Microspheric zeolite catalyst for the conversion of aliphatic hydrocarbons, c2- c10

 

(57) Abstract:

The inventive catalyst contains high-silica zeolite of the type pentasil in the hydrogen form with a ratio Si/Al=12 - 30 25 - 35 wt%, binder - zirconium oxide 5 to 10 wt%, (BF ZrO2), the promoter is zinc oxide, 1 to 2 wt% (ZnO, ) phosphate Zirconia 25 - 30 wt.%(CF Zr3(PO4)4) and alumina rest (BF Al2O3). The content of compounds of zirconium in the catalyst does not exceed 35 wt.%. In the apparatus with stirrer and heating load condensate and water pellet of aluminum hydroxide. Mix and add an aqueous solution of nitric acid Zirconia and an aqueous solution of zinc nitrate, stirred for 1 h Type zeolite CBM - III in the ammonium form. After stirring gradually add the aqueous solution of orthophosphoric acid. The temperature was raised to 90 To 60 °C and the suspension is incubated 3 hours is Subjected to spray drying at 190 to 220°C. Calcined granules in a muffle furnace at 550°C 5 h 4 table.

The invention relates to compositions resulting zeolite-containing catalyst for the conversion of aliphatic hydrocarbons2-C10contained in the low-octane gas condensate or straight-run gasoline and Shir the liquids.

In aromatization reactions of olefins WITH2-C4and paraffins WITH2-C10high activity is exhibited by zeolites groups of pentelow - ZSM - 5, ZSM - 11, DCM, WHC and others. The zeolite is usually used in the hydrogen form (the content of Na2O less than 0.1 wt.%) [1, 2] and as a binder is alumina - Al2O3. The content of zeolite in the catalyst varies widely - from 1 to 99 wt.%. In addition, the catalyst may contain promoters that increase output arenes is one or more metals II, III or VIII groups of the Periodic system is typically Zn, Cd, Ga, Pt or Pd in an amount of 0.1-10 wt.%, preferably 0.1 to 2%.

Known [3] the catalyst dehydrocyclization aliphatic hydrocarbons2-C5comprising 40-60 wt. % of phosphorus-containing alumina (P/Al = 0,01-1). 0.1 to 5 wt. % gallium and crystalline aluminosilicate with SiO2/Al2O31 2 (ZSM - 5). The catalyst is prepared as follows. In a mixture of freshly prepared Hydrosol Al2O3and zeolite injected mixture glioblastomas agent is hexamethylenetetramine and source of P (usually phosphoric acid or its salts) and get a homogeneous mass which is dispersed in the oil. The catalyst particles, remove the wear on the catalyst impregnated or mixed with the zeolite and the Hydrosol Al2O3. Introduction to the catalyst dehydrocyclization phosphorus-containing aluminum oxide provides improved resistance to the formation of coke.

Known introduction of salts of zirconium in the bifunctional catalyst. The catalyst for the isomerization of n-paraffins in the patent [4] contains a 49.9-97 wt.% zeolite (mordenite or fogasa), a 49.9 - 1 wt.% metal oxide (Al2O3the binding agent), 0.1 to 1% of the mass. Pt or Pd and 0.1-1 wt.% Zn (but not less than noble metal). The zeolite is impregnated with a solution of Zn salt prior to its mixing with the binder, the compounds of Pt (Pd) is applied by impregnation on the calcined catalyst. The use of bimetallic couples Zn and Pt or Zn and Pd increase the activity and selectivity of the catalyst for isomerization of n-paraffins.

It is known that salts of Zr have a weak acidic properties and can be used as catalysts. Patented catalyst for the conversion of methanol or dimethyl ether to olefins WITH2-C6[5] containing 1-60 wt.% (preferably 5-20%) partially hydrated zirconium sulfate Zr(SO4)2on-Al2O3, SiO2or ZrO2.

In the patent [6] proposed the closest to the proposed invention the composition bi the pore size (ZSM - 5, ZSM - 23, ) and binder (Al2O3, SiO2or aluminosilicate) in any proportion, as well as noble metal). Introduction to the catalyst components containing complex cation zirconium (hydroxychloride Zr or Al3Zr(OH)9Cl4improves the hydrothermal stability of the catalyst and the dispersion of the noble metal. The compound containing a complex cation Zr, mixed with the zeolite or with a binder at any stage of the preparation of the catalyst. It is assumed that during annealing the pellets of the catalyst complexes of Zr into ZrO2. Is an example of the preparation of the catalyst of the following composition (wt.%): zeolite ZSM - 5-65, Al2O3- 32,5; ZrO2- 2,5; Pd - 0,39. Zeolite is stirred with Pd(NH3)4Cl2dissolved in water, containing products of reaction of equimolar amounts of glycine and Al3Zr(OH)9Cl4add Al2O3and a lot ekstragiruyut. Bulk density of the calcined catalyst was 0.63 g/cm3the density of 2.65 g/cm3.

