JPS6064631A - Method for preparing high calorie gas and catalyst therefor - Google Patents

Abstract

PURPOSE:To obtain gas containing a large amount of C2-4 hydrocarbon by bringing a catalyst, which is obtained by combining a carrier such as titanium oxide and a catalyst component having a three-component composition, into contact with low calorie gas. CONSTITUTION:A molded carrier, which is formed by subjecting titanium oxide to heat treatment at 500-800 deg.C, is impregnated with an aqueous solution containing platinum nitrate of chloride in an amount equal to the fine pore volume of said carrier and the impregnated carrier is dried in air while slowly tumbled at an atmospheric temp. Subsequently, this treated carrier is exposed to an atmosphere containing 10-20% of ammonia and 1-10% of steam for 2-3min and, thereafter, heated to 350 deg.C to form oxide which is, in turn, heated to 400 deg.C in a 10-20% hydrogen-containing stream diluted with inert gas and reduced while held at said temp. to obtain a platinum supported carrier. This carrier is further impregnated with, for example, an aqueous solution mixture containing ferrous metal nitrate and manganese nitrate and dried by air, subsequently dried under heating and subjected to ammonia treatment and treatment such as thermal decomposition or hydrogen reduction.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides high calorie residue from low calorie gas (11)
A catalyst for producing carbon dioxide, and using the catalyst to produce high-calorie fuel gas containing mono-combusted hydrogen having 1 to 4 carbon atoms from a gas containing hydrogen and carbon monoxide or a gas containing hydrogen, carbon monoxide, and carbon dioxide. It's about how to do it.

Coke oven gas has traditionally been the main source of city gas, but in recent years there has been an increase in protection of the living environment, rationalization of supply methods,
Gas is being reviewed from the viewpoint of non-toxicity and safety, and the transition to high-calorie natural gas is progressing at a rapid pace. For this reason, the use of coke oven gas as city gas is being limited, but since a huge amount is produced as a by-product with the production of '3A coke, which is the main industry, it is important to develop effective uses for this. However, in order to continue to utilize this coke oven scum as a fuel source, it is necessary to improve its current low calorie property and make it comparable to natural scum. One solution to this problem would be to convert it into a high-calorie gas.

The low calorie nature of gasified scum, such as coke oven dregs, coal or heavy oil, is due to its high content of hydrogen, carbon oxides and carbon dioxide. Therefore, in order to make them high in calories, it is necessary to convert the above substances into hydrocarbons such as methane, ethane, ethylene, propane, propylene, and butane. In view of the above-mentioned circumstances, Nagisa et al. of the present invention developed a fuel gas having a higher calorific value.
As a result of extensive research, the present invention was completed.

That is, to describe the object of the present invention more specifically, gas containing water 2← and carbon monoxide, or sludge containing hydrogen, carbon monoxide, and carbon dioxide (hereinafter referred to as low-calorie sludge) ) For example, coke oven gas can be converted into a gas with a much higher calorie content than previously known methods.
An object of the present invention is to provide an original composition catalyst and a method for producing high-calorie gas using the catalyst. That is, the present invention aims to convert a low-calorie gas into a high-calorie gas containing not only methane but also hydrocarbons having 2 to 4 carbon atoms by bringing the low-calorie gas into contact with the above-mentioned catalyst. . In addition, when converting a low-calorie gas into a high-calorie gas containing hydrocarbons, carbon dioxide is generally produced as a by-product, and conventionally this has been separated and removed. Therefore, one object of the present invention is to provide a method for simultaneously converting this by-product carbon dioxide into hydrocarbons by combining two systems of catalysts, the above-mentioned ternary composition system and the ternary composition system described below. This provides the advantage of not requiring a splitting operation of carbon dioxide.

The present invention will be explained in further detail. First, II! in the catalyst of the present invention! The body is made of titanium oxide, but commercially available titanium oxide can be used. Iron group metals are used as substrates for catalysts supported on such carriers, and cobalt and iron are particularly preferred as the iron group metals. The catalyst of the present invention has a ternary composition in which manganese oxide and platinum group metal are combined with Ml on the substrate metal and supported on the carrier. Examples of platinum group metals include ruthenium, rhodium, palladium, platinum, and iridium.

