JPS614786A - Method for reforming hydrocarbon fraction - Google Patents

Abstract

PURPOSE:To produce efficiently hydrocarbon oil having excellent low-temperature flow characteristics, by bringing a hydrocarbon fraction having a boiling range of 200-600 deg.C into contact with a catalyst contg. zeolite, alumina and a metallic component in a hydrogen atmosphere. CONSTITUTION:A catalyst contg. zeolite (A) which exhibits an X-ray diffraction pattern of Table 1 in the alkali type of the formula (wherein M is an alkali metal or alkaline earth metal; n is the valence of M; X is 15-60; Y is 0-25) and has a mesitylene adsorption (JIS-K-1412) of 16wt% or above in the acid type, alumina (B) (pref. gamma- or eta-alumina) and at least one metallic compd. (C) selected from among compds. of Group VIb and VIII metals (e.g. CoO, MoO2 and WO3) (the weight ratio of A to B is 10/1-1/10, the quantity of component C is 10-40wt% based on that of component B) is used. When said catalyst is used, hydrocarbon fraction can be dewaxed and desulfurized at a relatively low temp. stably over a long period of time to obtain hydrocarbon oil having low-temperature flow characteristics in high yields.

Description

[Detailed Description of the Invention] [Object of the Invention] Industrial Field of Application The present invention relates to a method for reforming a hydrocarbon fraction.
The present invention relates to a method for reforming the hydrocarbon fraction by contact membrane brazing and desulfurization.

BACKGROUND OF THE INVENTION The recent state of demand for petroleum products shows that demand for so-called middle distillates such as kerosene, light oil, and A heavy oil has been increasing markedly, while demand for B and C heavy oils has been on the decline. Under these circumstances, in order to secure the amount of light oil and A heavy oil, the weight of light oil and heavy oil has increased, and as a result, the wax content in light oil and A heavy oil has increased significantly, ensuring good low-temperature fluidity. It is becoming difficult to do so.

Therefore, improving the low-temperature fluidity of petroleum products not only increases the yield of middle distillates, but also increases the flexibility of crude oil selection in petroleum refining, and greatly improves the handling of petroleum products in winter. The effect can be said to be very large. In fact, dewaxed oil or a mixture of dewaxed oil and other hydrocarbon fractions obtained by the contact membrane waxing method has a low pour point and good low-temperature fluidity, so it is suitable for light oil for cold regions and heavy oil A and B. As is well known, it has shown excellent performance as

As a method for hydrogenation treatment after contact membrane brazing, the hydrocarbon fraction is passed together with hydrogen over a catalyst consisting of crystalline mordenite and a hydrogenation component to remove n-paraffins, and then alumina or the like is used as a carrier to remove n-paraffins. A method of removing sulfur by passing it over a catalyst composed of cobalt, molybdenum, etc.
Japanese Patent Publication No. 48-3887), a method in which gas oil is subjected to contact membrane brazing with ZSM-5 zeolite and then hydrodesulfurization (
JP-A-50-17401) or a mixture of ZSM-5 zeolite and alumina with Ni, Co, Mo;'z
A method has been proposed (Japanese Unexamined Patent Publication No. 56-20087) in which hydrocracking and hydrodesulfurization of hydrocarbon oil are carried out simultaneously using a catalyst supporting a hydrodesulfurization component.

However, in these conventional techniques, the catalyst used is very expensive, the catalyst activity is insufficient, the reaction temperature is high, the operating time until catalyst regeneration is not long enough, or the recovery rate of dewaxed oil is low. There are disadvantages such as low

Problems to be Solved by the Invention The present invention involves bringing a hydrocarbon fraction into contact with a specific catalyst under a hydrogen atmosphere, and subjecting it to constant contact membrane brazing for a long period of time at a lower reaction temperature than in conventional methods. The objective is to desulfurize and obtain a high yield of product oil with excellent low-temperature fluidity.

[Structure of the invention]

Means for Solving the Problems The present invention uses a hydrocarbon fraction as a zeolite having the X-ray diffraction pattern shown in Table 1 and having a mesitylene adsorption t of 1°6 times or more, alumina, and periodic. The present invention relates to a method for reforming a hydrocarbon fraction by bringing it into contact with a catalyst containing at least one metal component selected from Group 1b and Group 1 of the Table of Contents in the presence of hydrogen.

