JP2013199533A - Method for producing desulfurized gaseous fuel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing a desulfurized gaseous fuel, which is a simple system, and which uses a desulfurization agent having the same life even if moisture is present in a fuel gas as in the case where no moisture is present in the fuel gas, and having performance nearly equal to or higher than the case where a fuel gas containing no moisture is used nearly at room temperature.SOLUTION: A method for producing a desulfurized gaseous fuel includes bringing a gaseous fuel containing sulfur compounds into contact with a nickel-containing desulfurization agent. The nickel-containing desulfurization agent contains 50 to 85 mass% of nickel in terms of nickel oxide (NiO) based on the nickel-containing desulfurization agent. The method for producing a desulfurized gaseous fuel includes the following step (1). The step (1): a gaseous fuel containing sulfur compounds and having a moisture dew point of ≥-10°C is brought into contact with the nickel-containing desulfurization agent at a temperature in the range of 100 to 300°C to thereby produce the desulfurized gaseous fuel.

Description

  The present invention relates to a method for producing a desulfurized gas fuel, and more specifically, by contacting a high dew point gas fuel containing a sulfur compound with a nickel-containing desulfurizing agent to effectively remove the sulfur compound, The present invention relates to a method for efficiently producing a gaseous fuel.

New energy technologies are attracting attention due to environmental problems, and fuel cells are attracting attention as one of the new energy technologies. This fuel cell converts chemical energy into electrical energy by electrochemically reacting hydrogen and oxygen, and has a feature of high energy use efficiency. Research into practical application in various fields such as for automobiles has been actively conducted.
Various types of fuel cells such as a phosphoric acid type, a molten carbonate type, a solid oxide type, and a solid polymer type are known according to the type of electrolyte used.

  On the other hand, as a hydrogen source, liquefied natural gas mainly composed of methanol and methane, city gas mainly composed of this natural gas, and petroleum hydrocarbons such as liquefied petroleum gas (LPG), dimethyl ether, naphtha, kerosene, etc. The use of is being studied. When hydrogen is produced using these hydrocarbons, a method is generally implemented in which hydrocarbons are reformed by partial oxidation reforming, autothermal reforming or steam reforming in the presence of a reforming catalyst. Has been. In the case of producing hydrogen for fuel cells by reforming hydrocarbons such as LPG, city gas, and LNG, in order to prevent poisoning of the reforming catalyst, the sulfur content in the hydrocarbons is 0.01 ppm. It is necessary to reduce to the following.

  On the other hand, when fuel gas such as city gas is sent out, the city gas is dehydrated by cooling it to the extent that moisture does not condense even at low temperatures in winter using a cooling device, etc., so the moisture concentration in city gas is very high. Low. However, fuel gas such as city gas may contain a very small amount of water in the production process or supply process, and the water dew point of the fuel gas may increase and become very high. The cause of the increase in the water dew point is, for example, a trouble that occurs due to corrosion of buried gas conduits or damage during sandblasting, which causes water intrusion into the gas conduit, called water, or from a water-containing gas holder. It is conceivable that the ratio of the gas to be delivered becomes high. (For example, Patent Document 1)

  As described above, the city gas containing moisture does not sufficiently exhibit the performance of the desulfurizing agent. Furthermore, if the life of the desulfurizing agent is different between the case of not containing water and the case of containing water, the usable period of the desulfurizing agent is different, which is not preferable in terms of product design. Therefore, various techniques are being studied.

For example, Patent Document 2 discloses that when a fuel gas containing moisture is treated with zeolite, moisture is selectively adsorbed, so that moisture is not contained, or compared with a case where it is extremely small. Since the adsorption performance of sulfur compounds is greatly reduced, one or more transition metals selected from Ag, Cu, Zn, Fe, Co and Ni are supported on hydrophobic zeolite by ion exchange. A desulfurizing agent is disclosed.
However, even when this desulfurizing agent is used, it is still affected by moisture in the presence of moisture, and the performance of the desulfurizing agent is not sufficiently exhibited.

