JP3057651B2 - Hydrocracking method for hydrocarbons - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for hydrocracking hydrocarbons, particularly heavy hydrocarbons such as vacuum gas oil and heavy oil.

[0002]

2. Description of the Related Art In recent years, in petroleum refining, the crude oil to be treated tends to be heavier, and the demand for white oil and lighter weight has been progressing. Conversion to fractions is being attempted.

[0003] Many technologies for this conversion have been developed, and among them, the hydrocracking of heavy hydrocarbons such as vacuum gas oil and heavy oil can produce good quality light oil, and secondary treatment etc. Since it is not necessary, it is considered the most preferred method.

In this hydrocracking method, a catalyst in which an active metal is supported on an amorphous inorganic oxide carrier such as alumina or a carrier containing a crystalline aluminosilicate zeolite has been used. The method using a catalyst composed of the amorphous inorganic oxide carrier is excellent in decomposability of a high boiling point fraction and has a high middle distillate yield, but a high temperature is required to achieve this high decomposition rate. Therefore, there is a disadvantage that the deterioration of the desulfurization activity and the denitrification activity is remarkably accelerated, and the life of the catalyst is shortened. On the other hand, the zeolite-containing carrier is 10 to 2 times smaller than the amorphous inorganic oxide carrier catalyst.
Although a high decomposition rate can be obtained at a temperature lower by 0 ° C., it is susceptible to poisoning by heavy metals, residual carbon, asphaltenes and the like in heavy hydrocarbons, and has a disadvantage that decomposition activity is rapidly deteriorated.

For this purpose, a hydrogenation treatment is carried out with a pretreatment catalyst comprising an inorganic oxide, a metal component of group VI of the periodic table and a metal component of group VIII of the periodic table, and thereafter, a predetermined crystalline aluminosilicate zeolite A method has been proposed in which hydrogenolysis is carried out with a catalyst composed of an inorganic oxide, a Group VI metal component of the Periodic Table, a Group VIII metal component, phosphorus, boron, etc.
-126196). However, this method is not always satisfactory in cracking performance, kerosene oil fraction yield, and the like.

[0006]

Generally, a support comprising a zeolite which is a crystalline aluminosilicate and an inorganic oxide matrix such as alumina is mixed with a Group VI metal compound having a pH value of 3.0 or less in the periodic table. When it is brought into contact with an aqueous solution of a Group VIII metal compound and phosphorus, the crystal structure of zeolite is destroyed due to strong acidic conditions, and the hydrocracking activity is significantly reduced.

For this reason, in order to avoid the destruction of the zeolite crystal structure, a method using an aqueous solution having a pH value higher than 3 has been proposed (JP-A-59-216635). However, according to this method, when the isoelectric point of the inorganic oxide matrix is low, it cannot be uniformly supported on the carrier. Also, pH
In aqueous solutions having a pH of more than 3, some of the Group VI metal components of the periodic table with phosphorus form polymerized complexes, but some are present as mononuclear ions. It is known that this mononuclear ion enters the pores of the zeolite, partially destroys the crystal structure of the zeolite, and lowers the decomposition activity (for example, see JP-A-59-21).
No. 6635, JP-B-59-40058).

The inventor of the present invention has made intensive studies to solve such a problem, and as a result, has performed a specific treatment on the Y-type zeolite,
When a crystalline aluminosilicate having a predetermined lattice constant is used, even if it is brought into contact with an aqueous solution having an initial pH value of 3.0 or less, the crystal structure does not collapse, and the catalyst prepared by this method is used. When the hydrocracking reaction of hydrocarbons was carried out, it was found that an extremely high cracking activity and a kerosene oil fraction yield could be obtained.

Further, if hydrogenation treatment is carried out using a catalyst having an active metal supported on an inorganic oxide carrier before hydrocracking with the above-mentioned catalyst, the poisoning of the above-mentioned catalyst can be remarkably reduced, and high decomposition activity can be obtained. It turns out that it can be maintained for a long time.

