JPH0811794B2 - Contact dewaxing method for light oil fraction and lubricating oil fraction - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for catalytically dewaxing a light oil fraction or a lubricating oil fraction using a novel crystalline aluminosilicate having molecular shape selectivity and catalytic ability.
More particularly, the present invention is unique have a crystalline structure, SiO suitable selective catalytic reaction of hydrocarbons ₂ /
Provided is a method for catalytically dewaxing a light oil fraction or a lubricating oil fraction using a crystalline aluminosilicate belonging to the monoclinic system and having a high Al ₂ O ₃ ratio.

[0002]

BACKGROUND OF THE INVENTION Crystalline aluminosilicates are commonly known as crystalline zeolites, both natural and synthetic.
Its crystal structure is SiO ₄ tetrahedron in which four oxygen atoms are formed at the center of silicon (Si), and AlO ₄ tetrahedron is replaced by aluminum (Al) instead of silicon (Si). It is an aluminosilicate hydrate having a structure based on the three-dimensional skeleton of the body. SiO ₄ tetrahedron and A
lO ₄ tetrahedra, 4-membered ring formed 4, 5, 6, 8 or 12 connected to, 5-membered ring, 6-membered ring, 8-membered ring or 12
The member ring and the double ring in which these 4-, 5-, 6-, 8- and 12-member rings overlap each other form a basic unit, and these are linked to determine the skeleton structure of the crystalline aluminosilicate. There are specific cavities in the skeletal structure determined by these connection schemes, and the inlets of the cavities are 6, 8, 10 and 12
An open part consisting of a member ring is formed. The formed cavities have a uniform pore size, and molecules with a specific size or smaller are adsorbed, but large molecules cannot enter the cavities. Such crystalline aluminosilicate is a "molecular sieve" because of its action.
Is utilized as an adsorbent for various chemical processes and as a catalyst and a catalyst carrier for a chemical reaction by utilizing the above characteristics.

The charge of the aluminum-containing tetrahedron of the crystalline aluminosilicate as described above is maintained in equilibrium by containing a cation in the crystal. In natural crystalline aluminosilicates, the cation is a metal of Group I or Group II of the Periodic Table of the Elements, especially sodium, potassium, calcium, magnesium and strontium. The above-mentioned metal cations are also used in synthetic crystalline aluminosilicates, but in addition to metal cations, organic nitrogen cations, for example, quaternary alkylammonium ions such as tetraalkylammonium ions have recently been proposed. There is. It has been said that the use of the above organic nitrogen-containing compound as an alkali source is indispensable for the synthesis of crystalline aluminosilicate having a high silica / alumina ratio.

[0004]

However, when an organic nitrogen-containing compound is used, in addition to the disadvantage that the raw material cost is high, the synthetic aluminosilicate produced is used as a catalyst in the synthetic product. It is necessary to remove the organic nitrogen compound existing in the product by calcination at high temperature, which has a disadvantage of complicating the manufacturing process.

Further, as described above, in the conventional production method using a tetraalkylammonium compound or an amine-based organic compound such as a C ₂ -C ₁₀ primary amine, the synthesis step and drying and firing are performed. There was a physiological danger due to the potential toxicity of the organic substance or the decomposition of the organic substance during the process, and there was a problem in terms of work safety.

As a result of various studies and experiments, the present inventors
A crystalline aluminosilicate having a novel crystal structure that has excellent shape selectivity and catalytic ability and exhibits excellent performance as an adsorbent is used as a mineralizer in a reaction mixture consisting essentially of an inorganic reaction material. We have found a method that can be produced from an aqueous reaction mixture obtained by mixing.

Therefore, the main object of the present invention is to obtain an aqueous reaction mixture obtained by mixing a mineralizer with a reaction mixture consisting essentially of a silicon compound, an aluminum compound, an alkali metal compound and water. Can be manufactured,
It is intended to provide a catalytic dewaxing method for a light oil fraction and a lubricating oil fraction, which has a unique crystal structure and uses a high degree of catalytic activity with a high SiO ₂ / Al ₂ O ₃ molar ratio.

Another object of the present invention is a gas oil fraction using a crystalline aluminosilicate having a remarkably excellent activity of selectively decomposing chain hydrocarbons and having a unique crystal structure characterized by an X-ray diffraction pattern. , A method for catalytic dewaxing of lubricating oil fractions.

It is still another object of the present invention, the synthetic aluminosilicates _{M 2 / n O-Al 2} O 3 -SiO 2 -H 2 O ( wherein, M is a metal cation having a valence of n valence is there.)
It uses a crystalline aluminosilicate which has the following composition and does not require the heat treatment step of the synthetic material required in the prior art, thus making the manufacturing process easy and simple and reducing the manufacturing cost. A method for catalytically dewaxing a light oil fraction and a lubricating oil fraction.

[0010]

The present invention has been completed based on the above-mentioned findings, and can effectively achieve the above object.

[0011] Namely, the present invention may display in a molar ratio of oxides _{0.8-1.5M 2 / n O · Al 2} O 3 · 10-100SiO 2 · ZH 2 O ( wherein, M is a metal A cation, n is the valence of the metal cation, and Z is 0-40.), And at least the lattice spacing shown in Table 1, that is, d- distance have a powder X-ray diffraction pattern showing a single
The present invention relates to a method for catalytically dewaxing light oil fractions and lubricating oil fractions using a crystalline aluminosilicate belonging to the orthorhombic system .

[0012]

[Table 1]

An aluminosilicate having a crystal structure characterized by an X-ray diffraction pattern as described above is conventionally unknown and is hereinafter referred to as TSZ.

