The method of purification of gasolines from thermal processes (options)

 

(57) Abstract:

Usage: gasoline thermal processes is subjected to hydrogenation in the presence of the product of the sulfuric acid alkylation catalyst. As catalyst, a mixture of BaCl2and clay containing aluminum oxide, taken in a mass ratio of 1 : 1. The mass ratio of the gasoline-product sulfuric acid alkylation is (1,5 - 2,3):1. The process is carried out at 0 to 10oC, atmospheric pressure, space velocity of the raw material 1 - 2 r-1. It is also possible hydrogenation of a mixture of gasoline and alkylation product in two stages. The first stage is conducted as described above, the second used catalyst - NaAlCl4caused - Al2O3and the process is carried out at 200 - 250 oS. 2 S. p. f-crystals, 1 table.

The invention relates to the refining, in particular to a method of cleaning gasoline thermal origin from unsaturated hydrocarbons and sulfur compounds for use as gasoline.

Gasoline fractions from thermal processes thermal cracking, delayed coking, visbreaking and pyrolysis are characterized by a high content of unsaturated walking is a process of catalytic reforming with platinum catalyst [1] However, the catalyst is easily deactivated by sulfur compounds and resins. So gasolines from thermal processes require careful cleaning and hydrofining.

There is a method of Hydrotreating gasoline, thermal cracking on aluminoborosilicate catalyst in two stages. In the first stage of unsaturated hydrocarbons are subjected to hydrogenation with hydrogen at a temperature of 100-200aboutC. In the second stage at a temperature of 360-400aboutWith hydronauts hetero-organic compounds [2]

The disadvantage of this method is the low octane number of the resulting product (49 points in m m).

The closest technical result of the claimed method is clean gasoline thermal cracking [3] consists in the fact that the hydrogenation is subjected to a mixture of the cracking gasoline with diesel fuel or vacuum gasoil on the type hydrotreatment at a temperature of 370-380aboutC, a pressure of 50 ATM. space velocity of the raw materials 3 h-1, the ratio of hydrogen containing gas to the raw material 500 n/l lookbetteronline.com catalyst.

As a source of raw materials used gasoline, thermal cracking (N. K. 200about(C) with a sulfur content of 1.1% and an iodine number 97 g J/100 g of product octane number 68 n at m m in a mixture of c diesel topo 34 g J/100 g of product.

Product Hydrotreating has octane number 55 p. in M. M. and sulphur content less than 0.1 wt. and is the raw material for catalytic reforming.

The disadvantages of this method are: low octane number of the resulting product, low productivity of raw materials and the need for additional processing of the product on the catalytic reformer and hard process conditions of high pressure, temperature, the use of a special hydrogen-containing gas.

The technical result of receiving quality gasoline with simplified technology achieve that clean gasoline fraction thermal process from unsaturated hydrocarbons and organic sulfur compounds is carried out by saturation of monoolefins, diolefins and degradation of organic sulfur compounds by ion mechanism in the presence of a catalyst consisting of a mixture of BaCl2and polymineral (clay, containing in its composition aluminum oxide) in the ratio of 1:1 and donor of the hydride ion product of the sulfuric acid alkylation of isobutane by olefins (butane-butylene fraction) in a mass ratio of the raw material 1: (1,5-2,3) and the hydrogenation is carried out at a temperature of 0 to 10aboutC, atmospheric pressure, flow rate model fractions from unsaturated and sulfur compounds and increase the octane number reach those the hydrogenation is subjected to a mixture of gasoline and product sulfuric acid alkylation of isobutane by olefins in a mass ratio of 1.5 to 2.3)-1 at atmospheric pressure and feed rate of raw materials 1-2 h-1and the hydrogenation is carried out in two stages, the first stage in the presence of a catalyst consisting of a mixture of BaCl2and clay, containing in its composition alumina mass ratio of 1:1 at a temperature of 0 to 10aboutSince there is a saturation of mono - and diolefins and partial hydrodesulphurization unit, and the second stage in the presence of a catalyst NaAlCl4at a temperature of 220-250aboutWith the almost complete saturation of the olefins and the hydrogenolysis of organic sulfur compounds to H2S. At the same time, apparently, reactions proceed alkylation and isomerization with the formation of branched hydrocarbons, which increases the octane number of the resulting gasoline.

Of scientific and technical literature and patent documents is not known to use a mixture of gasoline thermal process and product of the sulfuric acid alkylation for the hydrogenation with the aim of refining gasoline. However, it is known that the product of the sulfuric acid alkylation butane-butylene fraction, sustaim gasoline to increase the octane number [4] advantages of the proposed method are the use of relatively inexpensive catalysts, made from available materials by simple technology, atmospheric-pressure process, a relatively low temperature and the absence of a hydrogen-containing gas. As well as the method allows to efficiently convert low-quality gasoline secondary origin to obtain commercial gasoline.

The catalyst used in the first embodiment, is prepared by mixing BaCl2and clay (polymineral of the following composition: xAl2O3ySiO2H2O) in a mass ratio of 1: 1. The mixture was transferred to a pasty state by the addition of distilled water (not more than 10%) ekstragiruyut using a handheld extruder. Received slightly dried filaments with a diameter of 0.3-0.4 cm pulverized and dried to constant weight at T 185-190aboutC.