Patent Document 3 discloses a fuel cell including a dehumidifying part that selectively absorbs moisture contained in fuel, and a desulfurizing part that absorbs sulfur compounds contained in fuel that has passed through the dehumidifying part. A desulfurization apparatus is disclosed. However, there is a problem that the desulfurization apparatus is complicated because it has two stages of a dehumidification part and a desulfurization part.
Patent Document 4 discloses a method for desulfurization of a hydrocarbon fuel containing methanol and water, and as a desulfurization agent, a Y-type zeolite desulfurization agent containing at least copper in the former stage and an X-type containing at least silver in the latter stage. A hydrocarbon-based fuel desulfurization method using a zeolitic desulfurization agent is disclosed. However, since two types of desulfurization agents are used, the apparatus is complicated as in Patent Document 3.

  Patent Document 1 discloses an adsorbent for removing an odorant in a fuel gas containing an odorant under a high dew point condition. The adsorbent is an adsorbent in which Ag is supported on an MFI zeolite by ion exchange. Although an adsorbent for removing odorants in fuel gas under high dew point conditions is disclosed, the desulfurization capacity is not yet sufficient at both low and high humidity, and depending on the amount of moisture There is a problem that there is a difference in performance.

  Patent Document 5 discloses a fuel cell power generation system including heating means for heating a desulfurizing agent so as to be in a heated state of 50 ° C to 200 ° C. However, this system is a complicated system in which the required amount of the desulfurizing agent increases as the water content increases, and the water concentration is monitored and the temperature of the desulfurizer is controlled.

  Further, Patent Document 6 discloses a desulfurization method for desulfurizing a fuel gas containing a sulfur component using a room temperature desulfurization agent, and when the dew point of the fuel gas supplied to the desulfurization agent is higher than a set temperature, A desulfurization method in which a desulfurization agent is heated is disclosed, and a copper oxide-manganese oxide system and a copper-zeolite system are shown as the desulfurization agent. Moreover, when the dew point of fuel gas is 0 degreeC or more, it is shown that the operating temperature of a desulfurization agent shall be 50-80 degreeC. However, in this technique, it is disclosed that the system is a complicated system in which the moisture concentration is monitored and the temperature of the desulfurizer is controlled, and at the high temperature, the performance difference is eliminated depending on the moisture content in the fuel gas. There is a problem that the performance is lower than room temperature desulfurization when water is not included in the fuel gas.

JP 2011-201975 A JP 2001-286753 A JP 2008-277300 A JP 2008-218308 A JP 2011-96400 A JP 2011-184630 A

  The present invention has been made under such circumstances, and is a simple system having a life equivalent to that in the case where moisture is present in the fuel gas, even if moisture is not present in the fuel gas. Another object of the present invention is to provide a method for efficiently producing a desulfurized gas fuel by using a desulfurizing agent having a performance equal to or higher than that when a fuel gas containing no moisture is used near room temperature.

As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge.
As the desulfurizing agent, a nickel-containing desulfurizing agent having a nickel content within a specific range, preferably a nickel-containing desulfurizing agent in which nickel and copper are supported on a silica carrier, containing a sulfur compound, and having a moisture dew point. It has been found that the object can be achieved by contacting the above gaseous fuel at a temperature within a predetermined range.
The present invention has been completed based on such findings.

