WO2020055280A1 - Collagen-containing petroleum sorbent and method for producing same - Google Patents

Collagen-containing petroleum sorbent and method for producing same Download PDF

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WO2020055280A1
WO2020055280A1 PCT/RU2018/000593 RU2018000593W WO2020055280A1 WO 2020055280 A1 WO2020055280 A1 WO 2020055280A1 RU 2018000593 W RU2018000593 W RU 2018000593W WO 2020055280 A1 WO2020055280 A1 WO 2020055280A1
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sorbent
collagen
plasticizer
reticular
hydroxyl groups
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French (fr)
Russian (ru)
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Ефим Семёнович ВАЙНЕРМАН
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Общество с ограниченной ответственностью "ФМ Лаб"
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Priority to PCT/RU2018/000593 priority Critical patent/WO2020055280A1/en
Publication of WO2020055280A1 publication Critical patent/WO2020055280A1/en

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    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • C08H1/06—Macromolecular products derived from proteins derived from horn, hoofs, hair, skin or leather
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof

Definitions

  • the invention relates to the field of environmental protection and can be used to remove liquid hydrocarbons, including oil and oil products, from the surface of the water, as well as other natural and man-made objects.
  • liquid hydrocarbons for reversible sorption including oil, motor oils, and other similar liquids, both from a solid surface and from the surface of water, of reticular polymer poroplasts has been shown.
  • Polymeric reticular poroplasts represent a special class of porous polymeric bodies, the gas-structural elements of which are limited by the edges of their cellular spatial structure (A.A. Berlin, F.A. Shutov. "Chemistry and technology of gas-filled high polymers", Nauka, 1980, p. 177) .
  • the potentially high capacity in relation to liquid hydrocarbons determines the prospects of using reticular poroplasts as oil sorbents.
  • a method of producing a polyurethane sorbent using this method was that the polyurethane sponge was crushed into fragments and treated with an organic compound (trimethylaluminum or diethylzinc), after which it was purged with pure nitrogen gas, exposed in water vapor and again purged with nitrogen.
  • an organic compound trimethylaluminum or diethylzinc
  • the technical problem to be solved by the invention is to develop a sorbent and a method for its production, devoid of the above disadvantages.
  • the technical problem is solved by the method of producing a sorbent of liquid hydrocarbons, namely, that the collagenic reticular poroplast is placed in an aqueous solution of a plasticizer containing hydroxyl groups, kept at a temperature of 10-50 ° C for 10-30 minutes, squeezed, dried and a finished sorbent is obtained with the plasticizer content is from 10 to 50 wt.%.
  • glycerin or ethylene glycol or polyethylene glycol is used as a plasticizer.
  • a sorbent of liquid hydrocarbons which is a collagen reticular porous plastic layer obtained by cryostructure based on collagen-containing dispersions and plasticized by a water-soluble substance containing hydroxyl groups.
  • the foam can be plasticized with glycerol, or ethylene glycol, or polyethylene glycol.
  • collagen reticular poroplasts described in US Pat. 5,494,939.
  • Collagenic reticular poroplasts possess the structure and properties characteristic of polymeric reticular poroplastics and are distinguished by the fact that their polymer skeleton is formed by collagen macromolecules, the formation of which occurs from collagen dispersions provided that the dispersion medium is cured.
  • collagenic reticular poroplasts have a number of properties that provide the possibility of their successful use for sorption of oil and oil products from solid and liquid surfaces, including the surface of sea water.
  • the structure and the physicochemical properties of reticular collagen poroplasts can vary widely by varying the concentration of collagen in the initial dispersion, the conditions of curing of the dispersion medium, the introduction of various functional additives, the nature and reactivity of the crosslinking agent, which ensures the binding of collagen macromolecules to a single mechanically strong structure.
  • collagen poroplasts are able to absorb a certain amount water, as well as insufficient mechanical strength, manifested in the destruction of the structure of the foam during repeated mechanical stress.
  • a method for producing a sorbent of liquid hydrocarbons is as follows.
  • a collagenic reticular poroplast is made by the method described in US Pat. 5.494.939.
  • the result is a mechanically strong foliage material with a solids content of about 10-20%, which has a characteristic reticular structure.
  • the resulting reticular collagen poroplast is plasticized by impregnating it with an aqueous solution of a plasticizer containing hydroxyl groups until the plasticizer concentration in the resulting porous plastic reaches a range of from 10 to 50 wt.%. At concentrations below 10 wt.%, The effect of plasticization is negligible, and its increase above 50 wt.% Is not accompanied by a significant improvement in the properties of the foam.
