    • 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
    • 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
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/681—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil

Definitions

  • Invention covers production method for exfoliated graphite, equipment for production of exfoliated graphite from expandable intercalation graphite compounds. Furthermore, the invention describes exfoliated graphite with very high adsorption properties and means of its use.
  • intercalation graphite compounds in which graphite is a bearer of positive charges and anions are intercalated between planar layers of graphite crystal lattice.
  • Graphite intercalation compounds are produced by many methods, the main principle of which consists in acting of different oxidants and hosting compounds, which are supposed to be intercalated, on dispersed graphite particles.
  • Nitric acid, hydrogen peroxide, potassium chlorate, ammonium nitrate, potassium dichromate, potassium permanganate and similar compounds (U.S. Pat. No. 4,091,083, U.S. Pat. No. 3,404,061) are mainly used as oxidants.
  • Concentrated sulphuric acid is used as a mixture element with substance, which is to be intercalated, whereas the reaction runs at 60 0 C till 13O 0 C for several hours, many times in the presence of chlorine gas (E. Stumpp., Physics, 1981, 9-16).
  • Expandable intercalated graphite compounds also called the expandable graphite
  • when heated to temperatures over 150 0 C are accompanied by a major volume expansion as the intercalated substances are transformed to a gas state.
  • Industrial production of exfoliated graphite is usually done by feeding of expandable graphite to the burner flame, resulting in creation of a "black snow”.
  • Expansion factor based on conditions varies from 80 till 300 times of original volume, as the result of expansion of graphene layers perpendicular to the surface (EP-B-008512). This property is used for sealing of cables, sealing of gaps for preventing fire propagation in buildings, extinguishing burning metals (mainly sodium, magnesium, aluminum, uranium and titanium) or for protection of melted metals against air in furnaces.
  • burning metals mainly sodium, magnesium, aluminum, uranium and titanium
  • the keystone of which is, that expandable graphite is fed on a plane surface, heated underneath to a temperatures between 200 0 C till 3300 0 C, resulting in very rapid heating of expandable graphite with the temperature rate increase of at least 150°C/s, followed by its rapid volume expansion and reduction of its pouring mass from 2200 kg/m3 to a value in a range of 30 kg/m3 till 10 kg/m3. After passing though the heating part, the product is cooled down in a cooling chamber.
  • Drift of expandable graphite along the heater plane can be provided mechanically, for example by rotating scoops. It is more of advantage if the expandable graphite along with produced exfoliated graphite moves along the heater plane by means of gravity, so that it moves from input to the output section of inclined heater plane. Produced exfoliated graphite continuously falls down at inclined plane with a slope of 5 till 60 degrees.
  • the delay time in the reaction zone and the rate of conversion of the feedstock to exfoliated graphite is controlled. From the point of view of desired properties of resulting exfoliated graphite and to reach the lowest rate of non reacted expandable graphite, it is desirable that the heater plane temperature is between 1050 0 C and 125O 0 C and the heater surface inclination angle is between 25 till 30 degrees.
  • the expanding reaction may be performed in the presence of helium and/or argon.
  • the exfoliated graphite including gaseous products of expansion reaction is fed into a separator, where the exfoliated graphite is separated from the gaseous products.
  • Exfoliated graphite is retrieved from separator and gaseous products are further cleaned in washers and/or are exhausted to the atmosphere.
  • exfoliated graphite may be cooled down in a cooling chamber on the outlet section of heater to less than -2O 0 C by a liquefied gas.
  • the equipment for production of exfoliated graphite contains above all a heater, temperature controllers, storage tank, feeder and a cooling chamber.
  • the heater is inclined having adjustable inclination within a range of 5 till 60 degrees, in the upper part a storage tank including feeder is located and in the lower part on the heater outlet is a cooling chamber.
  • the feeder gas tight seals and separates the heater chamber from the storage tank to prevent the gas flow in the inclined heater to rise by a chimney draft, which could heat up expandable graphite in the storage tank, thus decreasing temperature gradient, which expandable graphite is exposed to at falling to input section of the heater. Heating the expandable graphite while still in the storage tank would result in an uncompleted, therefore undesired expansion reaction.