The raw material hydrocarbon oil fraction used in the present invention is not particularly limited, but hydrocarbon fractions having a boiling point range of 100°C to 600°C obtained from petroleum, shale oil, coal liquefied oil, etc. preferable.

The zeolite used in the present invention must have an X-ray diffraction pattern as shown in Table 1 in an alkaline form, and more specifically, it is desirable to have an X-ray diffraction pattern as shown in Table 2. . Measurement of the X-ray diffraction pattern is carried out according to conventional methods. That is, X-ray irradiation is performed using a Geiger counter spectrometer equipped with a recording device to obtain a diffraction pattern. From this diffraction pattern, the relative intensity 100 I/IMAX (I is the strongest line) and the lattice spacing d (unit angstrom A) are determined.

In the following margin, the relative strength (100■/■1X) is expressed as vs - very strong, S - strong, M - intermediate strength, W = weak.

The zeolite used in the present invention has the general formula (1,0±0.2) M2/n0-Al2O3.X510 in alkaline form.
2-YH20, where M is an alkali metal and/or alkaline earth metal, n is the valence of M, X is 15-60, and Y is O-25.

Furthermore, the zeolite used in the present invention must be in the acid form and adsorb mesitylene of 1.6 weight or more under the conditions described below.

Particularly preferred is one that adsorbs styrene of more than 'L8 weight.

The adsorption amount of mesitylene is measured by a method according to JIS K-1412. The obtained zeolite is thoroughly dealkalized in an ammonium chloride water bath W.Then, the sample is molded into a size of 20 to 32 meshes without a binder,
Calcinate in air at 550°C for 16 hours. The zeolite thus obtained was subjected to an adsorption test under the measurement conditions described below. Adsorption amount: approximately 42 Adsorption concentration: 25°C Carrier gas: N2.800 N-m/min Mesitylene partial pressure α51 Hg adsorption time: 6 The zeolite used in the present invention may be produced by any method as long as it has the above characteristics.

One of the specific examples is shown below. That is, an aqueous reaction mixture consisting of a silica source, an alumina source, an alkali source, and an organic compound containing a carboxyl group (represented by SiO2+ A120a+OH- and A, respectively) has the following composition range SiO2/A120a 20-60H20/S expressed in molar ratio.
i 02 5~1000H7S io 2
It can be produced by adjusting the ratio to be 0.1 to 0.35A/Al2O80 to 100 and reacting until crystals are formed.

As the silica source, for example, silica sol, silica gel, silica airgel, silica hydrogel, silicic acid, silicate ester, sodium silicate, etc. are used.

Alumina sources include sodium aluminate, aluminum sulfate, aluminum nitrate, alumina sol, alumina gel,
Activated alumina, γ-alumina, α-alumina, etc. are used.

As the alkali source, caustic soda, caustic potash, etc. are used, and caustic soda is preferably used.

These alkali sources are added so that OH- is present in the system preferably in the above composition.As the organic compound containing a carboxyl group, various carboxylic acids such as aromatic, aliphatic, and ring group are used. or,
The organic compound having a carboxyl group may contain a functional group other than the carboxyl group, such as an aqueous group or an amine group. Typical examples include cono-phosphoric acid,
Tartaric acid, citric acid, toluic acid, salicylic acid and the like can be mentioned. Although these are thought to become alkali metal salts in the reaction system, it goes without saying that they can be used in advance as alkali metal salts.

The aqueous reaction mixture thus prepared is made into a slurry as uniform as possible and crystallized by placing it in a closed container, such as an autoclave made of iron, stainless steel, or lined with fluororesin. The reaction conditions for crystallization include a reaction temperature of 80-250°C, preferably 100-250°C.
The reaction time is 5 hours to 30 days, preferably 10 hours to 10 days. The reaction mixture is preferably kept in a homogeneous state by stirring continuously or periodically during crystallization. After cooling, the crystallized reaction product is taken out from the closed container, washed with water, passed through the mouth, and dried if necessary. The crystalline aluminosilicate thus synthesized has the X-ray diffraction pattern shown in Table 2.

The amount of mesitylene adsorbed can be determined by appropriately selecting the ratio of the starting materials silica and alumina and the type of organic compound used! l) It can be made to be more than 1.6 weight class.

The crystalline aluminosilicate synthesized in this way is alkaline as it is and does not have sufficient solid acidity. When used in the reaction of the present invention, it is necessary to impart solid acidity to the crystalline aluminosilicate to make it into an acid form.