Catalysts used in fluid-the process should have a bulk density 0,80-0,85 g/cm3to avoid uncontrolled release of catalyst from the reaction products, when acceptable to the practical is Oh resistant to abrasion. These qualities are provided by the composition of the catalyst and the technology of its preparation. When this catalyst should contain the maximum number of active component is a zeolite, components with high specific gravity and sufficient plastic component.

The increase of the content in the catalyst ZrO2up to 20 wt.%, permitted in [6] , is insufficient to obtain a catalyst with the desired bulk weight, and leads to the decrease of the specific surface of the catalyst and the specific pore volume.

In accordance with the invention catalysts for the conversion of aliphatic hydrocarbons2-C10in a high-octane component of gasoline, is enriched in aromatic hydrocarbons, contains the group zeolite with Si/Al= = 12-30 in the hydrogen form, aluminum oxide and zirconium oxide as a binder, zinc oxide as promoter and zirconium phosphate in the following ratio, wt.%: Zeolite 25-35 ZrO25-10 Zr(PO4)425-30 ZnO 1-2 Al2O3Else

The content of compounds of zirconium in the catalyst does not exceed 35 wt.%.

The proposed composition of the catalyst differs from the known to the introduction of a new comp the number of Zirconia ZrO(NO3) 2H2O and phosphoric acid, H3PO4. Thus, the claimed solution meets the criterion of "novelty."

Known zeolite-containing catalysts include phosphorus-containing alumina [3] or zirconium dioxide [6]. However, their use in these cases, in combination with other components do not provide compositions such properties that they are sharing in the inventive solution, namely the increase in the activity of the catalyst with suitable for practical purposes, the bulk weight 0,80-0,85 g/cm3.

The observed effect is explained by the fact that in the conditions of preparation of the catalyst of phosphoric acid reacts with nitric acid zirconium with the formation of phosphates of zirconium conditional composition Zr3(PO4)4that possess catalytic activity in reactions acid-base type and are involved in the conversion of aliphatic hydrocarbons WITH2-C10. Therefore, when close physical characteristics of the zeolite catalyst containing zirconium oxide and zirconium phosphate is more active than the catalyst containing only zirconium oxide. This is manifested in higher stemperature process or reduce the content of zeolite in the catalyst. Thus, the catalyst of the proposed composition has new properties and meets the criterion of "inventive step".

The catalyst is prepared as follows. In steel apparatus with stirrer and heating receive aqueous suspension of the catalyst mass of a given composition. For this, the device loads the estimated amount of condensation and water pellet of aluminum hydroxide and after stirring the aqueous solution of nitric acid Zirconia ZrO(NO3)22H2O and an aqueous solution of zinc nitrate Zn(NO3)26H2O. the resulting suspension is stirred for 1 hour. Then in a mixer add the estimated amount of the zeolite CBM-III in ammonium form (degree of relative crystallinity, x-ray, 100%. Si/Al = 15,7. - static capacity for water vapor of 0.08 cm3/g pairs heptane 0,24 cm3/g). After 30 minutes stirring the resulting suspension into it gradually add the estimated amount of the aqueous ortho-phosphoric acid (H3PO4. The temperature in the apparatus is increased up to 50-60aboutAnd the suspension is maintained at this temperature and stirring for 3 hours After that, the suspension is drained and sent for spraying onto the laboratory is kasperesky granules are calcined in a muffle furnace at 550aboutWith over 5 hours of Calcined pellets scatter on the screens and separate the fraction of 20-150 μm, and the fraction of 20-50 μm 70 wt.%.

The following examples illustrate the preparation of catalysts according to the alleged invention and for comparison and the results of their testing in the reactions of conversion of hydrocarbons WITH2-C10containing aliphatic hydrocarbons - low-octane gas condensate and gasoline fractions of light hydrocarbons in a high-octane component of gasoline.

