Catalyst and method for producing the synthesis gas conversion of hydrocarbons

 

(57) Abstract:

The invention relates to catalysts and methods of producing synthesis gas from organic materials and may find application in chemical processing of natural materials or synthetic organic products. The catalyst is a layered phase hydrosilicate with structure type stevensite General formula (NixMe1-x)3Si4O10(OH)2nH2O, where Me is one or more alkaline earth metals, x takes values from 0.01 to 1 and n is less than 50, or phase metasilicate with the structure type of enstatite General formula (NixMe1-x)3SiO3where Me is one or more alkaline earth metals, x takes values from 0.01 to 1 and n is less than 50, or phase hydroaluminosilicates with the structure of amesite General formula (Ni1-x-yMexAly)3(Al3ySi2-3yO5)(OH)4nH2O, where Me is one or more alkaline earth metals, x is less than 0.8, takes values from 0.02 to 0.64, and n is less than 50, or phase hydroaluminosilicates with the structure of chlorite General formula (Ni1-x-yMexAly)3(Al3ySi2-3yO5)(OH)4nH2O, where Me is one or more of the deposits of Nickel to silicon of from 0.01 to 75. Method for production of synthesis gas from hydrocarbons is suggested by the interaction in the gas phase hydrocarbons from a mixture containing water and/or oxygen, carbon dioxide and possibly diluted with nitrogen, using catalysts of the present invention. The proposed catalyst shows higher activity in the target process and significantly less active in the undesirable formation of carbon than known catalysts. No phase of silicon oxide in the catalyst composition guarantees the stability of the process. 2 S. and 4 C.p. f-crystals, 1 table.

The invention relates to catalysts and methods of producing a mixture of CO and hydrogen (synthesis gas) from organic materials and may find application in chemical processing of natural raw materials (e.g., methane) or synthetic organic products (e.g., lower hydrocarbons, and others). In further synthesis gas can be used to produce many useful chemical compounds (for example, higher alcohols, aldehydes, hydrocarbons), combustion in catalytic thermal systems, and also to produce hydrogen.

Apparently, the most common currently, JV and O2reactions:

CH4+H2O=CO+3H2< / BR>
CH4+CO2=2CO+2H2< / BR>
CH4+1/2O2= CO+2H2< / BR>
in the presence of a catalyst. Oxidizing reagent may be a mixture of water, carbon dioxide and oxygen to produce synthesis gas required composition, and may be diluted with nitrogen (in the case of using air as the oxygen source). The mixture of carbon monoxide and hydrogen (synthesis gas) at the present time are usually obtained with the use of Ni-containing catalysts in accordance with the invention [US Pat. 5399537, B 01 J 21/16, 21.03.1995; US Pat. 5591238, C 01 B 3/32, 07.01.1997; US Pat. 5653774, C 01 B 3/32, 5.08.1997].

The main requirements of the catalyst is a high activity and resistance to nauglerozhivaniya.

Among the catalysts for production of synthesis gas from organic compounds can be divided into two groups. The first group, called "massive" catalysts, characterized in that the active component (Nickel) is included in the homogeneous phase composition, for example - gidroksicarbonata Ni-Al structure hydrotalcite or Ni-Al spinel. The second group - "supported catalysts" - distinguished by the fact that the Ni-containing compound (nprime conventional methods (impregnation), or some original applying.

Solid catalysts.

The Nickel content in the solid catalyst varies from 0.1 to 30 wt. %. The catalyst composition is very diverse.

So in inventions [US Pat. 5399537, B 01 J 21/16, 21.03.1995; US Pat. 5591238, C 01 B 3/32, 07.01.1997; US Pat. 5653774, C 01 B 3/32, 5.08.1997] proposed to use as a catalyst for production of synthesis gas Ni-containing compounds with the structure of hydrotalcite with widely varying composition. During heat treatment of these catalysts receive spinalator Nickel-containing structures, which exhibit high activity in the above-mentioned processes for production of synthesis gas, showing low activity in the undesirable formation of carbon (soot formation).