As mentioned above, the catalyst of the present invention is characterized in that a carrier made of titanium oxide is used as a carrier, and this carrier and
By combining the catalyst components of the original composition, when a low calorie gas is brought into contact with the catalyst components, it is possible to remove scum containing a large amount of 02 to C4 hydrocarbons. However, the details of why such an effect is produced are unknown, but -1
By combining Ml of the above-mentioned solids and the catalyst component, the combined effect of the support and the catalytic metal is promoted, the CO adsorption is increased, the carbon binding activity is increased, and C2 to C4 hydrocarbons are produced. It is assumed that this is due to an improvement in the 4 fl. In the above combination, the supported amount of the iron group metal serving as the catalyst substrate is 3 to 15%, particularly preferably 5 to 12%, based on the total catalyst. In addition, the amount of acid (IZ manganese) is determined when the atomic ratio of iron group metal element to manganese element is (5:1) to (5:1).
: 4), and the atomic ratio of iron group metal elements to platinum group metal elements is (
It is set to satisfy the range of 30:1) to (5:2).

In preparing the catalyst of the present invention, an impregnation method or a precipitation C method is usually used.

The catalyst of the present invention is produced by the above-mentioned basic structure, but to describe it more specifically, a platinum group metal, an iron group metal, or manganese is added to a phase consisting of titanium oxide, and a nitrate aqueous solution or a chloride is added to the phase. First, a ternary composition system 111 is prepared by impregnating it in the form of an aqueous solution by means such as spraying, scattering, and dipping, and then sequentially performing steps such as drying, ammonia treatment, thermal decomposition, and hydrogen reduction. Note that in this preparation, the ammonia treatment step may be omitted in some cases. A manufacturing example of the catalyst of the present invention will be explained in more detail.

First, a phase consisting of titanium oxide or 500 to 8
The molded phase heat-treated at 00° C. is impregnated with an aqueous solution of a platinum group metal nitrate or chloride in its pore volume and ring portion, and air-dried at room temperature while gently rolling. In order to speed up drying.

A commercially available dryer regulated at a temperature of 150°C may be used. Next, the treated product is exposed to an atmosphere containing 10 to 20% ammonia and 1 to 10% water vapor for 2 to 3 minutes. Thereafter, it is heated to about 350° C. in air to thermally decompose the impregnated platinum group metal nitric acid 111 or its chloride into an oxide. This is heated from room temperature to 400° C. in air J& diluted with an inert gas and having a hydrogen concentration of 10 to 20%, held at the same temperature for 30 minutes for reduction, and then cooled to room temperature in the same air flow. The platinum group total yield IL obtained in this way! The support is impregnated with a mixed solution of an aqueous solution of iron group metal, for example, a nitrate, and a 1:1 aqueous solution of mankan, for example, nitric acid, by the same impregnation method as described above. Then, in the same manner as in the case where the platinum group metal is loaded with 10% of the platinum group metal, a ternary composition catalyst is obtained by performing treatments such as air drying or heating drying, ammonia treatment, thermal decomposition, and hydrogen reduction.

In practice, this catalyst may be used as it is, or may be used after being subjected to heat treatment (450 to goo'c) in an H2 atmosphere.

With the catalyst of the present invention, low-calorie gases containing hydrocarbons having 1 to 4 carbon atoms, such as coke oven gas, naph gas, and heavy oil reformed gas, as well as water gas and coal gasification gas, can be used. The conversion into high calorie gas can be carried out, for example, as follows. That is, the catalyst obtained in the following manner is packed into a reaction tower, and the temperature of the catalyst layer is controlled at 150-400°C, preferably 260-350°C, at a rate of 5-30 kg/cm G, preferably lo ~
1 per liter of catalyst capacity under application of 20 kg/cm2G
By introducing a low calorie gas of ~10m''/hr, preferably 2~5II13/h, within the catalyst bed,
A high-calorie gas containing hydrocarbons with a prime number of 1 to 4 is generated, but at that time, the by-produced water is converted into carbon monoxide and carbon monoxide in the paper calorie gas, as shown in the following equation. A reaction occurs and carbon dioxide is produced as a by-product.

