Method of producing adsorbents and supports for catalysts

Abstract

The invention relates to the field of producing spherical aluminium oxide-based adsorbents, desiccants and supports for various catalysts used in oil refining, petrochemical and gas processing processes. Aluminium oxide-based adsorbents and supports are produced from oxygen-containing aluminium compounds having an Аl2О3∙nН2О composition, where 0.25<n<2.0, in the form of aluminium hydroxide or a mixture thereof with aluminium oxide, by rolling a finely ground powder in the presence of seed particles on a rotating disc granulator while simultaneously wetting the powder by spraying with an aqueous binder solution. The formed granules are then treated with water vapour at a temperature of 60-90°С, dried at 60-160°С and calcined at a temperature of 400-1100°С. The following may be used as the binder: water or an aqueous solution of a monobasic alcohol, or of an acid, or of an alkali, or of a soluble metal compound, or of polyethylene glycol. The obtained aluminium oxide-based adsorbents and supports have a high pore volume and specific surface area. The composition and bulk density of the granules of the obtained product may vary within a wide range according to the forming conditions.

Description

[0001] METHOD FOR PRODUCING SPHERICAL ADSORBENTS AND CARRIERS BASED ON ALUMINUM OXIDE FOR CATALYSTS IN OIL REFINING AND PETROCHEMICAL PROCESSES

[0002] Field of technology

[0003] The invention relates to the field of production of spherical adsorbents, desiccants and carriers based on aluminum oxide for catalysts in oil refining, oil and gas chemistry processes.

[0004] Prior art

[0005] To improve the efficiency of various catalytic processes in the petrochemical and oil refining industries, the adsorbents and catalysts used are constantly being improved by optimizing their synthesis parameters and introducing various modifying and active additives. The production of spherical alumina adsorbents and supports remains a topical issue.

[0006] The most common method for producing spherical carriers is the drop molding of a plasticized mass based on aluminum hydroxide, which is carried out either in a layer of hot oil, followed by washing the granules and drying and heat treatment, for example, as described in the method [Patent RF No. 2765118, 2022], or in a layer of kerosene or diesel fraction, followed by neutralization of the granules with an aqueous solution of ammonia and their drying and heat treatment, for example, as described in the methods [Patent RF No. 2560161, 2015; Patent RF No. 2739560, 2020]. The main disadvantage of both variants of the drop molding method is the increased cost of the manufactured products, which is due to the following:

[0007] - the need to use specific technological column equipment in which the stage of forming spherical granules is carried out;

[0008] - increased energy consumption in case of molding in a layer of hot oil;

[0009] - the need to dispose of waste ammonia solutions - in the case of hydrocarbon-ammonia molding;

[0010] - large quantities of wash wastewater in case of washing of formed granules.

[0011] A method for preparing an alumina support for catalysts is known [Patent of the Russian Federation No. 2103059, 1998], according to which it is possible to obtain a spherical support. The spherical support is prepared as follows. The main component of the raw material is an alumina mass in the form of alumina, which is mixed with a number of additives - plasticizing, modifying and burnout. Active oxide and / or reprecipitated aluminum hydroxide are used as a plasticizing additive; solutions of zirconium and / or lanthanum salts in nitric acid are used as a modifying additive, and graphite is used as a burnout additive. After mixing the dry mass, it is peptized by stirring with a nitric acid solution with zirconium and / or lanthanum salts dissolved in it. After mixing the wet mass, it is formed by extrusion to obtain extrudate granules.To produce a spherical carrier, wet extrudates are rolled into balls using a ball rolling machine or other centrifugal rolling device with a rotating disk (a disk granulator). The resulting granules are dried for 24-48 hours and calcined at 1000-1200°C. The main disadvantage of this method and its analogues is its multi-stage nature: first, extrudates (cylinders) are produced, and then the spherical carrier is formed from these cylinders by rolling the extrudate granules.