In publications [K. Tomishige, Y. G. Chen, K. Fujimoto, "Studies on carbon deposition in CO2reforming of CH4over nickel-magnesia solid solution catalysts" J. Catal. 181(1), 91-103 (1999); Y. G. Chen, K. Tomishige, K. Yokoyama, K. Fujimoto, "Catalytic performance and catalyst structure of nickel-magnesia catalysts for CO2reforming of methane" J. Catal. 184(2), 479-490 (1999)] it is noted that a very low ability to sazheobrazovanie have solid catalysts which are solid solutions of Ni in the oxide of Mg, NixMg1-xO low content which I the specific activity of these catalysts is not high enough.

For all currently known "massive" catalysts for production of synthesis gas from organic compounds significant is the absence of silica in their composition. This is because the presence of silicon oxide in the catalyst composition adversely affects the performance of the catalyst in terms of conducting the process, the silicon oxide is highly volatile and evaporates in the low molecular weight form, condenses on the heat exchange equipment in the direction of gas flow and degrades its performance.

Applied catalysts.

As well as solid catalysts deposited catalysts for production of synthesis gas from hydrocarbons and do not contain phase containing Nickel and silicon at the same time. The reasons for this have already been discussed above. Thus the invention [US Pat. 4888131, 01 3/28, 19.12.1989] describes the process for production of synthesis gas using a catalyst comprising a Nickel deposited on the oxide-Al2ABOUT3. The invention emphasizes the significance of the absence of silica in the catalyst.

Many applied catalysts have a high activity side is known Ni-Al-Ca catalyst steam reforming of methane [Ed. St. USSR 1502078, B 01 J 37/04, 23.08.89], which receives the catalyst by successive preparation of granules carrier of alumina, calcium aluminate and plasticizing agents and impregnating the calcined pellets with a solution of Nickel nitrate. In addition to low stability, this catalyst has a low level.

To improve the stability in the number of inventions proposed to use the promoted catalysts. A known process for steam reforming of methane using a Nickel catalyst promoted with alkali metals [US Pat. 3417029, 17.12.1968] in order to reduce soot formation. However, when using this catalyst at high temperatures in the reaction environment is the loss of alkali metals as a result of evaporation, which leads to superusuario catalyst and deposition of alkali in the heat exchange equipment in the course of the reaction gas, which greatly impairs his work.

In the invention [JP Pat. 2245239 A2, B 01 J 23/78, 01.10.1990] proposed a method of preparing a highly active catalyst for production of synthesis gas from hydrocarbons by reaction with water vapor, wherein the Nickel compound is applied to ultrafine echo of magnesium oxide, MgO.

In all the above methods for catalysts significant is the absence of silica in their composition. In the known catalysts for production of synthesis gas from hydrocarbons and the presence of silicon is allowed only in the structure of the media.

The closest is the process of steam reforming of hydrocarbons [JP Pat. 1288340 A2, B 01 J 23/85, 20.11.1989] and [JP Pat. 2043953 A2, B 01 J 23/85, 14.02.1990] using catalysts prepared by deposition of Nickel oxide on a carrier - mullite composition 3l2ABOUT32SiO2. The stability of the medium under the reaction conditions guarantees the absence of free silica in the reaction volume. Characteristics of the catalyst prepared according to the invention prototype, in the target process for production of synthesis gas from methane, as well as in adverse the formation of carbon in the table. The disadvantage of this catalyst is relatively high activity in the processes of formation of carbon.

The problem solved by the present invention is to develop an efficient catalyst and a method of catalytic conversion of hydrocarbons to obtain a mixture of carbon monoxide and hydrogen (synthesis gas).