Further, in some cases, carbon monoxide itself in the raw material low-calorie gas may undergo a disproportionation reaction according to equation (M), and bicarbonate may be produced as a by-product.

CO+H20=CO2+H2CO 2CO=CO2+C"j) In the present invention, Ci"Ca gas mixed with by-product carbon dioxide gas from the above hydrocarbonization reaction is treated with silica and/or
Alternatively, the by-product carbon dioxide can also be converted into methane by subsequently contacting it with a ternary composition catalyst in which nickel, rare earth element oxide, and platinum deposit 14 are supported on a phase made of alumina, and the present invention also includes such effects.

To explain the three-component catalyst that converts by-product carbon dioxide into methane, it is necessary to use granular silica or alumina (Ichisaka product) with a particle size of, for example, 2 to 4IIff+, as necessary. The carrier may be dried and dehydrated). The catalyst supported on the above-mentioned phase has a substrate of nickel, (the negative metal being one of the oxides of rare earth elements such as lanthanum, cerium, praseodymium, thorium or samarium and a platinum group metal such as ruthenium). It is a combination of one of platinum, palladium, rhodium, or iridium, but when considering the catalytic effect and economic efficiency, it is ranked as oxidation as an oxide of the rare earth element.

Among the platinum group metals, ruthenium and palladium are most preferred.゛〕;In the above combination, touch + y? ! ,
t: The amount of nickel supported is 3 to 1 for the total catalyst
2%, particularly preferably in the range 4-8%. In addition, the oxide of rare earth elements is set so that the atomic ratio of nickel element to rare earth element satisfies (2:1) to (10:1), and the atomic ratio of nickel element to platinum group metal element is set for platinum group metals. It is preferable to set and support each so as to satisfy (10:1) to (30:1). It should be noted that even if each catalyst component is supported in an amount exceeding the above-mentioned range, the catalytic effect will not be improved any further, but rather the pores of the carrier will be clogged and the catalytic performance will tend to deteriorate, which is not preferable. In producing this ternary composition catalyst, a granular support of silica and/or alumina is impregnated with nickel, rare earth elements, and platinum group metals, for example in the form of an aqueous nitrate solution, by means such as spraying, scattering, or dipping. , air dry or 60~150°
After heating and drying C, ammonia treatment was performed.

Performs thermal decomposition and hydrogen reduction. In preparing this catalyst, nickel, rare earth element oxides, and platinum group metals may be used individually in any order, or in combination of two or more of them on a granular carrier of silica and/or alumina. First, a platinum group metal is supported on the support, and then nickel and a rare earth element oxide are simultaneously supported on the support II! Catalysts obtained by such a procedure have particularly excellent conversion properties from carbon dioxide to hydrocarbons.

A specific example of preparation of the ternary composition catalyst is as follows. That is, a granular support of silica and/or alumina is coated with platinum group metals JiX, such as nitric acid 11!
Only the pore volume and the ring portion of the carrier are impregnated with an aqueous solution of chloride or chloride, and the carrier is air-dried or dried by heating at 60 to 150°C. At this time, the concentration of the platinum group metal nitrate fIII salt or the same chloride is determined by making sure that the impregnating solution contains a predetermined amount of the nitrate, and heating the impregnated product to 350°C in the atmosphere after drying and ammonia treatment. Decomposes the nitrates and chlorides. The platinum group metal support thus prepared in step (1) is impregnated with a mixed solution of an aqueous solution of nickel acetic acid n1, such as nitrate, and an aqueous solution of an inorganic acid salt of a rare earth element, such as nitrate, to support the platinum group metal. Drying, ammonia treatment, and
This is thermally decomposed, then heated from room temperature to 400℃ in an air stream with a hydrogen concentration of 10 to 20% diluted with an inert gas, kept at the same temperature for 30 minutes to reduce, and then heated to room temperature in the same air stream. The production of the catalyst is completed by cooling to