As is well known, acid type crystalline aluminosilicate has polyvalent cations of divalent or higher valence, such as hydrogen ions, ammonium ions, or rare earth ions, as cations in crystalline aluminosilicate. It can be obtained by ion-exchanging at least a portion of the alkali metal ions of a crystalline aluminosilicate containing monovalent alkali metal ions such as sodium with hydrogen ions, ammonium cations, or polyvalent cations. This ion exchange is preferably carried out using a solution containing an acid and/or an ammonium salt compound to introduce hydrogen ions and/or hydrogen ion precursors into the crystalline aluminosilicate. Ion exchange treatments are generally performed with water-soluble enemies. Acids that can be used include inorganic acids and organic acids, with inorganic acids being the most common. Examples of the inorganic acid include hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, etc., but of course other acids may be used as long as they contain hydrogen ions. When an inorganic acid is used, it is not preferable to treat it with a highly concentrated solution since this will cause structural changes.

Since the concentration of the acid preferably used varies greatly depending on the type of acid, it is necessary to define it uniquely and take sufficient care to avoid large structural changes when using it.

As ammonium salt compounds, inorganic ammonium salts such as ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium carbonate, aqueous ammonia, etc., or ammonium salts of organic acids such as ammonium formate, ammonium acetate, ammonium citrate, etc. can be used as well. Preferred is an inorganic ammonium salt. The ammonium salt used is preferably used as an α05 to 4 normal solution, more preferably about 01 to 2 normal.
Used as a prescribed solution. As a method for ion exchange treatment of crystalline aluminone silicade with an acid and/or ammonium salt solution, either a batch method or a flow method is preferably used. In the case of batchwise treatment, the solid-liquidization is preferably at least an amount that allows the crystalline aluminosilicate to come into sufficient contact with the liquid, specifically at least about I A /Kp.

A treatment time of about α1 to 72 hours is sufficient, preferably about 0.5 to 24 hours. The treatment temperature may be below the boiling point, but it is preferable to heat it to promote the ion exchange rate. In the case of flow treatment, a fixed bed method, a fluidized bed method, etc. can be used, but it is necessary to take measures to prevent uneven flow of the fluid or non-uniform ion exchange treatment. The ion exchange treated crystalline aluminosilicate is then washed with water. Distilled water is preferably used as the washing liquid, and the washing may be carried out in either a batch type or a flow type. In this way, hydrogen ions and/or ammonium ions, which are hydrogen ion precursors, are introduced into the crystalline Al-minosilicate to impart solid acidity.

Hydrogen ions and/or cations other than their precursors may be present in the crystalline aluminosilicate; the type and amount thereof are not particularly limited.

The alumina used in the present invention together with the zeolite obtained as described above is χ, ρ, excluding inert α-alumina.
, η, γ, δ, θ, and other metastable aluminas, or their precursor vialite.

Alumina hydrates such as boehmite and coagulated boehmite can be used, but γ- or η-alumina is particularly preferred.
And/or the Group Ⅰ metal component is used as a nitrogen active component in hydrodesulfurization and hydrogenation film, such as Ni, Cot, etc.
Mo, "vV Q, etc. are preferred, and MO-Co.

More preferably, it is a combination of two metals such as Mo-Ni and W-Ni.

Although the catalyst of the present invention must contain the zeolite, alumina, and metal components described above, the method and order of mixing these components are not particularly limited. Although it is possible to make alumina support a metal component and then mix it with zeolite powder, a particularly preferred method is to mix zeolite and alumina and then support a metal component.

The mixing ratio of zeolite and alumina is about 1=10 to 10:1 by weight, but preferably 3 to 7:3. Although the content of the metal component may vary depending on the type of metal, the amount of total metal oxide supported on the alumina component is approximately 10 to 40% by weight.For example, Coo is 2 to 8% by weight, Mo0a is 10 to 30% by weight. Section, N Eri is 2-10
By weight, WO3 may contain 5-10% by weight.

The apparatus that can be used for the reaction of the present invention may be either a fixed method or a fluidized bed method, but a fixed bed method is preferably used because the apparatus is simple and operation is easy. In the case of a fixed bed system, the smaller the catalyst particle size is, the more preferable it is from the point of view of the catalyst effectiveness coefficient, but if the particle size is too small, pressure loss increases, which is not preferable. Therefore, there is a preferable range for the catalyst particle size. Preferably used particle size is 005~
It is 10 mm, and more preferably α3 to 3 m.