These values are the results measured by the usual method. The irradiation line was a copper K-α double line, and a scintillation counter equipped with a Striptchatven recorder was used. The peak height and its position were read from the chart as a function of 2θ (θ is the black angle). From these, the relative intensities corresponding to the recorded lines and the lattice spacing (d) Å expressed in Angstrom units were measured. At the relative intensities in Table 1, V.I. S. Is the strongest, S. Is strong, M. Medium and strong, W. Is weak, V.I. W. Indicates very weak. The crystalline aluminosilicate (TS
Z) is characterized by the X-ray diffraction pattern obtained by the usual method of powder X-ray diffraction. That is, 2θ = 14.7 °
The diffraction line of (d = 6.03Å) is a single line (Single
t) and 2θ = 23 ° (d = 3.86)
It is the greatest feature that can be distinguished from the crystal structure of the conventionally proposed crystalline zeolite that both the diffraction lines of Å) and 2θ = 23.3 ° (d = 3.82Å) are clearly separated.

Separately from the conventional method, powder X-ray diffraction analysis was carried out to measure particularly accurate 2θ (θ is the Black angle) and the result was analyzed. As a result, the crystalline aluminosilicate (TSZ) according to the present invention was obtained. Was found to belong to the monoclinic system crystallographically. For example, the product of Example 7 below _{1.02Na 2 O · Al 2 O 3} · 26.2SiO 2 · 1
TSZ having a composition of 2.2H ₂ O has a = 20.159.
(± 0.004) Å, b = 19.982 (± 0.00
6) Å, c = 13.405 (± 0.005) Å, α = 9
A monoclinic lattice constant of 0.51 ° (± 0.03 °) is shown. Table 2 shows measured and calculated values of the lattice spacing of the typical TSZ and Miller indices.

[0016]

[Table 2]

The peculiar X-ray diffraction pattern shows that the lattice spacing of the synthetic aluminosilicate varies depending on the substitution cation, especially the hydrogen ion type, the SiO ₂ / Al ₂ O ₃ ratio, and the like. Is not significantly affected.

[0018] Preferred compositions of the TSZ in the form of as-synthesized displayed in a molar ratio of _{oxides, 0.8-1.3M 2 / n O · Al} 2 O 3 · 25-80SiO 2 · O-40H 2 O (where M is at least one of metal cations,
n is the valence of the metal cation. ). At least a part of the metal cation present at the time of synthesis can be replaced by ion exchange or the like. Ion exchange can be carried out using hydrogen ions such as metal ions or acids of Groups II to VIII of the Periodic Table of the Elements or ammonium ions. By exchanging with hydrogen, ammonium, a noble metal, a rare earth metal, or the like, it is possible to impart catalytic activity, particularly activity as a hydrocarbon conversion catalyst. SiO ₂ / Al
_{When the 2} O ₃ molar ratio is in the range of 25-80, even if TSZ is converted to the hydrogen ion type, there is no change in that it is a monoclinic system, and the crystal structure is not affected.

Such crystalline aluminosilicate, namely TSZ, can be produced by the following method. That is, TSZ contains a silica source, an alumina source, an alkali source and water, and consists essentially of an inorganic reaction material, and
The following composition was indicated by the following molar _{ratios: SiO 2 / Al 2 O 3} 10-130 M 2 / n O / SiO 2 0.03-0.5 H 2 O / M 2 / n O 100-1, 000 X ⁻ / SiO ₂ 0.01-20 (where M is group I and II of the periodic table).
Is a metal cation selected from the group, n is the valence of the metal cation and X ⁻ is the anion of the salt of the mineralizer. Can be prepared by preparing an aqueous reaction mixture having a) and maintaining at a pressure of about 120 ° C. to about 230 ° C. for about 10 hours to about 20 hours at self pressure .

The preferred composition of the aqueous reaction mixture in terms of molar ratio is as follows.

SiO ₂ / Al ₂ O ₃ 20-120 Na ₂ O / SiO ₂ 0.03-0.3 (Na ₂ O + M _{2 / n} O) / SiO ₂ 0.03-0.3 H ₂ O / ( Na ₂ O + M _{2 / n} O) 150-800 X ⁻ / SiO ₂ 0.05-15

Further, the composition of the optimum range of the aqueous reaction mixture, expressed in terms of the molar ratio of oxides, is as follows.

SiO ₂ / Al ₂ O ₃ 30-115 Na ₂ O / SiO ₂ 0.05-0.3 (Na ₂ O + M _{2 / n} O) / SiO ₂ 0.05-0.3 H ₂ O / ( Na ₂ O + M _{2 / n} O) 200-700 X ⁻ / SiO ₂ 0.1-10 In the above description, in the formula, M is a group I or a group II of the periodic table of elements, particularly lithium, barium, or calcium. And a metal cation selected from strontium, n
Is the valence of the metal cation. The M _{2 / n 2} O and Na ₂ O are free M _{2 / n 2} O and Na ₂ O, and are generally very weak acid salts such as aluminates, silicates which are effective in hydroxide and zeolite synthesis. Is in the form of. Further, the above-mentioned "free Na ₂ O" can be adjusted by adding aluminum sulfate, sulfuric acid, hydrochloric acid, nitric acid or the like.

In preparing the reaction mixture, the source of the reaction reagent for the oxide of the above composition used is that commonly used in the manufacture of synthetic zeolites. For example, silica sources include sodium silicate, silica gel, silicic acid, aqueous colloidal silica gel, fused silica, powdered silica and amorphous silica. As the alumina source, activated alumina, γ
-Alumina, alumina trihydrate, sodium aluminate and various aluminum salts such as aluminum chloride, nitrate and sulfate can be used. M2 _/ nO
The metal oxide represented by is added to the reaction mixture in the form of a salt or hydroxide which coexists with the silica and alumina sources. Na ₂ as a source of sodium cations
O is added in the form of sodium hydroxide, sodium aluminate or sodium silicate, and Li ₂ O as a lithium cation source is hydroxide, halide,
It is added in the form of sulfate, nitrate and chlorate (LiClO ₄ ). The aqueous reaction mixture is prepared by mixing the above silica source, alumina source, alkali source, and water. Particularly suitable silica sources are sodium silicate, water glass, colloidal silica and the like, and alumina sources are sodium aluminate, aluminum sulfate and the like.

