RU2685263C1 - Aluminum oxide-based support for catalysts for processing hydrocarbon material and method of its preparation - Google Patents

Abstract

FIELD: technological processes.

SUBSTANCE: invention relates to catalysis and oil refining. Disclosed is a carrier for a catalyst for processing hydrocarbon material, which includes aluminum oxide and zeolite, wherein as zeolite, the support contains crystalline ferroaluminosilicate or ferrogallium alumosilicate with zeolite structure ZSM-5 or ZSM-11 in amount of 1–75 wt%. Invention also relates to a method of preparing a catalyst support for processing hydrocarbon feedstock by mixing aluminum hydroxide with zeolite, peptizing with a solution of a mineral and / or organic acid, granulation, thermal treatment of obtained carrier granules, wherein zeolite is crystalline ferroaluminosilicate or ferrogallium aluminosilicate with ZSM-5 or ZSM-11 zeolite structure in amount of 1–75 wt%.

EFFECT: technical result consists in lower temperature of the complete burning out of the catalyst coke at the stage of catalyst regeneration.

13 cl, 1 tbl, 3 dwg, 23 ex

Description

The invention relates to zeolite-containing carriers for catalysts for the processing of hydrocarbons, and in particular to methods for their preparation. A carrier for oil and gas processing catalysts is proposed which contains gamma alumina and crystalline ferroaluminosilicate or ferroallium aluminosilicate with a zeolite structure of ZSM-5 or ZSM-11.

To improve the efficiency of various hydrocarbon processing processes, the catalysts used in them are constantly being improved by modifying them — chemical, structural, textural, including when preparing carriers by optimizing the synthesis parameters and introducing various active additives into their composition. One of the ways to change the physicochemical properties of catalysts for the processing of hydrocarbons in the processes of reforming, isomerization, hydrogenation, etc., is the introduction of a zeolite component into their composition.

A known catalyst for the hydrogenation of aromatic hydrocarbons in petroleum fractions and a method for producing it, in which the step of preparing a zeolite-containing carrier is described [US Pat. Of the Russian Federation No. 2096084, B01J 23/4888, 37/02, 1997]. According to this method, the carrier is prepared from aluminum hydroxide by continuous precipitation by treating it with solutions of hydrochloric acid and tin tetrachloride pentahydrate, followed by introducing with stirring a CMV type zeolite (similar to pentasil, ZSM-5 zeolite), an aqueous solution of silicotungstic acid and triethylene glycol. After evaporation of the resulting mass to a moisture content of 60-70%, it is molded by extrusion, dried in the temperature range of 60-110 ° C and calcined at 550 ° C. The resulting carrier contains 3-9% wt. zeolite, 0.4-2% tin, 4-8% tungsten and 1-5% chlorine.

Known catalyst carrier for reforming of gasoline fractions and the method of its preparation [US Pat. RF 2458103, C10G 35/085; B01J 29/540, 29/67, 21/04, 21/12, 32/00, 37/04, 2011]. According to this method, a zeolite-containing carrier for the catalyst is prepared by mixing dry powders of aluminum hydroxide and zeolite, peptizing the mixture with an aqueous solution of 1-10% citric acid with continuous stirring, granulating the gel by extrusion, heat treatment of freshly formed extrudates at a temperature not lower than 630 ° C. As zeolite used erionite or ferrierite, or phypsite in the H-form or in the NH ₄ -form. The result is an alumina carrier containing 1-10% wt. zeolite and 1-10% amorphous aluminosilicate formed by the interaction of citric acid with aluminum hydroxide and zeolite.

Known catalyst for the reforming of gasoline fractions and the method of its preparation, which describes the stage of preparation of the carrier [US Pat. Of the Russian Federation No. 2471854, C10G 35/085, 35/095; B01J 23/42, 23/36, 21/04, 29/00, 27/047, 37/02, 2011]. The carrier is prepared by mixing powders of aluminum hydroxide with zeolite, peptizing the mixture with an aqueous solution of acid, granulating, heat treating the obtained granules of the carrier with subsequent application of active components to the surface of the carrier; a solution of an organic acid, such as citric, acetic, oxalic, and the heat treatment of the carrier is carried out at a temperature of 630-700 ° C. As a zeolitic component of the catalyst, porous zeolites are used — erionite and / or phillipsite, and / or ferrite in the hydrogen or ammonium form.

Known catalyst for hydroisomerization of petroleum fractions and the method of its preparation, including the stage of preparation of the carrier [US Pat. Of the Russian Federation №2162012, B01J 29/44, 37/02; C10G 5/095, 1999]. According to this method, the carrier for the catalyst is prepared by peptization precipitated aluminum hydroxide with hydrochloric acid solution of indium oxycarbonate, followed by the introduction of 10-50% wt. zeolite CVM (analogue of pentasil, zeolite ZSM-5) in the NH ₄ form into an indium modifiable mass of aluminum hydroxide, and subsequent molding, drying and calcining.

Known catalyst isodewaxing petroleum fractions and the method of its preparation, including the stage of preparation of the carrier [US Pat. Of the Russian Federation No. 2302407, B01J 23/652, 29/44, 23/62, 21/04, 37/02; C10G 35/095, 2006]. According to this method, a zeolite-containing support for the catalyst is prepared as follows. Highly dispersed powdered aluminum oxide of high purity, having a particle size of not more than 100 microns and a specific surface area of not less than 260 m ² / g, is used as a raw material. Aluminum oxide is pre-moistened, after which it is gelled with a solution of 3-15% nitric acid at a temperature of 5-10 ° C, then with stirring, sequentially add a solution of silicotungstic acid, a solution of indium chloride and 5-40% wt. zeolite, after which the resulting mass is formed into granules, dried and calcined. Zeolite ZSM-5 in the H-form with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 25-80 or zeolite beta in the H-form with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 25 is used as the zeolite component of the carrier. -40

.Known catalyst, a method of obtaining a carrier, a method of producing a catalyst and the process of hydrodesulfurization of diesel fractions [US Pat. Of the Russian Federation No. 23111959, B01J 37/02, 23/88, 29/40, 29/18, 32/00; S10G 45/06, 2007]. According to this method, a zeolite-containing carrier for the catalyst is prepared by continuous or periodic precipitation of aluminum hydroxide, mixing aluminum hydroxide with zeolite powder, peptizing the resulting mixture with monobasic acid, extrusion molding, drying and calcining the molded granules at a temperature of 450-600 ° C. As a zeolite, zeolites ZSM-5, mordenite, zeolite Y or beta are used in the H-form or in the cation-substituted (Ni or Co) form, and nitric acid or acetic acid is used as the peptizing additive of monobasic acid. The resulting media contains 5-15% wt. zeolite and has a specific surface area of 230-400 m ² / g, pore volume is 0.5-0.9 cm ³ / g, and the prevailing pore radius is 80-120

.

Known zeolite-containing catalyst for dewaxing oil fractions, which describes the stage of preparation of its carrier [US Pat. Of the Russian Federation No. 2518468, B01J 29/076, 29/48, 23/28, 23/06, 27/14, 21/02; C10G 47/20, 2014]. According to this method, a catalyst carrier is prepared by mixing aluminum hydroxide grade A-64 with boric acid, adding a calculated amount of ZSM-5 zeolite, peptizing the resulting mixture with a calculated amount of nitric acid, molding, wilting at room temperature for 24 hours, drying at 100 -120 ° C for 2 hours and calcined at a temperature of 350-650 ° C. The applied zeolite ZSM-5 has a silicate module - the molar ratio SO ₂ / Al ₂ O ₃ in the range of 30-55.