[0012] A method for producing spherical aluminum oxide is known [Patent of the Russian Federation No. 2096325, 1997], which can be used as a support in the production of a number of catalysts. According to this method, spherical aluminum oxide is prepared by rolling a moistened powder of an oxygen-containing aluminum compound as follows. Initially, aluminum hydroxide is mixed with oxygen-containing aluminum compounds of the general composition Al2O3 nH2O, where 0.25 <n<2,0, с получением смеси, содержащей 10-90% мае. гидроксида алюминия. Кислородсодержащие соединения алюминия могут быть приготовлены различными способами. Далее полученную смесь подвергают механохимической активации в дезинтеграторе путем ударного воздействия при скорости соударения частиц между собой или частями ротора дезинтегратора со скоростью 80-200 м / с. Активированную смесь, а также воду, подают на тарельчатый гранулятор, где её формуют в сферические гранулы диаметром 2-6 мм.Freshly formed granules are conditioned for 1-5 hours in water vapor at a temperature of 25-100°C, then dried and calcined in a stream of air, nitrogen, or flue gases at a temperature of 350-500°C. The resulting spherical aluminum oxide granules have a high specific surface area of ​​340-480 m2. 2 / g. The main disadvantages of this method are the relatively low strength characteristics and low bulk density of the resulting granules, which is due to the very high specific surface area of ​​aluminum oxide. A desiccant adsorbent and a method for its preparation are known [Patent. Russian Federation No. 2455232, 2012], which is used to prepare a spherical adsorbent. According to this method, the adsorbent is prepared as follows. Powder of a nanostructured oxygen-containing aluminum compound of the composition Al2O 3-x (OH) x·nH2O, where 0<x<0.28 and 0.25 <n<2,0, вв ссммеессии с модифицирующей добавкой скатывают на тарельчатом грануляторе сс одновременной подачей воды через форсунки. В качестве модифицирующей добавки используют СаО, и / или Na2О, и / или MgO, и / или один из цеолитов NaA, СаА, NaX, СаХ или их смесь. Свежесформованные гранулы выдерживают 5-21 ч в парах воды при температуре 70-110°С, затем сушат вначале при температуре 20-25°С, затем при 100-120°С и прокаливают в токе осушенного воздуха при температуре 450-600°С. В результате получают сферические гранулы адсорбента- осушителя диаметром 2-10 мм, имеющие удельную поверхность 200-400 м 2 / g and pore volume 0.3-0.4 cm 3 / g. The main disadvantage of this method is the relatively low pore volume of the resulting adsorbent. Furthermore, catalyst supports cannot be produced using this method.

[0013] A selective hydrogenation catalyst and a method for its production are known [Patent of the Russian Federation No. 2490060, 2013], which describe the preparation of an alumina support in the form of extrudates and beads. The support in the form of beads is prepared as follows. Aluminum hydroxide (gibbsite or bayerite) or aluminum oxyhydroxide (boehmite or diaspore) is flash-calcined in a hot gas stream at a temperature of 400-1200°C to obtain an active alumina powder. The resulting powder is crushed and washed with water or an aqueous acid solution. Next, the washed alumina powder is molded in a rotating drum to form balls with a diameter of 0.8-10 mm. It is possible to mold aluminum oxide powder mixed with burnable blowing agents such as wood flour, charcoal, sulfur, tars, plastics or plastic emulsions, polyvinyl alcohol, naphthalene or their analogs.The formed granules are heat-treated at 200-1200°C, followed by hydrothermal treatment by impregnating the granules with water or an aqueous solution of one or more mineral and / or organic acids and then holding the granules in an autoclave at 100-300°C for 1 to 24 hours. Following the hydrothermal treatment, the granules are calcined at 850-1100°C. By varying the conditions of the preparation stages, it is possible to obtain a spherical alumina carrier with a specific surface area of ​​30-130 m. 2 / g. The main disadvantages of this method are:

[0014] - high multi-stage technology of carrier production;

[0015] - increased energy consumption of the method - three stages of high-temperature processing;

[0016] - large quantities of acidic effluent wastewater caused by washing of crushed active aluminum oxide powder;

[0017] - low specific surface area of ​​the resulting carrier.