  • the feeder and/or the storage tank are equipped by a cooler.
  • the equipment for production of exfoliated graphite according this invention has a separator and gas washers, where the separator is attached to the cooling chamber.
  • the cooling chamber in this arrangement has a feeding input for the surrounding air, by which the cooling chamber is cooled down and enables the suction of exfoliated graphite into the separator. Exfoliated graphite is sucked from the cooling chamber into the separators by means of a common fan or an exhauster. After separation of exfoliated graphite apart from gaseous products of expansion reaction, gas products are cleaned and neutralized in the washers and are exhausted to the atmosphere.
  • Exfoliated graphite produced according to this invention dominates by extraordinary adsorption properties, caused mainly by vacancies in graphene layers with sizes of 0,245 nm till 500 nm and violations of bonds between particular parallel graphene layers, so that the distance of graphene layers in the places of violated bonds is bigger than 0,335 nm.
  • exfoliated graphite contains clamps of tubular nanostructures, of which ratio of length to diameter is at least 5: 1 and the diameter of tubular nanoparticles is maximum 500nm.
  • Tubular nanoparticles are connected to the supporting material of exfoliated graphite.
  • Exfoliated graphite produced according to this invention is featured by a low pouring density and by low heat conductivity, will not catch fire or inflame till the temperature of minimum 650 0 C. It has a form of flakes and extrudates mostly with diameter of 0.1 mm till 0.7 mm of dark grey, almost black color, containing 90 till 99.6% of carbon (aside a rest of oxygen), it is hydrophobic, does not contain water nor is easily mixed with water.
  • Exfoliated graphite represents a special physically treated form of graphite and as so, it is ecologically clean and is harmless for health.
  • Graphite is characterized by strong covalent bindings inside the horizontal graphene layer; build by hexagons of carbon atoms 0,142nm from each to the other. Each layer thus creates a giant stable macromolecule, while the bond between individual horizontal layers is
  • each carbon atom is bound to the three other atoms lying in the same layer, while the bond to the fourth atom laying in a parallel surface is much weaker. Exactly this bound is target of creation of intercalated compounds and is expansion area in the production method of exfoliated graphite according to this invention.
  • nanoholes On the attached pictures made by Ultra-High Resolution Field Emission SEM microscope JEOL JSM-7400F notice randomly distributed defects - vacancies of the graphitic structure sized from 0,245nm till 500 nm, we named nanoholes. These nanoholes along with earlier discovered fullerenes and nanotubes make-up kaleidoscope of nano-structures and significantly participate in the extraordinary adsorption properties of exfoliated graphite according to this invention. Size of the nanohole depends on a number of missing carbon atoms in a given graphene macromolecule.
  • Exfoliated graphite produced by the method according to this invention reaches the following values of adsorption of particular substances expressed by grams of adsorbed material per gram of product according to this invention:
  • the exfoliated graphite produced according to this invention can be implemented for adsorption of oils, crude oils, acids, alcohols, cyclic, aromatic hydrocarbons as well as other toxic and chemical substances, for eliminatipn of combat gasses from contaminated areas, to skim anions and cations including heavy metals and radionuclides, as a filling of filters and filtering equipment for drinking water cleaning, for pool water, waste industrial and rain waters, for cleaning of leaks and drains of gas stations, harbors, industrial equipments, industrial and communal waste dumps, as a medium for air filters, cleaning of flue gases and disposal of hazardous substances, as well as a neutron moderator, capturing and storing of radioactive materials.
  • the exfoliated graphite produced according to this invention may also be used as a thermal, electromagnetic and sound insulating material, as a filter for capturing off-gasses and vents from tanks, from automobile tanks in particular, as well as a filter for elimination of odors and bad smells from wines and of alcoholic beverages.
  • Exfoliated graphite is put into a direct contact with oils and/or crude oil products and/or with acids and/or with alcohols and/or with cyclic aromatic hydrocarbons and/or toxic substances where after their adsorption by exfoliated graphite these substances are recuperated by applying of pressure and/or centrifugal force and/or by extraction.
