JP3763628B2 - Sulfur-containing hydrocarbon hydrogenation catalyst and hydrodesulfurization method using the same - Google Patents

Description

【００３１】
【発明の効果】
本発明の水素化脱硫触媒を用いれば、特に原料油である灯油留分，軽油留分又はこれらの混合物に接触させて水素化脱硫するに際し、脱硫度が高く、該原料油から硫黄分を効率よく除去することが可能である。
また、本発明の水素化脱硫方法によれば、含硫黄炭化水素類を効率よく脱硫することができ、性状のよい有用な炭化水素油（脱硫灯油や脱硫軽油）を生産性よく、効率的に製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrodesulfurization method for sulfur-containing hydrocarbons, and more specifically, sulfur is efficiently removed from sulfur-containing hydrocarbons, and useful hydrocarbons having a high desulfurization rate are efficiently and efficiently produced. The present invention relates to a hydrodesulfurization catalyst and a hydrodesulfurization method for production.
[0002]
[Prior art and problems to be solved by the invention]
Many technologies have been developed as hydrodesulfurization technologies for sulfur-containing hydrocarbons. In these conventional techniques, many catalysts having high activity in the hydrodesulfurization reaction have been proposed. In particular, periodic group 6 (VIA group) metals and periodic tables 8, 9, 10 have been proposed. Based on a group (Group VIII) metal supported on alumina, various improvements thereof are known as typical ones and are widely used.
For example, a method in which an alumina carrier is impregnated with an aqueous cobalt nitrate solution and an aqueous ammonium molybdate solution to obtain a highly active hydrodesulfurization catalyst is disclosed in J. Org. Catal., 158 , 411 (1996); Catal., 159 , 212 (1996).
JP-A-4-166232 discloses that a refractory oxide carrier such as alumina carries a group 6 metal salt and a group 8, 9, 10 metal salt of the periodic table. There has been proposed a method of obtaining a hydrodesulfurization catalyst by adding a polyhydric alcohol to a catalyst precursor and drying at a temperature of 200 ° C. or lower.
[0003]
However, the catalysts prepared by these methods do not have sufficient desulfurization activity at low temperatures, and two kinds of metals (Group 6 of the periodic table and Groups 8, 9, and 10 of the periodic table) are supported. And the preparation process is complicated. In addition, when molybdenum is included as group 6 of the periodic table, there is a disadvantage that the catalyst itself is expensive and inferior in economic efficiency.
On the other hand, in addition to the catalyst in which the metals of Group 6 of the periodic table and metals of Groups 8, 9, and 10 of the periodic table are supported on alumina, those using clay minerals have also been proposed as hydrodesulfurization reaction catalysts. ing.
For example, in JP-A-8-182930, a composite comprising a saponite and / or laponite carrying a group 6 metal and a group 8, 9, 10 metal of the periodic table and a silica-containing alumina, It has been proposed as a hydrodesulfurization catalyst. However, this catalyst system carries two kinds of metals and has a disadvantage that the preparation process becomes complicated because a plurality of clay minerals are used as a carrier. Furthermore, when molybdenum is included as a metal of Group 6 of the periodic table, it becomes expensive and inferior in economic efficiency.
Appl. Catal., 97 , 77 (1993) discloses the result of using nickel-impregnated montmorillonite crosslinked with alumina as a hydrodesulfurization catalyst. However, since this catalyst supports nickel after immobilizing alumina on montmorillonite, it has a drawback that the preparation process becomes complicated.
[0004]
Under such circumstances, the present inventors solved the above-mentioned problems of the prior art, efficiently removed sulfur from sulfur-containing hydrocarbons, and efficiently produced useful hydrocarbons with a high desulfurization rate with high productivity. In order to develop a hydrodesulfurization catalyst and hydrodesulfurization method for this purpose, an extensive study was conducted.
[0005]
[Means for Solving the Problems]
As a result, only cobalt (Co) is selected from the metals of Groups 8, 9, and 10 of the periodic table as the metal species exhibiting hydrodesulfurization activity, and a kind of smectite clay mineral as a high specific surface area carrier. It was found that the above-mentioned problem can be solved by selecting saponite which is and supporting cobalt on the high specific surface area saponite.
The present invention has been completed based on such findings.