In the present of the new phase hydrocarbons from the mixture, containing water and/or oxygen, carbon dioxide and possibly diluted with nitrogen, using catalysts containing in its composition phase, which contains both the cations of Nickel and silicon, while respecting the atomic content of Nickel to silicon of from 0.01 to 75. Process for production of synthesis gas from hydrocarbons, it is also possible to use catalysts containing in its composition phase, which, in addition to the cations Ni2+and Si4+also contains cations Al3+while respecting the atomic relations of the content of Ni to the total content of Al and Si from 0.01 to 1.5, and the atomic relations of the content of Al to Si content of 0.1-50. Part discussed the Nickel and the silicon-containing phases may include additional other cations, preferably cations of alkaline earth metals such as magnesium, as well as cations of alkali metals such as potassium.

Among the catalysts, which contains Nickel-silicon-containing phase, which does not contain aluminum, it is preferable to use catalysts containing phase layered hydrosilicate (phyllosilicate) structure type stevensite, (NixMe1-x)3Si4ABOUT10(OH)2mo2Oh, where Me is one or more alkali catalysts product heat treatment of the above compositions at elevated temperatures up to 800oC.

For these catalysts, preferred is the incorporation in the catalyst phase oxide and/or hydroxide, gidroksicarbonata, carbonate of alkaline earth metal such as magnesium, in an amount corresponding to the ratio of the content of this metal to silicon is not less than 0.5. The Nickel content in this phase permitted, but is not essential for the present invention. Otherwise, it is possible to introduce into the composition of the catalyst salts, alkaline earth metal is one of the known methods (for example, by impregnation on capacity).

Among the catalysts, which contains the phase, which contains cations of Nickel, silicon and aluminum, it is preferable to use catalysts containing phase hydrosolubility aluminum, Nickel, and possibly even one or more metals of groups Ia and IIA. The composition of this phase is described by the formula (Ni1-x-yIUxAly)3(Al3USi2-3UO5)(OH)4mo2O, where Me is one or more alkaline or alkaline earth metals, x is less than 0.8, takes values from 0.02 to 0.62, and n is less than 50. The structure of this phase is close to structures septo-chlorite (amesite), infrared spectra which features the s of which may be poorly resolved or poorly expressed due to their low intensity. Otherwise, it is possible to use as a catalyst for production of synthesis gas from hydrocarbons, the product of the heat treatment described above hydrosolubility at elevated temperatures from 400 to 900oC. during this heat treatment phase septo-chlorite (amesite) undergoes a polymorphic transition into a phase with the structure of chlorite, infrared spectra which are characterized in the field of 400-1200 cm-1a set of absorption bands at 490, 670, 930, 1013 cm-1.

If the Nickel-silicon-containing phase represents the above girasolereale, the introduction of any additional phases in the catalyst composition is valid but is not essential for this invention.

Use to produce synthesis gas from hydrocarbons and catalysts, containing in its composition phase, which contains both cations Ni2+and Si4+ensures the flow of the target process at high speed. Thus the flow speed of the undesirable side of the formation process of carbon (soot formation) are comparable or lower than in the known methods for production of synthesis gas. In the case of using the catalyst of the above composition, in Rea is ational silicon in the proposed catalysts may not have a negative impact on the stability of the process.

The invention is illustrated by the following examples:

Example 1

Process for production of synthesis gas from methane are using as the oxidizing reagent water. The process is carried out using a catalyst containing Nickel, magnesium and silicon in the ratio of the atomic fractions of cations Ni:Mg:Si=5:8:8. The catalyst was prepared by deposition of cations Ni and Mg in the presence of suspended stevensite Mg, Mg3Si4O10(OH)2nH2O, at pH 10 and T=70oC, the precipitate was washed with distilled water and dried at 80oC. the Catalyst contains phase hydrosilicate Ni-Mg structure stevensite, (Nifor 0.6Mgfor 0.4)3Si4O10(OH)2nH2O, as evidenced by the presence in the IR spectrum of the catalyst of the absorption bands with maxima at 463, 659, 1012, 3650 cm-1and x-ray diffraction data. The value of n depends on the temperature and duration of drying and ranges from 0.5 to 30. For the described catalyst n=101. The presence of Nickel in the structure of the hydrosilicate is proved by the position of the maximum absorption band HE-groups (at 3650 cm-1), which is significantly shifted compared to the band stevensite Mg, not containing Ni (3687 cm-1). Produce The Catalyst, subjected to sequential processing at a temperature of 750oC in hydrogen for 1 hour and the reaction medium (a mixture of 33.3% vol. methane and 66.7% vol. water vapor) within 30 minutes, does not contain phase of silicon oxide (which was confirmed by x-ray analysis and IR spectroscopy).

Catalytic properties determined in a flow-circulation installation at atmospheric pressure. The measurements were carried out during the initial composition of the reaction mixture 33% vol. CH4and 67% H2O, atmospheric pressure and a temperature of 750oC. was charged To the reactor 5 g of catalyst and heated in a current of N2to a temperature of 750oWith, then restore the catalyst pure H2for 1 hour, then replace the hydrogen in the mixture of hydrogen and water, then the reaction mixture and conducting measurements at three contact times.

Speed supervivencia catalyst after the reaction is determined WITH current at a temperature of 720oWith using thermal analysis Netzsch STA 409. The accuracy of determining the weight of 0.05% by weight of the sample.

The results of the measurement of catalytic properties shown in the table. As can be seen from the above data, the catalyst exhibits a higher act shall autotip. No phase of silicon oxide in the catalyst composition guarantees the stability of the process.

Example 2

Analogously to example 1, but the process is conducted using a catalyst comprising the product of the heat treatment of the catalyst described in example 1, 600oWith in a stream of nitrogen for 3 hours. Prepared catalyst contains a phase metasilicate Ni-Mg structure of enstatite, (Ni0,5Mg0,5)SiO3that is proved by the data of x-ray phase analysis and IR spectroscopy. The catalyst further comprises a phase composition of Niof 0.2Mg0,8O.

The catalyst was subjected to sequential processing at a temperature of 750oC in hydrogen for 1 hour and the reaction medium (a mixture of 33.3% vol. methane and 66.7 about. % water vapor) within 30 minutes, does not contain phase of silicon oxide (which was confirmed by x-ray analysis and IR spectroscopy).

Catalytic properties in relation to the target process for production of synthesis gas and in relation to the adverse reactions of formation of carbon was determined similarly to example 1.

The results of the measurement of catalytic properties shown in the table. As can be seen from the above data, getprocesses education carbon than the prototype. No phase of silicon oxide in the catalyst composition guarantees the stability of the process.

Example 3

Process for production of synthesis gas from methane are using as the oxidizing reagent water. The process is carried out using a catalyst containing Nickel, magnesium, aluminum and silicon, with a ratio of atomic fractions of cations Ni:Mg:Al:Si=1:3:4:2. The catalyst was prepared by mixing Nickel nitrate, magnesium hydroxide, and silicon-aluminum gel, followed by hydrothermal treatment of the mixture at T=200oAnd calcining the resulting mass at 300oWith the current of inert gas. The silicon-aluminum gel was obtained by deposition of aluminium cations with ammonia in the presence of suspended silicon oxide at pH 8 and T=80oC. the Catalyst is a phase hydroaluminosilicates Al-Ni-Mg, (Ni0,17Mg0,5Al0,33)3(lSiO5)(OH)4n N2Oh, with the structure type leptokaria (amesite), as evidenced by the presence in the IR spectrum of the catalyst of the absorption bands with maxima at 468, 543, 619, 684, 781, 833, 910 and 1006 cm-1and x-ray diffraction data. The value of n depends on the temperature and duration of calcination and ranges from 0.1 to 10 the second sequential processing at a temperature of 750oC in hydrogen for 1 hour and the reaction medium (a mixture of 33.3% vol. methane and 66.7% vol. water vapor) within 30 minutes, does not contain phase of silicon oxide (which was confirmed by x-ray analysis and IR spectroscopy).