[0018] The closest in its technical essence to the claimed method is the method for producing spherical aluminum oxide [Patent. Russian Federation No. 2102321, 1998], which can be used as a support in the production of a number of catalysts. This method will be adopted as a prototype of the present invention. According to this method, spherical aluminum oxide is prepared as follows. Oxygen-containing aluminum compounds of the general composition Al2O3 nH2O, where 0.25 <n<2,0, которые могут быть приготовлены различными способами: частичной дегидратацией, термохимической активацией или терморазложением гиббсита или гидроксида алюминия. Сырье подвергают механохимической активации в дезинтеграторе при скорости соударения частиц между собой и с ротором дезинтегратора 80-200 м / с, при этом происходит уменьшение размера частиц сырья. Активированное сырье, а также воду, подают на тарельчатый гранулятор, где его формуют в сферические гранулы диаметром 2-8 мм.Freshly formed granules are kept for 1-5 hours in water vapor at a temperature of 25-100°C, then they are dried and calcined in a stream of air or flue gases at a volumetric velocity of 500-3000 h. -1 and a temperature of 330-900°C. The result is spherical aluminum oxide granules with a specific surface area of ​​150-330 m 2 / g, pore volume 42-53 cm 3 / g and crushing strength of 42-200 kg / cm 2 The main disadvantage of this method is the relatively low pore volume of the resulting adsorbent, which greatly limits the scope of application of the resulting granules as a catalyst support.

[0019] Disclosure of invention

[0020] The objective of the invention is to develop a method for producing spherical adsorbents and carriers based on aluminum oxide for catalysts in oil refining and petrochemical processes in order to expand the range of pore volumes obtained and to expand the range of carriers and adsorbents produced.The problem is solved by proposing a method for producing spherical adsorbents and carriers for catalysts in petrochemical and oil refining processes from a powder of oxygen-containing aluminum compounds of the composition Al2O3 nH2O, where 0.25 <n<2,0, гранулированием путем закатки на вращающейся наклонной тарели тарельчатого гранулятора с одновременным увлажнением посредством распыления связующего, в качестве которого используют воду или водные растворы одноатомного спирта или кислоты, или щелочи, или растворимого соединения металла, или полиэтиленгликоля в массовом соотношении сырьё: связующее в интервале (1,2÷ З,5):1, и последующей обработки сформованных гранул парами воды при температуре 60-90°С, сушки гранул при температуре 60-160°С и прокаливания высушенных гранул при температуре при температуре 400-1100°С.

[0021] Preferably, the powder granulation stage is carried out together with seed particles with a size of no more than 5 mm, which are oxygen-containing aluminum compounds of the composition Al2O3 nH2O, where 0.25 <n<2,0, и / или оксид алюминия, и / или полученные после стадии рассева сформованные гранулы.

[0022] It is possible that oxygen-containing compounds of aluminum of the composition Al2O3·nH2O, where 0.25 <n<2,0, используют тонкоразмолотый гидроксид алюминия или его смесь с оксидом алюминия.

[0023] It is possible that the molded mass additionally contains at least one soluble compound of a metal selected from the series: zirconium, titanium, tin, boron, lanthanum in an amount of 0.1-20.0% by weight of the metal in the finished carrier.

[0024] It is possible that the molded mass additionally contains a modifying additive in the form of silicon oxide or starch, or dextrin in an amount of 3-20% by weight.

[0025] It is possible that the molded mass additionally contains a modifying additive in the form of zeolite type A, X, L, beta, mordenite, ZSM-22 (TON), ZSM-23 (MTT), zeolite or ferroaluminosilicate with the structure ZSM-5 (MFI) or ZSM-11 (MEL) in the amount of 3-25% by weight in the finished carrier.

[0026] The technical result of the proposed solution is the production of spherical adsorbents and carriers based on aluminum oxide for catalysts in oil refining and petrochemical processes with an extended range of pore volumes and an expansion of the range of produced carriers and adsorbents.

[0027] Adsorbents and supports for spherical catalysts based on aluminum oxide for oil refining and petrochemical processes are obtained as follows. Finely ground powder of oxygen-containing aluminum compounds of the composition Al2O3 nH2O, where 0.25 <n<2,0, в виде гидроксида алюминия или его смеси с оксидом алюминия, возможно в смеси с зародышевыми частицами, возможно в смеси с модифицирующей добавкой, формуют путем закатки на тарельчатом грануляторе с добавлением путем распыления связующего при массовом соотношении сырьё: связующее в интервале (1, 2÷ 3, 5): 1. В качестве связующего применяют воду и / или водный раствор реагента, выбранного из ряда: одноатомный спирт, органическая или минеральная кислота, щелочь, растворимое соединение металла, полиэтиленгликоль. Сформованные гранулы округлой формы обрабатывают парами воды при температуре 60-90°С, затем сушат при температуре 60-160°С, возможно в токе воздуха, и прокаливают при температуре 400-1100°С.Compared to using water as a binder, the use of the above solutions allows for an increase in the strength and / or specific surface area of ​​the formed granules and an expansion of the range of adsorbents and carriers produced.