In producing high calorie gas according to the present invention,
A low-calorie gas as a raw material is introduced under the above-mentioned conditions into the reaction tower filled with the ternary composition catalyst consisting of iron group metal-manganese oxide-platinum group metal. The gas generated here contains by-product carbon dioxide, and the gas is then transferred to a second ternary composition catalyst consisting of nickel, rare earth element oxide, and platinum group metal. Alternatively, the above two types of catalysts may be packed in series in one reaction column, and the low calorie gas may be first brought into contact with the first ternary composition catalyst layer of the present invention. , and then may be brought into contact with the second ternary composition catalyst layer. In this case, the first catalyst volume has a carbon monoxide conversion rate of 100
%, the second catalyst volume may be as much as 6 required to reach 100% conversion of the carbon dioxide contained.

When the catalyst of the present invention is brought into contact with a low-calorie gas, [complete utilization of all carbon oxides in the raw material gas], which was not achieved with conventional catalysts, is achieved, and moreover, the number of carbon atoms is higher than that of conventional catalysts. A high-calorie gas containing more 2-4 hydrocarbons can be collected 1j). Furthermore, in order to obtain a high-calorie gas containing hydrocarbons having 2 to 4 carbon atoms in addition to methane using the catalyst of the present invention, a second tertiary gas consisting of nickel, a dilute J2 element oxide, and a platinum group metal is used. By bringing the original composition catalysts together and bringing them into contact, by-product carbon dioxide can be completely methanized, so a carbon dioxide separation and recovery device is not required, which is extremely effective in terms of the process.

Next, the present invention will be described with reference to examples, but the present invention can be modified in various ways by modifying the following examples without departing from the gist thereof. In the explanation, "part" refers to the heavy bathing part.

Example 1 A commercially available titanium oxide carrier was heated in an electric furnace from room temperature to 500° C. over 4 to 6 hours, and then maintained at the same temperature for 30 minutes for heat treatment. To 20 parts of the heat-treated carrier cooled to room temperature, R
The sample was impregnated with an aqueous solution prepared by dissolving 1 part of IJC13.3H201 in 5 parts of water by a spraying method, and then air-dried overnight while gently rolling to obtain an impregnated product. This impregnated material was ammonia-treated by exposing it to an atmosphere pre-adjusted to 10-11% ammonia and 6% water vapor by volume for 2 minutes, and then heated in air to about 350°C to impregnate it. The Ru metal salt was thermally decomposed to form an oxide. This was placed in an electric furnace, and the temperature was raised from room temperature to 400°C in 1 hour while passing a nitrogen stream containing 20 volumes of hydrogen at a concentration of 5%, and after reducing by holding that temperature for 30 minutes, the same air stream was heated. The mixture was cooled to room temperature to obtain 20.5 parts of RuJ11 carrier. Next, Co (NO3)2 ・6 was added to 21.0 parts of the Ru support.
H2012, 3 parts and Mn (NO3) 2 ・6H
205.3 parts of a solution dissolved in 5 parts of wood was impregnated by the same spraying method as above, followed by ammonia treatment, thermal decomposition, and after cooling, the remaining solution was added to the above solution. Impregnation, drying, ammonia treatment, and thermal decomposition were carried out in the same manner as above, and the same procedure as above was performed to prepare a catalyst with a ternary composition of io%C0-6%Mn203-2%Ru24.4 I got the department.

Example 2 A low-calorie test gas having a composition shown in Table 1 was heated to a pressure of 10 k to the catalyst obtained by the method of Example 1.
g/cm G, S■5500hr-', temperature 3
After one pass at 20°C, CO conversion rate was 100%.
A gas having the composition shown in Table 2 was obtained.

