Catalyst and method for producing liquid hydrocarbons from dimethyl ether

 

(57) Abstract:

The invention relates to a process for production of liquid hydrocarbons enriched ISO - and cycloparaffins, which can be used as an additive in the production of high-octane gasoline with a content of aromatic hydrocarbons of not more than 30 wt.%. Liquid hydrocarbons produced from dimethyl ether using a catalyst based on crystalline aluminosilicate type of pentelow with SiO2/Al2O3=25-100 containing 0.05-0.1 wt.% sodium oxide, and a binder component, which additionally contains zinc oxide and oxides of rare earth elements in the following ratio, wt.%: Zn0 0,5-3,0, oxides REE 0.1 to 5.0, crystalline aluminosilicate 65-70, the rest of the binder. The catalyst was activated in air at 540-560C. the Process is carried out at a pressure of 0.1-10 MPa, a temperature of 250-400C., space velocity of the raw material 250-1100 h-1. 2 S. and 1 C.p. f-crystals, 2 tab.

The invention relates to methods of producing hydrocarbons from dimethyl ether, in particular a mixture of hydrocarbons enriched ISO - and cycloparaffins. Such liquid hydrocarbons can be used as an additive for high octane is dimetilovogo ether into valuable hydrocarbons (liquefied gas, motor gasoline, aromatic hydrocarbons, and others) is determined by the properties of the catalyst and process conditions. It is known that effective catalysts for the conversion of dimethyl ether in a mixture of hydrocarbon compositions are inorganic metallic components and zeolites, in particular decationizing of pentelow H-ZSM-5, H-ZSM-11. [Proc. Int. Zeolite Conf. , 6th. Meeting Date 1983, 316-324, 489-96: Guildford, UK. (English) 1984; S. African ZA 8401683 A 19841128].

A known method of producing a liquid hydrocarbon or mixture of olefins, C2+of dimethyl ether on a modified zeolite catalyst or metallothionine at 300-700oC, a pressure of 0.1 MPa and a mass flow rate of feed of 2.3 h-1[S. African ZA 9004752 A; 19920226]. With increasing temperature from 300 to 600oC increases the selectivity of the formation of olefins, C2-C4. The total yield of these olefins reaches 74-75%, the rest is liquid hydrocarbons.

A method of obtaining isoparaffin hydrocarbons from dimethyl ether, described in [U.S. Pat. USA 4579999, 1986].

In accordance with the patent dimethyl ether at high catalyst ZSM-5 in the first stage turns into a mixture of olefins, C2-C4and hydrocarbon, C5+. itogo catalyst. The second stage of the process is carried out at elevated pressure and moderate temperatures. Also recycling of light hydrocarbons to the first stage of the process. The disadvantage of this method is its multi-stage.

Closest to the claimed method is a process of obtaining olefins C2-C5and liquid hydrocarbons at a pressure of from 0.1 to 5.0 MPa, a temperature of 360oC and mass flow rate of feed of 1.65 h-1[Pat.USA 3894106, 1975] . As a catalyst is proposed catalytic system containing 65% HZSM and 35% Al2O3. The disadvantages of this process are the formation of large quantities of gaseous hydrocarbons (25-40 wt.%) and high yield of aromatic hydrocarbons (up to 45 wt.%).

The technical result of the invention is to increase the output of high-octane components of motor fuels with a low content of aromatic hydrocarbons from dimethyl ether or gas containing dimethyl ether.

This technical result is achieved by the fact that during production of liquid hydrocarbons from dimethyl ether using a catalyst based on crystalline aluminosilicate type of pentelow with SiO2/Al2
ZnO - 0,5 - 3,0

oxides REE - 0,1-5,0

crystalline aluminosilicate - 65 - 70

binding - rest

The catalyst was activated in air at a temperature of 540 to 560oC.

The process is carried out at pressures of 0.1-10 MPa, a temperature of 250-400oC, space velocity of the raw material 250-1100 h-1.

The observed effect of increasing the yield of liquid hydrocarbons is explained, apparently, by modifying the acid properties and catalytic activity of the zeolite component and, possibly, the promoting effect of REE oxides on the surface of the zeolite crystallites.