[0006]
That is, the present invention provides a sulfur-containing hydrocarbon hydrodesulfurization catalyst comprising cobalt supported on a saponite having a specific surface area of 400 m ² / g or more. The present invention also provides a hydrodesulfurization method characterized in that sulfur-containing hydrocarbons are desulfurized in the presence of a cobalt-supported hydrodesulfurization catalyst on a saponite having a specific surface area of 400 m ² / g or more. Is.
Hereinafter, the hydrodesulfurization catalyst and hydrodesulfurization method of the present invention will be described.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
There is no restriction | limiting in particular as a cobalt raw material used in preparing the catalyst of this invention, A various thing is used. However, cobalt compounds (II) hexahydrate (Co (NO ₃ ) ₂ -6H ₂ 0), cobalt chloride (II) hexahydrate ( CoCl ₂ -6H ₂ O) and the like, and preferably, cobalt (II) nitrate hexahydrate (Co (NO ₃ ) ₂ -6H ₂ O) is used.
The saponite used in the present invention is a compound represented by the following general formula (I).
[(Si _6-x Al _x ) (Mg _6-y Al _y ) · O ₂ O · (OH) ₄ ] ^-(xy) Na ^{+ (xy)} (I)
[Wherein, x and y each represent an integer of 1 to 6, and xy> 0. ]
[0008]
In the catalyst of the present invention, the supported amount of cobalt may be appropriately selected according to the application and the like, but is generally 10 to 120 mg, preferably 30 to 100 mg per 1 g of the catalyst. Although the specific surface area of saponite is to 400 meters ² / g or more as described above, preferably 400 meters ² / g or more, more preferably 500~600m ² / g. Here, when the specific surface area is less than 400 m ² / g, there is a disadvantage that the reaction rate is lowered due to the decrease in the number of active sites on the catalyst surface as a reaction field, and the object of the present invention cannot be achieved. Here, the specific surface area is a value measured by the BET method.
[0009]
The cobalt-supported saponite (catalyst of the present invention) used as a catalyst can be prepared by various methods. For example, it is prepared through the following steps (a) to (b).
(I) First, water is added to cobalt nitrate or chloride and mixed, followed by aging at a temperature of room temperature to 100 ° C. for 0 to several hours, preferably 60 to 100 ° C. for 1 to 2 hours. Here, the aging time of 0 hour means that aging is not necessary (the same applies hereinafter).
(B) Next, powder or thriller saponite is added, and after stirring at room temperature to 100 ° C. for 5 minutes to several weeks, preferably at 60 to 100 ° C. for 1 to 2 hours, filtration, water , Washed with alcohol, etc., and then aged in water at a temperature of 50 to 100 ° C. for 0 hour to several weeks, followed by filtration, freeze drying or air drying after alcohol washing.
By passing through the said process, the hydrodesulfurization catalyst which concerns on this invention which carry | supported cobalt in the saponite is obtained.
Here, examples of the incorporated cobalt include cobalt oxide, cobalt hydroxide, partially dehydrated cobalt hydroxide, and a mixture thereof.
[0010]
In the hydrodesulfurization method of the present invention, as the raw material sulfur-containing hydrocarbons, crude oil, various petroleum fractions and various residual oils can be used, of which kerosene fraction or light oil fraction or Mixtures of these are preferred. In the method of the present invention, the raw material hydrocarbons are hydrodesulfurized by contacting them with the hydrodesulfurization catalyst prepared as described above in the presence of hydrogen gas, thereby efficiently removing sulfur from the raw material hydrocarbons. As a result, it is possible to efficiently produce a useful hydrocarbon oil (desulfurized kerosene or desulfurized light oil) having a high desulfurization degree and good properties as a result.
[0011]
In carrying out the hydrodesulfurization method of the present invention, the hydrodesulfurization catalyst may be used for the reaction as it is, but if necessary, pretreatment such as reduction treatment with hydrogen or the like or presulfidation with hydrogen sulfide or the like is performed. You may use for reaction after performing suitably. The conditions for the desulfurization method of the present invention are not particularly limited and may be appropriately selected depending on the situation. In general, the temperature is 210 to 440 ° C, preferably 260 to 370 ° C, and the hydrogen pressure is 10 to 100 kg. / Cm ² , preferably 30 to 70 kg / cm ² . The hydrogen / raw material (sulfur-containing hydrocarbons) ratio is usually 0.5 to 200 mol / g, preferably 1 to 180 mol / g.