The crystalline aluminosilicate T used in the present invention
In producing SZ, the water content of the aqueous reaction mixture is important, and as mentioned above, the reaction mixture contains H ₂ O / (N
_{a 2 O + M 2 / n} O) represented by the molar ratio of 100 or more, preferably should have a moisture content in the range of 200-700. By setting the water content in the above range, the gel of the reaction reagent can be easily mixed and stirred.

After mixing the reaction reagents, as described above, the reaction mixture is maintained at autogenous pressure in the range of about 120 ° C. to about 230 ° C. for about 10 hours to about 20 hours.

At the time of crystallization, the crystallinity of the main crystallization product can be further improved by adding a mineralizer to the reaction mixture, and the formation of amorphous aluminosilicate can be suppressed. As a mineralizer, NaCl, Na ₂
CO ₃ , Na ₂ SO ₄ , Na ₂ SeO ₄ , KCl, KB
Neutral salts of alkali metals or alkaline earth metals such as r, KF, BaCl ₂ or BaBr ₂ can be used. The preferred mineralizer is NaCl. In this case, the addition amount, the anion of the salt as a mineralizer X ^-
(The n-valent anion has a monovalent equivalent.) The preferable X ⁻ / SiO ₂ molar ratio is in the range of about 0.01 to about 20. Further, the preferable addition amount is in the range of about 0.05 to about 15, and the optimum addition amount is in the range of about 0.05 to about 10.

The produced crystalline aluminosilicate is separated from the solution by filtration, washed with water and dried. After drying, the product is dried in air or an inert gas atmosphere for about 200
It is dehydrated by baking at a temperature of ℃ or more. The dehydrated product is useful as a catalyst for a chemical reaction or a catalyst support. More preferably, the cations in the product are at least partially removed or replaced by heat treatment and / or ion exchange. In this case, those subjected to cation exchange are particularly useful as a hydrocarbon conversion catalyst. The substituting ion can be selected according to the intended reaction, but it can be selected according to IIa and III of the periodic table of elements.
a, IVa, Ib, IIb, IIIb, IVb and V
At least one selected from Group III metals is preferred. Further, hydrogen ions can be substituted by acid treatment or substitution with NH ₄ ⁺ and heat treatment. Preferred substitution ions for conversion reactions such as hydrocarbon decomposition, isomerization, and alkylation are hydrogen ion and Group VIII metal ion.

Cation exchange can be carried out by contacting the crystallized product with the desired exchange cation or salt of the cations. In this case, various metal salts can be used, and chlorides, nitrates, sulfates, acetates and the like are particularly preferable.

The hydrogen ion-exchanged crystalline aluminosilicate obtained by substituting TSZ produced above with hydrogen ions is further contacted with an acid to extract alumina, and SiO ₂ / Al ₂ O ₃ is extracted. The molar ratio can be increased to 100 or more. As a result, the acid strength and the decomposition activity can be further improved.

The acid used in the acid extraction treatment is
Various mineral acids are suitable, for example hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid, as well as organic acids such as acetic acid and formic acid. A particularly preferred acid is hydrochloric acid. The concentration of the acid used is in the range of 1 to 12 N. The temperature of the acid extraction process is from room temperature to about 9
Up to 5 ° C, but as high as possible is preferred. When the above-mentioned acid extraction treatment is carried out, for example, with hydrochloric acid having a concentration of 3 N for 4 hours at 90 ° C., the SiO ₂ / Al ₂ O ₃ molar ratio of the starting material can be made 100 or more.

In order to use the above TSZ as a catalyst, it is preferable to improve the catalytic activity by introducing an active metal component by ion exchange or introducing hydrogen ions by acid treatment as described above. Also, normal silica-alumina,
Mixing with a carrier such as alumina is performed. TSZ
When the active ingredient is included in
Temperature of about 5 to about 50 Kg / cm ² , preferably about 1
0 ~ about 30Kg / cm ² pressure, about 0.5 ~ about 5.0V
/ H / V, preferably about 1.0 to about 3.0 V / H / V, the reforming raw material can be catalytically reformed under the reaction conditions of liquid hourly space velocity. In addition, transition metals such as Co and Ni, or
When a precious metal component such as platinum or palladium is included,
TSZ can be used as a catalyst for catalytic dewaxing of light oil fractions and lubricating oil fractions. Catalytic dewaxing is from about 250 ° C. ~ about 450 ° C., preferably about 300 ° C. ~ about 400 ° C. to a temperature of about 5Kg / cm ² ~ about 50 Kg / cm ^2, preferably, from about 10 Kg / cm ² ~ about 30 Kg / cm ² pressure,
About 0.25 V / H / V to about 3 V / H / V, preferably
Liquid space velocity reaction conditions of about 1.0 V / H / V to about 2.0 V / H / V can be employed. Furthermore, TSZ is a catalyst for the conversion reaction of organic compounds such as isomerization of normal paraffin, dehydrogenation, conversion of alcohols to hydrocarbons, alkylation of aromatic rings with alcohols, and disproportionation between aromatic compounds. Exert activity.

As described above, the TSZ used in the present invention has a specific chemical composition and a lattice spacing shown by a powder X-ray diffraction pattern, and is remarkable in the conversion reaction of an organic raw material, especially in the decomposition reaction of hydrocarbons. It has a great effect.

[0034]

EXAMPLES The method for producing the crystalline aluminosilicate and TSZ used in the present invention will be described below with reference to examples.