Catalytic properties in relation to the target process for production of synthesis gas and in relation to the adverse reactions of formation of carbon was determined similarly to example 1.

The results of the measurement of catalytic properties shown in the table. As can be seen from the above data, the catalyst exhibits a higher activity in the target process and significantly less active in the undesirable formation of carbon than the prototype. No phase of silicon oxide in the catalyst composition guarantees the stability of the process.

Example 4

Analogously to example 3, but the process is conducted using a catalyst comprising the product of the heat treatment of the catalyst described in example 3, at 600oWith in a stream of nitrogen for 3 hours. Prepared catalyst is a phase hydroaluminosilicates Al-Ni-Mg, (Ni0,17Mg0,5Al0,33)3(lSiO5)(OH)4nH2O, with the structure of chlorite, which manifest the x-ray diffraction data. The value of n depends on the temperature and duration of calcination and ranges from 0.1 to 3. For the described catalyst n=0,5. The catalyst does not contain other phases.

The catalyst was subjected to sequential processing at a temperature of 750oC in hydrogen for 1 hour and the reaction medium (a mixture of 33.3% vol. methane and 66.7% vol. water vapor) within 30 minutes, does not contain phase of silicon oxide (which was confirmed by x-ray analysis and IR spectroscopy).

Catalytic properties in relation to the target process for production of synthesis gas and in relation to the adverse reactions of formation of carbon was determined similarly to example 1.

The results of the measurement of catalytic properties shown in the table. As can be seen from the above data, the catalyst exhibits a higher activity in the target process and significantly less active in the undesirable formation of carbon than the prototype. No phase of silicon oxide in the catalyst composition guarantees the stability of the process.

Example 5

Analogously to example 3, but the process is conducted using a catalyst containing Nickel, magnesium, aluminum and silicon in the ratio of the atomic fractions of Ni: Mg:A8Si1,2O5)(OH)4nH2O structure type leptokaria (amesite). The value of n depends on the temperature and duration of calcination and ranges from 0.1 to 10. For the described catalyst n=30,5.

The catalyst does not contain other phases.

The catalyst was subjected to sequential processing at a temperature of 750oC in hydrogen for 1 hour and the reaction medium (a mixture of 33.3% vol. methane and 66.7% vol. water vapor) within 30 minutes, does not contain phase of silicon oxide (which was confirmed by x-ray analysis and IR spectroscopy).

Catalytic properties in relation to the target process for production of synthesis gas and in relation to the adverse reactions of formation of carbon was determined similarly to example 1.

The results of the measurement of catalytic properties shown in the table. As can be seen from the above data, the catalyst exhibits a higher activity in the target process and significantly less active in the undesirable formation of carbon than the prototype. No phase of silicon oxide in the catalyst composition guarantees the stability of the process.

Example 6

Analogously to example 3, but the process is carried out with the use of the Ca:K:Al:Si=1:1.1:0.9:0.6:2:1. The catalyst was prepared by mixing Nickel nitrate, calcium and potassium, magnesium hydroxide and silicon-aluminum gel, followed by hydrothermal treatment of the mixture at T=200oAnd calcining the resulting mass at 300oWith the current of inert gas. The silicon-aluminum gel was obtained by deposition of aluminium cations with ammonia in the presence of suspended silicon oxide at pH 8 and T=80oC. the Catalyst contains a phase hydroaluminosilicates Ni and the promoting metals, with the structure type leptokaria (amesite), which was confirmed by IR spectroscopy. The sample additionally contains a hydroxide of Ni-Mg-Ca with the structure of brucite.

