The catalyst for producing ethylene, the method of preparation of the catalyst for producing ethylene and method for producing ethylene

 

(57) Abstract:

In the application described catalysts on the substrate, deposited on inorganic carriers, the following formula (I), for producing ethylene by conversion of methane or purified natural gas, and their receipt and method of producing ethylene by means of direct conversion of methane or purified natural gas with the use of these catalysts:

MA Pc/S (I)

where M means a compound selected from the group RuCl2(PPh3)3, RuCl2(CO)2(PPh3)2, Ru3(CO)12, RhCl(CO) (PPh3)2, IrCl(CO) (PPh3)2Pd(PPh3)4Pt(PPh3)4, RuCl3xH2O, S means inorganic carrier selected from-Al2O3, -Al2O3, SiO2, SiO2-Al2O3, Y-zeolite, Mgo and TiO2P means the connection of phosphorus as a promoter selected from the PPh3P(OCH3)3P(OC2H5)3, P(O)(OC2H5)3and' means the weight percentage of metal in the catalyst varying from 0.25 to 5 wt.% and means the weight percentage of the promoter in the catalyst varying from 1.0 to 20.0 wt. %). Catalysts simplify the process of obtaining ethylene and increases the m on inorganic carriers, the following formula (I) ethylene, which is used in the basic reactions, including polymerization, copolymerization and polycondensation in the petrochemical industry and in fine organic synthesis, and their preparation

MA Pc/S

In addition, the invention relates to a new method of producing ethylene by means of direct conversion of methane or purified natural gas in the presence of the above catalyst and nitrogen at a temperature of from about 670 to 810oC, preferably in the range from 710 to 810oC, which is significantly below the reaction temperature normal synthesis of hydrocarbon(s) by dehydrogenation. According to this method, ethylene receive for a short time with high yield and without by-product, such as CO, CO2in contrast to the reaction of oxidative combination, when administered oxygen.

Little is known of the literature and patents on the catalyst, which can be used to produce ethylene by direct conversion of methane; moreover, known methods differ from the present invention in a technical sense. As a result of implementation of traditional methods turn out large quantities of by-product, such as a TLD is C hydrocarbon(s) in the usual dehydrogenation is carried out at relatively high temperatures of around 1500-1550oC using the process of thermal or electric cracking that causes a number of problems, such as the need to supply large amounts of energy, the high cost of high-temperature equipment (schema), as well as a huge loss of thermal energy, such as severe corrosion of the reactor.

As known sources describing the synthesis of hydrocarbon oxidation by the combination of or the reaction of dehydrogenation, it is possible to bring the U.S. patent 5066629, 5068486 and 5118654, patent Canada 2016675 and the Japan patent 04352730, 04368342.

Closest to the invention is a method of producing ethylene conversion of methane at high temperature, including 670-850oC and a pressure of 1-5 atmospheres in the presence of a catalyst [1]. The catalyst contains a compound of General formula AnB2O7-Xwhere A is a cation of one-, two - and trivalent metal; B is a cation of three-, four-, five -, and hexavalent metal, 0n2, 0X1.

The closest to the method of preparation of the catalyst according to the invention is a method of producing catalyst for conversion of methane into higher hydrocarbons, comprising a mixture of compounds active ingredients with the carrier followed by heat treatment [2].

Sadacia, using which you can make the method of producing ethylene in a short period of time, with high yield, with traces of impurities, by the conversion of methane or purified natural gas in the presence of the specified catalyst at a significantly lower temperature than the temperature of the synthesis of hydrocarbons by dehydrogenation or oxidative combinations. This direct conversion of methane is carried out at considerably lower temperatures, avoids the huge consumption of heat energy required for the synthesis reaction of hydrocarbon (s) by dehydrogenation or oxidative combinations, and significantly reduce environmental pollution due to reduced amounts of impurities, namely CO2.

The task is solved in that the catalyst for producing ethylene by conversion of methane or purified natural gas corresponds to the General formula MA Pc/S, where M is a compound selected from the group RuCl2(PPh3)3, RuCl2(CO)2(PPh3)2, Ru3(CO)12, RhCl(CO)(PPh3)2, IrCl(CO)(PPh3)2Pd(PPh3)4Pt(PPh3)4, RuCl3xH2O, S - Neorganicheskie carrier selected from-Al2O3, -Al2Oe of PPh3P(OCH3)3P(OC2H5)3, P(O)(OC2H5)3, a' - bulk metal content in the catalyst varying from 0.25 to 5 wt.%, c is the weight percent of the promoter in the catalyst varying from 1.0 to 20.0 wt.%.

