JPS60250090A - Process for treating heavy oil - Google Patents

Abstract

PURPOSE:To carry out hydrotreatment of heavy oil producing little coke in the product oil and giving a prolonged catalyst life, by hydrotreating the heavy oil using a catalyst comprising V and Ni supported on allophane and an inorg. heat- resistant binder. CONSTITUTION:Heavy oil is hydrotreated under conditions including a reaction temp. of 400-600 deg.C and a pressure of 1atm-200kg/cm<2> using a catalyst comprising V and Ni supported on a carrier consisting of 50-80wt% allophane and 20- 50wt% inorg. heat-resistant binder, in which 1-20pts.wt. V and 0.5-10pts.wt. Ni are supported on 100pts.wt. carrier. Said allophane is colloidal soil usually called Kuri-soil, Miso-soil, Mizu-soil, or Uki-ishi-soil, which has unigue adsorptivity. The inorg. binder includes alumina gel, silica gel, or the like. The component binds allophane particles to enhance mechanical strength of the whole body and itself is porous and has a catalytic activity.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a method for hydrocracking heavy oil in a suspended bed reactor. The present invention relates to a method for treating heavy oil using a suspended bed catalyst that provides a high yield of kerosene and gas oil fractions and is inexpensive.

[Technical background of the invention and its problems] Heavy oils such as atmospheric distillation residual oil, vacuum distillation residual oil, oil sand oil, shale oil, etc. are hydrocracked using various catalysts to produce kerosene, gas oil, etc. Operations are being carried out to increase the yield of so-called middle distillates. Such a catalyst is
For example, synthetic silica alumina amorphous gel catalysts or catalysts containing zeolites are known.

In addition, recently, allophane (a Iophane
) has also been proposed.

For example, in Japanese Patent Publication No. 58-50874, the first stage is a catalyst bed of a catalyst in which one or more of vanadium, molybdenum, and nickel and cobalt and/or nickel are supported on an aluminum or alumina-silica carrier. can be,
A method for hydrotreating heavy oil in a system in which the second stage is a catalyst bed composed of allophane is disclosed, and in JP-A-59-81344, allophane with an average particle size of 5 gm or less is mixed with silica alumina. Hydrogel treated catalysts are disclosed.

However, in the case of the latter catalyst, a large amount of coke is produced. Further, the former catalyst has low mechanical strength, and therefore, when it is used in a suspended bed system in which the catalyst, hydrogen, heavy oil, etc. are brought into intense contact, it is unsuitable because it causes wear, damage, etc.

[Object of the invention] The present invention is characterized in that allophane constitutes a part of the carrier, and when heavy oil is hydrocracked using a suspended bed method, the amount of coke produced in the produced oil is small, and the wear resistance is improved. The purpose of the present invention is to provide a method for hydrotreating heavy oil using a catalyst that has excellent properties and has a long service life.

[Summary of the Invention] The heavy oil processing method of the present invention is a method for hydrotreating heavy oil, comprising: a carrier comprising 50 to 70% by weight of allophane and 30 to 50% by weight of an inorganic heat-resistant binder; A catalyst comprising vanadium and nickel supported on the support, the amount of vanadium and nickel supported is 100
1 to 20 parts by weight, 0.5 to 1 part by weight, respectively
Using a catalyst that is 0 parts by weight, the reaction temperature is 400 to 600°C.
, the hydrogenation reaction is carried out under conditions of normal pressure to 200 kg/cm2.

First, the catalyst carrier used in the method of the present invention is composed of allophane and an inorganic heat-resistant binder. Here, allophane refers to colloidal soils commonly referred to as chestnut soil, miso soil, and suitozo, and is a substance that has a unique adsorption ability. And this allophane has a particle size of 0. ! It is a porous body in which fine particles with a diameter of less than 100 m are aggregated, and its composition is generally as follows:
A sentence, 03・(1~2)Si201(2~3)H2O+
(0-2) A is represented by 03 (H2O) and is a mixture or composite of amorphous hydrated aluminum silicate and the same type of alumina gel.

Examples of materials forming the inorganic heat-resistant bonding material include alumina gel, silica-alumina gel, alumina sol, and silica sol. This component is a component that binds the allophane particles and contributes to improving the overall mechanical strength, and is itself porous and has catalytic ability.

In layer 4, the proportion of allophane and inorganic heat-resistant binder is 50 to 70% by weight, S-type heat-resistant binder 3
It is set at 0 to 50% by weight. When the proportion of inorganic heat-resistant binder becomes less than 30% by weight (allophane exceeds 70% by weight), the mechanical strength of the carrier decreases.

In particular, the abrasion resistance decreases, making it difficult to apply to the suspended bed system. Conversely, if the content exceeds 50% by weight (less than 50% by weight), the amount of coke and asphaltene produced increases. This may cause inconvenient problems such as the catalyst's performance not being exhibited. Preferably, the allophane content is 80-80% by weight and the inorganic heat-resistant binder content is 40-20% by weight.

The catalyst of the present invention is constructed by simultaneously supporting vanadium and nickel on the above-mentioned carrier.

