Catalyst for conversion of methane into higher hydrocarbons.

 

(57) Abstract:

Usage: petrochemistry. The inventive catalyst corresponds to the empirical f-Le: A1B1-2C1-3Ox, where A is titanium, zirconium or silicon; B-lanthanum or yttrium; C-sodium, lithium, potassium, cesium, magnesium, calcium, strontium or barium; X is the number of oxygen atoms determined by the valence state of items in the Inbox. Characterization of the catalyst: the selectivity for C2H4up to 33%, C2H6up to 42%. 5 table.

The invention relates to a heterogeneous catalytic system capable of converting methane into higher hydrocarbons, mainly in C2the hydrocarbons.

The largest source of methane is natural gas, the provision of energy is of paramount importance, whose role seems to be to increase in the future, it is also becoming a source of chemicals.

In fact, currently, approximately 90% of natural gas used as fuel, with the remaining 10% are used for the indirect production of methanol, ammonia and its derivatives, chlorinated compounds and other minor compounds. The composition of natural gas varies depending on IP in order to stigate to 99% by volume, moreover, the residual quantity is light hydrocarbons, inert gases and chemical compounds with acidic character (CO2N2S).

Therefore, the full use of this source of carbon atoms is of great importance.

Weak reactivity to functionali shown light hydrocarbons, especially methane, always defines the limit for its use, for this reason, methane is mainly used as fuel. In the list of issues you can include the transportation of methane, because methane sources are usually located in regions that are removed from regions of the use of methane. Transportation techniques, known from the description above, associated with certain financial expenses. They may arise from the transportation by pipeline and gas liquefaction/re-transfer in the gaseous state.

Hence the conversion of methane in an easily manipulated compound is of the utmost importance.

The conversion of methane can be performed according to several methods, including the use of coreagent and/or catalysts, or without them.

Simple Chino short contact times due to thermodynamic limitations. Patent literature reports some examples of catalytic systems with the ability to direct response. These methods do not have high selectivity and are rarely used in practice.

Using coreagent can be carried out in the presence of a catalyst or without it.

Regarding the first version of the response, was asked the following: oxygen obtaining methanol and formaldehyde [Chem. Ruv. 85(4), 235 (1985)], or chlorine (Benson method, U.S. patent 4 199 533), with higher hydrocarbons. The last publication of the Japan patent J 88/222126 discloses the synthesis of hydrocarbons, mainly WITH2hydrocarbons, the direct reaction of methane and oxygen under pressure.

The conversion of methane is mostly carried out through catalytic methods, and coreagent take part in the reaction.

The first attempts to relate to the forties: in industrial scale oxygen-containing products were obtained when using as oxidant (Fial Report N 1085, 31.03.1947).

The reaction of production of methanol and formaldehyde mainly catalyzed by variously modified compounds based on molybdenum (see UK patent 1 398 385, 1971) Mega acid solution.

The formation of hydrocarbon mixtures with a predominant content2compounds called "oxidative combination" and is usually conducted in the presence of oxygen or air, and the catalysts are predominantly oxidic character.

The catalyst reagents can do or alternately or in parallel. In the first case, the active oxides are the oxides of low-melting metals such as cadmium, indium, tin, antimony, thallium, pigs, bismuth, magnesium, or as such or modified [J. Catal. 73 - 9-19 (1982) Union Carbide; U.S. patent No. 4 443 644 to 7, 4,444,984, 4,495,374, 4, 499:322 and 4,560,821 Atlantic Richfield Co].

In the second case are mainly used oxides of alkaline-earth metals, modified alkali metals [U.S. patent 4 057 620 and 4 654 460 Phillips Petroleum; U.S. patent 4 801 7632 Atlantic Richfield Co.].

Specific catalysts are catalysts made as a solid super-acid (G. A. Olan U.S. patent 4 513 164), in which in the presence of oxidants always come out WITH2the hydrocarbons.

From the existing technical literature, there are other systems that have the ability to turn the methane into higher hydrocarbons: referred to the metals belonging to the first transition group is the NID, and rare-earth elements.