In the preparation method of the catalyst for producing ethylene mixing ingredients is carried out in a solvent or solvent mixture consisting of dichloromethane and acetone, the resulting suspension is stirred under reflux at a temperature of from 30 to 250oC with subsequent evaporation of the solvent by distillation under reduced pressure and drying under vacuum to obtain a catalyst corresponding to the General formula MA Pc/S, where M, P, S, a', c have the above values.

Preferably the suspension is stirred under reflux at a temperature of 40-150oC. In the method of producing ethylene conversion of methane at a temperature of from 670 to 850oC and a pressure of 1-5 atmospheres conversion is subjected to methane or natural gas in the presence of nitrogen using a catalyst composition corresponding to the General formula MA Pc/S, where M, P, S, a', c have the above values.

The invention is described below more EU metal promoter on inorganic carriers, i.e. applying different ORGANOMETALLIC complexes and promoter on inorganic carriers.

In this way the process of synthesis and purification catalyst is simpler than other methods.

With the emergence of this catalyst reaction conditions, such as temperature, pressure, significantly reduced and the ethylene is obtained with high yield.

Further, by creating a method using a catalyst according to the invention the process of producing ethylene is simplified, resulting in increased productivity.

According to the invention is creating a new way in which methane or purified natural gas is converted directly into ethylene and which differs from the synthesis of hydrocarbons by dehydrogenation or oxidative combination, leads to simplification of the entire process, then, the reaction temperature is reduced to a temperature of from about 670 to 850oC, preferably it is within 710-810oC, and significantly reduced amounts of impurities, such as carbon dioxide.

According to the invention with the addition of triphenylphosphine as a promoter to the Ru complex, such as RuCl2(PPh3)3, RuCl2(CO)2(PPh3

In other words, because of the chemical reactions on a solid surface using as the catalyst of Ru complex on the media significantly mitigated such reaction conditions as the reaction temperature and pressure, at the same time simplifies the hardware design of reaction.

The method of preparation of the catalyst, deposited on inorganic carriers, is as follows.

Metal clearcommand and organometallics complex dissolved in a mixed solvent consisting of dichloromethane and acetone.

Then this solution is added an inorganic carrier, and the metal cluster and organometallics complex penetrate the inorganic carrier with stirring at about 20-200oC, then the product is subjected to drying in a vacuum dryer to obtain a catalyst.

Used inorganic carriers are-Al2O3, -Al2O3, SiO2, SiO2-Al2O3, Y - zeolite, MgO and TiO2.

Used metal cluster compound and ORGANOMETALLIC complexes are RuCl2(PPh3)3, RuCl2(CO)2(PPh3)2, Ru3(CO)12,

RhCl (the accordance with the experimental data optimal inorganic carriers according to this invention upon receipt of ethylene are-Al2O3and MgO, and among the metals of group VIII - Ru and Rh.

According to the invention when using a new catalyst is used, the following reaction conditions.

The volume ratio of nitrogen to methane or purified natural gas is 1-6, preferably 1-3 in the calculation of the methane.

The reaction temperature is about 670-850oC, preferably it is located within 710-810oC.

The concentration of the catalyst is equal to less than 5 wt.%, preferably equal to 1-3 wt.%.

The volumetric rate of the source gas is approximately 75-1200 h-1preferably it is in the range 150-600 h-1.

The pressure in the reaction is usually about 1-5 atmospheres, preferably normal pressure. The rate of conversion of methane or purified natural gas and the yield and selectivity of ethylene are defined as follows.

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The reagents and the resulting products analyzed by gas chromatography.

Examples 1-11 refer to a new catalyst and method of its production.

Examples 12-22 relate to a new method of producing ethylene by conversion of methane or purified natural gas in the presence of a new catalyst p is (4,16 mmol) PPh3added to a mixed solvent consisting of 20 ml of dichloromethane and 10 ml of acetone. This suspension is stirred for about 30 min at a temperature of approximately 40oC and evaporated to dryness by distillation under reduced pressure, then dried in a vacuum drier for about 20 hours, getting RuCl2(PPh3)3PPh3/Al2O3as the catalyst. The content of Ru is 1.45 wt.%.

Example 2. 0.56 g (0,744 mmol) of RuCl2(CO)2(PPh3)2and 0.78 g (2,97 mmol) PPh3added to a mixed solvent consisting of 40 ml of dichloromethane and 10 ml of acetone and dissolved in it, then there enter 3,68 g-Al2O3. This suspension is stirred for about 30 min at a temperature of approximately 40oC and evaporated the solvent by distillation under reduced pressure. Then the obtained residue is dried in a vacuum drier for about 20 hours, obtaining a catalyst RuCl2(CO)2(PPh3)2-Al2O3. The content of Ru is 1,49 wt.%.