  • Exfoliated graphite is mildly pressed to a specific weight of over 30kg/m3, followed by flowing water solutions and/or waste water where adsorbed anions and/or cations and/or heavy metals and/or radionuclides and these afterwards can be recuperated from the exfoliated graphite.
  • Exfoliated graphite is put into cartridges of through-flow drinking water filters and/or swimming pool filters and/or filtering devices for industrial waste water and/or rain water filters.
  • Exfoliated graphite can be put as background underneath gas stations and/or harbors and/or industrial equipment and/or industrial and municipal waste dumps and is compressed by the weight of a layer. In case of leakage of harmful substances, these are caught in the background layer of exfoliated graphite.
  • Exfoliated graphite will be used as filter filling for fresh air and/or flue gases filters.
  • Exfoliated graphite will be used as a neutron moderator.
  • Exfoliated graphite will be used for collection, solidification, concentration, and storage of radioactive materials.
  • Exfoliated graphite will be used for production of non flammable thermo- insulating panels. It is mixed with binding material and is expanded in a proper form to create plates for thermal, electromagnetic, sound and fire insulation.
  • Exfoliated graphite will be used to improve soil structure. It is put on the soil then covered by a sand layer, which prevents exfoliated graphite to fade away by wind due to its low specific weight. Exfoliated graphite prevents soil to dehydrate, which is very important at fertilization of soil/sand areas.
  • Picture 1 shows the equipment for execution of method according to this invention with adjustable angle of inclination.
  • Picture 2 shows equipment according to picture 1 including separator and a gas washers.
  • Picture 3 is exfoliated graphite scanned by an electron microscope with visible nanoholes.
  • Picture 4 is exfoliated graphite scanned by an electron microscope so that the graphene layers can be seen.
  • Pictures 5 and 6 are exfoliated graphite scanned by an electron microscope, so that the clumps of tubular nanosized particles can be seen.
  • Picture 1 shows equipment for production of exfoliated graphite containing heater I, storage tank 3, feeder 2 and a cooling chamber 4.
  • Heater I is of a pit shape with rectangular cross-section with detachable lid for cleaning purposes.
  • Heater i is heated electrically, where the temperature controller 6 is computer controlled system with a feed-back.
  • Storage tank 3 with feeder 2 is situated in the upper part of the heater I.
  • Cooling chamber 4 is in the lower part on the exit.
  • Feeder 2 consists of a roller with a longitudinal groove through the whole roller length dosing expandable graphite feedstock from the storage tank 3_ while rotating.
  • Lubrication between rolling body and outer surface of feeder 2 is performed by expandable graphite itself. Feeding is not continuous and is regulated by rotation frequency of the roller. Length dimension of the roller of feeder 2 corresponds with width of an input section S of the heater L Feeder 2 hermetically seals and separates pit area of the heater 1 and feeder 3_ and is concealed with a cooler 5.. Cooler 5. is equipped by an air cooled metal ribs. Cooling chamber 4 is of a barrel shape and acts as a collecting area for the produced exfoliated graphite.
  • Example 2 Picture 2 shows equipment for production of exfoliated graphite according to picture 1 amended with a separator 9 and gas washers JJ),
  • LL Separator 9 is a common cyclone separator and is connected to the cooling chamber 4 by a pipe. Cooling chamber 4 has suck-in opening for surrounding air input.
  • separator 9 In the bottom part of separator 9 is a space for short-term storage of produced exfoliated graphite and the separator is equipped with components for holding and filling of sacks by the produced exfoliated graphite 12.
  • the water washer ⁇ _ is connected, followed by the caustic gas washer K), and the cleaned gasses are exhausted H to the atmosphere.
  • Picture 3 shows exfoliated graphite scanned by an electron microscope with visible nanoholes .14.
  • picture 4 is exfoliated graphite scanned by an electron microscope where graphene layers 15., ⁇ 6_ can be seen as well as a captured molecule of foreign substance 17.
  • tubular nanoparticles 18 By catalytic activity of iron compound at reaction of expansion, clamps of tubular nanoparticles 18, has been created.
  • the tubular nanoparticles 18 can be seen on pictures 5 and 6.
  • exfoliated graphite is used as medium in a through-flow filter.
  • the ability to adsorb the metals was monitored. Following values were measured in mg/kg:

Abstract

L'invention concerne le procédé de production de graphite exfolié à partir de graphite dilatable, que l'on entre dans la section d'entrée (8) du plan de l'appareil de chauffage (1), après contact avec le plan chauffé rapidement à une température d'au moins 150 °C/s qui modifie son poids spécifique de 30 kg/m3 à 10 kg/m3. L'appareil de chauffage (1) a une température comprise entre 200 °C et 3300 °C. Le graphite dilatable et le graphite exfolié produit à l'intérieur de l'appareil de chauffage sont déplacés vers la section de sortie (7) et traversent la chambre de refroidissement (4). En outre, l'invention concerne l'équipement qui permet de réaliser ce procédé, qui comporte au moins un appareil de chauffage (1), des régulateurs de température (6), une cuve de stockage (3), un dispositif d'alimentation (2), et une chambre de refroidissement (4). L'appareil de chauffage est doté d'un plan chauffé incliné dont on peut régler l'angle (X) d'inclinaison de 5 à 60 degrés. Le graphite exfolié ainsi produit possède des propriétés d'adsorption extraordinaires; il peut adsorber 20 à 90 fois son poids, grâce aux trous présents dans les couches de graphène (14) dont les dimensions sont comprises entre 0,245nm et 500nm. Le graphite exfolié peut, par exemple, être utilisé pour la filtration et la purification de l'eau de boisson et des gaz, pour l'élimination de catastrophes dues au pétrole, et pour l'isolation contre le rayonnement thermique, électromagnétique et sonore.
PCT/SK2005/000016 2004-08-27 2005-08-26 Procede et equipement de production de graphite exfolie et moyen de l'utiliser WO2006022599A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
SK332-2004A SK3322004A3 (sk) 2004-08-27 2004-08-27 Spôsob výroby exfoliovaného grafitu, zariadenie na jeho vykonávanie, exfoliovaný grafit a spôsoby jeho použitia
SKPP0332-2004 2004-08-27
SKPUV0243-2004 2004-08-31
SK2432004 2004-08-31

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WO2006022599A1 true WO2006022599A1 (fr) 2006-03-02
WO2006022599B1 WO2006022599B1 (fr) 2006-05-18

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Cited By (11)

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WO2009050485A1 (fr) * 2007-10-18 2009-04-23 Arvia Technology Limited Traitement de gaz contaminés
WO2011026025A1 (fr) * 2009-08-28 2011-03-03 Bdnp Technologies, Llc Dispositifs et procédés destinés à éliminer des contaminants et d'autres éléments, des composés, et des espèces à partir de fluides
RU2502680C2 (ru) * 2009-02-03 2013-12-27 Алексей Владимирович Тарасевич Способ очистки воды и устройство для его осуществления
US20140081067A1 (en) * 2011-02-25 2014-03-20 William Marsh Rice University Sorption and separation of various materials by graphene oxides
JP2015212267A (ja) * 2007-11-30 2015-11-26 アッヴィ バイオテクノロジー リミテッド タンパク質製剤及びその製造方法
US9309122B2 (en) 2009-11-03 2016-04-12 Centre National De La Recherche Scientifique Preparation of graphene by mechanically thinning graphite materials
IT201600085194A1 (it) * 2016-08-12 2018-02-12 Directa Plus Spa Processo per il trattamento di acque contenenti idrocarburi mediante grafite espansa
US10155039B2 (en) 2012-09-07 2018-12-18 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US11071782B2 (en) 2016-04-20 2021-07-27 Coherus Biosciences, Inc. Method of filling a container with no headspace
US11229702B1 (en) 2015-10-28 2022-01-25 Coherus Biosciences, Inc. High concentration formulations of adalimumab
CN116354340A (zh) * 2023-03-14 2023-06-30 昆明理工大学 一种高质量石墨烯的低成本规模化制备方法

