The catalyst for the production of liquid hydrocarbons of low molecular weight oxygen-containing organic compounds

 

(57) Abstract:

The invention relates to improved compared with the prior art catalyst to produce liquid hydrocarbons of low molecular weight oxygenated organic compounds comprising crystalline aluminosilicate type pentasil with the value of the molar relationship of silicon oxide to aluminum oxide from 25 to 120, sodium oxide, zinc oxide, oxides of rare earth elements and a binder, where the oxides of rare earth elements it contains the oxides of the following composition, mol.%:

the cerium oxide - 3,0

the oxide of lanthanum - 65,0

the oxide of neodymium - 21,0

the oxide of praseodymium - Rest

moreover, each value of silicon oxide to aluminum oxide in the crystalline aluminosilicate type pentasil corresponds to a certain range of values of the content of sodium oxide, in the following ratio of catalyst components, wt.%:

Crystalline aluminosilicate type pentasil - 63,0-70,0

The sodium oxide - 0,12-0,30

Zinc oxide - 0,5-3,0

The oxide of rare earth elements in the specified composition - 0,1-3,0

Binding - Rest

This catalyst has a higher activity. 1 C.p. f-crystals, 1 tab., 2 Il.

Sorgulama oxygen-containing organic compounds with the number of carbon atoms in the molecule C1-C6(methanol, dimethyl ether, ethanol, propanol and so on), which can be used as an additive for producing high-octane gasoline with a content of aromatic hydrocarbons of not more than 30 wt.%.

Know the use of the modified zeolite catalyst to produce liquid hydrocarbons or mixture of olefins, C2+of dimethyl ether (see application ZA 9004752 AND 1992.02.26), providing a total yield of olefins (C2-C4) to 74-75% (the rest is liquid hydrocarbons).

A method of obtaining isoparaffin hydrocarbons from dimethyl ether, described in the patent US 4579999 And 1986, according to which dimethyl ether is converted into a mixture of olefins WITH2-C4and hydrocarbons WITH5+using high catalyst ZSM-5, and the mixture of olefins is directed to oligomerization using srednevoljskogo acidic zeolite catalyst.

Known also use as catalyst for the conversion of low molecular weight oxygen-containing organic compounds (dimethyl ether) in a mixture of hydrocarbons catalytic system containing 65 wt.% zeolite type pentasil H-ZSM-5, H-ZSM-984.11.28).

In addition, from patent US 3894106 And 1975 is known to use as catalysts for olefin production WITH2-C5and liquid hydrocarbons catalytic system containing 65% HZSM and 35% Al2ABOUT3(exit of gaseous hydrocarbons 25-40 wt.%, the yield of aromatic hydrocarbons to 45 wt.%).

The closest analogue of the claimed invention is a catalyst for the production of liquid hydrocarbons of low molecular weight oxygen-containing organic compounds (dimethyl ether), disclosed in the patent RU 2160160 C1, 10.12.2000 and represents a catalyst based on crystalline aluminosilicate type pentasil with a molar ratio of SiO2/Al2O3=25-100 containing 0.05-0.1 wt.% sodium oxide and a binder component that contains zinc oxide and oxides of rare earth elements in the following ratio, wt.%:

Zinc oxide - 0,5-3,0

The oxides of rare earth elements - 0,1-5,0

Crystalline aluminosilicate 65-70

Binding - Rest

The common disadvantage of the process disclosed in the above analogues and providing for the use of the described catalysts is the formation of large amounts of gaseous prevalidation of the invention, is to increase the yield of high-octane hydrocarbons with a low content of aromatic hydrocarbons and improve the operational properties of the catalyst, namely to increase the mechanical strength of the granules and increases the ability of the catalyst to the oxidative regeneration.

The catalyst for the production of liquid hydrocarbons of low molecular weight oxygen-containing organic compounds, for achieving the above technical result in all cases covered by the amount of the requested legal protection, can be characterized by the following set of essential features.