The closest in technical essence and the achieved effect is the catalyst for the reforming of gasoline fractions and the method of its preparation, which describes the preparation of the carrier for this catalyst [Pat. Of the Russian Federation No. 2043149, B01J 29/44; C10G 35/09, 1995]. According to the selected prototype, the carrier is prepared by mixing aluminum hydroxide with zeolite in sodium form, adding nitric acid as a peptizer, molding the mixture into extrudates, drying and calcining extrudates in air flow at 500 ° C. Zeolites of the ZSM-5 or ZSM-8 or ZSM-11 type are used as the zeolite component of the support.

The main disadvantages of the above analogs and prototypes are the relatively high temperatures of burnout of coke formed on the zeolite component of the carrier during the processing of hydrocarbons, and incomplete burnout at moderate temperatures of regeneration of the catalyst.

During the processing of hydrocarbon feedstocks on metal-containing catalysts, the catalyst gradually coagulates, resulting in a decrease in its catalytic activity, which in turn leads to an increase in the slip of the raw material and to a decrease in the yield and / or quality of the product produced. To restore the initial level of catalyst activity, it is regenerated, consisting of controlled burning of coke deposits from the catalyst surface with a regenerating gas with a certain oxygen content. However, coke burnout on the metal component of the catalyst located on alumina occurs more completely and at lower temperatures than burnout of coke formed inside the crystals of the aluminosilicate (zeolite) component, since Polyvalent metal cations (Ni, Cr, Pt, Re, Pd, etc.) introduced at the catalyst impregnation stage do not penetrate into ZSM-5 and ZSM-11 zeolite crystals and therefore do not affect the process of burning catalyst coke inside the zeolite channels. As a result, coke deposits located inside the zeolite crystals may not completely burn out at moderate regeneration temperatures and gradually accumulate from regeneration to regeneration, leading to a decrease in the level of activity and / or to a reduction in the time for the regeneration of the catalyst. The introduction of iron and gallium atoms into the crystalline skeleton of a zeolite at the stage of hydrothermal synthesis during the synthesis of ferroaluminosilicate or ferrogallium aluminosilicate with the structure of ZSM-5 and ZSM-11 leads to the formation in the volume of their crystals of active centers that accelerate the reaction of burnout of catalyst coke, which in turn leads to reducing the temperature and increasing the burning depth of coke in the zeolite component of the catalyst carrier.

The objective of the invention is to develop a carrier for catalysts for the processing of hydrocarbon raw materials with reduced temperature of complete burnout of coke formed on the zeolite component of the carrier under the process conditions, as well as the method of preparation of such a carrier.

The task is achieved by the fact that the carrier for the catalyst for the processing of hydrocarbons contains 1-75% of the mass. crystalline ferroaluminosilicate or ferrohalium aluminosilicate with the structure of zeolite ZSM-5 or ZSM-11, possibly 0.05-5.0% tin and / or zirconium and / or lead, possibly up to 1.5% chlorine, and the rest is gamma alumina.

The task is achieved by the fact that the carrier for the catalyst for the processing of hydrocarbon raw materials is prepared by mixing a powder or paste of aluminum hydroxide with a solution of mineral and / or organic acid, followed by mixing the plasticized mass of aluminum hydroxide with crystalline ferroaluminosilicate or ferrohalium aluminosilicate with the structure of zeolite ZSM-5 or ZSM-11 possibly with a pore-forming substance, then molding the mixture obtained, neutralizing the formed granules with an ammonia solution, drying and alivaniya carrier granules molded at a temperature of 500-650 ° C. It is possible to add tin and / or zirconium and / or lead and / or chlorine compounds to the carrier by mixing them with a plasticizable mass or by impregnating molded granules with an additional drying step and heat treating the impregnated granules.

The task is also achieved by the fact that ferroaluminosilicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 38-310 and contains 0.1-1.5% of the mass. iron, and ferrogallium silicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 61–320 and contains 0.1–1.2% of iron and 0.1–1.5% of gallium, and these silicates can be used in decationized acidic H-form or in cationic Na-form.

, а порообразующим веществом является крахмал и/или древесная мука.The task is also achieved by using pseudo-boehmite aluminum hydroxide single-flow or continuous, or mixed deposition with the size of OCD (coherent dispersion region) in the direction [020] in the range of 30-100 as a raw material for the production of gamma-alumina.

, and the pore-forming substance is starch and / or wood flour.

The main distinguishing feature of the proposed method is the use of crystalline ferroaluminosilicate or ferrohallyaluminosilicate with zeolite structure ZSM-5 or ZSM-11 as part of a carrier.

Other distinctive features of the proposed method are:

;- application for receiving carrier pseudoboehmite aluminum hydroxide single-flow or continuous, or mixed deposition, with the size of the ROC in the direction [020] in the range of 30-100

;

- the possibility of using tin and / or zirconium and / or lead and / or chlorine compounds as a carrier modifier;

- the possibility of using starch and / or wood flour as a pore-forming substance.

The media is prepared as follows. Pseudoboehmite aluminum hydroxide, obtained by aluminate technology using a single-flow or continuous or mixed method, is treated with a solution of mineral and / or organic acid, and then the plasticized mass of aluminum hydroxide is mixed with crystalline ferroaluminosilicate or ferro gallium aluminosilicate, it is possible to mix with the mixed with agroaluminate or ferro gallium aluminosilicate; flour. The resulting mass is granulated with known methods in the form of extrudates or spheres, dried and calcined in a stream of air at a temperature of 500-650 ° C. In the case of the use of starch and / or wood flour, they completely burn out during calcination of the molded granules. The resulting carriers have high strength, high specific surface area and good water absorption, which allows further on their basis to prepare various catalysts for the processing of hydrocarbons by known methods.

It is possible to add tin and / or zirconium and / or lead and / or chlorine compounds to the carrier by mixing them with a plasticizable mass or by impregnating the formed granules. In the latter case, after the impregnation stage, additional heat treatment of the granules is carried out by drying and calcining them.

The essence of the proposed method and its practical applicability is illustrated by the examples below. Examples No. 1-20 describe the preparation of a carrier for catalysts for the processing of hydrocarbon raw materials according to the prototype (example No. 1) and the proposed method (examples No. 2-20), and show the change in textural characteristics of the obtained aluminum oxide depending on the composition and processing conditions . The characteristics of the carriers are additionally presented in Table 1. To illustrate the attainability of the goal set — to reduce the burn-out temperature of coke formed on the zeolite-containing catalyst carrier and to increase the burnout completeness, examples No. 21-23 and FIG. 1-3. Example No. 21 (Fig. 1) shows the burnout of coke formed on a zeolite-containing carrier prepared similarly to the prototype, and examples No. 22 and 23 (Figs. 2 and 3) illustrate the burnout of coke on the proposed zeolite-containing carrier.

Example 1 (for comparison).

The carrier for the catalyst is prepared similar to its preparation of the prototype. For the preparation of the carrier used paste aluminum hydroxide with a moisture content of 30%. An amount of 43 g of aluminum hydroxide paste is mixed with 70 g of ZSM-5 zeolite in decationized H-form, having a SiO ₂ / Al ₂ O ₃ molar ratio = 91, and a solution of 57% nitric acid is added as a peptizer to obtain an acid modulus M _to = 0.05. The mixture is molded on an extruder into cuttings with a diameter of 3-4 mm and a length of 5-7 mm, dried in air for 10 hours and calcined in a stream of air at a temperature of 500 ° C for 4 hours. The obtained carrier granules have a crush strength of 5.1 MPa and a specific surface area of 340 m ² / g and contain 30% wt. γ-Al ₂ O ₃ and 70% zeolite.