  • the processing time of the plasticizer depends on the temperature and viscosity of the plasticizer used, it is precisely set in preliminary experiments and ranges from 10 to 30 minutes.
  • the temperature range of the plasticization process is in the range from 10 to 50 degrees C. At lower temperatures, an increase in the viscosity of the plasticizer is observed, and therefore, the processing time increases. At temperatures above 50 degrees C, shrinkage of the poroplast can be observed, accompanied by a deterioration in its properties.
  • Collagen reticular poroplast obtained from a dispersion containing 2 wt.% Chromed collagen chips, 0.5 wt.% Acetic acid collagen solution, 0.5 wt.% Glutaraldehyde by the method described in US Pat. 5,549,939, in the form of a sheet measuring 100x100 mm, 10 mm thick, placed in a 10-fold by weight 20% aqueous glycerol solution and kept therein for 30 minutes at a temperature of 25 degrees.
  • the impregnated with a solution of glycerol foam is removed from the solution of glycerol, squeezed on the mechanical rollers from the remains of the impregnating solution, and dried to air-dry state.
  • the result is a sheet of reticular collagen sorbent containing 12 wt.% Glycerol and having the following characteristics:
  • the amount of absorbed URALS brand oil is 1500%; the number of possible sorption-spin cycles is not less than 50
  • the table shows examples of sorbents obtained by the proposed method, and their characteristics.
  • the oil sorbent obtained according to the invention has a set of properties ensuring its successful practical application for the removal of oil pollution. At the same time, it is not unimportant that, to obtain it, leather wastes generated at any tannery can be used, which ensures a relatively low cost of the sorbent.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to the field of environmental protection and can be used to remove liquid hydrocarbons from bodies of water and solid surfaces. A method of producing a liquid hydrocarbon sorbent consists in that a collagen reticular plastic foam is placed in an aqueous solution of a plasticizer containing hydroxyl groups, held at 10-50°C for 10-30 minutes, squeezed out, and dried, and a finished sorbent is obtained with a plasticizer content of from 10 to 50 wt%. The resulting liquid hydrocarbon sorbent is a collagen reticular plastic foam plasticized by a substance containing hydroxyl groups. Moreover, said plastic foam may be plasticized with glycerin, or ethylene glycol or polyethylene glycol. The sorbent has high strength, high hydrocarbon capacity and a high rate of hydrocarbon sorption.

Description

КОЛЛАГЕНСОДЕРЖАЩИЙ НЕФТЕСОРБЕНТ И СПОСОБ ЕГО  COLLAGEN-CONTAINING OIL AND SORBENT AND METHOD OF ITS
ПОЛУЧЕНИЯ  OBTAINING
Область техники Technical field
Изобретение относится к области охраны окружающей среды и может быть использовано для удаления жидких углеводородов, в том числе нефти и нефтепродуктов, с поверхности воды, а также других природных и техногенных объектов. The invention relates to the field of environmental protection and can be used to remove liquid hydrocarbons, including oil and oil products, from the surface of the water, as well as other natural and man-made objects.
Уровень техники State of the art
В последнее время проблема очистки от нефтяных загрязнений стала особенно актуальной из-за участившихся случаев катастрофических розливов нефти в результате аварий нефтеналивных судов, на нефтепромыслах и нефтепроводах. Recently, the problem of cleaning up oil pollution has become especially urgent due to the frequent cases of catastrophic oil spills as a result of accidents of oil vessels at oil fields and oil pipelines.
Недавно была показана возможность использования для обратимой сорбции жидких углеводородов, включая нефть, моторные масла и другие подобные жидкости, как с твердой поверхности, так и с поверхности воды, ретикулярных полимерных поропластов. Recently, the possibility of using liquid hydrocarbons for reversible sorption, including oil, motor oils, and other similar liquids, both from a solid surface and from the surface of water, of reticular polymer poroplasts has been shown.
Полимерные ретикулярные поропласты представляют собой особый класс пористых полимерных тел, газоструктурные элементы которых ограничены ребрами их ячеистой пространственной структуры (А.А.Берлин, Ф.А.Шутов. «Химия и . технология газонаполненных высокополимеров», Наука, 1980, стр.177). Polymeric reticular poroplasts represent a special class of porous polymeric bodies, the gas-structural elements of which are limited by the edges of their cellular spatial structure (A.A. Berlin, F.A. Shutov. "Chemistry and technology of gas-filled high polymers", Nauka, 1980, p. 177) .