[0010] The present invention has been made based on such findings, and an object of the present invention is to provide a hydrocracking method which has a high yield of a kerosene oil fraction and can be operated for a long period of time.

[0011]

According to the present invention, there is provided a first catalyst in which a hydrocarbon is supported on an inorganic oxide carrier at least one of metals belonging to Group VI and VIII of the periodic table. Hydrogenation at a temperature of 330 to 400 ° C. using
Then, the content of Na ₂ O is 0.3 wt% or less, SiO ₂
/ Al ₂ O ₃ molar ratio is 5-9 and the lattice constant is 24.
A transition metal-containing aluminosilicate obtained by treating a crystalline aluminosilicate having a lattice constant of 42 to 24.30 ° and / or a crystalline aluminosilicate having a lattice constant of 24.42 to 24.30 ° with a transition metal-containing solution, and an inorganic oxide matrix; Impregnating the carrier with an aqueous solution having a pH of 3 or less containing at least one metal belonging to Group VI of the periodic table and phosphorus,
After drying or without drying,
Using a second catalyst obtained by impregnating, drying and calcining an aqueous solution containing at least one metal belonging to Group VIII, 36
This is a method of hydrocracking at a temperature of 0 to 420 ° C.

In the present invention, all hydrocarbons obtained from crude oil, coal liquefied oil, shale oil and the like can be used as raw materials. Those containing residual carbon and asphaltenes, such as residual oil, are preferred.

The first catalyst of the present invention refers to a conventionally known inorganic oxide carrier such as one or two of alumina, silica, titania, boria, zirconia, and magnesia.
Carrier consisting of at least one kind of refractory inorganic oxide,
A metal which supports 8 to 20% by weight of a Group VI metal such as molybdenum or tungsten and one or two or more of Group VIII metals such as cobalt or nickel. It is preferable to use those supporting molybdenum at 2 wt% and nickel or cobalt at 2 to 5 wt%. This catalyst has 15
0 m ² / g or more surface area, 0.5-0.8 ml / g pore volume, 8
Those having an average pore diameter of 0 to 150 ° are preferred.

In particular, the inorganic oxide containing or supporting 0.01 to 3% by weight of phosphorus and / or boron is excellent in the hydrogenation treatment capacity of heavy hydrocarbon oil, and the second catalyst It is effective in suppressing deterioration of the resin and is preferable.

On the other hand, the second catalyst of the present invention has a Na ₂ O content of 0.3% by weight or less, a molar ratio of SiO ₂ / Al ₂ O ₃ of 5 to 9, and a lattice constant of 24%. .42 to 24.30
It is prepared using the crystalline aluminosilicate of Å.

In this case, if the Na ₂ O content is 0.3% by weight or more, the crystal structure collapses upon contact with an aqueous solution having a pH of 3 or less, the decomposition activity decreases, and the yield of the kerosene oil fraction decreases. I do. If the molar ratio of SiO ₂ / Al ₂ O ₃ is 5 or less, the skeleton is not sufficiently stabilized, and the above Na ₂ O
As in the case of the above, crystal disintegration is caused by the acid, and when it is 9 or more, the decomposition activity is reduced due to the decrease of the acid point. Further, even when the lattice constant is 24.42 ° or more, the crystal structure collapses due to contact with an acid as described above, and the lattice constant becomes 24.30 °.
In the following, since the crystallinity is poor and the amount of acid is small, the decomposition activity similarly decreases, and the yield of the kerosene oil fraction decreases. Note that the lattice constant is calculated by the following equation 1 from the value of the plane distance d obtained by the X-ray diffraction method.

(Equation 1)

The crystalline aluminosilicate having such properties can be prepared from a Y-type zeolite. Any of the Y-type zeolites having a ratio of aluminum to silicon of 1: 2.2 to 1: 3.0 and having a faujasite structure, regardless of the production method, will not hinder any of them. It can be used without. This Y
The crystalline aluminosilicate having the above properties can be obtained by first subjecting the zeolite to a dealkalization treatment, followed by a steam treatment and / or an acid treatment.