The zeolites used in the composition of the proposed catalyst, are the domestic counterparts of pentelow computers, CVMS (both on THE 38.401528-85), WHC and PPM (on THE 38.102168-85), containing 0.2 to 0.5 mol.% Na2O, and obtained by direct synthesis (WHC) or when exchanging the original Na-form of the zeolite in the H+or NH4+form.

As a binder component can be used synthetic silicates, aluminium oxide.

The REE oxides formed on the surface of the catalyst during calcination at 550oC zeolite impregnated industrial concentrate nitrates R is containing in 1 l 200 g REE oxides of the following composition, mol. %: CeO2- 48); the amount of La2O3PrO3and Nd2O3- 52 or an aqueous solution of neodymium nitrate.

Below are examples that prove the effectiveness of the proposed method to obtain the target product.

Example 1. Zeolite WHC synthesized with SiO2/Al2O3equal to 42, with the use of monoethanolamine. The hydrogen form of the zeolite with the specified residual content of Na2O (0.05 to 0.1 wt.%) obtained in a double exchange of Na in 30% ammonium nitrate solution followed by drying and calcination in air for 3 hours at 500-550oC. the Zn Oxide is introduced into the zeolite in the ammonium exchanged form with an aqueous solution of zinc nitrate. The estimated number of Nd2O3inflicted on the zeolite method residue impregnation from an aqueous solution of neodymium nitrate. Zeolite with a specified content of oxides was obtained by calcination of the treated sample at 500-550oC. the Estimated amount of the calcined zeolite is mixed with a binder is aluminum hydroxide (p. M. p. p. - 70%), formed by extrusion. Catalyst pellet (2x2 mm), dried at 100oC for 2 hours, then activated by calcination in air at 550oC for 3 hours. The composition of the obtained BR> Example 2. The catalyst was prepared analogously to example 1, with the difference that at the stage of impregnation of ammonium form of the zeolite instead of an aqueous solution of neodymium nitrate was used an aqueous solution of REE concentrate composition (calculated on the resulting oxides) GeO2- 48); the amount of La2O3PrO3and Nd2O3- 52 mol%. The composition of the obtained catalyst below, wt.%:

ZnO - 2,0

Oxides REE - 1,0

Zeolite WHC - 67,0

Al2O3- 30

Examples 3-18. The catalysts obtained in examples 1, 2, is used to produce hydrocarbons from dimethyl ether in the instantaneous isothermal reactor with a catalyst loading of 10 g at the temperature of the reactor 250-400oC, a pressure of 0.1-10.0 MPa, the space velocity of the gas 250-1100 h-1. Liquid and gaseous reaction products were analyzed by chromatographic methods. The raw material used pure dimethyl ether (raw material 1) or a gas mixture of the following composition containing dimethyl ether (raw material 2), see table. 1.

The results of the experiments are given in table. 2.

In the presented examples the proposed method of producing liquid hydrocarbons from dimethyl octane number (I. M.) IDI can be used as the basis for producing high-octane gasoline with a low content of aromatic hydrocarbons. The high octane number of the produced hydrocarbons is achieved not only due to aromatic hydrocarbons, but also due to the higher (than in the prototype) content of paraffins ISO - and cycloserine.

1. The catalyst for the production of liquid hydrocarbons from dimethyl ether on the basis of the crystalline aluminosilicate type of pentelow with SiO2/Al2O3= 25 - 100 containing 0.05 - 0.1 wt.% sodium oxide, and a binder, characterized in that it additionally contains zinc oxide and oxides of rare earth elements in the following ratio, wt.%:

ZnO - 0,5 - 3,0

Oxides REE - 0,1 - 5,0

Crystalline aluminosilicate - 65 - 70

Binding - Rest

2. The method of obtaining liquid hydrocarbons from dimethyl ether in the presence of a catalyst based on crystalline aluminosilicate type of pentelow with SiO2/Al2O3= 25 - 100 containing 0.05 - 0.1 wt.% sodium oxide, and a binder, characterized in that the used catalyst, optionally containing zinc oxide and oxides of rare earth elements in the following ratio, wt.%:

ZnO - 0,5 - 3,0

Oxides REE - 0,1 - 5,0

Crystalline aluminosilicate - 65 - 70

Tie the persons under item 2, characterized in that the contact dimethyl ether with a catalyst is carried out at a volumetric feed rate of dimethyl ether 250 - 1100 h-1(gas), a pressure of 0.1 - 10 MPa and a temperature of 250 - 400oC.

 

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