Потенциально высокая емкость по отношению к жидким углеводородам, определяют перспективность использования ретикулярных поропластов как нефтесорбентов. The potentially high capacity in relation to liquid hydrocarbons determines the prospects of using reticular poroplasts as oil sorbents.
Известно применение в качестве сорбента нефти и продуктов ее переработки ретикулярных синтетических пенополиуретанов. (US Patent No. 3,679,058, 1972). Однако, их существенными недостатками является низкая избирательность и относительно невысокая динамика сорбции. С целью улучшения характеристик был предложен ряд методов модификации поверхности полиуретановых сорбентов. Один их них описан в работе Edward Barry et.al, “Advanced oil sorbents using sequential infiltration synthesis”, Journal of Material Chemistry A, 2017. Метод позволяет не только поднять селективность ретикулярного полиуретанового сорбента, но также увеличить его емкость и скорость поглощения сорбентом гидрофобных жидкостей. Способ получения полиуретанового сорбента с использованием данного метода, заключался в том, что полиуретановую губку измельчали на фрагменты и обрабатывали металл органическим соединением (триметилалюминием или диэтилцинком), после чего продували чистым газообразным азотом, экспонировали в парах воды и вновь продували азотом. It is known that reticular synthetic polyurethane foams are used as a sorbent for oil and products of its processing. (US Patent No. 3,679,058, 1972). However, their significant drawbacks are low selectivity and relatively low dynamics of sorption. In order to improve the characteristics, a number of methods for modifying the surface of polyurethane sorbents were proposed. One of them is described in Edward Barry et.al, “Advanced oil sorbents using sequential infiltration synthesis”, Journal of Material Chemistry A, 2017. The method allows not only to increase the selectivity of the reticular polyurethane sorbent, but also to increase its capacity and absorption rate of the hydrophobic sorbent liquids. A method of producing a polyurethane sorbent using this method was that the polyurethane sponge was crushed into fragments and treated with an organic compound (trimethylaluminum or diethylzinc), after which it was purged with pure nitrogen gas, exposed in water vapor and again purged with nitrogen.
Однако, модификация, заключающаяся в формировании на поверхности пор ретикулярного пенополиуретана металлорганического комплексного соединения, представляется весьма сложным и трудно осуществимым в промышленном масштабе процессом. However, the modification, which consists in the formation on the pore surface of the reticular polyurethane foam of an organometallic complex compound, seems to be a very complex and difficult process on an industrial scale.
Сущность изобретения Техническая проблема, решаемая изобретением, заключается в разработке сорбента и способа его получения, лишенных вышеуказанных недостатков. SUMMARY OF THE INVENTION The technical problem to be solved by the invention is to develop a sorbent and a method for its production, devoid of the above disadvantages.
Техническая проблема решается способом получения сорбента жидких углеводородов, заключающимся в том, что коллагеновый ретикулярный поропласт помещают в водный раствор пластификатора, содержащего гидроксильные группы, выдерживают при температуре 10-50 °С в течение 10-30 минут, отжимают, сушат и получают готовый сорбент с содержанием пластификатора от 10 до 50 мас.%. The technical problem is solved by the method of producing a sorbent of liquid hydrocarbons, namely, that the collagenic reticular poroplast is placed in an aqueous solution of a plasticizer containing hydroxyl groups, kept at a temperature of 10-50 ° C for 10-30 minutes, squeezed, dried and a finished sorbent is obtained with the plasticizer content is from 10 to 50 wt.%.
Кроме того, в качестве пластификатора используют глицерин, или этиленгликоль, или полиэтиленгликоль. Техническая проблема также решается сорбентом жидких углеводородов, представляющим собой коллагеновый ретикулярный поропласт, полученный методом криоструктурирования на основе коллагенсодержащих дисперсий, и пластифицированный водорастворимым веществом, содержащим гидроксильные группы. In addition, glycerin or ethylene glycol or polyethylene glycol is used as a plasticizer. The technical problem is also solved by a sorbent of liquid hydrocarbons, which is a collagen reticular porous plastic layer obtained by cryostructure based on collagen-containing dispersions and plasticized by a water-soluble substance containing hydroxyl groups.