As is clear from the results from Table 1 and Table 2 onward, 02-C in the produced gas
It can be seen that a high-calorie residue with a high hydrocarbon content can be obtained.

Example 3 The same catalyst as in Example 1 was used, and 7.5% Ni-3, 6% La203-0.
In combination with a second catalyst containing 5% Ru at J11,
A test gas containing hydrogen and carbon monoxide having the same composition as in Example 1 was passed over the first catalyst and then through the second catalyst once every second. In addition, the conditions at this time are the first catalyst.
When passing through the second catalyst, Sv]000h r-'
, temperature 290°C - C - Yes, Se (7) Other conditions are the first
The same procedure was used for passing the sample over the catalyst. This result C
The O conversion rate is 100% and the high calorie gas having the composition shown in Table 3 is 77+.

As is clear from the results in Table 3 and 1-1, the first approach of the present invention 6
By combining M and a second catalyst and bringing them into contact with a test gas having a composition shown in Table 1, l
1, 800 kcal/Nm3 can be reduced to tIL, and if this principle is applied to increase the calorie content of low-calorie waste fuel, it is understood that considerably high-calorie waste fuel can be obtained.

Applicant Tomoyuki Inui Same Yoshinobu Takegami Kansai Thermochemical Co., Ltd.

Claims (1)

[Claims] (+) II consisting of titanium liquefied by combining an iron group metal as a catalyst substrate with mankanoxide and a platinum group metal!
A catalyst for producing high-calorie gas, which is characterized by being supported on the body. (2) The catalyst for producing high-calorie gas according to claim 1, wherein the iron group metal as the catalyst substrate is either cobalt or iron. (3) The catalyst for producing high-calorie gas according to claim 1 or 2, wherein the platinum group metal is ruthenium, rhodium, palladium, platinum or iridium. (4) Iron group metal: 3 to 15% (meaning by weight %, the same applies hereinafter), Manganese oxide: an amount where the atomic ratio of iron group metal element to manganese element satisfies (5:I) to (5:4) , Platinum group metal: The atomic ratio of iron group metal element to platinum group metal element satisfies (30:1) to (5:2), according to any one of claims 1 to 3. Catalyst for high calorie gas production. (5) 11, which is made of titanium oxide by combining manganese oxide and platinum group metal with iron group metal as a catalyst substrate;
2. A method for producing a high-calorie gas, which comprises conducting a gas containing hydrogen and carbon oxide, or a gas containing hydrogen, carbon monoxide, and carbon monoxide. (6) The method for producing a high-calorie waste according to claim 5, wherein the iron group metal as the substrate is either cobalt or iron. (7) The method for producing a high-calorie gas according to claim 5 or 6, wherein the platinum group metal is ruthenium, rhodium, palladium, platinum or iridium. (8) Iron group metal: 3 to 15%, an amount that satisfies the atomic ratio of manganese secondary group metal element to mankane element (5:I) to (5:4), platinum group metal: iron group metal element A method for producing high-calorie scum in one night according to any one of claims 5 to 7, wherein the atomic ratio of platinum group metal element to platinum group metal element satisfies (30:I) to (5:2). . (9) A first compound in which an iron group metal consisting of either cobalt or iron as a catalyst substrate is combined with mancan oxide and a platinum group metal, and 111 is supported on a support consisting of titanium oxide.
A gas containing hydrogen and carbon monoxide or a scum containing hydrogen, carbon monoxide and carbon dioxide is passed over the catalyst, and then a rare earth element oxide and a platinum group metal are introduced into the catalyst (nickel as a material). A method for producing a high-calorie scum, characterized by conducting on a second catalyst supported on a carrier made of All alloy, silica and/or alumina. (lO) iron h'j metal: 3 to 15%, Manganese acidified: The atomic ratio of the iron group metal element to the manganese element satisfies (5:1) to (5:4), Platinum group metal: The atomic ratio of the iron group metal element to the platinum group metal element satisfies (30: The method for producing a high-calorie gas according to claim 9 or 10, which is a product that satisfies conditions 1) to (5+2).