Furthermore, the type of desulfurization reaction may be either a batch type or a flow type. In the case of the flow type, the liquid hourly space velocity (flow rate of raw material per unit amount of catalyst; LHSV) is ^{1 to} 10 hr ⁻¹ , preferably 2 It should be set in the range of ˜5 hr ⁻¹ .
As described above, by performing hydrodesulfurization using the hydrodesulfurization catalyst, sulfur-containing hydrocarbons can be efficiently desulfurized, and hydrocarbons with extremely low sulfur content can be obtained.
[0012]
【Example】
The preparation examples, examples and comparative examples of the present invention will be shown below and the present invention will be described more specifically. However, the present invention is not limited to these preparation examples and examples.
[0013]
Preparation Example 1 Preparation of cobalt ion exchange saponite [A '] catalyst
Co (NO ₃ ) ₂ · 6H ₂ O was dissolved in 18.3 g and 500 ml of pure water. This solution was sufficiently stirred and then aged at 80 ° C. for 2 hours. Next, 10 g of saponite [A] (specific surface area of 514 m ² / g) was added to this solution as a powder, stirred at 80 ° C. for 1.5 hours, and then cooled to room temperature. Further, this solution was filtered, washed with pure water and alcohol, air-dried at 120 ° C. for about 16 hours, and then calcined at 400 ° C. for about 16 hours, whereby a cobalt ion exchange high specific surface area saponite catalyst [A ′] (Denoted as Co-saponite [A ′] in Table 1) was prepared.
[0014]
Preparation Example 2 Preparation of Cobalt Ion Exchange Saponite [B ′] Catalyst In Preparation Example 1, Saponite B was used in the same manner as Preparation Example 1 except that saponite B (specific surface area of 224 m ² / g) was used instead of saponite A. A catalyst (denoted as Co-saponite [B ′] in Table 1) was prepared.
[0015]
Preparation Example 3 Preparation of cobalt molybdenum supported alumina catalyst
_{Co (NO 3) 2 · 6H} 2 O and 0.96g and _{(NH 4) 6 Mo 7 O} 24 · 4H 2 O and 1.14 g, was dissolved in pure water 0.5 ml. This solution was impregnated into 5 g of a commercial alumina as a carrier, then dried at 120 ° C. for about 16 hours, and further calcined at 400 ° C. for about 16 hours, whereby 4.0 wt% CoO and 15.0 wt% MoO ₃ A cobalt-molybdenum-supported alumina catalyst (denoted as CoMo-Al ₂ O _{3 in} Table 1) was prepared.
[0016]
Preparation Example 4 Preparation of nickel molybdenum supported alumina catalyst
(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O was dissolved in 0.14 g and 0.5 ml of pure water. This solution was impregnated with 5 g of commercially available alumina as a carrier, then dried at 120 ° C. for about 16 hours, and further calcined at 400 ° C. for about 16 hours. This is molybdenum-supported alumina. Ni (NO ₃ ) ₂ · 6H ₂ O was dissolved in 0.96 g and 0.5 ml of pure water. The molybdenum-supported alumina obtained by the above method was impregnated with this solution, then dried at 120 ° C. for about 16 hours, and further calcined at 400 ° C. for about 16 hours, whereby 4.0 wt% NiO and 15.0 were obtained. A nickel-molybdenum-supported alumina catalyst (expressed as NiMo—Al ₂ O _{3 in} Table 1) containing wt% MoO ₃ was prepared.
[0017]
Example 1
The Co-saponite [A ′] catalyst obtained in Preparation Example 1 was evaluated for the following hydrodesulfurization activity by thiophene decomposition using a pulse reactor. This catalyst was subjected to the following presulfidation treatment before the hydrodesulfurization activity evaluation.
[Pre-sulfurization]
0.1 g of catalyst (particle size: 600 to 850 microns) was fixed to the center of the reaction tube, and mixed with hydrogen (H ₂ ) and hydrogen sulfide (H ₂ S) in the reaction tube under a pressure of ² kg / cm ² ( Mixing ratio: 95% hydrogen, 5% hydrogen sulfide) was passed at a rate of 60 ml / min, and the reaction tube was heated at 400 ° C. for 2 hours.
[Evaluation of hydrodesulfurization activity]
After the preliminary sulfidation treatment, the reaction tube temperature is set to 250 ° C. under a pressure of ² kg / cm ² , and hydrogen (H ₂ ) gas is circulated at a rate of 60 ml / min from the upstream of the catalyst fixing part. Inject 0.3 μl of thiophene. The reaction product was analyzed by gas chromatography, and the hydrodesulfurization activity of the catalyst was evaluated from the conversion rate of thiophene. The results are shown in Table 1.