The above dealkalization treatment is performed, for example, by immersing a Y-type zeolite in an ammonia-containing solution or the like,
An alkali metal such as a + is ion-exchanged with ammonium ions or the like and calcined. By repeating this series of treatments several times, Na ₂ O is reduced to 0.1.
It can be 3% by weight or less.

The steam treatment can be carried out by a method in which the dealkalized zeolite is brought into contact with steam, preferably at a temperature of 500 to 800 ° C. Further, the acid treatment may be performed by immersing in an aqueous solution of nitric acid having a pH of 3 or less. Either one of the steam treatment and the acid treatment may be used, but partial dealuminization is performed by using both treatments at a molar ratio of SiO ₂ / Al ₂ O ₃ of 5 to 5.
9 are obtained, and by drying and firing, a crystalline aluminosilicate having the above lattice constant can be prepared.

Further, the crystalline aluminosilicate having predetermined characteristics obtained in this manner is made of zinc, copper, iron,
By immersing these ions in a solution containing a salt of a transition metal such as cobalt, nickel, titanium, vanadium, zirconia, cadmium, tin, and lead, these ions are introduced,
It can be a transition metal-containing aluminosilicate.
This transition metal-containing aluminosilicate can be used for the preparation of the second catalyst instead of the crystalline aluminosilicate. In this case, zinc is particularly preferred as the transition metal. This transition metal-containing aluminosilicate may be used in combination with the above-mentioned crystalline aluminosilicate.

The above-mentioned crystalline aluminosilicate and / or transition metal-containing crystalline aluminosilicate is mixed with an inorganic oxide matrix to form a carrier. Preparation of this carrier can be carried out by a conventional method. That is, the crystalline aluminosilicate having the above-mentioned lattice constant and / or the transition metal-containing aluminosilicate and the hydrogel of the inorganic oxide matrix are sufficiently mixed, and molded into a predetermined shape. ~ 130 ° C
After drying for 0.5 hours or more, the support can be obtained by calcining at 350 to 800 ° C, preferably 450 to 600 ° C for 0.5 hours or more. In this case, the activity of the catalyst is such that the crystalline aluminosilicate and / or the transition metal-containing crystalline aluminosilicate is 5 to 90% by weight, particularly 20 to 50% by weight, and the inorganic oxide matrix is 95 to 10% by weight. It is preferable in terms of life and life. As the inorganic oxide matrix, a porous and amorphous material such as alumina, silica-alumina, titania-alumina, and zirconia-alumina is preferably used. These inorganic oxide matrices act as a support for the active metal and also act as a binder for the crystalline aluminosilicate and / or the transition metal-containing crystalline aluminosilicate, and serve to improve the strength of the catalyst. The surface area of the matrix is desirably 30 m ² / g or more.

Next, the thus obtained carrier is impregnated with an aqueous solution containing phosphorus and a metal component of Group VI and having a pH of 3 or less. By adjusting the pH of the aqueous solution containing phosphorus and the Group VI metal component to 3 or less, most of the Group VI metal ions are present as a polymer complex. Due to the formation of this polymer complex, the metal ions of Group VI do not enter the pores specific to the zeolite of the crystalline aluminosilicate and the transition metal-containing aluminosilicate, destroying these crystal structures and reducing the decomposition activity No longer. Actually, even when impregnated with such an aqueous solution, a decrease in crystallinity of about 3 to 20% is observed, but at this level, no significant reduction in degradation performance, desulfurization performance, and denitrification performance is observed. .