Example 2

в направлении [020] и суммарной влажностью 80%. В смеситель с Z-образными лопастями загружают 3000 г пасты гидроксида алюминия и при постоянном перемешивании добавляют 19,1 мл раствора 69% азотной кислоты. После перемешивания пластифицированной массы в течение 15 минут к гидроксиду добавляют 1400 г порошка кристаллического ферроалюмосиликата со структурой цеолита ZSM-5 в декатионированной Н-форме, имеющего мольное отношение SiO₂/Al₂O₃ = 96 и содержащего 0,5% мас. железа. Полученную массу с суммарной влажности 50% формуют на экструдере в черенки с диаметром 3-4 мм и длиной 5-7 мм. Экструдаты выдерживают на воздухе в течение 10 часов, сушат при температуре 110°С в течение 4 часов и прокаливают при 500°С в течение 4 часов. Полученные гранулы экструдатов содержат 30% мас. γ-Аl₂O₃ и 70% цеолита, гранулы имеют прочностью на раздавливание по образующей 7,1 МПа и удельную поверхностью 340 м²/г.As raw materials for the preparation of the catalyst carrier use aluminum hydroxide continuous deposition with the value of OCD equal to 40

in the direction [020] and a total humidity of 80%. 3000 g of aluminum hydroxide paste are loaded into a mixer with Z-shaped blades and 19.1 ml of a solution of 69% nitric acid are added with constant stirring. After mixing the plasticized mass for 15 minutes, 1400 g of crystalline ferroaluminosilicate powder with ZSM-5 zeolite structure in decationated H-form, having a SiO ₂ / Al ₂ O ₃ molar ratio of 96% and containing 0.5% wt., Are added to the hydroxide. gland. The resulting mass with a total moisture content of 50% is molded on an extruder into cuttings with a diameter of 3-4 mm and a length of 5-7 mm. The extrudates are kept in air for 10 hours, dried at 110 ° C for 4 hours and calcined at 500 ° C for 4 hours. The obtained extrudate granules contain 30% wt. γ-Al ₂ O ₃ and 70% zeolite, granules have a crush strength of 7.1 MPa and a specific surface area of 340 m ² / g.

Example 3

в направлении [020] и суммарной влажностью 75%. В смеситель с Z-образными лопастями загружают 2000 г пасты гидроксида алюминия и при постоянном перемешивании добавляют 222 мл 69% азотной кислоты. После перемешивания пластифицированной массы в течение 15 минут к гидроксиду добавляют при постоянном перемешивании 4000 г порошка смесевого гидроксида алюминия, полученного после сушки влажной лепешки смесевого гидроксида алюминия при 110°С до влажности менее 25% и размола его на шаровой мельнице до частиц с размером менее 50 мкм. Через 30 минут перемешивания в полученную пластифицированную массу гидроксида алюминия вводят 10500 г порошка кристаллического феррогаллийалюмосиликата со структурой цеолита ZSM-11 в декатионированной Н-форме, имеющего мольное отношение SiO₂/Al₂O₃ = 105 и содержащего 0,4% мас. железа и 0,1% галлия. Полученную пластифицированную массу гидроксида алюминия с суммарной влажностью 50% экструдируют в гранулы диаметром 5-7 мм и длиной 7-10 мм. Экструдированные гранулы выдерживают на воздухе при комнатной температуре в течение 10 часов, сушат при 110°С в течение 4-х часов и прокаливают в токе воздуха при объемной скорости подачи 500 ч^-1 при температуре 550°С в течение 2-х часов. Полученные гранулы экструдатов содержат 25% мас. γ-Аl₂O₃ и 75% цеолита, гранулы обладает прочностью на раздавливание по образующей 4,8 МПа и удельной поверхностью 350 м²/г.As raw materials for the preparation of the catalyst carrier use aluminum hydroxide continuous deposition with the value of OCD equal to 40

in the direction [020] and a total humidity of 75%. 2000 g of aluminum hydroxide paste are loaded into a mixer with Z-shaped blades and 222 ml of 69% nitric acid are added with constant stirring. After stirring the plasticized mass for 15 minutes, 4000 g of the mixed aluminum hydroxide powder obtained after drying the wet cake of mixed aluminum hydroxide at 110 ° C to a moisture content of less than 25% and grinding it into a ball mill to a particle size of less than 50 is added to the hydroxide with constant stirring. um After 30 minutes of stirring, 10,500 g of crystalline ferrohallium aluminum silicate powder with ZSM-11 zeolite structure in decationized H-form, having a SiO ₂ / Al ₂ O ₃ molar ratio of 105% and containing 0.4% wt., Are introduced into the resulting plasticized mass of aluminum hydroxide. iron and 0.1% gallium. The resulting plasticized mass of aluminum hydroxide with a total moisture content of 50% is extruded into granules with a diameter of 5-7 mm and a length of 7-10 mm. Extruded granules are kept in air at room temperature for 10 hours, dried at 110 ° C for 4 hours and calcined in a stream of air at a flow rate of 500 h ^-1 at a temperature of 550 ° C for 2 hours. The obtained extrudate granules contain 25% wt. γ-Al ₂ O ₃ and 75% zeolite, granules have a crush strength of 4.8 MPa and a specific surface of 350 m ² / g.

Example 4

и 100

соответственно. Смесевой гидроксид алюминия высушивают при 110°С до суммарной влажности 25% и размалывают на шаровой мельнице до порошкообразного состояния с размером частиц не более 50 мкм. Полученный порошок гидроксида алюминия в количестве 10,0 кг последовательно смешивают с 27,0 л деионизированной воды, 382 мл раствора 69% азотной кислоты до получения М_к=0,08, с 2,25 кг порошка крахмала и с 400 г порошка кристаллического ферроалюмосиликата со структурой цеолита ZSM-5 в декатионированной Н-форме, имеющего мольное отношение SiO₂/Al₂O₃ = 38 и содержащего 0,1% мас. железа. Стадию пластификации и смешивания с порошком цеолита осуществляют при температуре 28°С до содержания в массе 190 г Аl₂O₃/кг смеси. Полученную массу пластифицированного гидроксида алюминия выдерживают в течение 24 часов при температуре 22°С и формуют в сферические гранулы в углеводородной жидкости с последующей нейтрализацией в 15% водном растворе аммиака. Полученные гранулы провяливают на воздухе при температуре 20°С в течение 24 часов, затем сушат при 110°С в течение 2 часов и прокаливают при температуре 600°С в течение 4 часов в токе сухого воздуха с объемной скоростью подачи 600 ч^-1. Полученные сферические гранулы носителя на основе γ-Аl₂O₃ имеют диаметр 1,4-1,8 мм, прочность на раздавливание 25 МПа, удельную поверхность 230 м²/г, средний диаметром пор оксида алюминия 65

с объемом пор 0,6 см³/г и содержат 5% мас. цеолита.The raw material for the preparation of the catalyst carrier is aluminum hydroxide of mixed deposition with a ratio of cold aluminum to aluminum hydroxide and hot 1: 1 with OCD values for the [020] direction equal to 40

and 100

respectively. Mixed aluminum hydroxide is dried at 110 ° C to a total moisture content of 25% and milled in a ball mill to a powder with a particle size of not more than 50 μm. The resulting aluminum hydroxide powder in an amount of 10.0 kg was mixed sequentially with 27.0 liters of deionized water, 382 ml of 69% nitric acid to give _A = 0.08 M, with 2.25 kg of powder with starch and 400 g of crystalline powder ferroalyumosilikata with the structure of zeolite ZSM-5 in decationized H-form, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 38 and containing 0.1% wt. gland. The stage of plasticization and mixing with the zeolite powder is carried out at a temperature of 28 ° C until the content in the mass of 190 g of Al ₂ O ₃ / kg of the mixture. The resulting mass of plasticized aluminum hydroxide is incubated for 24 hours at a temperature of 22 ° C and formed into spherical granules in a hydrocarbon liquid, followed by neutralization in a 15% aqueous ammonia solution. The obtained granules are dried in air at a temperature of 20 ° C for 24 hours, then dried at 110 ° C for 2 hours and calcined at a temperature of 600 ° C for 4 hours in a stream of dry air with a flow rate of 600 h ^-1 . The obtained spherical granules of the carrier on the basis of γ-Al ₂ O ₃ have a diameter of 1.4-1.8 mm, a crush strength of 25 MPa, a specific surface area of 230 m ² / g, an average pore diameter of aluminum oxide 65

with a pore volume of 0.6 cm ³ / g and contain 5% wt. zeolite.