[0028] It is possible to add seed particles of the aforementioned oxygen-containing aluminum compounds, smaller (no larger than 5 mm) than the granules of the resulting carrier, to the molded mass. To increase the yield of the target carrier fraction and reduce the yield of the smaller fraction, it is advisable to use the fine fraction obtained after screening and separating the target fraction of the molded granules after drying and / or calcination as seed particles.

[0029] In order to expand the range of the obtained adsorbents and carriers, it is possible to add to the molded mass at least a compound of one metal selected from the series: zirconium, titanium, tin, boron, lanthanum, introduced at the molding stage in an amount of 0.1-20.0% by weight of the metal in the finished carrier. To develop a porous system, it is possible to add silicon oxide, or starch or dextrin in an amount of 3-20% by weight in the molded mass and / or zeolite type A, X, L, beta, mordenite, ZSM-22 (TON), ZSM-23 (MTT), zeolite or ferroaluminosilicate with the zeolite structure ZSM-5 (MFI) or ZSM-11 (MEL) in an amount calculated to contain 3-25% by weight in the finished carrier.

[0030] The spherical adsorbents and carriers based on aluminum oxide obtained by the proposed method have a high pore volume - up to 0.85 cm 3 / g and specific surface area - up to 350 m 2 / g. The bulk density of the granules of the resulting carrier and their diameter can vary widely under molding conditions.

[0031] The best embodiment of the invention The essence and applicability of the proposed method for producing spherical adsorbents and carriers based on aluminum oxide for catalysts of various processes of oil refining, oil and gas chemistry are illustrated by the following examples Nos. 1-16 and table No. 1, and the adsorption and catalytic properties of catalysts prepared on their basis are illustrated by examples Nos. 17-22.

[0032] Example 1.

[0033] Spherical granules of the alumina carrier / adsorbent are produced from aluminum-containing raw materials by rolling them onto a rotating inclined plate of a disk granulator while simultaneously moistening them by spraying a binder through nozzles at a raw material / binder weight ratio of 3.0. The raw materials used are 11.5 kg of finely ground thermally activated aluminum hydroxide (TGA) powder with a microparticle size of no more than 20 μm, 0.6 kg of TGA seed particles with a particle size of less than 3 mm, and 4.0 kg of water as a binder. The TGA powder and seed particles are fed into the granulator, moistened with water, and formed into spherical granules. The formed granules are steamed at a temperature of 70°C for 2 hours, dried at a temperature of 60°C for 2 hours, then at 120°C for 2 hours. The dried TGA granules are dispersed, with the fraction less than 3 mm being selected, which is used as seed particles, and the fraction more than 3 mm.Spherical granules with a diameter greater than 3 mm, screened to obtain the target product, are calcined for 4 hours at 480°C in an air stream. The resulting granules, with a diameter of 3-8 mm, have the following characteristics: bulk density - 0.66 g / cm3. 3 , average crushing strength - 9.5 MPa, specific surface area - 262 m 2 / g, pore volume - 0.70 cm 3 / G.

[0034] Example 2.

[0035] Similar to Example 1, with the difference that finely ground TGA powder with a microparticle size of no more than 50 µm is used as raw material in an amount of 12.1 kg, and 4 kg of water is used as a binder at a raw material / binder mass ratio of 3.0. The resulting granules with a diameter of 3-8 mm have the following characteristics: bulk density - 0.66 g / cm 3 , average crushing strength - 9.1 MPa, specific surface area - 254 m 2 / g, pore volume - 0.68 cm 3 / G.

[0036] Example 3.