There are a variety of patented materials with different compositions:

France 2 607 804 Inst. Fr. Petrole (Lir/KBr); U.S. 4751336 Amoco Corp (1% by weight CVG/calstat D), Japan 88/77826.

The above-mentioned catalysts mostly do not allow obtaining high conversion of methane, which does not allow to obtain high productivity and selectivity.

Many of these catalysts is subject to rapid aging, respectively, rapidly lose their activity and selectivity.

Currently found a specific catalyst composition, which has high activity and selectivity in the oxidation combination of methane. Such a catalyst composition can reduce the disadvantages arising from the use of catalysts known from the prototype.

The catalytic system in accordance with the invention differs in that it is subject to the following empiricheskoi formula:

Aa Bb Cc Ox, where A is an element selected from the group consisting of germanium, silicon, tin, titanium, zirconium;

B is an element selected from the group consisting of lanthanum, scandium,yttrium;

With alkaline or alkaline-earth metal;

a but of 0.05-2.5;

with the number included in the range of 0.1 to 10 and preferably of 0.05-2.5;

x is a number which determines the valence state in which some elements are present in the catalytic system.

The preferred elements for A component are titanium and zirconium, for the B component is yttrium and lanthanum, for a component With alkali metals, particularly sodium.

The catalytic system in accordance with the invention can be obtained in accordance with one of the methods known from the literature for similar compounds.

Such methods can be: drying of sediment drying and mixing; drying raspadenie; gelatinization; deposition; coprecipitation, impregnation.

Methods preferably are selected depending on different raw materials.

Sometimes also conducting drying may be necessary or can achieve advantages.

The resulting material, called catalytic precursor, fired at high temperature (but not above than 1000about(C) in several ways.

thermal cycle used to produce the catalysts defined in the examples is as follows:
temperature

150 65,0 2,0

150 - 2,0

150->300 75,0 2,0

300 - 4,0

300->800 140,0 3,6

800 - 4,0

800->room tempera - 40,0 19,5

tours

P R I m e R 1. According to the following methodology has been the catalyst titanium, lanthanum: sodium = 1: 1:1. When heated in ethanol was dissolved 28,90 g LaNO36H2O and of 5.40 g NaNO3. Then added 15,73 g (equivalent to approximately 15,04 ml) of Ti (OEt)4mixed with 30 ml of ethanol. Pseudorelativistic solution caused by adding a small amount of N2O. Entire mixture was dried in an oven at 80aboutC for 22 h and the catalyst precursor has consistently probalily in accordance with the above scheme.

P R I m m e R 2. The catalyst is titanium, lanthanum:sodium = 1:2:1 was obtained by concentration by evaporation of an aqueous solution (250 ml) 2.86 g of TiO2, 25,81 g LaNO36H2O and 2,84 g NaNO3evaporation occurred before receiving thickened liquids. Thickened liquid is dried in an oven at about 100aboutC for 24 h, and the obtained solid substance was hot in accordance with the scheme presented above.

P R I m e R s 3-4. Acting the same way as in example 1 and had the following catalyst: titanium, lanthanum: Li = 1:1:1 catalyst (example 2) of 28,92 g LaNO36H2O and 4,60 g LiNO3150 Ali = 1:1:1 catalyst (example 4) of 28,95 g LaNO36H2O and 6.75 g KNO3in 150 ml ethanol + 30 ml of N2Oh, to which was added 15,57 g (equivalent 13,91 ml) of Ti(OEt)4mixed with 30 ml of ethanol.

P R I m e R s 5-6. Acting the same way as in example 2, using the reagents described in table.1, received the catalysts of titanium, lanthanum magnesium = 1:1:1 (example 5) and titanium, lanthanum, calcium = 1:1:1.

P R I m e R 7. In a similar manner as in example 1, a catalyst, titanium, yttrium:sodium = 1:1:1 received from 23,57 g Y(NO3)36H2O and 4,90 g NaNO3, which was dissolved in 160 ml of ethanol, to which was added 13,44 g (12,01 ml of Ti(OEt)4mixed with 20 ml of ethanol.