That is, the present invention provides the following [1] to [12].
[1] A method of producing a desulfurized gas fuel by contacting a gaseous fuel containing a sulfur compound with a nickel-containing desulfurizing agent, wherein the nickel-containing desulfurizing agent is oxidized on the basis of the nickel-containing desulfurizing agent. The manufacturing method of the desulfurization gas body fuel which contains 50-85 mass% nickel as nickel (NiO) conversion amount, and includes the following process (1).
Step (1): A step of producing a desulfurized gas fuel by contacting a gaseous fuel containing a sulfur compound with a water dew point of −10 ° C. or more with the nickel-containing desulfurizing agent at a temperature in the range of 100 to 300 ° C. [2] The method for producing a desulfurized gas fuel according to [1], including the following step (2).
Step (2): A gaseous fuel containing a sulfur compound and having a water dew point of −100 ° C. or higher and lower than −10 ° C. is contacted with the nickel-containing desulfurizing agent at a temperature in the range of 100 to 300 ° C. [3] The nickel-containing desulfurizing agent is at least selected from nickel and copper, manganese, chromium, vanadium, iron, cobalt, zinc, molybdenum, tungsten, bismuth, aluminum, cerium, and lanthanum The method for producing a desulfurized gas fuel according to [1] or [2], which includes one kind of metal.
[4] The method for producing a desulfurized gas fuel according to any one of [1] to [3], wherein the nickel-containing desulfurizing agent includes nickel and copper.
[5] The nickel-containing desulfurizing agent is an acid aqueous solution or aqueous dispersion containing a nickel source and a basic aqueous solution containing a silicon source and an inorganic base, respectively, heated and mixed, and then a temperature of 50 to 90 ° C. Any one of [1] to [4], which is obtained by washing and drying a solid obtained by solid-liquid separation after maintaining and reacting at 200 to 400 ° C. A method for producing a desulfurized gas fuel according to claim 1.
[6] The nickel-containing desulfurization agent is a desulfurization agent in which nickel and copper are supported on at least one of a silica carrier, an alumina carrier, and a silica-alumina carrier. Method for producing desulfurized gas fuel.
[7] After the nickel-containing desulfurizing agent is heated and mixed with an acidic aqueous solution or aqueous dispersion containing a nickel source and a copper source, and a basic aqueous solution containing a silicon source and an inorganic base, 50 to 90 [1] to [6], which are prepared by maintaining the temperature at ° C and reacting, and then washing and drying the solid material obtained by solid-liquid separation, followed by firing at a temperature of 200 to 400 ° C. ] The manufacturing method of the desulfurization gas body fuel in any one of.
[8] The method for producing a desulfurized gas fuel according to any one of [1] to [7], wherein a gaseous fuel containing no sulfur and containing a sulfur compound is brought into contact with the nickel-containing desulfurizing agent.
[9] The method for producing a desulfurized gas fuel according to any one of [1] to [8], wherein the desulfurization temperature is 190 to 300 ° C.
[10] The desulfurization according to any one of [1] to [9], wherein the gaseous fuel containing a sulfur compound is at least one selected from LNG, LPG, natural gas, city gas, and dimethyl ether. A method for producing a gaseous fuel.
[11] A gaseous fuel containing a sulfur compound is carbonyl sulfide, hydrogen sulfide, carbon disulfide, sulfur dioxide, dimethyl sulfide, methyl ethyl sulfide, diethyl sulfide, dimethyl disulfide, methyl ethyl disulfide, methyl mercaptan, ethyl mercaptan , A propyl mercaptan, a butyl mercaptan, a thiophene, tetrahydrothiophene, and the manufacturing method of the desulfurization gas body fuel in any one of [1]-[10] containing at least 1 sort (s) chosen from alkylthiophenes.
[12] The method for producing a desulfurized gas fuel according to any one of [1] to [11], wherein in step (1), the moisture dew point in the gas fuel containing a sulfur compound is 0 ° C. or higher.

According to the present invention, a simple system has a lifetime equivalent to that in the case where moisture is not present in the fuel gas even when moisture is present in the fuel gas, and the fuel gas containing no moisture is It is possible to provide a method for efficiently producing a desulfurized gas fuel by using a desulfurizing agent having a performance equal to or higher than that in the vicinity.
In addition, the method for producing a desulfurized gas fuel of the present invention has an effect that it is not necessary to measure the dew point and it is not necessary to perform temperature control according to the dew point.

It is a graph which shows the relationship between the operation time in Example 1 and Reference Example 1, and the sulfur concentration of a desulfurizer exit. It is a graph which shows the relationship between the operation time in Example 2 and Reference Example 2, and the sulfur concentration of the desulfurizer exit. It is a graph which shows the relationship between the operation time in the comparative example 1 and the comparative example 2, and the sulfur concentration of the desulfurizer exit.

The method for producing a desulfurized gas fuel according to the present invention is a method for producing a desulfurized gas fuel by bringing a gas fuel containing a sulfur compound into contact with a nickel-containing desulfurizing agent, wherein the nickel-containing desulfurizing agent comprises: This is a method for producing a desulfurized gas fuel that includes 50 to 85% by mass of nickel as a nickel oxide (NiO) equivalent amount based on the nickel-containing desulfurizing agent, and includes the following step (1).
Step (1): A step of producing a desulfurized gas fuel by contacting a gaseous fuel containing a sulfur compound with a water dew point of −10 ° C. or more with the nickel-containing desulfurizing agent at a temperature in the range of 100 to 300 ° C. According to the present invention, since the gaseous fuel is processed using the nickel-containing desulfurizing agent and under the temperature conditions, a high gaseous fuel having a water dew point of −10 ° C. or more can be sufficiently degassed. It is possible to perform a deflowing process equivalent to the case of processing a gaseous fuel having a moisture dew point of less than −10 ° C.

