The catalyst for the conversion of aliphatic hydrocarbons* s*001*002 and how transformations of aliphatic hydrocarbons*002-*001*002

 

(57) Abstract:

The invention relates to catalysts and methods of producing high-octane gasoline and aromatic hydrocarbons from a feedstock containing aliphatic olefins and paraffins WITH2-C12. High-octane gasoline or concentrate of aromatic hydrocarbons obtained when the contact of the feedstock at elevated temperature and pressure with a catalyst containing a group zeolite, zinc oxide, a mixture of oxides of rare-earth elements, boron oxide and fluorine in the following ratio, wt.%: zeolite 20.0-70.0; zinc oxide 1.0 to 4.0; REE oxides of 0.1-2.0; boron oxide is 0.1 to 3.0; a fluoride of 0.1 to 3.0; a binder component else. The use of a catalyst of the composition can increase the degree of conversion of raw materials and the yield of liquid high-octane hydrocarbons. 2 S. and 2 C.p. f-crystals, 4 PL.

The invention relates to catalysts for the conversion of aliphatic hydrocarbons to high octane gasoline and aromatic hydrocarbons and can be used in the refining and petrochemical industry.

The number of known catalysts and methods of producing high octane gasoline and aromatic hydrocarbons from a feedstock containing aliphatic hydrocarbons. Usually consisting Kats1-C12. The content of zeolite in the catalyst can vary within wide limits from 1 to 99 wt. and as the binder component used alumina, silica, aluminosilicates. The catalysts also contain metals or metal oxides (promoters) as components, increasing their activity and selectivity in the reactions of oligomerization and dehydrocyclization. The content of the promoters in the catalyst is generally 0.1-10 wt.

The most effective promoters of catalysts dehydrocyclization are zinc and gallium [1] However, gallium is expensive and scarce metal, and the main disadvantage of zinc-containing catalysts is reducing their activity as a result of ablation of zinc in the conditions of high temperature reaction and catalyst regeneration.

To reduce the loss of zinc and increase the yield of aromatic hydrocarbons in the catalyst to impose an additional one or more metals: gallium [1] gold, platinum, silver [2] rhenium or rare earth element [3]

To increase the activity and selectivity of zeolite catalysts used zeolite preparations diluted hydrofluoric acid solutions [4] the boron fluoride [5,6] Predam boron calcined zeolite (SiO2/Al2O3more than 100) with a binder, aluminum oxide and/or gallium oxide, suvcw residues of boron fluoride, hydrolysis of the zeolite, the processing of the ammonium salts, the process of calcination. The disadvantage of this catalyst is the complexity of the technology. According to [6] the group zeolite with SiO2/Al2O3= 30-300 treated with gaseous boron fluoride in the absence of binding under conditions that reduce the activity of the zeolite in the cracking of n-hexane, has a high activity in the conversion of methanol and oligomerization of propylene and is used in a patented way of turning raw materials containing olefins in the product, containing not more than 0.1 wt. aromatic hydrocarbons, and 96.4% of aliphatic hydrocarbons WITH4+and to 71.5% of olefins WITH6-C10. The catalyst for obtaining enriched in olefins liquid product, for use as a component of gasoline is limited and problematic, is complex technologies because of the need to handle loose component (zeolite) gas stream. Known catalyst [7] containing butatriene zeolite, solid fluorine-containing component from the group of fluorides, including ammonium fluoride. zinc, lanthanum, cerium and component zeolite, in which the metal is introduced by ion exchange or impregnation. The catalyst used for the conversion of hydrocarbons into aromatic hydrocarbons or high-octane gasoline. The catalyst containing 20% aluminum fluoride or 10% of the fluoride zinc, has a high selectivity in the formation of liquid and aromatic hydrocarbons from the butane-butylene fraction, as well as high stability actions. The composition of the catalysts depends on the process conditions, and the content of the fluorine-containing component can comprise 1-80 wt. preferably 5-40%

Closest to the proposed catalyst for the conversion of aliphatic hydrocarbons to high octane gasoline and aromatic hydrocarbons is the catalyst described in [2 prototype of the invention] the Patented catalyst contains zeolite group pentangelo a molar ratio of SiO2/Al2O3> 12; 0.1 to 5 wt. zinc and 0.1-2 wt. metal from groups IB or VIII of the periodic system, or germanium, or rhenium, or REE.