The Group VI metal component to be impregnated is an aqueous solution of a compound such as ammonium paramolybdate, molybdic acid, ammonium molybdate, phosphomolybdic acid, ammonium tungstate, tungstic acid, tungstic anhydride, tungstophosphoric acid or the like. It is good to use as. As the phosphorus for forming the polymer complex, an aqueous solution of an acid such as phosphoric acid, phosphorous acid, hypophosphorous acid, phosphomolybdic acid, phosphotungstic acid and a salt thereof is used. Of these, the use of phosphomolybdic acid or phosphotungstic acid is particularly preferable because the phosphorus and the group VI metal component can be simultaneously supported on the carrier as a polymer complex ion at a low PH, and the operation is simplified, which is particularly preferable. These supported amounts are, based on the final catalyst composition, about 5 to 25% by weight of the total amount of the Group VI metal component in terms of oxide, and phosphorus is also 0.05 to 5% by weight.
Preferably it is 5% by weight.

After the support is impregnated with phosphorus and a metal component of Group VI, the support is dried at room temperature to 150 ° C., preferably at 100 to 130 ° C. for 0.5 hours or more.
Alternatively, without drying, impregnated with an aqueous solution containing a Group VIII metal component, and dried at room temperature to 150 ° C, preferably at 100 to 130 ° C for 0.5 hours or more, and then at 350 to 800 ° C, preferably Is 450-600
Baking for 0.5 hours or more at
Can be prepared.

In this case, for the impregnation of the Group VIII component, an aqueous solution of nickel or cobalt nitrate, sulfate, chloride, fluoride, bromide, acetate, carbonate, phosphate or the like is used. It is preferable that the total content of the Group VIII metal component is about 0.5 to 7% by weight in terms of oxide.

When the hydrocarbons are hydrotreated using the first catalyst, the conditions for this reaction are as follows:
00 ° C, preferably 350-380 ° C, hydrogen partial pressure about 20
~ 200 kg / cm ² , liquid hourly space velocity about 0.2 ~ 2.0 hr ^-1 ,
Preferably, the ratio of hydrogen to hydrocarbons is selected in the range of about 200 to 2000 Nl / l. Generally, this catalyst is
Prior to treating the hydrocarbons, it is preferable to use the hydrocarbons containing sulfur compounds such as hydrogen sulfide and carbon disulfide after preliminary sulfurization.

Subsequently, the hydrotreated oil is hydrocracked using a second catalyst. The hydrotreated oil may be hydrocracked as it is. Hydrolysis of only the mass may be performed. The conditions for this reaction are a temperature of about 360-420 ° C., a hydrogen partial pressure of about 20-200 ° C.
kg / cm ² , a liquid hourly space velocity of about 0.2 to 2.0 hr ⁻¹ , a ratio of hydrogen to hydrocarbons, preferably in the range of about 200 to 2000 Nl / l. In addition, this catalyst is also preliminarily sulfurized with hydrocarbons containing sulfur compounds such as hydrogen sulfide and carbon disulfide before treating the hydrocarbons.
Good to use.

[0028]

EXAMPLE 2 Second Catalyst Production Example (Catalyst A) (a) Sodium-type Y-type crystalline aluminosilicate (Si)
O ₂ / Al ₂ O ₃ ratio 2.9, Na ₂ O content 12.3% by weight, lattice constant 2
4.60 °) 200 g was ion-exchanged with 2 liters of 1M aqueous ammonium nitrate solution at a temperature of 50 ° C., and filtered.
After being washed and dried at a temperature of 130 ° C. for 3 hours, it was baked at a temperature of 450 ° C. for 3 hours. This operation 9
As a result, the content of Na ₂ O was reduced to 0.5% by weight,
The SiO ₂ / Al ₂ O ₃ ratio was 5.8 and the lattice constant was 24.55 ° (hereinafter, this is referred to as “SY”). This was brought into contact with steam at 700 ° C. for 3 hours to adjust the pH value to about 1.5.
Immersed in 2 l of nitric acid aqueous solution for 2 hours, filtered, washed,
After drying at 0 ° C. for 3 hours, it was baked at 450 ° C. for 3 hours (hereinafter referred to as “USY”). The USY thus obtained had a lattice constant of 24.38 ° and a surface area of 400 m ² / g.