Example 3. 3,95 g-Al2O3, 0.17 g (0,266 mmol) Ru3(CO)12, 0.09 g (0,343 mmol) PPh3added to a mixed solvent consisting of 10 ml of dichloromethane and 100 ml of acetone and dissolved in it.

The resulting residue is dried in a vacuum drier for about 20 hours, obtaining a catalyst Ru3(CO)12PPh3/Al2O3. The content of Ru is 1,90 wt.%.

Example 4. 3.28 g-Al2O3, 0.45 g (0,652 mmol) RhCl(CO)(PPh3)2, of 0.68 g (2,59 mmol) PPh3added to a mixed solvent consisting of 10 ml dichloromethane and 30 ml of acetone and dissolved in it.

This suspension is stirred for about 30 min at a temperature of approximately 40oC and evaporated the solvent by distillation under reduced pressure. The resulting residue is dried for about 20 hours in a vacuum dryer, receiving the catalyst RhCl(CO)(PPh3)2PPh3/Al2O3. The content of Ru is of 1.52 wt.%.

Example 5. 3,14 g-Al2O3, 0.26 g (of 0.333 mmol) IrCl(CO)(PPh3)2, 0.35 g (1,33 mmol) PPh3added to a mixed solvent consisting of 60 ml of dichloromethane and 10 ml of acetone and dissolved in it.

This suspension is stirred for about 30 min at a temperature of approximately 40oC and evaporated the solvent by distillation under reduced pressure.

The resulting residue is dried in a vacuum drier for about 20 hours to obtain catalyst IrCl(CO)(P/SUB>O3, 0.84 g (0,727 mmol) of Pd(PPh3)4, 0.35 g (1,33 mmol) PPh3added to a mixed solvent consisting of 30 ml of dichloromethane and 10 ml of acetone and dissolved in it.

This suspension is stirred for about 30 min at a temperature of approximately 40oC and evaporated the solvent by distillation under reduced pressure.

The resulting residue is dried in a vacuum drier for about 20 hours to obtain catalyst Pd(PPh3)4PPh3/Al2O3. The Pd content is 1.45 wt.%.

Example 7. of 4.45 g-Al2O3, of 0.58 g (0,466 mmol) of Pt(PPh3)4, 0,49 g (of 1.87 mmol) PPh3added to a mixed solvent consisting of 30 ml of dichloromethane and 10 ml of acetone and dissolved in it.

This suspension is stirred for about 30 min at a temperature of approximately 40oC and evaporated the solvent by distillation under reduced pressure.

The resulting residue is dried in a vacuum drier for about 20 hours to obtain a catalyst of Pt(PPh3)4PPh3/Al2O3. The content of Pt is 1.63 wt.%.

Example 8. 4,39 g inorganic carrier MgO, and 1.00 g (1.04 mmol) of RuCl2(PPh3)3, 0,93 g PPh3(3,55 mmol) EXT is of about 30 minutes at a temperature of about 40oC, then evaporated to dryness by distillation under reduced pressure, and then dried in a vacuum drier for about 20 hours, obtaining a catalyst RuCl2(PPh3)3PPh3/MgO. The content of Ru is 1.66 wt.%.

Example 9. 5,16 g-Al2O3, 0.25 g (0,261 mmol) of RuCl2(PPh3)3, 0.27 g (1,03 mmol) PPh3add to the mixture solvent consisting of 20 ml of dichloromethane and 10 ml of acetone. This suspension is stirred for about 30 min at a temperature of approximately 40oC, then evaporated to dryness by distillation under reduced pressure, and then dried in a vacuum drier for about 20 hours, obtaining a catalyst RuCl2(PPh3)3PPh3/Al2O3. The content of Ru is 0.46 wt.%.

Example 10. 5,16 g-Al2O3, 3,82 g (3,992 mmol) of RuCl2(PPh3)3, 1,09 g (4,16 mmol) PPh3add to the mixture solvent consisting of 20 ml of dichloromethane and 10 ml of acetone. This suspension is stirred for about 30 min at a temperature of approximately 40oC, then evaporated to dryness by distillation under reduced pressure, and then dried in a vacuum drier for about 20 hours, obtaining a catalyst RuCl2(PPh3)3PPh3/Al2O3O, 1.06 g (4.04 mmol) PPh3added to a mixed solvent consisting of 20 ml of dichloromethane and 10 ml of acetone and dissolved in it.

This suspension is stirred for about 30 min at a temperature of approximately 40oC and evaporated the solvent by distillation under reduced pressure.