The technical problem solved by the invention is to increase the activity of the catalyst conversion of aliphatic hydrocarbons, increasing its selectivity in the formation of liquid high-octane hydrocarbons.

According to the invention the catalyst for obtaining aromatic hydrocarbons, and high-octane gasoline includes the group zeolite, zinc oxide, a mixture of two or more oxides of rare-earth elements and boron oxide and fluorine and a binder component, in the following, wt. zeolite 20,0-70,0; zinc oxide 1.0 to 4.0; the oxide of rare earth element 0,1-2,0; boron oxide is 0.1 to 3.0; a fluoride of 0.1 to 3.0; a binder component else.

The observed technical effects increase the degree of conversion of raw material, increasing the yield of liquid high-octane aromatic hydrocarbons, olefins and ISO-paraffins is probably the modifying influence of boron oxide and fluoride on acid and diffusion characteristics of the catalyst.

Used in the catalyst composition of the domestic high zeolites CVM and CUMS/TU 38.401528-85/ decationizing form or WHC /38.102168-85/ have the following characteristics: SiO2/Al2O320-80 mol/mol; the content of Na O less than 0.2 wt. the degree of crystallinity on rentgenophase component can be used synthetic silicates, silicon oxide, preferably aluminum oxide.

As a source of boron oxide is used orthoboric acid, H3IN3. An aqueous solution of boric acid is introduced into the catalyst mass at the stage of mixing zeolite and a binder. In the preferred embodiment, when used as a binder of aluminum oxide with an aqueous solution of boric acid can be used for peptization of aluminum hydroxide.

As a source of fluoride using a fluoride ammonium NH4F. an Aqueous solution of ammonium fluoride is introduced into the catalyst mass at the stage of mixing.

The rare-earth metal oxides is introduced into the catalyst solution of their nitrates, which upon calcination of the catalyst to form oxides REE. The nitrate solution is introduced into the catalyst mass in the mixing process or impregnate them calcined molded catalyst. Zinc oxide is introduced into the zeolite in the ammonium exchanged form with aqueous solutions of zinc salts, such as chloride or nitrate, or by impregnation of the zeolite or catalyst solutions of zinc salts, or injected into the catalyst mass in the mixing process.

Introduction to the catalyst of zinc oxides and REE by impregnation possible from one rasterization subjected to heat or thermoprotei treatment at 400-600oC.

The catalysts according to the invention can be prepared in different ways and to different method of granulation of the zeolite with a binder, the method of introduction of the promoters in the catalyst or zeolite, etc. However, when the same method of preparation of the catalyst and is equal to the content of the promoting metal oxides of zinc and a mixture of REE, the proposed catalysts containing certain amounts of boron oxide and fluorine, have a higher activity in the formation of liquid hydrocarbons from gaseous raw materials WITH a2-C4and upon receipt of high-octane gasoline of low octane provide increased yield of liquid products and detonation resistance.

The proposed method for the conversion of aliphatic hydrocarbons WITH2-C12in high-octane gasoline and aromatic hydrocarbons consists in contacting the feedstock at elevated temperature and pressure with a catalyst of the following composition, wt. zeolite group pectation with SiO2/Al2O320-80 20,0-70,0; zinc oxide 1.0 to 4.0; the oxide of rare earth element selected from the group of oxide laktan, cerium oxide, neodymium oxide, praseodymium oxide or a mixture of 0.1-2.0; boron oxide is 0.1 to 3.0; a fluoride of 0.1-II 0.5 to 3.0 MPa and space velocity of the raw material 0,5-6,0 h-1.

Preferably the raw material before it contacts the catalyst to be mixed with part of the gases evolved from the reaction products.

Example 1. and 63.3 g of dry zeolite NH4CVMS /SiO2/Al2O321.5 mol/mol, obtained by exchanging the original sodium form of zeolite CUMS 0.5 N ammonium nitrate solution containing 0.1 wt. sodium oxide, mixed with 99.0 g of aluminum hydroxide (humidity 79.1%) and 17 ml of an aqueous solution containing 1.6 g of orthoboric acid and 0.8 g of ammonium fluoride, mass, evaporated and formed by extrusion. Catalyst pellet (diameter 3 mm, length 2-3 mm), dried, and then treated with steam (flow rate of 0.5 g/1 g catalyst) at 500-550oC for 4 h the Cooled catalyst pellet fill in 70 ml of a solution containing 3.7 g of zinc nitrate Zn(NO3)2and 2.0 ml of a solution of nitrates of rare-earth elements (TU 95.120-84) with the concentration of REE oxides 200 g/l (cerium oxide 40-55 wt. the sum of the oxides of lanthanum, praseodymium, neodymium 60-45 wt.), incubated at room temperature for 2 h and evaporated. The catalyst was dried at 120oC and calcined at 550o4 o'clock