Example 5

и суммарной влажностью 85%. Гидроксид алюминия в количестве 500 г пластифицируют при температуре 20°С смесью кислот, добавляя 3,8 мл 69% азотной кислоты и 3,6 мл 46% уксусной кислоты из расчета получения суммарной величины Мк=0,12 и смешивают с 8,3 г порошка кристаллического ферроагаллийалюмосиликата со структурой цеолита ZSM-11 в декатионированной Н-форме, имеющего мольное отношение SiO₂/Al₂O₃ = 61 и содержащего 0,1% мас. железа и 0,3% галлия. Гранулирование полученной смеси в сферические гранулы осуществляют жидкостным методом в керосиновой фракции, а твердение и нейтрализацию гранул проводят в 18% водном растворе аммиака. Полученные гранулы сушат при температуре 110°С в течение 2 часов и прокаливают в токе сухого воздуха с объемной скоростью 1000 ч^-1 при температуре 550°С в течение 4 часов. Полученные сферические гранулы носителя на основе γ-Аl₂O₃ имеют диаметр 1,6-2,0 мм, прочность на раздавливание 20 МПа, удельную поверхность 240 м²/г, средний диаметр пор оксида алюминия 65

и содержат 10% мас. цеолита.As a raw material for the preparation of a catalyst carrier, aluminum hydroxide is used for continuous deposition with the size of OCD for the direction [020] of 40

and total humidity of 85%. Aluminum hydroxide in the amount of 500 g plasticized at a temperature of 20 ° C with a mixture of acids, adding 3.8 ml of 69% nitric acid and 3.6 ml of 46% acetic acid at the rate of obtaining a total value of MK = 0.12 and mixed with 8.3 g powder of crystalline ferroagallium silicate with the structure of zeolite ZSM-11 in the decationated H-form, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 61 and containing 0.1% by weight. iron and 0.3% gallium. Granulation of the mixture obtained in spherical granules is carried out by the liquid method in the kerosene fraction, and the hardening and neutralization of the granules is carried out in 18% aqueous ammonia solution. The obtained granules are dried at a temperature of 110 ° C for 2 hours and calcined in a stream of dry air with a bulk velocity of 1000 h ^-1 at a temperature of 550 ° C for 4 hours. The obtained spherical granules of the carrier on the basis of γ-Al ₂ O ₃ have a diameter of 1.6-2.0 mm, a crush strength of 20 MPa, a specific surface area of 240 m ² / g, an average pore diameter of aluminum oxide 65

and contain 10% wt. zeolite.

Example 6

в направлении [020] и суммарной влажностью 80%. Пасту гидроксида алюминия в количестве 500 г пластифицируют 5,4 мл 69% азотной кислотой из расчета получения М_к=0,08. Полученную тиксотропную массу гидроксида алюминия смешивают с 17,7 г порошка кристаллического ферроалюмосиликата со структурой цеолита ZSM-5 в катионной Na-форме, имеющего мольное отношение SiO₂/Al₂O₃=310 и содержащего 1,5% мас. железа, и с 10 г древесной муки. Полученную пластифицированную массу гидроксида алюминия формуют методом жидкостной формовки с последующей нейтрализацией в 20% водном растворе аммиака. Сформованные гранулы провяливают на воздухе при температуре 20°С в течение 24 часов, затем сушат при 110°С в течение 2 часов и прокаливают при температуре 650°С в течение 4 часов в токе сухого воздуха с объемной скоростью подачи 600 ч^-1. Полученные сферические гранулы носителя на основе γ-Аl₂O₃ содержат 15% мас. цеолита, имеют диаметр 1,6-1,9 мм, прочность на раздавливание 17 МПа, удельную поверхность 260 м²/г и средний диаметр пор оксида алюминия 75

.As raw materials for the preparation of the catalyst carrier use aluminum hydroxide continuous deposition with the value of OCD equal to 40

in the direction [020] and a total humidity of 80%. Paste aluminum hydroxide in the amount of 500 g plasticized 5.4 ml of 69% nitric acid at the rate of obtaining M _to = 0.08. The resulting thixotropic mass of aluminum hydroxide is mixed with 17.7 g of crystalline ferroaluminosilicate powder with the structure of zeolite ZSM-5 in the cationic Na-form, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 310 and containing 1.5% by weight. iron, and with 10 g of wood flour. The resulting plasticized mass of aluminum hydroxide is molded by the method of liquid molding, followed by neutralization in a 20% aqueous solution of ammonia. The formed granules are dried in air at a temperature of 20 ° C for 24 hours, then dried at 110 ° C for 2 hours and calcined at a temperature of 650 ° C for 4 hours in a stream of dry air with a flow rate of 600 h ^-1 . The obtained spherical granules media based on γ-Al ₂ O ₃ contain 15% wt. zeolite, have a diameter of 1.6-1.9 mm, crush strength of 17 MPa, a specific surface area of 260 m ² / g and an average pore diameter of aluminum oxide 75

.

Example 7

и суммарной влажностью 74%. Данный гидроксид в количестве 250 г пластифицируют 5,4 мл 30% соляной кислотой. Затем в течение 20 минут к гидроксиду алюминия добавляют при постоянном перемешивании 16,3 г порошка кристаллического ферроалюмосиликата со структурой цеолита ZSM-11 в катионной Na-форме, имеющего мольное отношение SiO₂/Al₂O₃ = 88 и содержащего 0,1% мас. железа, и 20 г порообразующей добавки в виде крахмала. Полученную смесь формуют в сферические гранулы в углеводородной жидкости с последующей нейтрализацией в 20% водном растворе аммиака. Сформованные гранулы сушат на воздухе, затем при температуре 120°С в течение 4 часов и прокаливают при температуре 550°С в течение 2 часов в токе воздуха. Полученные сферические гранулы оксида алюминия содержат 20% мас. цеолита и имеют удельную поверхность 240 м²/г, прочность на раздавливание 16 МПа, объем пор ~0,70 см³/г при среднем диаметре пор 80

.As a raw material for the preparation of a catalyst carrier, aluminum hydroxide is used single-flow deposition with the value of OCD in the direction [020] equal to 50

and a total humidity of 74%. This hydroxide in an amount of 250 g is plasticized with 5.4 ml of 30% hydrochloric acid. Then for 20 minutes to the aluminum hydroxide add with constant stirring 16.3 g of crystalline powder of ferroaluminosilicate with the structure of zeolite ZSM-11 in cationic Na-form, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 88 and containing 0.1% wt . iron, and 20 g of pore-forming additive in the form of starch. The resulting mixture is formed into spherical granules in a hydrocarbon liquid, followed by neutralization in a 20% aqueous solution of ammonia. The formed granules are dried in air, then at a temperature of 120 ° C for 4 hours and calcined at a temperature of 550 ° C for 2 hours in a stream of air. The resulting spherical granules of aluminum oxide contain 20% wt. zeolite and have a specific surface of 240 m ² / g, crushing strength of 16 MPa, pore volume ~ 0.70 cm ³ / g with an average pore diameter of 80

.