In order to obtain a catalyst having such a preferable range, it is necessary to mold the catalyst. Molding methods include compression molding,
Examples include extrusion molding.

The catalyst prepared as described above is dried prior to use and subsequently calcined. Drying is carried out at 50 to 250°C for 0.1 hour or more, preferably 0.5 to 48 hours.

Firing is performed at 300 to 700°C with the plate opened at 01 o'clock, preferably at 4 o'clock.
It is carried out at 00 to 600°C for α5 to 24 hours. Firing is performed in air, inert gas, or an atmosphere consisting of these and water vapor.

The catalyst prepared as described above can be used as it is, but it may be sulfurized with a sulfur compound before starting the reaction.

The reaction conditions in the present invention are that the reaction operation temperature is 200 to 5
00°C, preferably 250-450°C. The reaction operating pressure is 100 K9/arlG from atmospheric pressure, preferably 10 Kf/cr; 50 Kf/c from IG
a G.

Liquid time-space velocity (LH8V), which refers to the contact time of the reaction
) is 01~1Qhr, preferably 05~40hr""
It is. Hydrogen to hydrocarbon ratio is 100-100ON-
Silence/m', preferably 200-80 ON -rr? /
It is nl.

Example Hereinafter, the present invention will be explained with reference to examples.

Example 1 922 grams of solid caustic soda and 12.5 grams of tartaric acid were dissolved in 344.2 grams of water. 175 grams of sodium aluminate solution was added to this solution to form a homogeneous solution. 660 grams of silicic acid was gradually added to this mixture with stirring to prepare a homogeneous slurry-like aqueous reaction mixture.

The composition ratio (molar ratio) of this reaction mixture was determined as follows. Note that A represents tartaric acid.

5i02/A120a ・25H20/3 i
oz 20 0H7S ioz 0.16A/AI 20
3 1.0 This mixture was placed in a 500 TLe autoclave and sealed. Then, heat to 160°C while stirring, and
Crystallization was allowed for 2 hours. After the crystallization was completed, it was cooled, and then the product was taken out from the autoclave, washed with distilled water at 1 to bring the pH to approximately neutral, passed through the mouth, and dried at 110° C. overnight. The obtained product was a zeolite having the X-ray diffraction pattern shown in FIG. 1, and had an adsorption amount of mesitylene of 2.1 F/E.

For 100 parts by weight of the zeolite obtained in this way,
Set boehmite alumina powder and alumina sol were added in amounts of 50 parts by weight and 15 parts by weight, respectively, in terms of alumina (A1203), and thoroughly kneaded. After kneading 10 to 24 meters (J
It was molded into particles of the size of an IS sieve and heated at 110°C.
It was dried overnight and then calcined at 50 G°C for 2 hours in the presence of air. The particles consisting of zeolite and 72.Bena thus obtained were heated to 80 to 90°C in a 0.187N ammonium chloride aqueous solution at a solid-liquid ratio of 5 (4/Ni), and
The mixture was subjected to ion exchange treatment 4 times (for 4 minutes). After that, it was thoroughly washed with distilled water, dried at 110℃ overnight, and then dried at 550℃.
, and calcined for 1 hour to obtain a catalyst carrier. This carrier was immersed in an aqueous ammonium paramolybdate solution to support MOOa 8-fold Eri based on the carrier. Then 110℃
and baked at 500°C for 2 hours [7]. Zeolite-alumina particles carrying molybdenum were immersed in an aqueous cobalt nitrate solution, and the COO2 weight ratio was determined. After supporting cobalt, it was dried at 110°C and fired at 500°C for 2 hours.

Using the catalyst prepared in this manner, atmospheric distilled light oil having a pour point of ±0°C and a sulfur content of 1.1% by weight is converted into LH8V2. Ohr, hydrogen to feedstock oil ratio 35O
The reaction was carried out under the following conditions: N number 45π and reaction pressure 35 K9/crl·G7z. The reaction temperature is the boiling point of the produced oil.
The pour point of the fraction above 0°C was adjusted to 120°C.

The results are shown in Table 3.

Table 3 Example 2 Zeolite was synthesized in the same manner as in Example 1 using 0-toluic acid in place of tartaric acid.

The composition ratio (molar ratio) of the reaction mixture was as follows.

In addition, A represents o-)ruyl acid.