Example 1 4 g of aluminum sulfate was dissolved in 170 g of pure water,
Further, 5.7 g of concentrated sulfuric acid (95 wt%) and 18 g of sodium chloride were added to prepare an aluminum sulfate solution. 25 g of water and 63 g of water glass (Na ₂ O; 9.5 wt%, SiO ₂ ; 28.
6 wt%) (Japanese Industrial Standard No. 3 water glass) while mixing with stirring, and expressed as a molar ratio of oxides of 3.9.
Na ₂ O ・ Al ₂ O ₃・ 50SiO ₂・ 2184H ₂ O
An aqueous reaction mixture having the composition of In this case, the Cl ⁻ / SiO ₂ molar ratio of the mineralizer sodium chloride is 1.
It was 02. The aqueous reaction mixture was poured into a SUS autoclave and heated to 20 ° C. under self-pressure at 180 ° C.
It was kept heated for an hour. The crystallized solid product was separated by filtration, washed with water and dried at 110 ° C. When a sample of this solid product was subjected to chemical analysis, Na ₂ O; 2.6 wt
%, Al ₂ O ₃ ; 4.23 wt%, SiO ₂ ; 84.8
A chemical composition of wt%, H ₂ O; 8.4 wt% was obtained.

This was expressed in terms of oxide molar ratio as follows. 1.01Na ₂ O · Al ₂ O ₃ · 34.1SiO ₂ · 11.2H ₂ O When this product was subjected to X-ray analysis, the results shown in Table 3 were obtained.

[0037]

[Table 3]

This X-ray analysis was carried out by the usual method of powder X-ray diffraction. Irradiation line is K-α double line of copper, X
The tube voltage and tube current are 40 kV and 70 m, respectively.
A. To measure the diffraction angle 2θ and the intensity of the diffraction line,
A scintillation counter equipped with a goniometer and a strip chart pen recorder was used. At this time,
The operating speed was 2θ / min at 2 ° / minute, and the time constant of the rate meter was 1 second.

A portion of the product was calcined at 540 ° C. for about 3 hours and then degassed under vacuum at 300 ° C. for about 3 hours. The zeolite is 7.0 wt% water at 12 mmHg and 25 ° C, 10.5 wt% n-hexane at 20 mmHg and 25 ° C, 20 mmHg and 2%.
4.5% by weight of cyclohexane was adsorbed at 5 ° C. (Evaluation of activity) In order to clarify the catalytic action of TSZ, an activity comparison was performed with a conventionally known crystalline aluminosilicate having a powder X-ray diffraction pattern.

1% at 80 ° C. using a 5% NH ₄ Cl solution to ion exchange the sodium ions of TSZ.
Ion exchange operation was performed for 5 hours. This operation was performed 4 times, and after completion, firing was performed at 600 ° C. for 3 hours to prepare an H-type TSZ. Next, H-type TSZ powder was mixed with a separately manufactured alumina binder in a ratio of 7: 3 (weight ratio after firing), water was added and kneaded, and extrusion molding was performed to obtain a diameter of 1.5 mm.
Got a pellet.

Using the above TSZ catalyst, an n-hexane decomposition reaction was carried out as follows.

Catalyst 32 ground to 16/30 mesh
The glass reactor was charged with ml, and similarly, a silica chip 3.2 m nin, which was ground to 16/30 mesh, was charged in the upper part of the catalyst bed to improve the diffusion and heating of the reaction product. 3 catalyst beds
Hold at 00 ° C.

N-Hexane was placed in a saturater kept at 10 ° C. and nitrogen was passed as a carrier gas so that the concentration of n-hexane in the nitrogen gas was 10%.

After a certain period of time from the introduction of n-hexane / nitrogen into the reactor system, n-by gas chromatography.
The residual amount of hexane was measured and compared with the amount of n-hexane in the feed to obtain the conversion rate (Conversion).

After that, air was introduced into the reactor system, the carbonaceous material adhering to the catalyst was burned at a catalyst bed temperature of 500 ° C., the catalyst was returned to a fresh state, and the space velocity was changed again to conduct an experiment.

Thus, n at 300 ° C. and 275 ° C.
-The conversion rate of hexane was calculated and the following results were obtained (Table 4).
Similarly, a catalyst obtained by converting a crystalline aluminosilicate having a known powder X-ray diffraction pattern into a hydrogen exchange type was evaluated for its n-hexane decomposition activity, and the results are also shown in the table. From this result, it was found that TSZ used in the present invention has a remarkable hydrocarbon decomposing activity.

[0047]

[Table 4]

Comparative Example 1 9.8 g of aluminum sulfate was dissolved in 405 g of pure water, and 11.2 g of concentrated sulfuric acid (95 wt%), 34.3 g
Tetrapropylammonium bromide (TPAB
r) and 37.8 g of sodium chloride were added to prepare an aluminum sulfate solution. This aluminum sulfate solution was mixed with 76.5 g of water and 154.2 g of water glass (Na ₂
O; 9.13 wt%, SiO ₂ ; 28.6 wt%) (Japanese Industrial Standard No. 3 water glass) was mixed with stirring and displayed as a molar ratio of oxides of 4.4 (TPA). )
₂ O ・ 5.0 Na ₂ O ・ Al ₂ O ₃・ 50SiO ₂・ 2
An aqueous reaction mixture having a composition of 180H ₂ O was obtained.

The Cl ⁻ / SiO ₂ molar ratio in this case is
It was 0.9. The aqueous reaction mixture was put in an SUS autoclave, heated, and at self pressure 160 ° C.
It was kept heated for 20 hours. The crystallized solid product was separated by filtration, washed with water and dried at 110 ° C. When a sample of this solid product was submitted for chemical analysis, (TPA) ₂ ; 1
0.9 wt%, Na ₂ O; 1.38 wt%, Al
₂ O ₃ ; 3.83 wt%, SiO ₂ ; 78.8 wt%,
A chemical composition of H ₂ O; 5.0 wt% was obtained.