Example 8

и суммарной влажностью 80%. Гидроксид алюминия в количестве 1000 г пластифицируют при температуре 22°С органической кислотой - раствором 56,5 г лимонной кислоты в 45 мл воды из расчета получения М_к=0,15. Полученную тиксотропную массу гидроксида алюминия смешивают с раствором 2,6 г тартрата олова в 30 мл воды и 35,3 г порошка кристаллического ферроалюмосиликата со структурой цеолита ZSM-5 в декатионированной Н-форме, имеющего мольное отношение SiO₂/Аl₂O₃ = 86 и содержащего 0,4% мас. железа. Гранулирование полученной смеси в сферические гранулы осуществляют жидкостным методом в керосиновой фракции, а нейтрализацию гранул проводят в 15% водном растворе аммиака. Сформованные гранулы провяливают на воздухе в течение 4 часов, сушат при температуре 110°С в течение 2 часов и прокаливают при 500°С в токе воздуха при объемной скорости подачи 1000 ч^-1 в течение 2 часов. Полученные сферические гранулы носителя на основе γ-Аl₂O₃ имеют удельную поверхность 230 м²/г, диаметр 1,6-1,8 мм, прочность на раздавливание 20 МПа, средний диаметр пор оксида алюминия 70

и содержат 15% мас. цеолита и 0,5% олова.As a raw material for the preparation of a catalyst carrier, aluminum hydroxide of cold mixture deposition with an OCD value for the [020] direction equal to 60 is used.

and a total humidity of 80%. Aluminum hydroxide in an amount of 1000 g is plasticized at a temperature of 22 ° C with an organic acid — a solution of 56.5 g of citric acid in 45 ml of water at the rate of obtaining M _c = 0.15. The resultant thixotropic mass of aluminum hydroxide is mixed with a solution of 2.6 g of stannous tartrate in 30 ml of water and 35.3 g of crystalline powder ferroalyumosilikata structure ZSM-5 zeolite in the decationized H form having a molar ratio SiO ₂ / Al ₂ O ₃ = 86 and containing 0.4% wt. gland. Granulation of the mixture obtained in spherical granules is carried out by the liquid method in the kerosene fraction, and the neutralization of the granules is carried out in a 15% aqueous solution of ammonia. The formed granules were dried in air for 4 hours, dried at 110 ° C for 2 hours and calcined at 500 ° C in air flow at a flow rate of 1000 h ^-1 for 2 hours. The obtained spherical granules of the carrier on the basis of γ-Al ₂ O ₃ have a specific surface of 230 m ² / g, a diameter of 1.6-1.8 mm, a crush strength of 20 MPa, an average pore diameter of aluminum oxide 70

and contain 15% wt. zeolite and 0.5% tin.

Example 9

и суммарной влажностью 73%. Гидроксид алюминия в количестве 1000 г пластифицируют раствором 31 г щавелевой кислоты в 124 мл воды при 45°С из расчета получения М_к=0,13. Полученную тиксотропную массу смешивают с 0,45 г тетрахлорида олова пятиводного в 5 мл воды и с 30 г порошка кристаллического феррогаллийалюмо силиката со структурой цеолита ZSM-11 в катион-декатионированной HNa-форме, имеющего мольное отношение SiO₂/Al₂O₃ = 320 и содержащего 1,1% мас. железа и 1,5% галлия. Гранулирование полученной смеси осуществляют углеводородным методом в углеводородной жидкости, а нейтрализацию сформованных гранул проводят в 18% водном растворе аммиака. Полученные гранулы выдерживают на воздухе в течение 10 часов, сушат при температуре 110°С в течение 4 часов и прокаливают при температуре 600°С в токе сухого воздуха при скорости подачи 1000 ч^-1 в течение 2 часов. Полученные сферические гранулы носителя на основе γ-Аl₂O₃ имеют диаметр 1,6-1,9 мм, прочность на раздавливание 25 МПа, удельную поверхность 250 м²/г и содержат 10% мас. цеолита и 0,05% олова.As a raw material for the preparation of the catalyst carrier, aluminum hydroxide is used single-flow deposition with the size of OCD for the direction [020] equal to 50

and a total humidity of 73%. Aluminum hydroxide in the amount of 1000 g plasticized with a solution of 31 g of oxalic acid in 124 ml of water at 45 ° C at the rate of obtaining M _to = 0.13. The resulting thixotropic mass is mixed with 0.45 g of pentahydrate tetrachloride in 5 ml of water and 30 g of crystalline ferrohallium-aluminum silicate powder with the structure of zeolite ZSM-11 in cation-decationated HNa-form, having a SiO ₂ / Al ₂ O ₃ molar ratio = 320 and containing 1.1% wt. iron and 1.5% gallium. Granulation of the mixture obtained is carried out by the hydrocarbon method in a hydrocarbon liquid, and the neutralization of the molded granules is carried out in an 18% aqueous solution of ammonia. The obtained granules are kept in air for 10 hours, dried at 110 ° C for 4 hours and calcined at 600 ° C in a stream of dry air at a feed rate of 1000 h ^-1 for 2 hours. The obtained spherical granules of the carrier on the basis of γ-Al ₂ O ₃ have a diameter of 1.6-1.9 mm, a crush strength of 25 MPa, a specific surface area of 250 m ² / g and contain 10% by weight. zeolite and 0.05% tin.

Example 10

и 100

соответственно. Смесевой гидроксид алюминия высушивают при 110°С до суммарной влажности 25%, размалывают на шаровой мельнице до порошкообразного состояния с размером частиц не более 50 мкм. Полученный порошок гидроксида алюминия в количестве 3,0 кг помещают в смеситель с Z-образными лопастями и смешивают при с 1,5 кг порошка кристаллического феррогаллийалюмосиликата со структурой цеолита ZSM-5 в декатионированной Н-форме, имеющего мольное отношение SiO₂/Al₂O₃=145 и содержащего 0,2% мас. железа и 0,6% галлия. К полученной смеси порошков добавляют при постоянном перемешивании раствор азотной кислоты, содержащий 114 мл 69% азотной кислоты для получения кислотного модуля равного 0,08 и 1930 мл воды. Полученную массу перемешивают в течение 20 минут и добавляют раствор 66 г тетрахлорида олова пятиводного в 400 мл воды. Смесь с суммарной влажностью 46% формуют в экструдаты диаметром 4-5 мм и длиной 5-8 мм. Гранулы выдерживают на воздухе в течение 10 часов и сушат при температуре 120°С в течение 4 часов. Прокаливание гранул проводят при температуре 550°С в токе сухого воздуха при его объемной скорости подачи 1000 ч^-1 в течение 4 часов. Полученные гранулы экструдатов на основе γ-Аl₂O₃ содержат 40% мас. цеолита, 0,6% олова и 0,4% хлора, гранулы обладают прочностью на раздавливание по образующей 8,9 МПа и удельной поверхностью 310 м²/г.As a raw material for the preparation of a catalyst carrier, aluminum hydroxide of mixed deposition is used at a ratio of cold aluminum to aluminum hydroxide and 1: 1 hot OCD with OCD values for the [020] direction equal to 40

and 100

respectively. Mixed aluminum hydroxide is dried at 110 ° C to a total moisture content of 25%, milled in a ball mill to a powder with a particle size of not more than 50 microns. The obtained aluminum hydroxide powder in the amount of 3.0 kg is placed in a mixer with Z-shaped blades and mixed with 1.5 kg of crystalline powder of ferroallium aluminosilicate with the structure of zeolite ZSM-5 in decationized H-form, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 145 and containing 0.2% wt. iron and 0.6% gallium. To the mixture of powders is added with a constant stirring a solution of nitric acid containing 114 ml of 69% nitric acid to obtain an acid module equal to 0.08 and 1930 ml of water. The resulting mass is stirred for 20 minutes and a solution of 66 g of tin tetrahydrate tetrachloride in 400 ml of water is added. A mixture with a total moisture content of 46% is molded into extrudates with a diameter of 4-5 mm and a length of 5-8 mm. The granules are kept in air for 10 hours and dried at 120 ° C for 4 hours. The calcination of the granules is carried out at a temperature of 550 ° C in a stream of dry air at its flow rate of 1000 h ^-1 for 4 hours. The obtained granules of extrudates on the basis of γ-Al ₂ O ₃ contain 40% wt. zeolite, 0.6% tin and 0.4% chlorine, granules have a crush strength of 8.9 MPa and a specific surface of 310 m ² / g.