P R I m e R 1. To prepare a homogeneous aqueous slurry of a catalyst mass of a given composition in a mixer load 20 l of condensate and 1400 g of water pellet of aluminum hydroxide (SPT = =80 wt.%) and get a homogeneous suspension. Then, the device loads the solution 523,7 g nitrate Zirconia ZrO(NO3)2x x2H2O in 2 liters of condensate and solution to 74.2 g of zinc nitrate Zn(NO3)26H2O in 1 liter of condensate. After stirring for 1 h in a mixer add 412 g of zeolite NH4CBM-III (SPT - 15 wt.%) and after 30 minutes of stirring the solution to 150.1 g of N3PO4in 5 l of condensate. The resulting mass is stirred until a homogenous mixture for 3 h at 50-60aboutWith, drained and eg is aboutC for 5 hours, the Catalyst has the following composition, wt.%: Zeolite CBM-III 35 ZrO210 Zr(PO4)225 ZnO 2 Al2O328

The catalysts according to examples 2-6 were prepared similarly to the catalyst of example 1. The number of the blend components and the composition calcined at 550aboutSince the catalysts are given in table. 1. The composition of the catalyst mass does not account for water condensation, the flow of which is to prepare the catalysts according to examples 1-6, the following: obtaining a water suspension of aluminum hydroxide - 20 l; obtaining solutions of nitric acid zirconyl - 2 l, nitrate zinc - 1 l, phosphoric acid - 5 l

The weight of the catalysts prepared according to examples 1-6 0,80-0,85 g/cm3.

Samples of the resulting catalysts were tested in the pilot unit.

The raw material passes through the heating furnace and heated to 250aboutComes with under a distribution grid of the reactor where the conversion of raw materials into a product enriched arenas. The process is carried out in a turbulent fluidized bed of partially spent catalyst at a pressure of 0.3-0.4 MPa, a temperature of 360-530aboutC, space velocity of the raw material 500 h-1and ratio of catalyst circulation 3-6 maticevski.

The reactor is equipped with independent electric heating zones. The temperature control on the height of the reactor is carried out using a chromel-aluminievyh thermocouple readings are recorded multi-point potentiometer PSC-4.

Charged to the reactor of 1 liter of the catalyst. Prior to testing, the catalyst is heated in a stream of nitrogen to 250-560aboutWith depending on the feedstock. In the case of turning registertimer gas heat withdrawn partially removed water refrigerator.

Turbulent fluidized bed of catalyst is achieved by maintaining the linear velocity of the vapor of the raw material of 0.15-0.25 m/s (based on the cross-section of the reactor).

The reaction products rise to the top of the reactor, separated from the catalyst particles in the cyclone and filter and fed into the separator, where the separated liquid phase is unstable condensate and gas. The condensate after stabilization and gaseous products analyze.

To maintain a constant catalyst activity part of it through a pipeline to bring in the regenerator. Regeneration is performed by air (volumetric feed rate of 600 h-1) if 600aboutC.

The duration of the catalyst in the reactor 1 h, the duration is 49-142aboutWith a density of 0,702 g/cm3with an octane number by the motor method 59,8 and wide fraction of light hydrocarbons (NGL) Nizhnevartovsk condensate and onefineday gas similar in composition to the greasy gas catalytic cracking. The composition of raw materials are given in table. 2.

Are given in table. 3 the results of the tests of catalysts indicate that samples containing 25-30 wt.% Zr3(PO4)4more active in the conversion of hydrocarbon feedstocks into high-octane component of gasoline. When turning retinotomies gas increases the conversion of olefins and the yield of liquid product. Similar activity is achieved on the catalyst comparison with the temperature increase on the 15aboutWith and on the catalyst according to example 4, containing 10 wt.% less zeolite than the catalyst of comparison. During the transformation of broad fraction of light hydrocarbons, the catalysts prepared in accordance with the claimed invention, have a higher yield of liquid products and a higher content of aromatic hydrocarbons. Liquid products obtained from gas-condensate gasoline on the catalysts according to examples 1-5, enriched with aromatic hydrocarbons, and you have more the scientists at the transformation of different kinds of raw materials for the catalyst prepared according to example 3, in accordance with the claimed invention.

MICROSPHERIC ZEOLITE CATALYST FOR THE CONVERSION OF ALIPHATIC HYDROCARBONS, C2-C10in high-octane component of gasoline containing high-silica zeolite of the type pentasil in the hydrogen form with a ratio Si/Al = 12-30, aluminum oxide, binder - zirconium oxide, the promoter is zinc oxide, characterized in that it further contains zirconium phosphate with the following content, wt.%:

High-silica zeolite 25 - 35

Zirconium oxide 5 - 10

The zirconium phosphate 25 - 30

Zinc oxide 1 - 2

Alumina Rest

the content of compounds of zirconium in the catalyst does not exceed 35 wt.%.

 

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