При этом указанный поропласт может быть пластифицирован глицерином, или этиленгликолем, или полиэтиленгликолем. In this case, the foam can be plasticized with glycerol, or ethylene glycol, or polyethylene glycol.
В качестве альтернативы полиуретановым ретикулярным сорбентам предлагаются коллагеновые ретикулярные поропласты, описанные в патенте US No. 5,494,939. As an alternative to polyurethane reticular sorbents, collagen reticular poroplasts described in US Pat. 5,494,939.
Коллагеновые ретикулярные поропласты обладают характерной для полимерных ретикулярных поропластов структурой и свойствами и отличаются тем, что их полимерный каркас образован макромолекулами коллагена, формирование которого происходит из коллагеновых дисперсий при условии отверждения дисперсионной среды. Collagenic reticular poroplasts possess the structure and properties characteristic of polymeric reticular poroplastics and are distinguished by the fact that their polymer skeleton is formed by collagen macromolecules, the formation of which occurs from collagen dispersions provided that the dispersion medium is cured.
Оказалось, что коллагеновые ретикулярные поропласты обладают целым рядом свойств, обеспечивающих возможность их успешного применения для сорбции нефти и нефтепродуктов с твердой и жидкой поверхности, в том числе, поверхности морской воды. It turned out that collagenic reticular poroplasts have a number of properties that provide the possibility of their successful use for sorption of oil and oil products from solid and liquid surfaces, including the surface of sea water.
При этом структура и комплекс физико-химических свойств ретикулярных коллагеновых поропластов могут меняться в широких пределах путем варьирования концентрации коллагена в исходной дисперсии, условий отверждения дисперсионной среды, введения различных функциональных добавок, природы и реакционной способности сшивающего агента, обеспечивающего связывание макромолекул коллагена в единую механически прочную структуру. Moreover, the structure and the physicochemical properties of reticular collagen poroplasts can vary widely by varying the concentration of collagen in the initial dispersion, the conditions of curing of the dispersion medium, the introduction of various functional additives, the nature and reactivity of the crosslinking agent, which ensures the binding of collagen macromolecules to a single mechanically strong structure.
Однако, существенным недостатком коллагеновых поропластов является невысокая избирательность сорбции: наряду с жидкими углеводородами они способны поглощать определенное количество воды, а также недостаточная механическая прочность, проявляющаяся в разрушении структуры поропласта при многократном механическом воздействии. However, a significant drawback of collagen poroplasts is the low selectivity of sorption: along with liquid hydrocarbons, they are able to absorb a certain amount water, as well as insufficient mechanical strength, manifested in the destruction of the structure of the foam during repeated mechanical stress.
Для устранения этого недостатка предложено пластифицировать коллагеновый ретикулярный поропласт веществом, содержащим гидроксильные группы, например, глицерином, этиленгликолем, или полиэтиленгликолем с молекулярной массой не выше 400 Д.  To eliminate this drawback, it is proposed to plasticize the collagenic reticular poroplast with a substance containing hydroxyl groups, for example, glycerin, ethylene glycol, or polyethylene glycol with a molecular weight of not higher than 400 D.
Получаемый в результате пластифицированный коллагеновый ретикулярный поропласт характеризуется следующими свойствами: The resulting plasticized collagenic reticular poroplast is characterized by the following properties:
-механической прочностью, - mechanical strength
-способностью выдерживать многократные деформации, - ability to withstand repeated deformations,
-селективностью по отношению к жидким углеводородам, -selectivity with respect to liquid hydrocarbons,
-емкостью по углеводородам в интервале от 1000 до 2000 %, - hydrocarbon capacity in the range from 1000 to 2000%,
-высокой скоростью сорбции жидких углеводородов, -high sorption rate of liquid hydrocarbons,
-способностью удерживать сорбированные жидкие углеводороды и десорбировать их в процессе механического прессования или отжима практически без потерь прочности и сорбционной емкости, -диапазоном рабочих температур от - 100 до +120 °С, -возможностью утилизации без нанесения ущерба окружающей среде, - the ability to retain sorbed liquid hydrocarbons and to desorb them during mechanical pressing or extraction with virtually no loss of strength and sorption capacity; - the range of operating temperatures from -100 to +120 ° C; - the possibility of disposal without harming the environment,
-низкой себестоимостью, допускающей широкое промышленное использование. Подобной совокупностью свойств не обладает ни один из известных ретикулярных поропластов, получаемых как из синтетических, так и биополимерных материалов. - low cost, allowing for wide industrial use. A similar set of properties does not possess any of the known reticular poroplasts obtained from both synthetic and biopolymer materials.