Moreover, in this invention, the following process (2) may be included further.
Step (2): A gaseous fuel containing a sulfur compound and having a water dew point of −100 ° C. or higher and lower than −10 ° C. is contacted with the nickel-containing desulfurizing agent at a temperature in the range of 100 to 300 ° C. According to the present invention, in order to treat the gaseous fuel using the nickel-containing desulfurizing agent and the temperature condition, as described above, the gaseous fuel having a water dew point of less than −10 ° C. An equivalent desulfurization treatment can be performed by treating any of the gaseous fuels, and a desulfurized gaseous fuel having a stable property can be obtained even if the moisture dew point of the gaseous fuel changes.

  For example, step (1) is performed when water enters into the conduit due to corrosion of the conduit of the gaseous fuel and the water dew point of the gaseous fuel increases. Step (2) is performed, for example, before the occurrence of the trouble or after the conduit is restored. Thus, even if the moisture dew point of the gas fuel changes due to some trouble or the like, according to the present invention, a desulfurized gas fuel with stable properties can be obtained.

[Gas fuel]
In the step (1) of the present invention, a gaseous fuel containing a sulfur compound and having a moisture dew point of −10 ° C. or higher is used as a raw material. Moreover, in the process (2) implemented as needed, the gaseous fuel which contains a sulfur compound and whose moisture dew point is -100 degreeC or more and less than -10 degreeC is used as a raw material.
When fuel gas such as city gas is sent out, the city gas is dehydrated by cooling it to the extent that moisture does not condense even at low temperatures in winter using a cooling device or the like, so the water concentration in the city gas is very low. However, fuel gas such as city gas may contain a very small amount of water in the production process or supply process, and the water dew point of the fuel gas may increase and become very high. The cause of the increase in the water dew point is, for example, a trouble that occurs due to corrosion of buried gas conduits or damage during sandblasting, which causes water intrusion into the gas conduit, called water, or from a water-containing gas holder. It is conceivable that the ratio of the gas to be delivered becomes high.

Usually, the fuel gas containing moisture does not sufficiently exhibit the performance of the desulfurizing agent. Furthermore, if the life of the desulfurizing agent is different between the case of not containing water and the case of containing water, the usable period of the desulfurizing agent is different, which is not preferable in terms of product design.
However, the nickel-containing desulfurization agent to be described later used in the production method effectively exhibits desulfurization performance even for gaseous fuel having a dew point of −10 ° C. or higher, and further a dew point of 0 ° C. or higher and 10 ° C. or higher. .
Although the upper limit of a dew point is not specifically limited, For example, a dew point is 40 degreeC.

In the method for producing a desulfurized gas fuel, the gas fuel containing a sulfur compound used as a raw material is not particularly limited, and examples thereof include LNG, LPG, natural gas, city gas, and dimethyl ether. In this invention, 1 type chosen from these may be used as a raw material, and 2 or more types may be mixed and used for it.
The sulfur compound content in the gas fuel containing the sulfur compound, which is the raw material used in the present invention, is preferably 50 ppm by volume or less, more preferably 20 ppm by volume or less as the sulfur content. A sulfur content of 50 ppm by volume or less is preferable because the life of the desulfurizing agent is prolonged and the frequency of replacement or regeneration of the desulfurizing agent is reduced. Accordingly, the sulfur content is more preferably 10 ppm by volume or less, and even more preferably 5 ppm by volume or less.

  Examples of the sulfur compound contained in the gaseous fuel include carbonyl sulfide, hydrogen sulfide, carbon disulfide, sulfur dioxide, dimethyl sulfide, methyl ethyl sulfide, diethyl sulfide, dimethyl disulfide, methyl ethyl disulfide, methyl mercaptan, and ethyl mercaptan. , Propyl mercaptan, butyl mercaptan, thiophene, tetrahydrothiophene, alkylthiophenes and the like.

[Nickel-containing desulfurization agent]
The nickel-containing desulfurizing agent used in the method for producing the desulfurized gas fuel is selected from nickel and copper, manganese, chromium, vanadium, iron, cobalt, zinc, molybdenum, tungsten, bismuth, aluminum, cerium, and lanthanum. Containing at least one kind of metal.