[0029] 150 g of this USY is mixed with 200 g of alumina powder (alumina pural SB manufactured by Condea), about 230 g of ion-exchanged water is added and kneaded, extruded into a cylinder having a diameter of 1 mm and a length of 5 mm, and extruded at 130 ° C After drying for 3 hours, it was calcined at 600 ° C. for 2 hours to obtain a carrier.

(B) Phosphomolybdic acid solution A
(PH = 0.85; yellow solution) was impregnated by a wet method in which loading was carried out using an impregnating solution in an amount corresponding to the pore volume, dried at 130 ° C. for 3 hours, and dried at a temperature of 550 ° C. 2
The catalyst was calcined for a period of time (catalyst A). At this time, the phosphomolybdic acid solution contains 80% by weight of Mo and P
Was adjusted to contain 0.2% by weight.

Second Comparative Catalyst Preparation Example (Catalyst B) In Example 1, phosphomolybdic acid solution B (pH = 6; colorless solution; ammonia water was added to solution A instead of phosphomolybdic acid solution A ) Catalyst B was prepared in the same manner as in Example 1 except that the pH was improved.

Second Catalyst Production Example (Catalyst C) (a) 150 g of USY obtained in Example 1
After contacting with 1.5 l of a 0.2 M zinc chloride solution at 2 ° C for 2 hours, the mixture was filtered, washed, dried and calcined. (This is ZnUS
Called Y. The transition metal-containing alumina silicate thus obtained contains about 2% by weight of zinc as Zn, and has a lattice constant of 24.38 ° and 380 m 2.
^It has a surface area of ² / g. 150 g of this ZnUSY
Was used as a carrier in the same manner as in the method described in (a) of Example 1.

(B) Ammonium molybdate, nickel nitrate and phosphoric acid are added to the carrier,
8.0 wt%, 2.2 wt% as o, Ni and P, respectively
% And 1.0 wt%, and the mixture was carried by a wet method. The pH of the impregnating liquid at this time was about 2.8. After the loading, the catalyst was dried and calcined under the same conditions as in Example 1 to prepare Catalyst C.

Second Comparative Catalyst Production Example (Catalyst D) The same procedure as in Example 2 was carried out except that an alumina-only formed body containing no ZnUSY was used as a carrier.
Catalyst D was prepared in the same manner as described above.

Second Comparative Catalyst Production Example (Catalyst E) The sodium type Y-type crystalline aluminosilicate of Example 1 was ion-exchanged to have a Na ₂ O content of 0.5% by weight and a sulfur content of 0.5% by weight.
iO ₂ / Al ₂ O ₃ ratio of 5.8, lattice constant of 24.55
Using the alkali-treated aluminosilicate SY of Å in place of USY in Example 2, M
8.0 wt%, 2.2 wt% as o, Ni and P, respectively
%, And 1.0 wt% to prepare Catalyst E.

Second Comparative Catalyst Production Example (Catalyst F) The sodium type Y-type crystalline aluminosilicate was ion-exchanged and further subjected to an acid treatment so that the Na ₂ O content was 0.03% by weight and the SiO ₂ / Al ₂ O ₃ ratio Is 14.6 and the lattice constant is 2
4.29% aluminosilicate was used in place of USY of Example 2, and Mo, Ni, and P were 8.0 wt%, 2.2 wt%, and 1.0 wt%, respectively, according to the method of Example 2.
To prepare Catalyst F.

[0037] As Examples 1-2 inorganic oxides, boron alumina support containing 6.0 wt%, obtained by 3 wt% on the 10 wt% and Co to Mo as the metal as a metal, 200 meters ² / g A catalyst having a surface area of 0.6 ml / g, a pore volume of 0.6 ml / g and an average pore diameter of 90 ° was used as the first catalyst, and the hydrogenation H ₂ pressure was 40 kg / c.
m ² , LHSV = 0.4 hr ⁻¹ , hydrogen / feed oil ratio = 400,
Hydrogenation was carried out using a vacuum distilled gas oil having the properties shown in Table 1 under the conditions of a reaction temperature of 360 ° C., and subsequently, using the catalyst A as a second catalyst, hydrogenation H ₂ pressure = 40 kg / cm ² ,
The decomposition reaction was carried out under the conditions of LHSV = 0.4 hr ⁻¹ , hydrogen / feedstock ratio = 400, and reaction temperature = 400 ° C. The decomposed oil was collected 10 hours and 80 hours after the start of the reaction, and the decomposition rate was determined.
(Calculated by the reduction rate of the fraction at 360 ° C. or higher) was measured. The results are shown in Table 2 as Example 1. Exactly the same operation was performed using catalyst C as the second catalyst. The results are shown in Table 2 as Example 2.