This was expressed in terms of the oxide molar ratio, and was as follows. _{0.75 (TPA) 2 O · 0.63Na} 2 O · Al 2 O 3 · 35.0SiO 2 · 7.4H 2 O A portion of this product about 3 hours, after baking at 540 ° C., in Example 1 When X-ray analysis was carried out in the same manner as described, the results shown in FIG. 1 were obtained. Further, FIG. 3 shows a secondary electron beam image (SEM) at a magnification of 5000 times of the product.

Example 2-4 2.5 g of aluminum sulfate was dissolved in 70 g of pure water,
To this, 5.4 g of concentrated sulfuric acid (95 wt%) was further added to prepare an aluminum sulfate solution (solution A). next,
25 g of pure water and 63 g of water glass (Na ₂ O; 9.5w
t%, SiO ₂ ; 28.6 wt%) and a mixed solution (B
Liquid) and further add 21 g of sodium chloride to 100
An aqueous solution of sodium chloride dissolved in g of pure water was prepared. Solution A and solution B were simultaneously added to the aqueous sodium chloride solution with stirring, and the molar ratio of the oxide was expressed as
8.8 Na ₂ O ・ Al ₂ O ₃・ 80SiO ₂・ 3485
An aqueous reaction mixture having a composition of H ₂ O was obtained. In this case, the concentration of sodium chloride as a mineralizer was 1.2 mol based on SiO ₂ .

The above aqueous reaction mixture was placed in an SUS autoclave and heated to 170 ° C. under self-pressure.
Crystallization was continued for 0 hours to obtain a solid product. The obtained solid product was separated by filtration, washed with water and dried at 110 ° C. A sample of this solid product was subjected to a chemical analysis to determine its chemical composition. Na ₂ O: 1.80 wt%, Al ₂ O
₃ ; 3.05 wt%, SiO ₂ ; 89.9 wt%, H ₂
O; 5.3 wt% results were obtained. This was expressed in terms of oxide molar ratio as follows. 0.97Na ₂ O · Al ₂ O ₃ · 50.1SiO ₂ · 9.8H ₂ O This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 5 were obtained. Obtained (Example 2).

The above-mentioned solutions A and B were respectively prepared, and 16 g of ammonium carbonate (containing 45% by weight of CO ₂ ) was simultaneously added to solutions A and B while stirring in an aqueous solution of ammonium carbonate dissolved in 100 g of pure water. Expressed as the molar ratio of the added oxide, 8.8Na ₂ O · Al ₂ O ₃ · 80S
to obtain an aqueous reaction mixture having a composition of iO ₂ · 3485H ₂ O. In this case, the concentration of the ammonium carbonate as a mineralizer was 0.54 mol with respect to SiO ₂ . The aqueous reaction mixture was placed in a SUS autoclave, heated, and kept at 170 ° C. for 20 hours under self-pressure to be crystallized to obtain a solid product. The obtained solid product was separated by filtration, washed with water and dried at 110 ° C.

When a sample of this solid product was subjected to chemical analysis, Na ₂ O; 1.92 wt%, Al ₂ O ₃ ;
10 wt%, SiO ₂ ; 89.0 wt%, H ₂ O;
A chemical composition of 0 wt% was obtained. This was expressed in terms of oxide molar ratio as follows. 1.02Na ₂ O · Al ₂ O ₃ · 48.9SiO ₂ · 10.9H ₂ O This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 5 were obtained. (Example 3).

Next, each of the above-mentioned solutions A and B was prepared,
At the same time, 6 g of sodium sulfate was added to an aqueous solution of sodium sulfate dissolved in 100 g of pure water with stirring, and the molar ratio of oxide was expressed as 8.8 Na ₂ O · Al ₂ O ₃ · 80.
An aqueous reaction mixture having a composition of SiO ₂ · 3458H ₂ O was obtained. In this case, the concentration of sodium sulfate as a mineralizer was 0.28 mol with respect to SiO ₂ . The aqueous reaction mixture was poured into an SUS autoclave, heated to a temperature of 70 ° C., and maintained at 170 ° C. for 20 hours under self-pressure. The solid product was separated by filtration, washed with water and dried at 110 ° C. When a sample of this solid product was subjected to chemical analysis, Na ₂
O; 2.15 wt%, Al ₂ O ₃ ; 3.16 wt%, S
A chemical composition of iO ₂ ; 88.8 wt% and H ₂ O; 5.9 wt% was obtained.

This was expressed in terms of oxide molar ratio as follows. 1.12 Na ₂ O. Al ₂ O ₃ · 47.8SiO ₂ · 10.6H ₂ O This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 5 were obtained (Example 4). .

[0057]

[Table 5]

Comparative Example 2 The same conditions and operations as in Example 2 were adopted except that no mineralizer was used. As a solid product, Na ₂ O: 2.43 wt%, Al ₂ O ₃ ; 3.17
wt%, SiO ₂ ; 88.1 wt%, H ₂ O; 6.3w
A chemical composition of t% was obtained. The molar ratio of oxides was as follows. 1.26Na ₂ O · Al ₂ O ₃ · 47.2SiO ₂ · 11.3H ₂ O This solid product was subjected to X-ray analysis in the same manner as in Example 1 to find that it was amorphous alumina / silica. It turned out to be

Example 5-6 20 g of pure water was added to 0.5 g of sodium aluminate (Na).
AlO ₂ ) (Note 1) and 0.63 g of sodium hydroxide were added to prepare a solution (Liquid A) and 30 g of colloidal silica (Note 2) at the same time, 55 g of sodium chloride was dissolved in 160 g of pure water. Was added to the prepared sodium chloride aqueous solution with stirring, and 5.6 Na ₂ O. Al ₂ O ₃
· 47SiO to obtain an aqueous reaction mixture having a composition of ₂ · 5314H ₂ O. In this case, the concentration of sodium chloride is
The Cl ⁻ / SiO ₂ molar ratio was 9.40. The aqueous reaction mixture was subjected to 180 ° C. under autogenous pressure as in Example 1.
A solid product was obtained by heating and maintaining at ℃. It was washed with water and dried at 110 ° C. to obtain Na ₂ O;
3.02 wt%, Al ₂ O ₃ ; 4.44 wt%, SiO
The chemical composition was ₂ ; 83.8 wt% and H ₂ O; 8.7 wt%. The molar ratio of oxides was as follows. 1.12 Na ₂ O · Al ₂ O ₃ · 32.1SiO ₂ · 11.1H ₂ O When this product was subjected to X-ray analysis in the same manner as described in Example 1, the results shown in Table 6 were obtained. (Example 5).