The nickel component in the nickel-containing desulfurizing agent is preferably normal nickel oxide and metallic nickel obtained by reducing the nickel oxide, and more preferably 60% by mass or more of the nickel component is metallic nickel. When the metallic nickel is 60% by mass or more, the number of active sites on the surface of the desulfurizing agent is large, and particularly high desulfurization performance is obtained.
Moreover, it is preferable that it is the range of 50-85 mass% as nickel oxide (NiO) conversion amount based on desulfurization agent whole quantity as content of nickel. A high desulfurization activity is obtained when the content in terms of nickel oxide (NiO) is 50% by mass or more. In addition, when the content is 85% by mass or less, the surface area of the desulfurizing agent is sufficient by ensuring the carrier content, and the desulfurization performance is not deteriorated. From this viewpoint, the content in terms of nickel oxide (NiO) is more preferably in the range of 60 to 80% by mass. In the case of a nickel-containing desulfurization agent containing nickel and copper, which will be described later, from the same viewpoint as described above, the content of nickel in terms of nickel oxide (NiO) is 60 to 80% by mass, copper copper oxide (CuO) The content in terms of conversion is 1 to 20% by mass, and the sum of the content in terms of nickel oxide and copper in terms of copper oxide is 65 to 85% by mass based on the total amount of the desulfurizing agent. Is preferred.

As the nickel-containing desulfurization agent, one containing nickel and copper is preferably used from the viewpoint of desulfurization performance.
The nickel-containing desulfurizing agent may be in a form in which a metal such as nickel is supported on a porous inorganic oxide support. In a form in which a metal such as nickel is supported on a porous inorganic oxide carrier, the desulfurization effect may be higher than that of a desulfurization agent composed of only metal because nickel or the like is held in a highly dispersed state.
Examples of the porous inorganic oxide include silica, alumina, silica-alumina, titania, zirconia, ceria, diatomaceous earth, clay, and zinc oxide. Among these, a silica carrier, an alumina carrier, and a silica-alumina carrier are preferable from the viewpoint of desulfurization effect and availability, and a silica carrier is particularly preferable.
These porous inorganic oxides may be used alone or in combination of two or more.

As the nickel-containing desulfurizing agent, a desulfurizing agent in which nickel and copper are supported on a silica carrier is preferably used.
As the nickel-containing desulfurization agent in which nickel and copper are supported on a silica carrier, an acidic aqueous solution or aqueous dispersion containing a nickel source and a copper source and a basic aqueous solution containing a silicon source and an inorganic base are added. After heating and mixing, the reaction is carried out while maintaining the temperature at 50 to 90 ° C., and the solid obtained by solid-liquid separation is washed and dried, and then fired at a temperature of 200 to 400 ° C. Is preferred.

(Method for producing nickel-containing desulfurization agent)
Examples of the method for producing the nickel-containing desulfurizing agent include the following methods.
For example, a nickel-containing desulfurization agent in which a metal such as nickel is supported on a porous inorganic oxide carrier is obtained by bringing the water-soluble compound of the metal component and the porous inorganic oxide into contact with each other by a coprecipitation method or the like. It is obtained by appropriately drying after washing and baking.

Specifically, a nickel-containing desulfurization agent in which nickel and copper are supported on a silica carrier can be produced by, for example, the following method.
First, an acidic aqueous solution or aqueous dispersion containing a nickel source and a copper source and a basic aqueous solution containing a silicon source and an inorganic base are prepared.
Examples of the nickel source used in the acidic aqueous solution or aqueous dispersion include nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, nickel carbonate, and hydrates thereof.
Examples of the copper source include copper chloride, copper nitrate, copper sulfate, copper acetate, and hydrates thereof.
These nickel sources and copper sources may be used alone or in combination of two or more.

  The silicon source used in the basic aqueous solution is not particularly limited as long as it is soluble in an alkaline aqueous solution and becomes silica upon firing. For example, orthosilicic acid, metasilicic acid, and these sodium salt, potassium salt, water glass, etc. are mentioned. And as a silicon source, these may be used independently or may be used in combination of 2 or more type. In particular, water glass which is a kind of sodium silicate hydrate is suitable.