The composition of the obtained catalyst, wt. zeolite 70,0; zinc oxide 2,0; REE oxides of 0.5; boron oxide 1,1; fluorine 0,5; aluminum oxide 25,9.

Example 3. The catalyst prepared according to example 1, but the consumption of reagents the following, g: dry zeolite CUMS 18,1; aluminum hydroxide 260,0; orthoboric acid 4,3; ammonium fluoride 4,7; nitrate zinc 7,5; concentrate salts REE 8,0 ml

The calcined catalyst has the following composition, wt. zeolite 20,0; zinc oxide 4,0; REE oxides 2,0; boron oxide 3,0; fluoride of 3.0; aluminum oxide 68,0.

Example 4. Mix of 50.4 g of dry zeolite DCM containing 0.9 wt. zinc and received by the exchange of NH4DCM (SiO2/Al2O339,3 mol/mol) 0.4 N solution of zinc chloride, 117,5 g of aluminum hydroxide, 20 ml of an aqueous solution containing 2.8 g of orthophosphoric acid and 1.1 g of ammonium fluoride. Catalyst mass ekstragiruyut. The catalyst was dried, calcined and impregnated with 70 ml of a solution containing 4.7 g of zinc nitrate and 2.0 ml of the concentrate nitrates of rare-earth elements (neodymium, praseodymium, lanthanum and cerium). The catalyst was dried, calcined at 550o4 o'clock

The composition of the catalyst, wt. zeolite WHC (SiO2/Al2O380,0), obtained with a content of Na2O 0.1 wt. calcined 6 hours at 400-550oWith, mixed with 129,4 g of aluminum hydroxide, 20 ml of an aqueous solution containing 3.5 g of orthoboric acid and 2.5 g of ammonium fluoride and 5.9 ml of a solution of salts of the REE concentrations of the REE oxides 150 g/l, containing equimolar mixture of nitrates of lanthanum and cerium, 15 ml of an aqueous solution containing 1.9 grams of zinc nitrate. Catalyst mass ekstragiruyut. Granules of the catalyst is dried and calcined 4 h at 550oC.

The composition of the catalyst, wt. zeolite 60,0; zinc oxide 1,0; REE oxides 1.1 boron oxide 2,5; fluorine 1,6; aluminum oxide 33,8.

Example 6. The catalyst prepared according to example 5, however, boric acid and ammonium fluoride in the catalyst mass is not injected. The consumption of reagents the following g: dry zeolite WHC 54,2; aluminum hydroxide 129,4; nitrate zinc 1,9; concentrate salts REE of 5.9 ml.

The composition of the calcined catalyst, wt. zeolite 60,0; zinc oxide 1,0; REE oxides 1.1 alumina 37,9.

Example 7. The catalyst prepared according to example 1, but the consumption of reagents the following, g: dry zeolite CUMS 54,20; aluminum hydroxide 120,0; arterberry acid 0,14; ammonium fluoride 0,16; nitrate zinc 6,60; concentrate salts REE of 0.4 ml.

The composition of catalysate 8-19. The catalysts obtained in examples 1-7, experience in obtaining high-octane gasoline and aromatic hydrocarbons. The process is carried out by running the install with catalyst loading of 20 ml. of the Composition of raw materials are given in table. 1. In table.2 shows the conversion of various feedstocks containing aliphatic hydrocarbons2-C12. Products derived from gasoline fraction, accumulate within 24 h, and gas fractions for 6 h, then chromatographic determine their composition.