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Cited By (34)

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WO2009050485A1 (fr) * 2007-10-18 2009-04-23 Arvia Technology Limited Traitement de gaz contaminés
US20100251890A1 (en) * 2007-10-18 2010-10-07 Nigel Willis Brown Treatment of contaminated gases
US8317903B2 (en) 2007-10-18 2012-11-27 Arvia Technology Limited Treatment of contaminated gases
US8585803B2 (en) 2007-10-18 2013-11-19 Arvia Technology Limited Treatment of contaminated gases
JP2015212267A (ja) * 2007-11-30 2015-11-26 アッヴィ バイオテクノロジー リミテッド タンパク質製剤及びその製造方法
RU2502680C2 (ru) * 2009-02-03 2013-12-27 Алексей Владимирович Тарасевич Способ очистки воды и устройство для его осуществления
WO2011026025A1 (fr) * 2009-08-28 2011-03-03 Bdnp Technologies, Llc Dispositifs et procédés destinés à éliminer des contaminants et d'autres éléments, des composés, et des espèces à partir de fluides
US9309122B2 (en) 2009-11-03 2016-04-12 Centre National De La Recherche Scientifique Preparation of graphene by mechanically thinning graphite materials
US20140081067A1 (en) * 2011-02-25 2014-03-20 William Marsh Rice University Sorption and separation of various materials by graphene oxides
US9511346B2 (en) * 2011-02-25 2016-12-06 James M. Tour Adsorption of actinides in cationic form from aqueous solutions
US10207000B2 (en) 2012-09-07 2019-02-19 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10780163B2 (en) 2012-09-07 2020-09-22 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10155039B2 (en) 2012-09-07 2018-12-18 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10159733B2 (en) 2012-09-07 2018-12-25 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10159732B2 (en) 2012-09-07 2018-12-25 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10195275B2 (en) 2012-09-07 2019-02-05 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10799585B2 (en) 2012-09-07 2020-10-13 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10286072B2 (en) 2012-09-07 2019-05-14 Coherus Biosciences, Inc. Methods of manufacturing stable aqueous formulations of adalimumab
US10286071B2 (en) 2012-09-07 2019-05-14 Coherus Biosciences, Inc. Syringe containing stable aqueous formulations of adalimumab
US10688183B2 (en) 2012-09-07 2020-06-23 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10716852B2 (en) 2012-09-07 2020-07-21 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10716853B2 (en) 2012-09-07 2020-07-21 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10716854B2 (en) 2012-09-07 2020-07-21 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10722579B2 (en) 2012-09-07 2020-07-28 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10772960B2 (en) 2012-09-07 2020-09-15 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10772959B2 (en) 2012-09-07 2020-09-15 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US10786566B2 (en) 2012-09-07 2020-09-29 Coherus Biosciences, Inc. Stable aqueous formulations of adalimumab
US11229702B1 (en) 2015-10-28 2022-01-25 Coherus Biosciences, Inc. High concentration formulations of adalimumab
US11071782B2 (en) 2016-04-20 2021-07-27 Coherus Biosciences, Inc. Method of filling a container with no headspace
US11576971B2 (en) 2016-04-20 2023-02-14 Coherus Biosciences, Inc. Method of filling a container with no headspace
WO2018029277A1 (fr) * 2016-08-12 2018-02-15 Directa Plus S.P.A. Procédé de traitement d'eau contenant des d'hydrocarbures au moyen de graphite expansé
IT201600085194A1 (it) * 2016-08-12 2018-02-12 Directa Plus Spa Processo per il trattamento di acque contenenti idrocarburi mediante grafite espansa
US10913666B2 (en) 2016-08-12 2021-02-09 Directa Plus S.P.A. Process for treating water containing hydrocarbons by means of expanded graphite
CN116354340A (zh) * 2023-03-14 2023-06-30 昆明理工大学 一种高质量石墨烯的低成本规模化制备方法

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