As the inorganic base used in the basic aqueous solution, an alkali metal carbonate or hydroxide is preferable. Examples thereof include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like. These may be used alone or in combination of two or more. In particular, sodium carbonate alone or a combination of sodium carbonate and sodium hydroxide is suitable. The amount of the inorganic base used is set so that the mixed solution is substantially neutral to basic when the acidic aqueous solution or aqueous dispersion and the basic aqueous solution are mixed in the next step.
The entire amount of the inorganic base may be used for the preparation of this basic aqueous solution, or a part thereof may be added to the acidic aqueous solution or the mixture of the aqueous dispersion and the basic aqueous solution in the next step.

The acidic aqueous solution or aqueous dispersion prepared as described above and the basic aqueous solution are preferably mixed after heating to 40 ° C to 70 ° C, more preferably 40 ° C to 60 ° C, respectively. And after mixing, after adding further the aqueous solution containing the inorganic base heated preferably at 40 degreeC-70 degreeC more preferably 40 degreeC-60 degreeC as needed, the mixture liquid becomes like this. Preferably it is 50 degreeC-95 degreeC. , More preferably 50-90 ° C., more preferably 60 ° C.-80 ° C. while maintaining, preferably 0.5-5 hours, more preferably 1-4 hours, still more preferably 2-4 hours with stirring. .
Thereafter, the produced solid is sufficiently washed and then subjected to solid-liquid separation, or the produced solid is separated into solid and liquid and then sufficiently washed, and the obtained solid is dried at about 80 ° C to 150 ° C. . The obtained dry solid is preferably 200 ° C to 400 ° C, more preferably 300 ° C to 400 ° C, more preferably 350 ° C to 400 ° C, preferably 1 to 5 hours, more preferably 2 to 4 hours. Preferably, it is calcined for 2 to 3 hours to obtain a nickel-copper desulfurization agent in which nickel and copper are supported on a support.

[Desulfurization method]
The desulfurization method in the present invention is to remove the sulfur compound contained in the gaseous fuel using the nickel-containing desulfurization agent, and the desulfurization method needs to satisfy the following conditions.
About desulfurization temperature, it is 100-300 degreeC. When the desulfurization temperature exceeds 300 ° C., the desulfurization life is shortened due to deterioration due to coke deposition. When the temperature is less than 100 ° C., the adsorption state of the sulfur compound to the desulfurization agent becomes physisorbent, so that the adsorption capacity is lowered, and as a result, the desulfurization agent filling amount is inevitably increased.
The desulfurization temperature is preferably 130 to 300 ° C., more preferably 170 to 300 ° C., from the viewpoint of promoting chemical adsorption of sulfur compounds and suppressing deterioration due to coke deposition. The desulfurization temperature is, for example, 190 ° C to 300 ° C, 200 ° C to 300 ° C.

Even if a small amount of hydrogen is added during desulfurization, it is not affected by moisture, but adding hydrogen complicates the system and is not preferable from the viewpoint of cost.
Therefore, in the method for producing a desulfurized gas fuel of the present invention, a method in which hydrogen gas is not added and the gas fuel is brought into contact with the nickel-containing desulfurizing agent is preferably used.
Further, the desulfurization pressure in the present invention is preferably normal pressure to 1.0 MPa, but is not particularly limited.
The gas space velocity (GHSV) is preferably 50 to 10,000 h- ¹ . If it is less than 50 h ⁻¹ , the use amount of the desulfurizing agent increases too much, which is not practical. If it exceeds 10,000 h ⁻¹ , the sulfur compound becomes difficult to decompose, so that the sulfur adsorption capacity becomes small, and the amount of the desulfurizing agent increases too much, which is not practical. More preferably, it is 100 to 2,000 h- ¹ .