[Table 1]

[Table 2]

Comparative Examples 1 to 4 The same catalyst as in Example 1 was used as the first catalyst, and catalysts B, D, E, and F were used as the second catalyst, respectively. Under the same conditions, hydrotreating and hydrocracking were performed. 10 hours and 80 as in Example 1.
The results of measuring the decomposition rate at the time are shown in Table 2.

Comparative Examples 5 to 7 The first catalyst, catalyst A and catalyst C of Example 1 were each used alone, hydrogenation H ₂ pressure = 40 kg / cm ² , LHSV = 0.8 hr
Hydrocracking was performed under the conditions of ^-1 , hydrogen / feed oil ratio = 400, and reaction temperature = 400 ° C. Table 2 shows the results of measuring the decomposition rates at 10 hours and 80 hours in the same manner as in Example 1.

Comparative Example 8 Using the first catalyst of Example 1 alone, hydrogenation H ₂ pressure = 4
0 kg / cm ² , LHSV = 0.8 hr ⁻¹ , hydrogen / feed oil ratio = 4
The hydrogenolysis was carried out under the conditions of 00 and a reaction temperature of 360 ° C. Table 2 shows the results of measuring the decomposition rates at 10 hours and 80 hours in the same manner as in Example 1.

As is clear from these results, the catalyst of the present invention is superior to the catalyst of the comparative example in terms of decomposition performance and life of decomposition activity.

【The invention's effect】

According to the present invention, in the hydrocracking reaction of hydrocarbons, high cracking performance can be obtained, the cracking activity can be maintained for a long time, the catalyst life can be prolonged, etc. Oil can be decomposed efficiently.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C10G 47/16 C10G 47/16 (56) References JP-A-61-126196 (JP, A) JP-A-53-101003 (JP) JP-A-2-174938 (JP, A) JP-A-3-212494 (JP, A) JP-A-2-289419 (JP, A) JP-A-59-92026 (JP, A) 63-270308 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C10G 65/12 C10G 45/08 C10G 47/16

Claims (3)

(57) [Claims] 1. The method according to claim 1, wherein the hydrocarbons are formed in an amount of 330 to 400 using a first catalyst in which at least one metal belonging to Group VI and Group VIII of the periodic table is supported on an inorganic oxide carrier.
Hydrogenation at a temperature of ° C., followed by a Na ₂ O content of less than 0.3% by weight and a SiO ₂ / Al ₂ O ₃ molar ratio of 5-9.
Crystalline aluminosilicate having a lattice constant of 24.42 to 24.30 ° and / or a lattice constant of 24.4
At least one metal belonging to Group VI of the periodic table and phosphorus are added to a carrier composed of an inorganic oxide matrix and a transition metal-containing aluminosilicate obtained by treating a crystalline aluminosilicate of 2 to 24.30 ° with a transition metal-containing solution. Including p
After impregnating and drying with an aqueous solution of H3 or less, or without drying, the second catalyst obtained by impregnating, drying and calcining an aqueous solution containing at least one metal belonging to Group VIII of the periodic table is used. A method for hydrocracking hydrocarbons at a temperature of 360 to 420 ° C. 2. A method for hydrocracking hydrocarbons, wherein the first catalyst according to claim 1 contains at least one of phosphorus and boron. 3. A method for hydrocracking hydrocarbons, wherein the transition metal-containing aluminosilicate in the second catalyst according to claim 1 is a zinc-containing aluminosilicate. [0001]