Next, the above-mentioned liquid A and colloidal silica 30
g simultaneously added with stirring sodium chloride 1.6g sodium chloride aqueous solution prepared by dissolving in pure water of 160 g, and displayed in a molar ratio of oxides, 5.6Na ₂
An aqueous reaction mixture was obtained having the composition O.Al ₂ O ₃ .47SiO ₂ 5314H ₂ O. In this case, sodium chloride had a concentration of 0.27 in terms of Cl ⁻ / SiO ₂ molar ratio. The aqueous reaction mixture was heated and maintained under the same crystallization conditions as above to obtain a solid product. It was washed with water and dried at 110 ° C. to obtain Na ₂ O;
3.47 wt%, Al ₂ O ₃ ; 4.18 wt%, SiO
The chemical composition was ₂ ; 86.6 wt% and H ₂ O; 6.9 wt%. This was expressed in terms of oxide molar ratio as follows. 1.23 Na ₂ O · Al ₂ O ₃ / 30.4SiO ₂ · 10.9H ₂ O This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 6 were obtained. Obtained (Example 6). Note 1) Sodium aluminate (Al ₂ O ₃ ; 43.5w
t%, Na ₂ O; 30.1 wt%) Note 2) Colloidal silica (SiO ₂ ; 20.0 wt%,
Na ₂ O; 0.35 wt%)

[0061]

[Table 6]

Comparative Example 3 The same crystallization conditions and procedures as in Example 5 were adopted except that sodium chloride was not used as a mineralizer, and the result of the chemical separation of the obtained solid product was Na ₂ O; 3.3
3 wt%, Al ₂ O ₃ ; 4.19 wt%, SiO ₂ ; 8
The content was 5.3 wt%, H ₂ O; 7.18 wt%. This is expressed as follows in terms of oxide molar ratio. 1.37Na ₂ O · Al ₂ O ₃ · 34.6SiO ₂ · 9.71H ₂ O When this product was subjected to X-ray analysis, it was found to be amorphous silica.
It was alumina.

From the above results, the TSZ used in the present invention
Was found to have a unique crystal structure.

Example 7 5.2 g of aluminum sulfate was dissolved in 70 g of pure water,
To this, 4.5 g of concentrated sulfuric acid (95 wt%) was further added to prepare an aluminum sulfate solution (solution A). Next, 25 g of pure water and 63 g of Japanese Industrial Standard No. 3 water glass (Na ₂ O; 9.5 wt%, SiO ₂ ; 28.6 wt)
%) Was prepared, and 18 g of sodium chloride was dissolved in 100 g of pure water to prepare an aqueous sodium chloride solution. Was added while stirring the same time aqueous sodium chloride solution the solution A and solution B, and displayed in a molar ratio of oxides, having a composition of _{3.8Na 2 O · Al 2 O 3} · 38SiO 2 · 1685H 2 O An aqueous reaction mixture was obtained. At this stage, the concentration of mineral chloride, sodium chloride, was 1.0 with respect to SiO _2.
It was 2 mol.

The above aqueous reaction mixture was placed in an SUS autoclave and heated to 2 ° C. under self-pressure at 170 ° C.
Crystallization was continued for 0 hours to obtain a solid product. The obtained solid product was separated by filtration, washed with water and dried at 110 ° C. A sample of this solid product was subjected to a chemical analysis to determine the chemical composition, and Na ₂ O: 3.23 wt%, Al ₂ O
₃ ; 5.21 wt%, SiO ₂ ; 80.3 wt%, H ₂
O; 11.2 wt% results were obtained. This was expressed in terms of oxide molar ratio as follows. 1.02Na ₂ O · Al ₂ O ₃ · 26.2SiO ₂ · 12.2H ₂ O This product was subjected to X-ray analysis in the same manner as described in Example 1, and Table 7 and FIG. The results shown in are obtained.
Further, FIG. 4 shows a secondary electron image (SEM) of this product at a magnification of 5000 times. Comparing this with FIG. 3, the characteristics of the monoclinic system crystal are remarkably exhibited.

Example 8 2.5 g of aluminum sulfate was dissolved in 130 g of pure water, and 9 g of concentrated sulfuric acid (95 wt%) and 21 g of sodium chloride were added to prepare an aluminum sulfate solution. This aluminum sulfate solution was mixed with 35 g of pure water and 90
Japanese Industrial Standard No. 3 water glass (Na ₂ O; 9.5 wt.
%, SiO ₂ ; 28.6 wt%) with stirring, and expressed as a molar ratio of oxide, 10.5 Na
To obtain an aqueous reaction mixture having a composition of _{2 O · Al 2 O 3 ·} 114SiO 2 · 3291H 2 O. In this case, the Cl ⁻ / SiO ₂ molar ratio of the mineralizer sodium chloride is 0.8.
It was 4. The aqueous reaction mixture was poured into an SUS autoclave, heated to 20 ° C. under self-pressure at 180 ° C.
It was kept heated for an hour. The crystallized solid product was separated by filtration, washed with water and dried at 110 ° C. When a sample of this solid product was subjected to chemical analysis, Na ₂ O; 1.11 w
t%, Al ₂ O ₃ ; 2.04 wt%, SiO ₂ ; 93.
A chemical composition of 8 wt%, H ₂ O; 3.0 wt% was obtained. This was expressed in terms of oxide molar ratio as follows. _{0.89Na 2 O · Al 2 O 3} · 78.1SiO 2 · 8.4H 2 O was subjected the product to X-ray analysis to obtain the results shown in Table 7.