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Production Example 1 (Preparation of nickel-containing desulfurizing agent)
An ion obtained by heating 1755.6 g of nickel sulfate hexahydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and 42.8 g of copper sulfate pentahydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) to 50 ° C. Dissolved in 4 L of exchange water to obtain Preparation Liquid A.
On the other hand, 1200 g of sodium carbonate was dissolved in 4 L of ion-exchanged water heated to 50 ° C., and 433.6 g of water glass (JIS-3, Si concentration 29 mass%, manufactured by Nippon Chemical Industry Co., Ltd.) was added. Was prepared separately.
Next, while maintaining the temperature of each of preparation solutions A and B at 50 ° C., they were introduced into a stainless steel reaction tube having an inner diameter of 10 mm and a length of 10 cm and mixed. Further, while stirring the mixed solution, the temperature was raised to 90 ° C. and maintained for 3 hours to obtain a precipitated cake.
Thereafter, the precipitated cake was washed with 100 L of ion-exchanged water, filtered, and dried for 12 hours in a 120 ° C. blower dryer. Then, the obtained dried product was pulverized using an agate mortar to obtain an average particle size of 0.8 mm, and calcined at 350 ° C. for 3 hours in an air atmosphere to obtain a nickel-containing desulfurizing agent A.
Nickel content of the resulting nickel containing desulfurizing agent A (NiO equivalent) 78.2 wt%, copper content (CuO equivalent) 2.1 wt%, the silicon content (SiO ₂ equivalent) 19.7 Weight %Met.

Reference Example 1 (220 ° C, dew point -90 ° C)
1 mL of the desulfurizing agent A obtained in Production Example 1 was weighed with a graduated cylinder and charged into a SUS cylindrical reactor (inner diameter: 9.4 mm). Hydrogen gas was supplied to the reactor at 100 cm ³ / min under atmospheric pressure, the temperature was raised from room temperature to 120 ° C., held for 1 hour, then further heated to 350 ° C. and held for 15 hours, thereby containing nickel The desulfurizing agent was reduced in the reactor.
Thereafter, the hydrogen supply was stopped, propane gas added with dimethyl sulfide and tertiary butyl mercaptan to desulfurized propane at 25 volppm each was adjusted to 220 ° C. and GHSV to 8000 h ⁻¹ at atmospheric pressure, and the desulfurization test was performed. Started. 97 hours after the start of gas introduction, the temperature of the desulfurizing agent layer was adjusted to 202 ° C. After 140 hours, the temperature was adjusted to 220 ° C. The dew point of the supplied gas was −90 ° C. The sulfur concentration at the outlet of the desulfurizer is automatically measured by a gas chromatograph with an SCD detector, and the result is shown in FIG.

Example 1 (220 ° C., dew point 20 ° C.)
A desulfurization test was performed under the same conditions as in Reference Example 1 except that the gas used for the desulfurization test was bubbled into a water tank adjusted to 20 ° C., and the sulfur concentration at the outlet of the desulfurizer was added to FIG. The desulfurization behavior at a cryogenic dew point and the desulfurization behavior at 20 ° C, which is a practically desired dew point at room temperature, are completely unchanged, and by adopting this desulfurization method, the gas dew point is not affected and efficient. It can be seen that it can be desulfurized.
Moreover, as shown in FIG. 1, the desulfurization behavior of Example 1 and Reference Example 1 is not changed at all. From this, it is considered that according to the present invention, the life of the desulfurization catalyst A can be made equal regardless of the difference in the dew point of the gas.

Reference Example 2 (140 ° C, dew point -90 ° C)
In the same manner as in Reference Example 1, the desulfurizing agent A was filled and reduction treatment was performed. Thereafter, the hydrogen supply was stopped, propane gas added with dimethyl sulfide and tertiary butyl mercaptan to desulfurized propane so as to be 20 volppm each was adjusted to 140 ° C. and GHSV to 8000 h ⁻¹ , and the desulfurization test was performed. Started. Similar to Reference Example 1, the sulfur concentration at the outlet of the desulfurizer was measured by a gas chromatograph with an SCD detector. The results are shown in FIG.

Example 2 (140 ° C., dew point 20 ° C.)
A desulfurization test was performed under the same conditions as in Reference Example 2 except that the gas used for the desulfurization test was bubbled into a water tank adjusted to 20 ° C., and the sulfur concentration at the outlet of the desulfurizer was added to FIG. There is no difference in performance depending on the dew point, and the performance is superior to Comparative Example 1 below.

Comparative Example 1 (70 ° C, dew point -90 ° C)
A desulfurization test was performed in the same manner as in Reference Example 2 except that the temperature during desulfurization was set to 70 ° C., and the sulfur concentration at the outlet of the desulfurizer was measured. The results are shown in FIG.

Comparative Example 2 (70 ° C., dew point 20 ° C.)
A desulfurization test was performed in the same manner as in Reference Example 2 except that the temperature during desulfurization was set to 70 ° C., and the sulfur concentration at the outlet of the desulfurizer was measured. The results are shown in FIG.