[0037] Similar to example 1, with the difference that finely ground TGA powder in the amount of 5.5 kg and 0.5 kg of seed particles - Al2O3 granules with a particle size of less than 3 mm - are used as raw materials, a 5% ethyl alcohol solution in the amount of 2.0 kg is used as a binder; the raw material / binder weight ratio is 3.0, the drying and calcination temperatures are 110 ° C and 450 ° C, respectively, and the sieving stage is carried out after calcination of the formed granules. Aluminum oxide granules Al2O3 with a size of less than 3 mm, obtained after the calcination stage and subsequent sieving into a fraction of <3 mm, a fraction of 3-8 mm and a fraction of >8 mm are used as seed particles. Granules with a diameter of 3-8 mm obtained after calcination and sieving have the following characteristics: bulk density - 0.72 g / cm 3 , average crushing strength - 13.2 MPa, specific surface area - 291 m 2 / g, pore volume - 0.66 cm 3 / G.

[0038] Example 4.

[0039] Similar to example 1, except that an acetic acid solution with a pH of 3.0 is used as a binder, the raw material / binder mass ratio is 2.7, and the calcination temperature is 460°C. The granules obtained after calcination and sieving have a diameter of 3-6 mm and the following characteristics: bulk density - 0.85 g / cm 3 , average crushing strength - 15.1 MPa, specific surface area - 288 m 2 / g, pore volume - 0.49 cm 3 / G.

[0040] Example 5.

[0041] Similar to example 1, with the difference that the carrier is obtained from 15 kg of TGA powder, 0.5 kg of TGA seed particles with a granule size of less than 3 mm, 0.5 kg of a modifying additive in the form of starch (3.2% of the TGA weight), 12 kg of a binder - 5% isopropyl alcohol solution, and the mass ratio of raw material to binder is 1.3. The granules obtained after calcination and sieving with a diameter of 3-6 mm have the following characteristics: bulk density - 0.69 g / cm 3, average crushing strength - 6.2 MPa, specific surface area - 282 m 2 / g, pore volume - 0.75 cm 3 / G.

[0042] Example 6.

[0043] Similar to example 1 with the difference that the carrier is obtained from 9 kg of finely ground TGA powder, 1 kg of finely ground γ-Al2O powder 3, 0.5 kg of TGA seed particles with a granule size of less than 3 mm and 4.5 kg of binder - 1% sodium hydroxide solution at a raw material / binder weight ratio of 2.3. The granules obtained after calcination and sieving with a diameter of 3-6 mm have the following characteristics: bulk density - 0.74 g / cm 3 , average crushing strength - 8.5 MPa, specific surface area - 306 m 2 / g, pore volume - 0.52 cm 3 / g and contain 0.3% sodium by weight.

[0044] Example 7. Similar to example 1, with the difference that the steaming temperature is 85°C, drying is 80°C and 120°C, calcination is 500°C, and a 6% boric acid solution is used as a binder with a raw material / binder weight ratio of 2.0. The granules obtained after calcination and screening with a diameter of 3-6 mm have the following characteristics: bulk density - 0.75 g / cm 3 , average crushing strength - 17.5 MPa, specific surface area - 284 m 2 / g, pore volume - 0.48 cm 3 / g and contain 0.56% by weight of boron.

[0045] Example 8.

[0046] Similar to example 1, with the difference that an aqueous solution of lanthanum nitrate with a lanthanum content of 3 g / l is used as a binder with a raw material / binder weight ratio of 3.2. The resulting granules with a diameter of 3-8 mm have the following characteristics: bulk density - 0.73 g / cm 3 , average crushing strength - 8.8 MPa, specific surface area - 276 m 2 / g, pore volume - 0.54 cm 3 / g and contain 0.1% wt. lanthanum.

[0047] Example 9.

[0048] Similar to Example 1, except that 6.5 kg of TGA powder and 0.5 kg of seed particles—Al2O3 granules with a particle size of less than 3 mm—are used as raw materials, and 2.0 kg of an aqueous solution containing 10 g / l of titanium in the form of titanium (III) oxalate and 2% oxalic acid are used as a binder; the raw material / binder weight ratio is 3.5, and the sieving stage is carried out after calcining the formed granules. Aluminum oxide granules less than 3 mm in size, obtained after the calcination and sieving stage of the formed granules, are used as seed particles. The resulting granules with a diameter of 3-8 mm have the following characteristics: bulk density - 0.73 g / cm 3 , average crushing strength - 7.8 MPa, specific surface area - 287 m 2 / g, pore volume - 0.71 cm 3 / g and contain 0.3% by weight of titanium.

[0049] Example 10.