Example 11

. Гидроксид алюминия в количестве 1000 г пластифицируют 36 мл раствора 46% уксусной кислоты из расчета получения М_к=0,12 при температуре 20°С и смешивают с 6,25 г древесной муки, 28 г порошка кристаллического феррогаллийалюмосиликата со структурой цеолита ZSM-5 в декатионированной Н-форме, имеющего мольное отношение SiO₂/Al₂O₃ = 92 и содержащего 0,3% мас. железа и 0,1% галлия, и с раствором 2,5 г тетрахлорида олова пятиводного в 10 мл воды. Полученную жидкотекучую тиксотропную смесь формуют методом жидкостной формовки в углеводородной жидкости в сферические гранулы и нейтрализуют их в 18% водном растворе аммиака. Сформованные гранулы провяливают на воздухе в течение 24 часов, сушат при температуре 120°С в течение 4 часов и прокаливают при температуре 550°С в течение 2 часов в токе воздуха с объемной скоростью подачи 500 ч^-1. Полученные сферические гранулы носителя на основе γ-Аl₂O₃ имеют диаметр 1,6-2,0 мм, прочность на раздавливание 25 МПа, удельную поверхность 220 м²/г и содержат 10% мас. цеолита, 0,3% олова и 0,1% хлора. Пористая структура оксида алюминия имеет объемом пор 0,7 см³/г со средним диаметром 70

.As a raw material for the preparation of a catalyst carrier, aluminum hydroxide is used single-flow deposition with a total moisture content of 75% and an ROC value for the [020] direction equal to 30

. Aluminum hydroxide in an amount of 1000 g is plasticized with 36 ml of a solution of 46% acetic acid to obtain M _c = 0.12 at a temperature of 20 ° C and mixed with 6.25 g of wood flour, 28 g of crystalline ferroglyallium silicate powder with a zeolite ZSM-5 structure decationized H-form, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 92 and containing 0.3% by weight. iron and 0.1% gallium, and with a solution of 2.5 g of pentahydrate tin tetrachloride in 10 ml of water. The obtained flowable thixotropic mixture is formed by the method of liquid forming in a hydrocarbon liquid into spherical granules and neutralized in an 18% aqueous solution of ammonia. The formed granules are dried in air for 24 hours, dried at 120 ° C for 4 hours and calcined at 550 ° C for 2 hours in an air stream with a flow rate of 500 h ^-1 . The obtained spherical granules of the carrier on the basis of γ-Al ₂ O ₃ have a diameter of 1.6-2.0 mm, a crush strength of 25 MPa, a specific surface of 220 m ² / g and contain 10% by weight. zeolite, 0.3% tin and 0.1% chlorine. The porous structure of alumina has a pore volume of 0.7 cm ³ / g with an average diameter of 70

.

Example 12

для направления [020] и суммарной влажностью 79%. Пасту данного гидроксида алюминия в количестве 500 г пептизируют при температуре 25°С 6,7 мл раствора 69% азотной кислоты из расчета получения кислотного модуля (М_к - мольное отношение кислоты к оксиду алюминия в гидроксиде) М_к=0,10 и смешивают с раствором 0,7 г тартрата олова в 20 мл воды, 27 г порошка крахмала и 1,1 г порошка кристаллического ферроалюмосиликата со структурой цеолита ZSM-5 в катионной Na-форме, имеющего мольное отношение SiO₂/Al₂O₃ = 88 и содержащего 0,1% мас. железа. Полученную жидкотекучую тиксотропную смесь формуют методом капельной формовки в углеводородной жидкости в сферические гранулы и нейтрализуют их в 20% водном растворе аммиака. Сформованные гранулы провяливают на воздухе в течение 10 часов и сушат первоначально при температуре 60°С в течение 2-х часов, а затем при температуре 110°С в течение 4 часов, после чего их прокаливают в течение 3 часов при температуре 550°С в токе сухого воздуха с объемной скоростью подачи 1000 ч^-1. Полученные гранулы γ-Аl₂O₃ размером 1,6-1,8 мм имеют прочность на раздавливание 18 МПа, удельную поверхность 210 м²/г, мо но дисперсную пористую структуру со средним диаметром пор 90

и объемом пор 0,55 см³/г, и содержат 1% мас. цеолита и 0,3% олова.As raw materials for the preparation of the catalyst carrier use aluminum hydroxide of continuous deposition with an amount of OCD in 40

for the direction [020] and the total humidity of 79%. A paste of this aluminum hydroxide in the amount of 500 g is peptized at 25 ° C with 6.7 ml of a solution of 69% nitric acid at the rate of obtaining an acid modulus (M _c is the molar ratio of acid to alumina in hydroxide) M _c = 0.10 and mixed with a solution of 0.7 g of tin tartrate in 20 ml of water, 27 g of starch powder and 1.1 g of crystalline ferroaluminosilicate powder with zeolite ZSM-5 structure in cationic Na-form, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 88 and containing 0.1% wt. gland. The obtained flowable thixotropic mixture is formed by the method of drop forming in a hydrocarbon liquid into spherical granules and neutralized them in a 20% aqueous solution of ammonia. The formed granules are dried in air for 10 hours and dried initially at a temperature of 60 ° C for 2 hours and then at a temperature of 110 ° C for 4 hours, after which they are calcined for 3 hours at a temperature of 550 ° C current of dry air with a volumetric feed rate of 1000 h ^-1 . The obtained γ-Al ₂ O ₃ granules with a size of 1.6-1.8 mm have a crush strength of 18 MPa, a specific surface of 210 m ² / g, a dispersed porous structure with an average pore diameter of 90

and a pore volume of 0.55 cm ³ / g, and contain 1% wt. zeolite and 0.3% tin.

Example 13

.Use raw materials of Example 7. 500 g of aqueous kneaded at a temperature of 20 ° C by adding 6.75 ml of 30% hydrochloric acid and 7.9 ml of 46% acetic acid, based obtain the total value M _k = 0.10 and mixed with 15 g of powder ferrohallyaluminosilicate with the structure of zeolite ZSM-5 in the decationized H-form, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 212 and containing 0.6% by weight. iron and 1.1% gallium, with 2.2 g of tetrahydrate tetrachloride pentahydrate in 10 ml of water and with a mixture of pore-forming additives, consisting of 3.25 g of wood flour and 13 g of starch. Granulation of the mixture obtained is carried out by the hydrocarbon method in a hydrocarbon liquid, and the neutralization of the formed granules is carried out in a 20% aqueous solution of ammonia. The formed granules are kept in air for 10 hours, dried at 110 ° C for 4 hours and calcined at 600 ° C in a stream of dry air at a feed rate of 1000 h ^-1 for 2 hours. The resulting spherical granules media based on γ-Al ₂ O ₃ contain 10% wt. zeolite, 0.5% tin and 0.5% chlorine, the granules have a diameter of 1.6-1.9 mm, a crush strength of 25 MPa and a specific surface area of 250 m ² / g and an average pore diameter of aluminum oxide 65

.