[0067]

[Table 7]

Example 9 The novel crystalline aluminosilicate (TS obtained in Example 1
Z) and commercially available synthetic zeolite (Zelon manufactured by Norton)
The alcohol conversion reaction was carried out using a glass reactor to compare the activity of 100 H).

0.35 g of TSZ zeolite (about 1.0
cc) Fill a glass reactor, hold the catalyst bed in a nitrogen stream at 500 ° C. for 2 hours, and let it stand under a nitrogen stream for 30 hours.
The temperature was lowered to 0 ° C. Keep the reactor temperature at 300
Nitrogen was introduced as a carrier gas into a saturater maintained at 0 ° C and then maintained at a partial pressure of methanol of 0.163 atm, and methanol was passed through the catalyst bed.

The reaction conditions at this time are shown below. Temperature: 300 ° C. Gas rate: 3216 cc / Hr Weight space velocity (SV): 2.32 W / H / W Methanol: 0.81 g / Hr Methanol partial pressure: 0.163 atm.

When the main decomposition products were analyzed by gas chromatography, the results shown in Table 8 were obtained.

From the above results, it was revealed that the zeolite TSZ used in the present invention has a remarkable catalytic ability in the alcohol conversion reaction and has a high selectivity for olefin, which is a useful raw material in the chemical industry. It was also proved that the activity maintaining ability was excellent.

[0073]

[Table 8]

Example 10 A crystalline aluminosilicate sample (identified as TSZ) prepared by the same method as in Example 1 was subjected to the same ion exchange operation as in Example 1 to obtain ammonium (NH ₄ ).
Form TSZ powder was prepared. Next, NH ₄ type TSZ powder was mixed with a separately prepared alumina binder at a ratio of 7: 3 (weight ratio after firing), water was added and kneaded, and then extrusion molding was performed to obtain a pellet having a diameter of 1.5 mm. It was And after drying 6
It was baked at 00 ° C. for 3 hours. Further, this pellet was treated with a 1N Ni (NO ₃ ) ₂ solution at 80 ° C. for 1 hour, washed with water, dried and then calcined at 600 ° C. for 3 hours to prepare a H containing 0.64 wt% Ni. Type T
An SZ catalyst was obtained.

A light oil fraction having the following properties was dewaxed by contacting it with the above catalyst under the reaction conditions shown in Table 9 in the presence of hydrogen. The results are shown in Table 9. The results of Comparative Example 4 are also shown in the table.

[0076]

Comparative Example 4 It was confirmed that the product prepared under the same conditions as in Comparative Example 1 had substantially the same powder X-ray diffraction pattern as in FIG. 1 after firing at 540 ° C. for about 3 hours. Using the sample, Example 1
A Ni-containing H-type zeolite catalyst was prepared in the same manner as described in No. 0. The Ni content of the catalyst was 0.67% by weight.

A catalytic dewaxing experiment was conducted using the same gas oil feedstock as in Example 10 using this catalyst. Table 9 shows the experimental results and reaction conditions obtained.

[0079]

[Table 9]

Comparative Example 5 0.7 g NaOH and 0.7 g in 39.8 g hot water.
_{9g NaAlO 2 (29.1wt% Na 2} O, 35 of.
7 wt% Al ₂ O ₃ , 35.2 wt% H ₂ O) was dissolved and stirred in 20.6 g of aqueous colloidal silica sol (40 wt% SiO ₂ , 0.4% Na ₂ O) in 3.7 g of water. While adding, a reaction mixture having a total oxide molar composition of 5.0Na ₂ O.Al ₂ O ₃ .50SiO ₂ 1800H ₂ O was prepared.

The reaction mixture was placed in an autoclave,
Maintained at about 200 ° C. and autogenous pressure for 72 hours. The solid product was separated by filtration, washed with water and dried at 110 ° C. When a sample of this product was subjected to powder X-ray diffraction analysis, the X-ray diffraction pattern shown in FIG. 5 was obtained, which confirmed that the crystalline aluminosilicate was partly contained in the amorphous substance. did.

A portion of this product was dried and Example 10
A Ni-containing H-type catalyst was prepared by the same method as described in 1. Using the catalyst thus obtained, catalytic dewaxing of the gas oil fraction described in Example 10 was carried out and the results shown in Table 10 were obtained.

[0083]

[Table 10]

From these results, the TS used in the present invention
It has been found that Z can produce low pour point gas oil in good yield compared to zeolite prepared by a method that does not use organic cations such as tetrapropylammonium bromide or mineralizers.

Example 11 In this example, production of a lubricating base oil by catalytic dewaxing will be described.

Boiling range obtained by vacuum distillation of Middle Eastern crude oil: about 232 ° C (630 ° F) to about 593 ° C (1100 ° F)
The lubricating base oil fraction was subjected to a phenol solvent extraction and a propane solvent dewaxing treatment, and a dewaxed feedstock having the following properties was used.

[0087]

Using the same Ni-containing H-type TSZ catalyst as in Example 10, the boiling point range is from about 260 ° C (500 ° F) to about 45 ° C.
A 4 ° C. (850 ° F.) lubricating base oil fraction was subjected to catalytic dewaxing for 18 days under the following reaction conditions.

Reaction conditions Temperature (° C.) 260 to 310 Liquid hourly space velocity (V / H / V) 1.1 Pressure (Kg / cm ² 2G) 42 Process gas velocity 450 (1-H ₂ / 1-feed oil) Next The above raw material oil was subjected to catalytic dewaxing. The reaction conditions and the dewaxing results are shown in Table 11.