[0050] Similar to example 1, with the difference that the carrier is obtained from 15 kg of TGA powder, 1 kg of TGA seed particles with a granule size of less than 5 mm, 0.5 kg of a modifying additive in the form of dextrin (20% of the TGA weight), 13 kg of a binder - 5% ethanol solution with a raw material / binder weight ratio of 1.2, and the drying temperature of the formed granules is 140 ° C and calcination is 500 ° C. The granules obtained after calcination and sieving with a diameter of 5-8 mm have the following characteristics: bulk density - 0.62 g / cm 3 , average crushing strength - 4.5 MPa, specific surface area - 268 m 2 / g, pore volume - 0.78 cm 3 / G.

[0051] Example 11.

[0052] Similar to example 1 with the difference that the carrier is obtained from 10 kg of powder

[0053] TGA, 0.5 kg of TGA seed particles with a granule size of less than 4 mm and 4.5 kg of binder - 30% polyethylene glycol solution at a raw material / binder weight ratio of 2.3, and the drying temperatures of the formed granules are 70 ° C and 140 ° C and calcination - 500 ° C. The granules obtained after calcination and sieving with a diameter of 4-8 mm have the following characteristics: bulk density - 0.66 g / cm 3 , average crushing strength - 6.5 MPa, specific surface area - 237 m 2 / g, pore volume - 0.72 cm 3 / G.

[0054] Example 12.

[0055] Similar to example 1, with the difference that the carrier is obtained from 9 kg of TGA powder, 1 kg of silica gel (SiO2) powder, 0.5 kg of TGA seed particles with a granule size of less than 3 mm and 3.5 kg of water as a binder with a raw material / binder mass ratio of 3.0. The granules obtained after calcination and sieving with a diameter of 3-8 mm have the following characteristics: bulk density - 0.69 g / cm 3, average crushing strength - 6.8 MPa, specific surface area - 246 m 2 / g, pore volume - 0.65 cm 3 / g and contain 4.4% by weight of silicon.

[0056] Example 13.

[0057] Similar to example 1, with the difference that 6.0 kg of finely ground powder of a mixture of TGA and titanium (IV) hydroxide in a ratio of 3:1 and 0.5 kg of seed particles of aluminum oxide less than 3 mm in size are used as raw materials, a solution of acetic acid with a pH of 3.0 is used as a binder with a raw material / binder weight ratio of 2.7, and a calcination temperature of 750 °C. The granules obtained after calcination and sieving with a diameter of 3-8 mm have the following characteristics: bulk density - 0.76 g / cm 3 , average crushing strength - 8.3 MPa, specific surface area - 211 m 2 / g, pore volume - 0.56 cm 3 / g and contain 10.2% by weight of titanium, the rest is Al2O3.

[0058] Example 14.

[0059] Similar to example 1, with the difference that 6.0 kg of finely ground powder of a mixture of TGA and zirconium (IV) hydroxide in a ratio of 2:1 and 0.5 kg of seed particles of aluminum oxide less than 3 mm in size are used as raw materials, a solution of acetic acid with a pH of 3.0 is used as a binder at a raw material / binder weight ratio of 2.7, and a calcination temperature of 750 °C. The granules obtained after calcination and sieving with a diameter of 3-8 mm have the following characteristics: bulk density - 0.82 g / cm 3 , average crushing strength - 6.7 MPa, specific surface area - 192 m 2 / g, pore volume - 0.59 cm 3 / g and contain 19.3% zirconium by weight, the rest is Al2O3.

[0060] Example 15.

[0061] Similar to Example 1, with the difference that 0.5 kg of seed particles less than 3 mm in size and a powder mixture containing 10.0 kg of finely ground TGA powder and 0.5 kg of ZSM-11 (MEL) zeolite are used as raw materials, with a raw material / binder weight ratio of 2.0, and a steaming temperature of 60°C, drying of 80°C and 120°C, and calcination of 500°C. Granules less than 3 mm in size, obtained by sieving the formed granules after the calcination stage, are used as seed particles. The granules with a diameter of 3-8 mm obtained after calcination and sieving have the following characteristics: bulk density - 0.68 g / cm 3 , average crushing strength - 6.4 MPa, specific surface area - 302 m 2 / g, pore volume - 0.64 cm 3 / g and contain 5.2% by weight of zeolite, the rest is Al2O3.