Примеры осуществления изобретения Способ получения сорбента жидких углеводородов осуществляют следующим образом. Examples of carrying out the invention A method for producing a sorbent of liquid hydrocarbons is as follows.
На первом этапе изготавливают коллагеновый ретикулярный поропласт способом, описанным в патенте US No. 5.494.939. In a first step, a collagenic reticular poroplast is made by the method described in US Pat. 5.494.939.
Для этого готовят уксуснокислую дисперсию коллагена, в которую вводят хромированные коллагеновые волокна и бифункциональный сшивающий агент. Полученную смесь гомогенизируют, помещают на поддон толщиной слой от 2 до 50 мм, замораживают, выдерживают в замороженном состоянии, размораживают, извлекают из поддона и отжимают от механически связанной влаги. For this, an acetic acid dispersion of collagen is prepared, into which chromium-plated collagen fibers and a bifunctional crosslinking agent are introduced. The resulting mixture is homogenized, placed on a tray with a layer thickness of 2 to 50 mm, frozen, kept frozen, thawed, removed from the tray and squeezed from mechanically bound moisture.
В результате получают механически прочный листвой материал с содержанием сухих веществ порядка 10-20%, обладающий характерной ретикулярной структурой. The result is a mechanically strong foliage material with a solids content of about 10-20%, which has a characteristic reticular structure.
Затем осуществляют пластификацию полученного ретикулярного коллагенового поропласта путем пропитки его водным раствором пластификатора, содержащего гидроксильные группы, до достижения концентрации пластификатора в получаемом поропласте в интервале от 10 до 50 мас.%. При концентрациях ниже 10 мас.% эффект пластификации незначителен, а ее увеличение выше 50 мас.% не сопровождается существенным улучшением свойств поропласта. Then, the resulting reticular collagen poroplast is plasticized by impregnating it with an aqueous solution of a plasticizer containing hydroxyl groups until the plasticizer concentration in the resulting porous plastic reaches a range of from 10 to 50 wt.%. At concentrations below 10 wt.%, The effect of plasticization is negligible, and its increase above 50 wt.% Is not accompanied by a significant improvement in the properties of the foam.
Время обработки пластификатором зависит от температуры и вязкости используемого пластификатора, точно устанавливается в предварительных экспериментах и составляет величину от 10 до 30 минут. Температурный интервал проведения процесса пластификации находится в пределах от 10 до 50 град.С. При более низких температурах наблюдается увеличение вязкости пластификатора, и, следовательно, возрастает время обработки. При температурах выше 50 град.С может наблюдаться усадка поропласта, сопровождающаяся ухудшением его свойств. The processing time of the plasticizer depends on the temperature and viscosity of the plasticizer used, it is precisely set in preliminary experiments and ranges from 10 to 30 minutes. The temperature range of the plasticization process is in the range from 10 to 50 degrees C. At lower temperatures, an increase in the viscosity of the plasticizer is observed, and therefore, the processing time increases. At temperatures above 50 degrees C, shrinkage of the poroplast can be observed, accompanied by a deterioration in its properties.
Пример 1. Example 1
Коллагеновый ретикулярный поропласт, полученный из дисперсии, содержащей 2 мас.% хромированной коллагеновой стружки, 0,5 мас.% уксуснокислого раствора коллагена, 0,5 мас.% глутарового диальдегида методом, описанным в патенте US No. 5,549,939, в виде листа размером 100x100 мм, толщиной 10 мм, помещают в 10 кратный по весу 20%-ный водный раствор глицерина и выдерживают в нем в течение 30 минут при температуре 25 град. С. Пропитанный раствором глицерина поропласт извлекают из раствора глицерина, отжимают на механических вальцах от остатков пропитывающего раствора, и высушивают до воздушно-сухого состояния. Collagen reticular poroplast obtained from a dispersion containing 2 wt.% Chromed collagen chips, 0.5 wt.% Acetic acid collagen solution, 0.5 wt.% Glutaraldehyde by the method described in US Pat. 5,549,939, in the form of a sheet measuring 100x100 mm, 10 mm thick, placed in a 10-fold by weight 20% aqueous glycerol solution and kept therein for 30 minutes at a temperature of 25 degrees. C. The impregnated with a solution of glycerol foam is removed from the solution of glycerol, squeezed on the mechanical rollers from the remains of the impregnating solution, and dried to air-dry state.