Example 14

в направлении [020] и суммарной влажностью 70%. В смеситель с Z-образными лопастями загружают 300 г пасты гидроксида алюминия и при постоянном перемешивании добавляют 19,8 мл 69% азотной кислоты. После перемешивания пластифицированной массы в течение 15 минут к массе добавляют при постоянном перемешивании 400 г порошка гидроксида алюминия, полученного после сушки влажной лепешки гидроксида алюминия при 110°С до влажности 25% и размола его на шаровой мельнице до частиц с размером менее 50 мкм. Через 30 минут перемешивания в полученную пластифицированную массу гидроксида алюминия вводят 43,3 г порошка кристаллического феррогаллийалюмосиликата со структурой цеолита ZSM-11 в декатионированной Н-форме, имеющего мольное отношение SiO₂/Al₂O₃ = 186 и содержащего 1,2% масс, железа и 0,3% галлия. После 15 минут перемешивания в пластифицированную кислотой массу добавляют 4,0 г тетрахлорида олова пятиводного в 50 мл воды, 28,9 г соединения циркония, содержащего 30,6% циркония, и порообразующих реагентов в количестве 19,5 г древесной муки и 58,5 г крахмала. После 30 минутного перемешивания смесь с влажностью 45% экструдируют в гранулы диаметром 5-7 мм и длиной 5-7 мм и сразу же направляются на закатку в устройство типа «марумерайзера», где формуют в гранулы шаровидной формы диаметром 5-8 мм. Сферические гранулы выдерживают на воздухе при комнатной температуре в течение 10 часов, сушат при 110°С в течение 4-х часов и прокаливают в токе воздуха при объемной скорости подачи 500 ч^-1 при температуре 650°С в течение 2-х часов. Полученные гранулы содержат 10% цеолита, 0,3% олова, 2,0% циркония и 0,1% хлора, гранулы обладает прочностью на раздавливание 5,1 МПа и удельной поверхностью 260 м²/г.As raw materials for the preparation of the catalyst carrier use aluminum hydroxide continuous deposition with the value of OCD equal to 50

in the direction [020] and a total humidity of 70%. 300 g of aluminum hydroxide paste are loaded into a mixer with Z-shaped blades and 19.8 ml of 69% nitric acid are added with constant stirring. After mixing the plasticized mass for 15 minutes, 400 g of aluminum hydroxide powder obtained after drying the wet aluminum hydroxide cake at 110 ° C to a moisture content of 25% and grinding it in a ball mill to a particle size of less than 50 microns is added to the mass with constant stirring. After 30 minutes of stirring, 43.3 g of crystalline ferrohallium aluminosilicate powder with ZSM-11 zeolite structure in decationized H-form, having a SiO ₂ / Al ₂ O ₃ molar ratio of 18% and containing 1.2% by mass, are injected into the resulting plasticized mass of aluminum hydroxide. iron and 0.3% gallium. After 15 minutes of stirring, 4.0 g of pentahydric tetrachloride in 50 ml of water, 28.9 g of zirconium compound containing 30.6% of zirconium and pore-forming reagents in the amount of 19.5 g of wood flour and 58.5 are added to the acid-plasticized mass. g starch. After 30 minutes of mixing, the mixture with a humidity of 45% is extruded into pellets with a diameter of 5-7 mm and a length of 5-7 mm and immediately sent for rolling into a device of the "marumeraiser" type, where it is formed into pellets of spherical shape with a diameter of 5-8 mm. Spherical granules are kept in air at room temperature for 10 hours, dried at 110 ° C for 4 hours and calcined in a stream of air at a flow rate of 500 h ^-1 at a temperature of 650 ° C for 2 hours. The obtained granules contain 10% zeolite, 0.3% tin, 2.0% zirconium and 0.1% chlorine, the granules have a crush strength of 5.1 MPa and a specific surface area of 260 m ² / g.

Example 15

и суммарной влажностью 85%. Гидроксид алюминия в количестве 500 г пластифицируют при температуре 20°С, добавляя 4,8 мл 69% азотной кислоты из расчета получения М_к=0,10 и смешивают с 8,3 г порошка ферроалюмосиликата со структурой цеолита ZSM-5 в декатионированной Н-форме, имеющего мольное отношение SiO₂/Al₂O₃ = 82 и содержащего 0,6% масс. железа, и с 14,3 г соединения циркония, содержащего 30,6% циркония. Полученную смесь формуют в сферические гранулы методом капельной формовки в углеводородной жидкости, а нейтрализацию сформованных гранул проводят в 15% водном растворе аммиака. Сформованные гранулы провяливают на воздухе в течение 10 часов, сушат при температуре 110°С в течение 4 часов и прокаливают в течение 3 часов при температуре 600°С в токе сухого воздуха с объемной скоростью 600 ч^-1. Полученные гранулы носителя γ-Аl₂O₃ размером 1,6-1,8 мм содержат 10% масс. цеолита и 5% циркония, гранулы обладают прочностью на раздавливание 20 МПа и удельной поверхностью 220 м²/г. Пористая структура оксида алюминия представлена порами со средним диаметром 90

и объемом пор 0,6 см³/г.As a raw material for the preparation of a catalyst carrier, aluminum hydroxide is used for continuous deposition with the size of OCD for the direction [020] of 40

and total humidity of 85%. Aluminum hydroxide in an amount of 500 g is plasticized at a temperature of 20 ° C, adding 4.8 ml of 69% nitric acid to obtain M _c = 0.10 and mix with 8.3 g of ferroaluminosilicate powder with the structure of zeolite ZSM-5 in decationized H- a form having a molar ratio of SiO ₂ / Al ₂ O ₃ = 82 and containing 0.6% of the mass. iron, and with 14.3 g of zirconium compounds containing 30.6% zirconium. The resulting mixture is formed into spherical granules by the method of drop forming in a hydrocarbon liquid, and the neutralization of the formed granules is carried out in a 15% aqueous solution of ammonia. The formed granules were dried in air for 10 hours, dried at 110 ° C for 4 hours, and calcined for 3 hours at 600 ° C in a stream of dry air with a flow rate of 600 h ^-1 . The obtained granules of the carrier γ-Al ₂ O _{3 the} size of 1.6-1.8 mm contain 10% of the mass. zeolite and 5% zirconium, granules have a crush strength of 20 MPa and a specific surface area of 220 m ² / g. The porous structure of alumina is represented by pores with an average diameter of 90

and a pore volume of 0.6 cm ³ / g.

Example 16

.The carrier is prepared according to example 7 with the difference that crystalline ferrohallyaluminosilicate with the structure of zeolite ZSM-11 in decationized H-form, having a SiO ₂ / Al ₂ O ₃ molar ratio of 105 and containing 0.4% wt., Is used as a zeolite. iron and 0.1% gallium, and at the stage of mixing aluminum hydroxide and zeolite, 7.8 ml of 10% lead nitrate solution is added to the stirred mixture. The resulting spherical granules of aluminum oxide contain 20% wt. zeolite, 0.6% lead and have a specific surface area of 240 m ² / g, crush strength of 15 MPa, alumina pore volume 0.70 cm ³ / g with an average pore diameter of 80

.

Example 17

The carrier is prepared according to example 4 with the difference that crystalline ferrolumosilicate with the structure of zeolite ZSM-5 in decationized H-form, having a SiO ₂ / Al ₂ O ₃ molar ratio of 86% and containing 0.4% by weight, is used as a zeolite. iron, and at the stage of mixing aluminum hydroxide and zeolite, a solution of 192 g of lead nitrate in 0.6 l of water is added to the stirred mixture. The resulting spherical granules of aluminum oxide contain 5% wt. zeolite and 1.5% lead and have a specific surface of 230 m ² / g.

Example 18

The calcined granules in the form of extrudates, containing 30% wt. γ-A1 ₂ O ₃ and 70% ferroaluminosilicate with the structure of zeolite ZSM-5, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 96 and containing 0.5% wt. iron, prepared according to example 2. Cooled granules in an amount of 500 g are treated for 2 hours with stirring and at a temperature of 60 ° C 1400 ml of an aqueous solution containing 31 g of oxalic acid dihydrate, 21 g of hydrochloric acid and 9 g of tin (IV) chloride after which the mixture is decanted, the catalyst granules are wiped in air for 10 hours, dried at 120 ° C for 2 hours and calcined at 500 ° C for 2 hours. The resulting carrier contains 70% zeolite, 0.4% tin, 0.3% chlorine and has a specific surface of 340 m ² / g.