[0018]
Comparative Example 1
In Example 1, the reaction was performed in the same manner as in Example 1 except that the cobalt molybdenum-supported alumina catalyst obtained in Preparation Example 3 was used instead of the cobalt ion exchange saponite [A ′] catalyst. The results are shown in Table 1.
[0019]
Comparative Example 2
In Example 1, the reaction was performed in the same manner as in Example 1 except that the nickel-molybdenum-supported alumina catalyst obtained in Preparation Example 4 was used instead of the cobalt ion exchange saponite [A ′] catalyst. The results are shown in Table 1.
[0020]
Comparative Example 3
In Example 1, the reaction was performed in the same manner as in Example 1 except that the commercially available desulfurization catalyst CDS-R95T was used instead of the cobalt ion exchange saponite [A ′] catalyst. The results are shown in Table 1.
[0021]
Example 2
In Example 1, the reaction was performed in the same manner as in Example 1 except that the reaction temperature was 275 ° C instead of the reaction temperature of 250 ° C. The results are shown in Table 1.
[0022]
Comparative Example 4
In Example 2, the reaction was conducted in the same manner as in Example 2 except that the cobalt molybdenum-supported alumina catalyst obtained in Preparation Example 3 was used instead of the cobalt ion exchange saponite [A ′] catalyst. The results are shown in Table 1.
[0023]
Comparative Example 5
In Example 2, the reaction was performed in the same manner as in Example 2 except that the nickel-molybdenum-supported alumina catalyst obtained in Preparation Example 4 was used instead of the cobalt ion exchange saponite [A ′] catalyst. The results are shown in Table 1.
[0024]
Comparative Example 6
In Example 2, the reaction was performed in the same manner as in Example 2 except that the commercially available desulfurization catalyst CDS-R95T was used instead of the cobalt ion exchange saponite [A ′] catalyst. The results are shown in Table 1.
[0025]
Example 3
In Example 1, the reaction was performed in the same manner as in Example 1 except that the reaction temperature was 300 ° C instead of the reaction temperature of 250 ° C. The results are shown in Table 1.
[0026]
Comparative Example 7
In Example 3, the reaction was carried out in the same manner as in Example 3 except that the cobalt molybdenum-supported alumina catalyst obtained in Preparation Example 3 was used instead of the cobalt ion exchange saponite [A ′] catalyst. The results are shown in Table 1.
[0027]
Comparative Example 8
In Example 3, the reaction was performed in the same manner as in Example 3 except that the nickel-molybdenum-supported alumina catalyst obtained in Preparation Example 4 was used instead of the cobalt ion exchange saponite [A ′] catalyst. The results are shown in Table 1.
[0028]
Comparative Example 9
In Example 3, the reaction was performed in the same manner as in Example 3 except that the commercial desulfurization catalyst CDS-R95T was used instead of the cobalt ion exchange saponite [A ′] catalyst. The results are shown in Table 1.
[0029]
Comparative Example 10
In Example 3, the reaction was conducted in the same manner as in Example 3 except that the cobalt ion exchange saponite [B ′] catalyst obtained in Preparation Example 2 was used instead of the cobalt ion exchange saponite [A ′] catalyst. It was. The results are shown in Table 1.
[0030]
[Table 1]

[0031]
【The invention's effect】
When the hydrodesulfurization catalyst of the present invention is used, particularly when hydrodesulfurization is carried out by bringing it into contact with a kerosene fraction, a light oil fraction or a mixture thereof, which is a raw material oil, the degree of desulfurization is high, and the sulfur content is efficiently obtained from the raw oil. It can be removed well.
Further, according to the hydrodesulfurization method of the present invention, sulfur-containing hydrocarbons can be efficiently desulfurized, and useful hydrocarbon oils having good properties (desulfurized kerosene and desulfurized light oil) can be efficiently and efficiently produced. Can be manufactured.

Claims (2)

A sulfur-containing hydrocarbon hydrodesulfurization catalyst comprising cobalt supported on a saponite having a specific surface area of 400 m ² / g or more.   A hydrodesulfurization method comprising desulfurizing a sulfur-containing hydrocarbon in the presence of the catalyst according to claim 1.