Предложенный сорбент с использованием других модификаторов получали аналогичным образом при тех же условиях. The proposed sorbent using other modifiers was obtained in a similar manner under the same conditions.
В результате получают листовой ретикулярный коллагеновый сорбент, содержащий 12 мас.% глицерина и обладающий следующими характеристиками:  The result is a sheet of reticular collagen sorbent containing 12 wt.% Glycerol and having the following characteristics:
-кажущаяся плотность - 50 кг/куб.м - apparent density - 50 kg / m3
-предел прочности при растяжении - 75 кРа  tensile strength - 75 kPa
- количество поглощаемой нефти марки «URALS» - 1500% -число возможных циклов сорбция-отжим - не менее 50  - the amount of absorbed URALS brand oil is 1500%; the number of possible sorption-spin cycles is not less than 50
-количество воды в отжатой нефти - не более 10 мас.%. В таблице приведены примеры сорбентов, полученных предложенным способом, и их характеристики. - the amount of water in pressed oil is not more than 10 wt.%. The table shows examples of sorbents obtained by the proposed method, and their characteristics.
Таблица  Table
Figure imgf000008_0001
Получаемый согласно изобретения нефтесорбент обладает комплексом свойств, обеспечивающим его успешное практическое применение для удаления нефтяных загрязнений. При этом немаловажным является то обстоятельство, что для его получения могут быть использованы отходы кожевенного производства, образующиеся на любом кожевенном предприятии, что обеспечивает сравнительно низкую себестоимость сорбента.
Figure imgf000008_0001
The oil sorbent obtained according to the invention has a set of properties ensuring its successful practical application for the removal of oil pollution. At the same time, it is not unimportant that, to obtain it, leather wastes generated at any tannery can be used, which ensures a relatively low cost of the sorbent.

Claims

Формула изобретения Claim
1. Способ получения сорбента жидких углеводородов, заключающийся в том, что коллагеновый ретикулярный поропласт помещают в водный раствор пластификатора, содержащего гидроксильные группы, выдерживают при температуре 10-50 °С в течение 10-30 минут, отжимают, сушат и получают готовый сорбент с содержанием пластификатора от 10 до 50 мас.%. 1. A method of producing a sorbent of liquid hydrocarbons, which consists in the fact that the collagenic reticular poroplast is placed in an aqueous solution of a plasticizer containing hydroxyl groups, kept at a temperature of 10-50 ° C for 10-30 minutes, squeezed out, dried and a finished sorbent is obtained containing plasticizer from 10 to 50 wt.%.
2. Способ по п. 1, в котором в качестве пластификатора используют глицерин, или этиленгликоль, или полиэтиленгликоль. 2. The method according to p. 1, in which glycerol, or ethylene glycol, or polyethylene glycol is used as a plasticizer.
3. Сорбент жидких углеводородов, представляющий собой коллагеновый ретикулярный поропласт, пластифицированный веществом, содержащим гидроксильные группы, при содержании пластификатора от 10 до 50 % от массы сорбента. 3. The sorbent of liquid hydrocarbons, which is a collagen reticular poroplast, plasticized with a substance containing hydroxyl groups, with a plasticizer content of 10 to 50% by weight of the sorbent.
4. Сорбент по п. 3, который включает в качестве пластификатора модифицирован глицерином, или этиленгликолем, или полиэтиленгликолем . 4. The sorbent according to claim 3, which includes as a plasticizer modified with glycerol, or ethylene glycol, or polyethylene glycol.
PCT/RU2018/000593 2018-09-11 2018-09-11 Collagen-containing petroleum sorbent and method for producing same WO2020055280A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005121251A1 (en) * 2004-06-07 2005-12-22 Zakrytoe Aktsionernoe Obshchestvo 'ostashkovsky Kozhevenny Zavod' Sheet porous collagen-containing material and method for the production thereof
WO2008013475A1 (en) * 2006-07-26 2008-01-31 Hidex Ltd. Collagenic reticular directed structure foamed plastic and a method for the production thereof.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005121251A1 (en) * 2004-06-07 2005-12-22 Zakrytoe Aktsionernoe Obshchestvo 'ostashkovsky Kozhevenny Zavod' Sheet porous collagen-containing material and method for the production thereof
WO2008013475A1 (en) * 2006-07-26 2008-01-31 Hidex Ltd. Collagenic reticular directed structure foamed plastic and a method for the production thereof.

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