The catalyst contains a crystalline aluminosilicate of the type pentasil with the value of the molar relationship SiO2/Al2O3being in the range from 25 to 120, sodium oxide, zinc oxide, oxides of rare earth elements, a binder, in the following ratio, wt.%:

Crystalline aluminosilicate - 63,0-70,0

The sodium oxide - 0,12-0,3

Zinc oxide - 0,5-3,0

The oxides of rare earth elements - 0,1-3,0

Binding - Rest

Each value of the molar relationship SiO2/Al2O3corresponds to a specific range value is correctly equal to the value of the ordinate of the curve point 1, presented on Fig.1, the value of the abscissa of which is at least approximately equal to said value of the molar relationship SiO2/Al2ABOUT3. The maximum value of the specified range, at least approximately equal to the value of the ordinate of the curve 2 shown in Fig. 1, the value of the abscissa of which is at least approximately equal to said value of the molar relationship SiO2/Al2O3.

In addition, for the implementation of the invention, the oxides of rare earth elements, the catalyst contains cerium oxide CEO2the oxide of lanthanum La2ABOUT3the oxide of neodymium Nd2ABOUT3and praseodymium oxide WG6O11when the following ratio of components, mol.%:

SEO2- 3

La2O3- 65

Nd2O3- 21

WG6O11- Rest

In addition, in the particular case of the invention as a binder, the catalyst may contain synthetic silicates or alumina Al2ABOUT3or silicon oxide SiO2or a mixture of Al2ABOUT3and SiO2.

In addition, in the particular case of implementation of the invention, the crystalline aluminosilicate and sodium oxide can sudermania the catalyst can be activated in air at a temperature of 540-560oC.

Presented on Fig.1 dependence between the value of the molar relationship SiO2/Al2O3and the corresponding range of values of the content of sodium oxide in the catalyst is determined experimentally and provide a degree of conversion of raw materials is not less than 90% with a selectivity for the target reaction products of at least 80%.

The zeolites used in the composition of the proposed catalysts are local analogues of zeolites of type pentasil computers, CVMS (both on THE 38.401528-85), WHC and CEC (on THE 38.102168-85) containing 0.03 to 0.3 wt.% sodium oxide (Na2O) and obtained by direct synthesis (WHC) or when exchanging the original Na+-form of the zeolite in the H+or NH4+form.

Zinc oxide (ZnO) is introduced into the zeolite in the ammonium exchanged form with an aqueous solution of zinc nitrate and subsequent calcining the thus treated samples at 550oC.

The oxides of rare earth elements are formed on the surface of the catalyst during calcination at 550oWith zeolite impregnated industrial concentrate nitrates of rare-earth elements. For modification of zeolites as a source of rare earth elements can be used vivamente 200 g of oxides of the following composition (mol.%): SEO2- 3,0; La2ABOUT3- 65; Nd2O321 and WG6ABOUT11- the rest.

The catalyst activated at a temperature of 540-560oC.

The catalyst with the above-mentioned ratio of the components used to produce liquid hydrocarbons of low molecular weight oxygen-containing organic compounds with the number of carbon atoms in the molecule C1-C6when the volumetric feed rate of the liquid raw material is 0.5 to 3.0 HR-1, a pressure of 0.1-1.0 MPa and a temperature of 250-400oC.

The graphic materials showing the following:

in Fig. 1 - graphical dependency between the value of the molar relationship SiO2/Al2O3and the corresponding range of values of the content of sodium oxide in the catalyst;

in Fig.2 - example determine the minimum and maximum values of the content of sodium oxide (Na2O) in accordance with the claimed method.

The possibility of carrying out the invention described above, a set of features, as well as the possibility of realization of the purposes of the invention can be confirmed by the description of specific examples of the catalyst for production of liquid hydrocarbons from Niska catalyst.

Pre-graphic dependences shown in Fig.1, determine the range of possible values of the content of sodium oxide, the minimum value of the content of sodium oxide for selected values of n molar relationship SiO2/Al2O3with confidence probability of at least 0.95 to equal the value of the ordinate of Aynpoint And curve 1 shown in Fig.1, the value of the abscissa of Axnwith confidence probability at least equal to 0,95 mentioned value n molar relationship SiO2/Al2O3and the maximum value of the content of sodium oxide, with confidence, at least 0,95 equal to the value of the ordinate Bynpoint In the curve 2 shown in Fig.1, the value of the abscissa Bxnwith confidence probability at least equal to 0,95 mentioned value n molar relationship SiO2/Al2ABOUT3. Then from the obtained range choose one of the values and accept it as the basis for the manufacture of the catalyst, which is as follows.