Example 19

The calcined granules in the form of spheres containing 15% wt. ferroaluminosilicate with the structure of zeolite ZSM-5, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 38 and containing 0.1% wt. iron is prepared according to example 6. Cooled granules in an amount of 100 g are treated for 1 hour at 20 ° C and stirring 150 ml of a solution of 1.1% hydrochloric acid, after which the mixture is decanted, catalyst granules are dried in air for 8 hours, dried at a temperature of 110 ° C for 2 hours and calcined at 500 ° C for 2 hours. The resulting carrier contains 15% zeolite, 1.5% chlorine and has a specific surface of 240 m ² / g.

Example 20

The calcined granules in the form of spheres containing 10% wt. ferrohallyaluminosilicate with the structure of zeolite ZSM-11, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 61 and containing 0.1% wt. iron and 0.3% gallium, prepared according to example 5. Cooled granules in an amount of 50 g are impregnated for 2 hours at a temperature of 20 ° C and stirring 100 ml of a solution of 1% nitric acid containing 0.5 g of lead nitrate, after which the mixture decanted, catalyst granules were fired in air for 6 hours, dried at 110 ° C for 2 hours and calcined at 500 ° C for 2 hours. The resulting carrier contains 10% zeolite, 0.5% lead has a specific surface of 250 m ² / g.

Example 21 (for comparison).

The study of the process of burning catalyst coke of a coked sample is carried out by controlling the change in mass of 0.2 g of the sample in the reactor, which is close to isothermal. The burning of coke is carried out by contacting with the catalyst a regenerating gas containing 1.3% vol. oxygen mixed with nitrogen, which is carried out at atmospheric pressure, a temperature of 500-600 ° C and a gas flow rate of 50 l / h.

The coke burning is subjected to the carrier of example 1, which has worked for 15 hours as a catalyst for the processing of the C ₆ -C ₈ hydrocarbon fraction and containing 5.1% by weight. coke.

The burning of coke starts at a constant temperature of 500 ° C and is carried out for 60 minutes until the mass of the catalyst sample is stabilized; as a result of the oxidative treatment of the catalyst, 39% of the initial coke content was removed. After the regeneration temperature increased to 520 ° C and the subsequent burning of coke for 60 minutes until the mass of the catalyst sample stabilized, another 22% of the initial coke content was removed. At a temperature of 550 ° C, another 8% of coke was removed. The residual coke in the amount of 31% of the initial coke content burned out at a temperature of 600 ° С in 70 minutes. The total time of burning coke was ~ 250 minutes. The curves of the mass loss of the sample over time, due to the burning of coke in the coked catalyst, are shown in FIG. one.

Example 22

It is similar to example 21 with the difference that the carrier of example 2 is subjected to burning coke, which has worked for 15 hours as a catalyst for processing the C ₆ -C ₈ hydrocarbon fraction and containing 5.2% wt. coke.

The burning of coke starts at a constant temperature of 500 ° C and is carried out for 85 minutes until the mass of the sample of catalyst is stabilized; As a result of the oxidative treatment of the catalyst, 62% of the initial coke content was removed. After the regeneration temperature was raised to 520 ° C and the subsequent burning of coke for 75 minutes until the mass of the catalyst sample stabilized, another 28% of the initial coke content was removed. Residual coke in the amount of 10% of the initial coke content burned out at a temperature of 550 ° С in 20 minutes. The control temperature increase to 600 ° С did not lead to a further change in the sample mass, which confirms the complete removal of coke at a temperature of 550 ° С. The total time of burning coke was ~ 180 minutes. The curves of the mass loss of the sample over time, due to the burning of coke in the coked catalyst, are shown in FIG. 2

Example 23

Similar to example 21 with the difference that the carrier of example 3 is subjected to burning coke, which has worked for 100 hours as a catalyst for the processing of the C ₆ -C ₈ hydrocarbon fraction and containing 10.2% by weight. coke.

The burning of coke starts at a constant temperature of 500 ° C and is carried out for 80 minutes until the mass of the catalyst sample is stabilized; as a result of the oxidative treatment of the catalyst, 81% of the initial coke content was removed. After the regeneration temperature was raised to 520 ° C and the subsequent burning of coke for 60 minutes until the weight of the catalyst sample stabilized, another 13% of the initial coke content was removed. Residual coke in the amount of 6% of the initial coke content burned out at a temperature of 550 ° C in 20 minutes. The control temperature increase to 600 ° С did not lead to a further change in the sample mass, which confirms the complete removal of coke at a temperature of 550 ° С. The total time of burning coke was ~ 160 minutes. The curves of the mass loss of the sample over time, due to the burning of coke in the coked catalyst, are shown in FIG. 3

As can be seen from the above examples No. 21-23 and FIG. 1-3, the proposed catalyst carrier for hydrocarbon processing has the ability to remove coke deposits from the surface of the zeolite component of the regenerated catalyst under milder conditions consisting in lowering the temperature of complete burning of coke from 600 ° C to 550 ° C and reducing the total regeneration time.

Claims (13)

1. The carrier for the catalyst for the processing of hydrocarbons, including aluminum oxide and zeolite, characterized in that the carrier contains crystalline ferroaluminosilicate or ferrohallium aluminum silicate with the structure of zeolite ZSM-5 or ZSM-11 in an amount of 1-75% by weight as zeolite. 2. The carrier under item 1, characterized in that the ferroaluminosilicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 38-310 and contains 0.1-1.5% wt. gland. 3. The carrier under item 1, characterized in that the ferrohallium silicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 61-320 and contains 0.1-1.2% by weight. iron and 0.1-1.5% gallium. 4. The carrier according to any one of paragraphs. 1-3, characterized in that the carrier additionally contains 0.05-5.0% wt. tin and / or zirconium and / or lead. 5. The media according to any one of paragraphs. 1-4, characterized in that the carrier additionally contains up to 1.5% wt. chlorine. 6. The method of preparation of the carrier for the catalyst for processing hydrocarbon raw materials by mixing aluminum hydroxide with zeolite, peptizing with a solution of mineral and / or organic acid, granulating, heat treating the obtained carrier granules, characterized in that crystalline ferroaluminosilicate or ferrogliallium silicate with zeolite ZSM- structure is used as zeolite 5 or ZSM-11 in the amount of 1-75% wt. 7. The method according to p. 6, characterized in that the ferroaluminosilicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 38-310 and contains 0.1-1.5% wt. gland. 8. The method according to p. 6, characterized in that the ferrohallyaluminosilicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 61-320 and contains 0.1-1.2% wt. iron and 0.1-1.5% gallium. 9. The method according to any one of paragraphs. 6-8, characterized in that as a source of raw materials for the production of gamma-alumina use aluminum hydroxide single-flow or continuous, or mixed deposition, having an OCD size in the direction [020] in the range of 30-100

10. A method according to any one of claims. 6-9, characterized in that at the stage of mixing aluminum hydroxide with zeolite, starch in the amount of 10-30% by weight is added to the mixture with stirring as a pore-forming reagent. and / or wood flour in the amount of 2.5-10%. 11. A method according to any one of claims. 6-10, characterized in that before forming in the peptized mixture is added with stirring the compounds of tin and / or zirconium and / or lead, based on the content in the carrier 0.05-5.0% wt. on the metal. 12. A method according to any one of claims. 6-11, characterized in that after the stage of heat treatment of the molded granules, the granules are impregnated with soluble compounds of tin or zirconium, or lead, based on the content in the carrier 0.05-5.0% wt. on metal, and / or chlorine compounds in the calculation of the content in the carrier to 1.5% wt. chlorine, and after the impregnation stage, the granules are subjected to additional drying and heat treatment. 13. A method according to any one of claims. 6-12, characterized in that at the stage of heat treatment, the obtained carrier granules are calcined at a temperature of 500-650 ° C.

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