The catalyst was subjected to sequential processing at a temperature of 750oC in hydrogen for 1 hour and the reaction medium (a mixture of 33.3% vol. methane and 66.7% vol. water vapor) within 30 minutes, does not contain phase of silicon oxide (which was confirmed by x-ray analysis and IR spectroscopy).

Catalytic properties in relation to the target process for production of synthesis gas and in relation to the adverse reactions of formation of carbon was determined similarly to example 1.

The results of the measurement of catalytic properties listed in the table is significantly less active in the undesirable formation of carbon than the prototype. No phase of silicon oxide in the catalyst composition guarantees the stability of the process.

Example 7

Analogously to example 3, but the process is conducted using a catalyst containing Nickel, magnesium, aluminum and silicon in the ratio of the atomic fractions of Ni: Mg: Al: Si = 3:3:15:2. The catalyst contains a phase hydroaluminosilicates Al-Ni-Mg, (Niof 0.25Mgof 0.25Al0,5)3(Al1,5Si0,5O5)(OH)4mo2Oh, with the structure type leptokaria (amesite). The value of n depends on the temperature and duration of calcination and ranges from 0.1 to 10. For the described catalyst n=10,3. The catalyst also contains phase of boehmite-aluminum hydroxide, Al(Oh)3. The catalyst does not contain other phases.

The catalyst was subjected to sequential processing at a temperature of 750oC in hydrogen for 1 hour and the reaction medium (a mixture of 33.3% vol. methane and 66.7 about. % water vapor) within 30 minutes, does not contain phase of silicon oxide (which was confirmed by x-ray analysis and IR spectroscopy).

Catalytic properties in relation to the target process for production of synthesis gas and in relation to the adverse reactions of formation of carbon was determined enlivening data the catalyst shows higher activity in the target process and significantly less active in the undesirable formation of carbon than the prototype. No phase of silicon oxide in the catalyst composition guarantees the stability of the process.

1. Catalyst for synthesis gas conversion to hydrocarbons, including Nickel, characterized in that it contains in its composition phase layered hydrosilicate with structure type stevensite General formula

(NixMe1-x)3Si4O10(OH)2nH2O,

where Me is one or more alkaline earth metals, x takes values from 0.01 to 1 and n is less than 50,

or phase metasilicate with the structure type of enstatite General formula

(NixMe1-x)3SiO3,

where Me is one or more alkaline earth metals, x takes values from 0.01 to 1 and n is less than 50,

or phase hydroaluminosilicates with the structure of amesite General formula

(Ni1-x-yMexAly)3(Al3ySi2-3yO5)(OH)4nH2O,

where Me is one or more alkaline earth metals, x is less than 0.8, takes values from 0.02 to 0.64, and n is less than 50,

or phase hydroaluminosilicates with the>(OH)4nH2O,

where Me is one or more alkaline earth metals, x is less than 0.8, takes values from 0.02 to 0.62, and n is less than 50,

while respecting the atomic relations of Nickel to silicon of from 0.01 to 75.

2. The catalyst p. 1, characterized in that the alkaline earth metal is used, the magnesium and/or calcium, barium.

3. The catalyst PP. 1 and 2, characterized in that the phase of the hydrosilicate or phase hydroaluminosilicates further comprises one or more alkali metals with respect to the ratio of the sum of the atomic fractions of alkali metals by atomic proportion of silicon is less than 1.

4. The catalyst PP. 1-3, characterized in that it further comprises a phase oxide or hydroxide or carbonate or gidroksicarbonata one or more metals from the group comprising aluminum, Nickel and alkaline earth metals.

5. Method for production of synthesis gas conversion of hydrocarbons in the gas phase at a temperature of 500-900oC and a pressure of 1-100 atmospheres, characterized in that the process is carried out with the use of the catalysts according to any one of paragraphs. 1-4.

6. The method according to p. 5, characterized in that the hydrocarbon use methane or ethane.

 

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