Example 1. Zeolite type computers with the value of the molar relationship SiO2/Al2O325 with "oxide" formula l, the number of ammonia with a concentration of 240 g/l, also containing 0.125 mol/l nitric acid. The ratio of aqueous solution/zeolite equal to 30 l/kg, the temperature of 955oC, mixing time 1 hour. After treatment, the zeolite is filtered off and get a sample with the content of sodium oxide and 0.15 wt.%.

Example 2. Zeolite type computers with the value of the molar relationship SiO2/Al2O325 with "oxide" formula l-2Na2Ol2ABOUT325SiO2(4,43% of sodium in terms of oxide) is treated with an aqueous ammonium nitrate solution with a concentration of 160 g/l, containing 1.5 mol/l of nitric acid. The ratio of aqueous solution/zeolite equal to 2.5 l/kg, the temperature of 955oC, mixing time 1 hour. After treatment, the zeolite is filtered off and get a sample with the content of sodium oxide was 0.026 wt.%.

Example 3. Zeolite type the CVM or the WHC with the value of the molar relationship SiO2/Al2O344 with the oxide formula of 0.8 Na2O0,2H2Ol2ABOUT344SiO2(1.77 per cent sodium in terms of oxide) is stirred in a hot aqueous ammonium nitrate solution with a concentration of 320 g/l at a temperature of 955oC for 2 hours. The ratio of aqueous solution/zeolite is 80 l/kg After treatment, the zeolite is filtered off and washed on the filter distillirovanna the I of 0.12 wt.%.

Example 4. Zeolite type the CVM or the WHC with the value of the molar relationship SiO2/Al2O344 with the oxide formula of 0.8 Na2O0,2H2l2ABOUT344Si2 (1.77 per cent sodium in terms of oxide) is stirred in a hot aqueous ammonium nitrate solution with a concentration of 240 g/l at a temperature of 955oC for 1.5 hours. The ratio of aqueous solution/zeolite is 60 l/kg After treatment, the zeolite is filtered off and washed on the filter with distilled or deionized water. The ratio of water/zeolite is 3 l/kg Receive a sample content of sodium oxide to 0.20 wt.%. The resulting zeolite is stirred for 48 hours with concentrated nitric acid (to 12.3 and 12.4 mol/l) at room temperature. The ratio of aqueous solution/zeolite is 1.0 l/kg Mixture is diluted with water, the zeolite is filtered, washed on the filter with distilled or deionized water. Get a sample with the content of sodium oxide to 0.08 wt.%.

Example 5. Zeolite type WHC with the value of the molar relationship SiO2/Al2O355 "oxide" formula of 0.14 Na2O0,N2Ol2ABOUT355SiO2(0,25. percent sodium oxide) obtained by direct synthesis on THE 38.102168-85, used for the preparation of the catalyst without preemie 5 hours with a dilute aqueous solution of sulfuric acid (4 g/l) at room temperature. The ratio of aqueous solution/zeolite is 3.0 l/kg Zeolite is filtered off. Get a sample with the content of sodium oxide to 0.18 wt.%.

Example 7. Zeolite type IEC-1 with the value of the molar relationship SiO2/Al2O390 "oxide" formula of 0.05 Na2O0,95H2Ol2ABOUT390SiO2(0,056% of sodium in terms of oxide) in an amount equal to the formula mass is stirred with 3-fold by weight of distilled water in which is dissolved in 100 ml of monoethanolamine and 4.2 g of sodium carbonate, considering anhydrous. The suspension of the zeolite in an aqueous solution stirred at room temperature for 0.5 hour, and then sprayed into a current of heated to 300-350oWith air in the spray dryer. The dried sample contains 0.10 wt.% sodium oxide.