Comparative Example 6 Using the same Ni-containing H-type zeolite catalyst used in Comparative Example 4, boiling point range of about 260 ° C. (500 ° F.) to about 4
A lubricating base oil fraction at 54 ° C. (850 ° F.) was subjected to catalytic dewaxing for 18 days under the following reaction conditions, and then the same feedstock as described in Example 11 was subjected to catalytic dewaxing. did.

Reaction conditions Temperature (° C.) 280-320 Liquid hourly space velocity (V / H / V) 1.1 Pressure (Kg / cm ² G) 42 Process gas velocity 450 (1-H ₂ / 1-feed oil)

[0092]

[Table 11]

Comparative Example 7 Using the same Ni-containing H-type zeolite catalyst used in Comparative Example 5, a lubricating base oil fraction having a boiling range of about 260 ° C. (500 ° F.) to about 454 ° C. (850 ° F.) was used. Minutes for 18 days,
Reaction temperature of 300 ° C. to 340 ° C., liquid hourly space velocity of 1.1 V / H / V, reaction pressure of 42 Kg / cm ² G and 450
After catalytically dewaxed under the reaction conditions of (1-H 2 / _1- feedstock), it was subjected to the same feedstock and the feedstock described in Example 11 to catalytic dewaxing. First, the reaction conditions of catalytic dewaxing and dewaxing results
The results are shown in Table 2.

[0094]

[Table 12]

From the results shown in Tables 11 and 12, according to the catalyst produced according to the present invention, the lubricating base oil having a lower reaction temperature and a lower pour point than the catalysts of Comparative Examples 6 and 7 was obtained. It is clear that fractions can be obtained.

[0096]

As described above, according to the method for catalytically dewaxing a light oil fraction and a lubricating oil fraction of the present invention, a silicon compound,
It can be produced from an aqueous reaction mixture obtained by mixing a mineralizer with a reaction mixture consisting essentially of an aluminum compound, an alkali metal compound and water, and a synthetic aluminosilicate M _{2 / n 2} O 3. -Al ₂ O ₃
-SiO ₂ -H 2 O _(wherein, M is a metal cation having a valence of n valence.) Has the composition, has a unique crystal structure which is characterized by X-ray diffraction pattern, SiO ₂
Monoclinic crystals with high catalytic activity of high molar ratio of Al / Al ₂ O ₃ and especially excellent selective decomposition activity of chain hydrocarbons
By using a crystalline aluminosilicate belonging to the system , (1) a low pour point gas oil can be produced in good yield. (2) A lubricating base oil fraction having a lower pour point can be obtained at a low reaction temperature. That effect is achieved.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction pattern of a crystalline aluminosilicate synthesized by the method described in Comparative Example 1.

FIG. 2 is an X-ray diffraction pattern of the synthetic crystalline aluminosilicate (TSZ) used in the present invention.

FIG. 3 is an electron micrograph of a crystal structure of a crystalline aluminosilicate synthesized by the method of Comparative Example 1.

FIG. 4 is an electron micrograph showing a crystal structure of a synthetic crystalline aluminosilicate (TSZ) used in the present invention.

5 is an X-ray diffraction pattern of the crystalline aluminosilicate synthesized by the method described in Comparative Example 5. FIG.

Claims (8)

[Claims] 1. A light oil fraction or a lubricating oil fraction is 0.8-1.5 M _{2 / n} O · Al ₂ O ₃ · 10 _expressed as a molar ratio of oxides under dewaxing reaction conditions. -100SiO ₂ · _{ZH 2} O (wherein, M is a metal cation, n is the valence of the metal cation, Z is 0 to 40.) having a chemical composition of, and, at least It has a powder X-ray diffraction pattern showing the lattice spacings expressed in the following table, the monoclinic
A method for catalytically dewaxing a light oil fraction or a lubricating oil fraction, which comprises contacting the catalyst with a crystalline aluminosilicate to which it belongs . 2. The gas oil fraction and the lubricating oil fraction according to claim 1, wherein M in the chemical composition is at least one selected from the group of metal cations of Group I and Group II of the Periodic Table of the Elements. Contact dewaxing method. 3. The gas oil distillate according to claim 2, wherein the metal cation of Group I and Group II of the Periodic Table of the Elements is at least one selected from the group of alkali metal cations and alkaline earth metal cations. Method for catalytic dewaxing of oil and lubricating oil fractions. 4. The gas oil fraction and the lubricating oil fraction according to claim 3, wherein the alkali metal cation and the alkaline earth metal cation are at least one selected from the group of sodium cation, lithium cation and calcium cation. Contact dewaxing method. 5. The method for catalytic dewaxing of a gas oil fraction and a lubricating oil fraction according to claim 4, wherein the alkali metal cation is a mixture containing sodium cation and lithium cation. 6. The gas oil fraction according to claim 1, wherein the crystalline aluminosilicate contains a transition metal such as CO or Ni or a noble metal component such as platinum or palladium.
Method for catalytic dewaxing of lubricating oil fraction. 7. The catalytic dewaxing reaction condition is about 250 ° C. to about 4 ° C.
Temperature of 50 ° C., about 5Kg / cm ² ~ about 50 Kg / cm ²
And a liquid hourly space velocity of about 0.25 V / H / V to about 3 V / H / V. The catalytic dewaxing of the gas oil fraction and the lubricating oil fraction according to any one of claims 1 to 6. Method. 8. The catalytic dewaxing reaction condition is about 300 ° C. to about 4 ° C.
Temperature of 00 ° C., about 10 Kg / cm ² to about 30 Kg / cm
^The method for catalytic dewaxing of a light oil fraction and a lubricating oil fraction according to claim 7, wherein the pressure is ² and the liquid hourly space velocity is about 1.0 V / H / V to about 2.0 V / H / V.