Comparison of transformation of the same species of the gas on the catalyst for the proposed method (examples 8, 9, and 10) and the prototype (examples 11,12 and 13) indicates an increase of the conversion of raw materials to the first group of catalysts, providing a higher yield of liquid products. In the conditions of the oligomerization of light olefins on the catalyst containing an oxide of boron and fluorine, increases the conversion of isobutane contained in raw materials, increases the ratio of ISO-paraffins/ n-paraffins in the liquid product. Upon receipt of high-octane gasoline from a gasoline feedstock to the proposed catalyst increases the yield of liquid product and the content of aromatic uglevodorodnogo fractions from the catalytic cracking unit with circulation of part of the gases, selected from the products of conversion of raw materials and components of recycle streams 1 and 11, miscible with the feedstock prior to making its contact with the catalyst. Conditions of transformation of raw materials: temperature 320-390oWith the pressure of 2.0 MPa, zsss fresh raw 0.9 h-1, Zsss recycling 10,8 h-1, Zsss recycling 11 1185,9 h-1. The composition of the feedstock and recycle streams are given in table.3.

Recycling the gases separated from the products of the conversion of raw materials and composed mainly of hydrogen and hydrocarbons1-C4allows to achieve a high degree of conversion of raw materials; conversion of propylene 96.7% of butene-1 94.3% of butene-2 to 98.6% ISO-butene to 96.8% Yield of gasoline 63,85 wt. for raw materials. Characteristics of gasoline: N. K. 40,5oC, 50% boils at 100,8oWith, K. K. 186,6oC; vapour pressure 67240 PA; olefins to 23.8 wt. the content of aromatic hydrocarbons of 12.2 wt.

Example 21. The catalyst according to example 7 perform the conversion of propane-propylene fraction (for example, options 1 and 11). According to the variant 1 of the products of transformation of raw materials allocate a portion of hydrogen containing gas consisting mainly of hydrogen and methane, and mix it with the raw material before it contacts the catalyst, organizing the yaschih mainly of hydrogen and hydrocarbons1-C4and mix them with the raw material before it contacts the catalyst. Conditions of transformation of raw materials: temperature 320-390oWith; zsss fresh raw 2,0 h-1; pressure of 2.0 MPa. The composition of raw materials, the reaction products and the circulating gases are given in table.4.

1. The catalyst for the conversion of aliphatic hydrocarbons2- C12containing group zeolite with silica module 20 80, oxide of zinc, oxide of rare earth element and a binder component, characterized in that it further contains an oxide of boron and fluoride and oxide of rare earth element, two or more oxides selected from the group of lanthanum oxide, cerium oxide, neodymium oxide, praseodymium oxide, with the following content, wt.

Zeolite 20,0 70,0

Zinc oxide 1,0 4,0

The oxide of rare earth element 0,1 2,0

The boron oxide is 0.1 to 3.0

Fluorine 0,1 3,0

Binder is the Rest

2. The method of transformation of aliphatic hydrocarbons2- C12in high-octane gasoline and aromatic hydrocarbons at elevated temperatures and pressures in the presence of a catalyst containing a group zeolite with silica module 20 80, zinc oxide, oxide readarray boron oxide and fluoride and oxide redkozemelnaja element two or more oxides, selected from the group of lanthanum oxide, cerium oxide, neodymium oxide, praseodymium oxide, with the following content, wt.

Zeolite 20,0 70,0

Zinc oxide 1,0 4,0

The oxide of rare earth element 0,1 2,0

The boron oxide is 0.1 to 3.0

Fluorine 0,1 3,0

Binder is the Rest

3. The method according to p. 2, characterized in that the process is carried out at a temperature of 280 550oC, a pressure of 0.5 to 3.0 MPa and space velocity of the raw material of 0.5 to 6.0 h-1.

4. The method according to p. 2, characterized in that the raw materials before making its contact with the catalyst is mixed with a part of the gases evolved from the reaction products.

 

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FIELD: petrochemical processes.

SUBSTANCE: high-octane fuels and propane-butane fraction are obtained via conversion of hydrocarbon feedstock on contact with hot catalyst placed in reactor, into which diluting gas is supplied at elevated pressure. Catalyst is Pentasil-type zeolite with general formula xM2/nO,xAl2O3,ySiO2,zMe2/mO wherein M represents hydrogen and/or metal cation, Me group II or VII metal, n is M cation valence, m is Me metal valence, x, y, z are numbers of moles of Al2O3, SiO2, and Me2/mO, respectively, and y/x and y/z ratios lie within a range of 5 to 1000. Metal oxide Me2/mO is formed during calcination, in presence of oxygen, of Me-containing insoluble compound obtained in zeolite reaction mixture.

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