Example 8. Zeolite type IEC-1 with the value of the molar relationship SiO2/Al2O3120 with the oxide formula of 0.12 Na2O0,88H2Ol2ABOUT3120SiO2(0.1% of sodium in terms of oxide) is mixed at room temperature with an aqueous solution of sulfuric acid (10.0 g/l in terms of 100-percent acid) with respect to the aqueous solution/zeolite, is 1.4 l/kg Doughy mass is left for 3 hours at room temperature, then diluted with di to a residual content of ions in the wash water SO42-not more than 100 mg/L. Get sample content of sodium oxide is 0.05 wt.%.

The zeolite obtained in accordance with Examples 1-8 were air-dried for 24 hours and was progulivali for 3 hours at 500oC. the Calculated amount of zinc oxide was introduced into the zeolite in the ammonium exchanged form with an aqueous solution of zinc nitrate. The estimated amount of the oxides of rare earth elements were applied to the zeolite method residue impregnation industrial concentrate nitrates of rare-earth elements composition (calculated on the resulting oxides) La2ABOUT3- 65,0, Nd2ABOUT3- 21, CEO2to 3.0, RG6ABOUT11- 11 mol.%. Zeolite with a specified content of oxides was obtained by calcination of the impregnated sample at 550oC. the Estimated amount of the calcined zeolite was mixed with a binder - water suspension of aluminum hydroxide (p. M. p. p. - 70%) and was molded by extrusion. Catalyst pellet (2 x 2 mm) were dried at 100oC for 2 hours, then was progulivali at 550oC for 3 hours.

The obtained catalysts were used to produce hydrocarbons from oxygen-containing organic compounds in an isothermal flow reactor with a load of catalysis of the/SUP>. Liquid and gaseous reaction products were analyzed by chromatographic methods. The raw material used pure dimethyl ether (Raw material 1), methanol (Raw material 2), ethanol (Raw 3), a mixture of alcohols (Raw materials 4) of the following composition, wt.%:

Methanol is 15.5

Ethanol - 78,0

Propanol - 3,3

Alcohols WITH4-C5- 3,2

The results of the conducted processes shown in the Table.

Examples 2, 4, 7 and 8, in which the content of sodium oxide is lower than according to the invention show lower selectivity of the catalyst in comparison with the parameters of the selectivity of the catalyst according to the invention. When using the catalyst according to the patent RU 2160160 in identical conditions (raw materials, temperature, pressure, volumetric feed rate) obtained lower selectivity of the catalyst and its ability to oxidative regeneration, which, in particular, due to the lower mechanical strength of its granules, which are the destruction of changing the specific surface of the catalyst.

1. The catalyst for the production of liquid hydrocarbons of low molecular weight oxygenated organic compounds comprising crystalline aluminosilicate type pentasil with the amount the selected elements and a binder, characterized in that as oxides of rare earth elements it contains the oxides of the following composition, mol. %:

The cerium oxide CEO2- 3,0

The oxide of lanthanum La2ABOUT3- 65,0

The oxide of neodymium Nd2O3- 21,0

The praseodymium oxide WG6O11- Rest

moreover, each value of the ratio of silicon oxide to aluminum oxide in the crystalline aluminosilicate type pentasil corresponds to a certain range of values of the content of sodium oxide, where the minimum value of the specified range at least equal to the value of the ordinate of the curve 1 shown in Fig. 1, the value of the abscissa of which is at least equal to the value mentioned molar ratios of silicon oxide to aluminum oxide, and the maximum value of the specified range at least equal to the value of the ordinate of the curve 2 shown in Fig. 1, the value of the abscissa of which is at least equal to said value of the molar relationship of silicon oxide to aluminum oxide, in the following ratio of catalyst components, wt. %:

Crystalline aluminosilicate type pentasil - 63,0-70,0

The sodium oxide - 0,12-0,30

Zinc oxide - 0,5-3,0

The oxide of rare earth elements specified with what it contains synthetic silicates, aluminum oxide, silicon oxide, or a mixture of silicon oxide to aluminum oxide.

 

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EFFECT: increased octane number of gasoline fractions with propane-butane fraction as chief component of gas products, and prolonged inter-regeneration time of catalyst.

11 cl, 4 dwg, 3 tbl, 16 ex

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