[0062] Example 16.

[0063] Similar to Example 1, except that 10.0 kg of finely ground TGA powder and 2.2 kg of ferroaluminosilicate with a ZSM-5 zeolite structure (MFI) and 0.5 kg of seed particles less than 3 mm in size are used as raw materials at a raw material / binder weight ratio of 1.5, and the drying temperature is 80°C and 120°C, calcination is 500°C. Granules less than 3 mm in size, obtained by sieving the formed granules after the drying stage, are used as seed particles. The granules with a diameter of 3-8 mm obtained after calcination and sieving have the following characteristics: bulk density - 0.66 g / cm 3 , average crushing strength - 5.2 MPa, specific surface area - 323 m 2 / g, pore volume - 0.76 cm 3 / g and contain 19.6% by weight of zeolite, the rest is Al2O3.

[0064] Example 17.

[0065] The product prepared according to Example No. 1 is used as a support for the production of a catalyst for the partial oxidation of methane to synthesis gas. The support granules are impregnated with an aqueous solution of nickel nitrate to their incipient moisture content. The impregnated granules are dried at 110°C for 3 hours and calcined at 700°C for 4 hours. The resulting catalyst contains 10% by weight nickel. Catalyst testing is carried out in a laboratory setup with a tubular isothermal reactor at a reaction temperature of 850°C, a pressure of 0.11 MPa, and a space velocity of 50,000 h . -1 A gas mixture containing 20% ​​methane and 10% oxygen in a flow of argon is used as feedstock. Under these conditions, methane conversion is 62%, H2 yields are 41%, and CO yields are 48%.

[0066] Example 18.

[0067] The product prepared according to Example No. 1 is used as an adsorbent-desiccant. The static capacity of the adsorbent for water is determined using the desiccator method over sulfuric acid. The established adsorption properties of the adsorbent-desiccant granules: static capacity at 10% air humidity - 6.0 g / 100 g, at 60% humidity - 20 g / 100 g; dynamic capacity - 5.0 g / 100 g at a dew point temperature of -40°C.

[0068] Example 19.

[0069] The product prepared according to Example No. 3 is used as an adsorbent-desiccant. The static capacity of the adsorbent for water was determined using the desiccator method over sulfuric acid. The established adsorption properties of the adsorbent-desiccant granules: static capacity at 10% air humidity - 6.2 g / 100 g, at 60% humidity - 21.7 g / 100 g; dynamic capacity at a dew point temperature of -40°C - 5.2 g / 100 g.

[0070] Example No. 20.

[0071] The support prepared in Example No. 14 is used to produce an n-hexane isomerization catalyst. The support granules are impregnated with an aqueous solution of chloroplatinic acid. The impregnated granules are dried at 110°C for 4 hours and calcined for 2 hours at 550°C in a stream of dry air. The resulting catalyst contains 0.3% by weight of platinum, 0.3% of chlorine, 19.2% of zirconium, and the remainder is Al2O.

[0072] Catalyst testing is conducted in a laboratory setup with a tubular isothermal reactor. The catalyst is activated in a flow of air for 1 hour at a temperature of 450°C, then purged with nitrogen and reduced in a flow of hydrogen at a temperature of 450°C for 6 hours. The catalyst is tested at a temperature of 300°C, a pressure of 3.0 MPa, and a liquid feed space velocity of 1.8 h . -1and the molar ratio of hydrogen to hydrocarbons H2 / CH = 8. Under these conditions, the conversion of n-hexane per pass is 76%, the yield of isoparaffins C6 is 54.9% by weight.

[0073] Example 21. The product prepared in Example No. 16 is used as a support for the production of a benzene hydrogenation catalyst. The support granules are impregnated with an aqueous solution of ammonium tetrachloropalladate. The impregnated granules are dried at 120°C for 3 hours and calcined at 550°C for 4 hours. The resulting catalyst contains 0.5% by weight of palladium, 0.64% chlorine, 19.6% ferroaluminosilicate with a ZSM-5 zeolite structure (MFI), and the remainder is Al2O3.