The resulting residue is dried in a vacuum drier for about 20 hours to obtain catalyst RuCl3xH2OPPh3/Al2O3. The content of Ru is of 1.62 wt.%.

The results of the analysis summarized in the tables below based on examples 12-22 and are approximate values.

As for temperatures, they represent the ambient temperature.

Example 12. The methane or purified natural gas) and nitrogen injected each with a flow rate of about 10 ml/min into the reactor continuous fixed bed (inner diameter: 0,70 cm; length 40 cm; material: 316 stainless steel) in the presence of a catalyst RuCl2(PPh3)3PPh3/Al2O3(2 wt.% Ru) obtained in example 1. The products obtained when a continuous reaction under a pressure of about 1 ATM at each reaction temperature, which is shown in table.1, where the decree is 22 raw materials are continuously fed back into the reactor conversion).

Example 13. Repeat example 12, but using as catalyst RuCl2(CO)2(PPh3)2-Al2O3. The results are shown in table.2.

Example 14. Repeat example 12, but using as the catalyst Ru3(CO)12PPh3/Al2O3(2 wt.% Ru). The results are shown in table.3.

Example 15. Repeat example 12, but using as the catalyst RhCl(CO)(PPh3)2PPh3/Al2O3(2 wt.% Rh). The results are shown in table.4.

Example 16. Repeat example 12, but using as catalyst IrCl(CO)(PPh3)2PPh3/Al2O3(2 wt.% Ir). The results are shown in table.5.

Example 17. Repeat example 12, but using as the catalyst Pd(PPh3)4PPh3/Al2O3(2 wt.% Pd). The results are shown in table.6.

Example 18. Repeat example 12, but using as the catalyst Pt(PPh3)4PPh3/Al2O3(2 wt.% Pt). The results are shown in table.7.

Example 19. Repeat example 12, but using as catalyst RuCl2(PPh3)3PPh3/MgO (2 wt.% Ru). The results are shown in table.8.

Example 20. Repeat example 12, but using in s in the table.9.

Example 21. Repeat example 12, but using as catalyst RuCl2(PPh3)3PPh3/Al2O3(4.0 wt.% Ru). The results are shown in table.10

Example 22. Repeat example 12, but using as catalyst RuCl3xH2OPPh3/Al2O3(2 wt.% Ru). The results are shown in table.11.

1. The catalyst for producing ethylene by conversion of methane or purified natural gas, containing the active part and the carrier, characterized in that its composition corresponds to the General formula

Ma'Pc/S

where M is a compound selected from the group RuCl2(PPh3)3, RuCl2(CO)2(PPh3)2, Ru3(CO)12, RhCl(CO)(PPh3)2, IrCl(CO)(PPh3)2Pd(PPh3)4Pt(PPh3)4, RuCl3xH2O;

S - inorganic carrier selected from-Al2O3, -Al2O3, SiO2, SiO2-Al2O3, zeolite Y, MgO, TiO2;

P - promoter - connection of phosphorus selected from the PPh3P(OCH3)3P(OC2H5)3, P(O)(OC2H5)3;

a' - bulk metal content in the catalyst, changing from 0.25 wt. % to 5 wt. %.

c is the weight percent promolocker ethylene by conversion of methane or purified natural gas, including original mix ingredients and drying, characterized in that the mixing is carried out in solution or solvent mixture consisting of dichloromethane and acetone, the resulting suspension is stirred under reflux at a temperature of 30-250oC with subsequent evaporation of the solvent by distillation under reduced pressure and drying under vacuum to obtain a catalyst corresponding to the General formula

Ma'Pc/S

where M, P, S, a', c have the meanings specified in paragraph 1.

3. The method according to p. 2, characterized in that the suspension is stirred while heating under reflux at a temperature of 40 - 150oC.

4. The method of producing ethylene conversion of methane in the presence of a catalyst at a temperature 670-850oC and a pressure of 1 to 5 ATM, characterized in that the conversion is subjected to methane or natural gas in the presence of nitrogen and the catalyst used, the catalyst composition corresponding to the General formula.

Ma'Pc/S

where M, P, S, a' and c has the values specified in paragraph 1.

5. The method according to p. 4, characterized in that the process is carried out at a temperature 710-810oC and at normal pressure.

6. The method according to p. 4 or the gas is 1 to 6, preferably 1 to 3, in the calculation of the methane, and the flow rate of the source gas 75 - 1200 h-1, preferably 150 to 600 h-1.

7. The method according to p. 4 ili, wherein the used catalyst at a concentration of 5 wt. % or less, preferably 1 to 3 wt. %.

 

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