The catalyst used in the second variant (stage II), for more deep desulfurization, are prepared by applying NaAlCl4on the surface of industrial-Al2O3[4]

Use-Al2O3brand RM-12, subjected to heat treatment in a stream of inert gas at 500aboutWith (3 h). Surface-Al2O3pre-treated with surfactant (0,05% solution of diethanolamine in hexane for 1 h at room tempitem-Al2O3immersed in the melt NaAlCl4(190-200about(C) when the mass ratio of the catalyst carrier, respectively, to 1.5: 1. The mixture is kept for 15 minutes the Excess catalyst is removed by garbage pellets in a sieve and calcined at a temperature of 300aboutC for 10-20 minutes as an additive to gasoline fractions use the product installation sulfuric acid alkylation gas fractions. The raw material used gasoline delayed coking fraction 27-167aboutWith a sulfur content of 0.95 wt. iodine number 132 g J/100g and octane 55 p. in M. M. and thermal cracking gasoline fraction 29-163aboutWith a sulfur content of 0.71 wt. iodine number 85 g J/100 g of product and octane 62 by p. M. m

P R I m e R 1. Raw gasoline fraction of delayed coking limits boiling 27-167aboutWith mixed with the product of the sulfuric acid alkylation mass ratio of 60:30. The resulting mixture with a sulfur content of 0.65 wt. and iodine number 95 g J/100 g of product is fed to the top of the reactor filled with catalyst BaCl2+ clay, with a bulk velocity of 1.0 h-1at a temperature of 0aboutC. the Bottom of the reactor selected target product with an iodine number of 5.8 g J/100 g, a sulfur content of 0.15 wt. octanol the th fraction of thermal cracking outside the boil 29-163aboutWith mixed with the product of the sulfuric acid alkylation mass ratio of 60:30. The resulting mixture with a sulfur content of between 0.46 wt. and iodine number 46 g J/100 g of product is fed to the top of the reactor filled with catalyst BaCl2+ clay, with a bulk velocity of 1.0 h-1at a temperature of 0aboutC. the Bottom of the reactor selected target product with an iodine number of 5.2 g J/100 g, a sulfur content of 0.14 wt. an octane rating of 75 points in M. m

P R I m e R 3. Raw gasoline fraction of delayed coking limits boiling 27-167aboutWith mixed with the product of the sulfuric acid alkylation mass ratio of 60:30. The resulting mixture with a sulfur content of 0.65 wt. and iodine number 95 g J/100 g of product is fed to the top of the reactor filled with catalyst BaCl2+ clay, with a bulk velocity of 1.0 h-1at a temperature of 0aboutC. the Bottom of the reactor are selected product and serves on second reactor filled with catalyst NaAlCl4at a temperature of 200aboutC. from the Bottom of the second reactor selected target product with an iodine number of 0.51 g J/100 g of product with a sulfur content of 0.07 wt. octane 83 n at m m the results of the experiments presented in the table.

P R I m e R 4. Raw gasoline fraction thermal crumbling 60: 30. The resulting mixture with a sulfur content of between 0.46 wt. and iodine number 46 g J/100 g of product is fed to the top of the reactor filled with catalyst BaCl2+ clay, with a bulk velocity of 1.0 h-1at a temperature of 0aboutC. the Bottom of the reactor are selected product and served in the second reactor filled with catalyst NaAlCl4at a temperature of 200aboutC. from the Bottom of the second reactor selected target product with an iodine number of 0.45 g J/100 g, a sulfur content of 0.06 wt. octane 84 by p. M. m

The results of the gasoline Hydrotreating delayed coking in a mixture with the product sulfuric acid alkylation butane-metilenovoj faction: I option one-step process in the presence of a catalyst BaCl2+ clay; option II two-stage process in the presence of a catalyst BaCl2+ clay (stage I) and NaAlCl4(II stage) are shown in table.

1. The method of cleaning gasoline thermal processes from unsaturated and sulfur compounds by hydrogenation in the presence of aluminium-containing catalyst, followed by separation of the target product, characterized in that the hydrogenation is subjected to a mixture of gasoline and product sulfuric acid alkylation of isobutane by olefins in the mass ratio (1,5 2,3) 1, it is to 1 1, and the process is carried out at a temperature of 0 +10oC, atmospheric pressure, space velocity of the raw material 1 2 h-1.

2. The method of cleaning gasoline thermal processes from unsaturated and sulfur compounds by hydrogenation in the presence of aluminium-containing catalyst, followed by separation of the target product, characterized in that the hydrogenation is subjected to a mixture of gasoline and product sulfuric acid alkylation of isobutane by olefins in the mass ratio (1,5 2,3) 1, the hydrogenation is carried out in two stages, with the first stage as the catalyst a mixture of BaCl2and clay containing aluminum oxide, taken in a mass ratio of 1 to 1, and the process is carried out at a temperature of 0 +10oWith the second as the catalyst used NaAlCl4printed at = Al2O3and the process is carried out at 200 to 250oC.

 

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