Sioz/Al 20a 30H20/S 1
o220 0H-/S ioz 0.17 A//A12032.5 The obtained product is a zeolite having basically the same X-ray diffraction pattern as in Fig. 1, and the adsorption amount of cymesitylene is L8
It was 8% by weight.

The zeolite thus obtained was molded, treated with ammonium, and calcined in the same manner as described in Example 1, and then treated with ammonium paramolybdate and an aqueous solution of nitrate, MoO 37% by weight, Ni 03 The catalyst was supported by weight% and dried at 110°C and then calcined at 500°C.

Table 4 shows the results of the reaction of Iranian heavy crude oil with atmospheric distillation gas oil using the catalyst thus obtained in the same manner as in Example 1.

Table 4 Comparative Example 1 A catalyst consisting only of zeolite catalyst and alumina was obtained in the same manner as described in Example 1 except for the step of supporting Mo5s and Coo. This product was reacted using the same raw material oil as in Example 1 under the same reaction conditions, and the results are shown in Table 5.

Table 5 Comparative Example 2 Synthesis of Zeolite ZSM-5
It was carried out according to the method described in No. The synthesis conditions are shown in the table below.

Starting component (r) A, hydrated silicic acid 6 & 3B
, Sodium aluminate solution W 10.
5 Tetraprobylammonium Noid 439.4
0° oxide aqueous solution (25% aqueous solution) reaction mixture composition ratio (mole ratio) Si02 1.00Al 2
0g 0.02Na20
o, 034[(CH8CH2
CH2)4N)20 (131H2020 Starting component CKB was added to form a homogeneous solution. Starting component A was gradually added to this mixed solution and stirred to prepare a homogeneous slurry-like reaction mixture. This reaction mixture was Pour into an auto crepe and heat to 160°C while stirring, 72
Time crystallization was performed.

After crystallization, wash with water until it becomes neutral, then wash for 12 hours.
It was dried at 0°C for 15 hours. The obtained zeolite was ZSM-5 showing the X-ray diffraction pattern shown in FIG. 2, and the amount of mesitylene adsorbed was α8% by weight.

To 100 parts by weight of the ZSM-5 zeolite thus obtained, 100 parts by weight and 15 parts by weight, respectively, of coagulated boehmite/alumina powder and alumina sol in terms of alumina CAL 20a) were added. A catalyst was prepared by adding Mo0a r Coo according to the method to treat gas oil. The results are shown in Table 6.

Table 6 Comparative Example 3 A catalyst made only of ZSM-5 zeolite and alumina was obtained in the same manner as described in Comparative Example 2 except for the step of supporting 1flo03 and Coo. This catalyst was used to treat light oil. The results are shown in Table 7.

Table 7 [Effects of the Invention] The results described in Examples 1 and 2 and Comparative Examples 1.2.3 are expressed in a graph as shown in Figure 3, with reaction temperature on the vertical axis and reaction days on the horizontal axis. . As is clear from Fig. 3, compared to the conventional method of treating hydrocarbon fractions using a known catalyst, the method of the present invention provides excellent low-temperature fluidity stably for a long period of time at a much lower reaction temperature. Produced oil can be obtained. Furthermore, according to this method, as described in Examples and Comparative Examples, the yield of produced oil is high, the produced oil is dewaxed and hydrodesulfurized, and storage stability is also improved.

Furthermore, from the results of Examples 1 and 2 and Comparative Example 1, it was found that the method of the present invention suppresses the deterioration of the dewaxing activity of the zeolite catalyst and adds the function of hydrodesulfurization. , the activity of the zeolite catalyst can be maintained over a long period of time.

[Brief explanation of the drawing]

Figure 1 shows the X-ray diffraction pattern of the zeolite used in Example 1, Figure 2 shows the X-ray diffraction pattern of the zeolite used in Comparative Example 2, and Figure 3 shows the change in reaction temperature depending on the number of reaction days. This is a graph showing.

Claims (1)

[Claims] A hydrocarbon fraction having a boiling point range of 200-600°C,
Under a hydrogen atmosphere, zeolite having the X-ray diffraction pattern shown in Table 1 and having an adsorption amount of mesitylene of 1.6% by weight or more, alumina, and Groups VIb and V of the periodic table.
A method for reforming a hydrocarbon fraction, which comprises bringing it into contact with a catalyst containing at least one metal component selected from Group III.