  The method for producing a desulfurized gas fuel of the present invention is a simple system, and even if moisture is present in the fuel gas, it has a life equivalent to that in the case where no moisture is present in the fuel gas, and the moisture is removed. By using a desulfurizing agent having a performance equal to or higher than that when a fuel gas not contained is used at around room temperature, a desulfurized gas fuel can be efficiently produced.

Claims (12)

A method of producing a desulfurized gas fuel by contacting a gas fuel containing a sulfur compound with a nickel-containing desulfurizing agent,
The nickel-containing desulfurizing agent contains 50 to 85% by mass of nickel as a nickel oxide (NiO) conversion amount based on the nickel-containing desulfurizing agent, and includes the following step (1). Production method.
Step (1): A step of producing a desulfurized gas fuel by contacting a gaseous fuel containing a sulfur compound with a water dew point of −10 ° C. or more with the nickel-containing desulfurizing agent at a temperature in the range of 100 to 300 ° C. The manufacturing method of the desulfurization gas body fuel of Claim 1 including the following process (2).
Step (2): A gaseous fuel containing a sulfur compound and having a water dew point of −100 ° C. or higher and lower than −10 ° C. is contacted with the nickel-containing desulfurizing agent at a temperature in the range of 100 to 300 ° C. Manufacturing process   The nickel-containing desulfurizing agent includes nickel and at least one metal selected from copper, manganese, chromium, vanadium, iron, cobalt, zinc, molybdenum, tungsten, bismuth, aluminum, cerium, and lanthanum. The manufacturing method of the desulfurization gas body fuel of Claim 1 or 2.   The manufacturing method of the desulfurization gas body fuel in any one of Claims 1-3 in which the said nickel containing desulfurization agent contains nickel and copper.   The nickel-containing desulfurizing agent is heated and mixed with an acidic aqueous solution or aqueous dispersion containing a nickel source and a basic aqueous solution containing a silicon source and an inorganic base, and then maintained at a temperature of 50 to 90 ° C. The desulfurization according to any one of claims 1 to 4, wherein the solid obtained by solid-liquid separation after the reaction is washed and dried, and then fired at a temperature of 200 to 400 ° C. A method for producing gaseous fuel.   The desulfurization gas fuel according to any one of claims 1 to 5, wherein the nickel-containing desulfurization agent is a desulfurization agent in which nickel and copper are supported on at least one of a silica carrier, an alumina carrier, and a silica-alumina carrier. Manufacturing method.   The nickel-containing desulfurizing agent is heated at 50 to 90 ° C. after mixing and heating an acidic aqueous solution or aqueous dispersion containing a nickel source and a copper source, and a basic aqueous solution containing a silicon source and an inorganic base, respectively. The solid obtained by separating and solid-liquid separation after being maintained at the temperature is washed and dried, and then fired at a temperature of 200 to 400 ° C. The manufacturing method of the desulfurization gas body fuel of description.   The method for producing a desulfurized gas fuel according to any one of claims 1 to 7, wherein a gaseous fuel containing no sulfur and containing a sulfur compound is brought into contact with the nickel-containing desulfurizing agent.   The manufacturing method of the desulfurization gas body fuel in any one of Claims 1-8 whose desulfurization temperature is 190-300 degreeC.   The production of a desulfurized gaseous fuel according to any one of claims 1 to 9, wherein the gaseous fuel containing a sulfur compound is at least one selected from LNG, LPG, natural gas, city gas, and dimethyl ether. Method.   Gas fuels containing sulfur compounds are carbonyl sulfide, hydrogen sulfide, carbon disulfide, sulfur dioxide, dimethyl sulfide, methyl ethyl sulfide, diethyl sulfide, dimethyl disulfide, methyl ethyl disulfide, methyl mercaptan, ethyl mercaptan, propyl mercaptan. The manufacturing method of the desulfurization gas body fuel in any one of Claims 1-10 containing at least 1 sort (s) chosen from butyl mercaptan, thiophene, tetrahydrothiophene, and alkylthiophenes.   The process for producing a desulfurized gas fuel according to any one of claims 1 to 11, wherein in step (1), the moisture dew point in the gas fuel containing a sulfur compound is 0 ° C or higher.

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