After adding an ethanol solution of Ti (OEt)4almost immediately there was pseudorelativistic, so did not add a small amount of water, as in example 1. P R I m e R s 8-9. In accordance with example 2, using the materials and amounts shown in the table.2, received Zirconia catalysts: lanthanum:sodium = 1:1:1 (example 8) and zirconium:yttrium:sodium = =1:1:1.

P R I m e R 10. In 16 ml of ethanol + 7.5 ml of water was dissolved 28,89 g LaNO36H2O and of 5.68 g NaNO3.

With a slight heating of the mixture of these solids dissolved. Added 14,85 g of Si(OEt)4and when neznacitC for 20 h, and the reaction mixture was hot in accordance with the cycle.

P R I m e R s 11-51. The materials obtained, as shown in examples 1-10, was subjected to tests to determine their catalytic activity in accordance with the following method. Granules with a size of 20-40 mesh. loaded in a quartz reactor (catalytic volume = 2 ml) and kept under a stream of nitrogen while the temperature was increased to 300aboutC. Then filed a methane/air mixture. Commonly used flow rate had the following values: methane 22 NML/min and air at the required flow rate to obtain the desired CH4/ABOUT2the attitude. The data below.

The results obtained are presented in table.4.

Additional examples A, B and stoichiometric calculations:

The General formula for the calculation can be written as follows:

A1B1-2C1-3, where A is Ti, Zr or Si;

B - La, or Y;

With - Na, Li, K, Mg or CA.

The atom A.

For each mol And 2 mol of oxygen. The General formula AO2.

Atom Century

For each mol to 1.5 mol of oxygen. The General formula IN1,5.

Atom With.

If - alkali metal (Li, Na,nd metal, then for each mol s - 1 mol of oxygen, then the General formula WITH.

Examples of stoichiometric calculations

Ti(La/Na = 1/1/1

1 mol Ti - 2 mol OF

1 La mole to 1.5 mole ON

1 mol Na - 0.5 mol OF

Ti LaNaO4< / BR>
Zr/La/Ba = 1/1/2,5

1 mol Zr - 2 mol OF

1 La mole to 1.5 mole ON

2.5 mol BA - 2.5 x 2 = 5 mol OF

ZrLaBathe 2.5O8,5< / BR>
P R I m e R A. the Catalyst Zr; Y; Sr 1/1/3 obtained as follows.

Ammonium carbonate (15.6 g) was dissolved in 150 ml of water and there admixed ZrO2.

Then add 5,6 n of yttrium nitrate and 12.7 g of strontium nitrate, dissolved in 250 ml of water.

The liquid is filtered off, washed for some time, dried and calcined as described above.

P R I m e R C. the Catalyst Zr; La; Ba 1/1/2,5 was obtained as follows.

Ammonium carbonate (45 g) was dissolved in 300 ml of water and there admixed ZrO2,

Then add a 32.5 g of uranyl nitrate lanthanum and 39.2 g of barium nitrate dissolved in 500 ml of water.

The liquid is filtered off, washed for some time, dried and calcined as described in the application.

P R I m e R S. In accordance with the process of example In the catalyst Zr:La: Cs 1/1/1 obtained using 1.9 grams ZrO

The results are shown in table.5.

CATALYST FOR CONVERSION of METHANE INTO HIGHER HYDROCARBONS containing an element selected from the group of titanium, zirconium or silicon, an element selected from the group of lanthanum or yttrium and an element selected from the group of sodium, lithium, potassium, cerium, magnesium, calcium, strontium or barium, in combination with oxygen, wherein the catalyst composition corresponds to the following empirical formula:

AND1IN1-2WITH1-3ABOUTx,

where a is titanium, zirconium or silicon;

In - lanthanum or yttrium;

With sodium, lithium, potassium, cesium, magnesium, calcium, strontium or barium;

x is the number of oxygen atoms determined by the valence state of items in the Inbox.

 

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