[0074] Catalyst testing is conducted in a laboratory setup with a tubular isothermal reactor. The catalyst is activated in a flow of air for 1 hour at a temperature of 450°C and then reduced in a flow of hydrogen at a temperature of 500°C for 6 hours. Benzene hydrogenation is carried out at a temperature of 340°C, a pressure of 3.5 MPa, and a liquid feed space velocity of 2.0 h . -1 and the molar ratio of hydrogen to hydrocarbons H2 / C Х N У =8. Under these conditions, the degree of benzene conversion is 82%, and the yield of the C5+ fraction is 75.5% by weight. The C5+ fraction contains 9.5% by weight of C5-C6 paraffins, 12.7% methylcyclopentane, 55.1% cyclohexane, 0.6% toluene, and 22.1% benzene.

[0075] Example 22.

[0076] The product prepared according to Example No. 16 is used as an adsorbent for n-paraffins. The dynamic capacity of the adsorbent for n-hexane vapor is determined at a temperature of 60°C by passing gas (helium) saturated with n-hexane vapor through the adsorbent bed at a gas flow rate of 1000 h / h. -1 , partial pressure of n-hexane 5 kPa and its concentration 0.173 g / dm3 3 Under these conditions, the dynamic capacity of the adsorbent is 3.2 g / 100 g.

[0077] As the examples show, the developed method enables the production of a wide range of aluminum oxide-based adsorbents and supports for various catalysts in petrochemical and oil refining processes. Compared to the prototype, the developed method produces a product with a larger pore volume, significantly expanding its applicability. The composition and physicochemical properties of the product can be varied over a wide range depending on the molding conditions.

[0078] Industrial applicability

[0079] Spherical adsorbents are used as desiccant adsorbents, while aluminum oxide-based carriers are used to produce various oil refining catalysts. Table 1. Formation conditions and properties of the resulting adsorbents and carriers.

[0080]

[0081] Designations: TGA - thermally activated aluminum hydroxide; MFI - zeolite or ferroalumosilicate with the structure of zeolite ZSM-5, MEL - zeolite or ferroalumosilicate with the structure of zeolite ZSM-11.

Claims

CLAUSES OF THE INVENTION 1. A method for producing spherical adsorbents and carriers based on aluminum oxide for catalysts in oil refining and petrochemical processes from a powder of oxygen-containing aluminum compounds of the composition Al2O3·nH2O, where 0.25 <n<2,0, гранулированием путем закатки на вращающейся наклонной тарели тарельчатого гранулятора с одновременным увлажнением посредством распыления связующего, последующей обработки сформованных гранул парами воды, сушки и прокаливания гранул при повышенной температуре, отличающийся тем, что в качестве связующего используют воду или водные растворы одноатомного спирта или кислоты, или щелочи, или растворимого соединения металла, или полиэтиленгликоля в массовом соотношении сырьё:связующее в интервале (1, 2÷ 3, 5):1, и стадию обработки гранул парами воды проводят при температуре 60-90°С, сушку гранул при температуре 60- 160°С, а прокаливание высушенных гранул осуществляют при температуре 400-1100°С.

2. The method according to paragraph 1, characterized in that the stage of granulating the powder is carried out together with seed particles with a particle size of no more than 5 mm, which are oxygen-containing compounds of aluminum of the composition Al2O3·nH2O, where 0.25 <n<2,0, и / или оксид алюминия, и / или полученные после стадии рассева сформованные гранулы.

3. The method according to paragraph 1 or paragraph 2, characterized in that the oxygen-containing compounds of aluminum of the composition Al2O3·nH2O, where 0.25 <n<2,0, используют тонкоразмолотый гидроксид алюминия или его смесь с оксидом алюминия.

4. The method according to claim 1, characterized in that the molded mass additionally contains at least one soluble compound of a metal selected from the series: zirconium, titanium, tin, boron, lanthanum in an amount of 0.1-20.0% by weight of the metal in the finished carrier.

5. The method according to claim 1, characterized in that the molded mass additionally contains a modifying additive in the form of silicon oxide or starch, or dextrin in an amount of 3-20% by weight.

6. The method according to claim 1, characterized in that the molded mass additionally contains a modifying additive in the form of a zeolite selected from the series: zeolite type A, X, L, beta, mordenite, ZSM-22 (TON), ZSM-23 (MTT), zeolite or ferroaluminosilicate with the structure ZSM-5 (MFI) or ZSM-11 (MEL) based on a content of 3-25% by weight in the finished carrier.

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