The amount of vanadium and nickel supported is set to 1 to 20 parts by weight, 0.5 to IO parts by weight, preferably 2 to 10 parts by weight, and 1 to 5 parts by weight, respectively, based on 100 parts by weight of the carrier, and The ratio (weight ratio) of the supported amounts of vanadium and nickel is set to 0.5 to 3.0, preferably 1 to 2.

If the supported amounts of vanadium and nickel components are both lower than the above ranges, the hydrogenation ability of the catalyst will decrease, coke yield and asphaltene yield will increase, and kerosene and asphaltene yields will increase.
If the yield of the gas oil fraction decreases and conversely exceeds the above range, these metal components will clog the pores of the catalyst and reduce the specific surface area of the catalyst, which will actually reduce the number of active sites and impair the catalyst performance. This is inconvenient because it causes problems such as a decrease in the temperature. Furthermore, if the ratio of the supported amount of vanadium and nickel is less than 0.3, hydrogen consumption will increase, which is undesirable, and if it exceeds 5.0, the amount of supported vanadium will increase due to melting of vanadium during catalyst regeneration. This is not preferable because the catalyst will deteriorate significantly.

The catalyst of the present invention is a porous body, and pores of various pore sizes are distributed therein. In this embodiment, the total pore volume is 0.03 to 0.3
cc/g, and its pore distribution is 40 to +000
The pore volume of = is 0.02 cc/g or more, 1000 to 10
The pore volume of 000A is less than O,lcc/g, and
It is desirable that the porous structure has a pore volume of 10,000 Å or more and 0.05 cc/g or less.

The catalyst of the present invention can be manufactured as follows.

First, the raw allophane is subjected to water sieving treatment to remove impurities such as magnetite, pyroxene, feldspar 9 quartz, etc.
After adjusting the particle size, it is fired to prepare an allophane slurry with a predetermined solid content concentration.

Next, this allophane slurry is mixed with, for example, silica alumina gel prepared separately to prepare a mixed slurry of both. The mixing amount of both at this time is selected so that when moisture is removed by the firing process described later, the amounts of both will be in the above-mentioned ratio.

This mixed slurry is subjected to a commonly used powder processing method, such as a spray drying method, to obtain a powder having a predetermined particle size, which is then dried or fired to form a carrier. The particle size is usually about 30 to 20 opLm by appropriately adjusting spray conditions and the like.

Next, vanadium and nickel are supported on the obtained carrier. As a mutual impregnation method, a vacuum impregnation method, a dipping method, etc., which are commonly used in this technical field, are applied. For example, in the case of a vacuum impregnation method, the supported amount and the ratio of vanadium to nickel 411 can be easily adjusted by changing the amount of ammonium vanadate and nickel nitrate dissolved in ion-exchanged water. Finally, dry
The catalyst used in the present invention is obtained by calcination.

In the method of the present invention, heavy oil is hydrotreated using the catalyst prepared as described above.

The reaction temperature at this time is 400-800"C, L HS
V is 0.2 to 10. Pressure is normal pressure □-200kg/cm2
There is.

The particle size of the catalyst used is determined as appropriate, but is 10-300.
gm, particularly preferably 40 to 150 pots m.

The suspension concentration of the slurry is such that when heavy oil and catalyst are mixed, the amount of catalyst in the mixture is 1 to 30% by weight, preferably 2 to 10% by weight.

[Examples of the Invention] Example 1.2 (1) Preparation of catalyst Raw material allophane was subjected to water sieving treatment to remove impurities, and the particle size was adjusted to 501 Lm or less using a wet disperser. Next, this was baked at 200"C for 2 hours to obtain a particle size of 30#L.
The particle size was again adjusted to less than m to obtain an allophane slurry with a solid content concentration of 10% by weight.

Separately, 538 g of an aqueous aluminum sulfate solution with a concentration of 8% by weight was added to a solution of 148 g of JIS No. 3 water glass and 10 g of sulfuric acid dissolved in 378 g of ion-exchanged water, and the whole was kept at 100°C and pH 8 for 30 minutes. A silica alumina gel was precipitated, which was collected and washed to obtain a silica alumina gel. 800% of this silica alumina gel
The total pore volume of the product fired at ℃ is 9.8 cc/g or more,
The pore volume of 80 Å or less was 35% or more of the total pore volume.

Allophane slurry and silica alumina gel were mixed at a concentration of 70% by weight and 30% by weight based on the weight after firing, and the resulting mixed slurry was heated at a nozzle pressure of 30 kg/c+.
s2. After spraying and drying under the conditions of a drying temperature of 200"O and a residence time of 1 second, it is fired at 500"O to obtain a particle size of 30~2.
A carrier of 00 JLm was used.

Next, after applying a vacuum impregnation method to this carrier, it was heated to 600°C.
It was fired to support vanadium and nickel. The amounts of vanadium and nickel supported were approximately 2 parts by weight and 1 part by weight, respectively, per 100 parts by weight of the carrier.

Therefore, the ratio of the mutual amount of vanadium and nickel is 2
It is. This catalyst is referred to as Example 1.

A catalyst was prepared in the same manner as the catalyst in Example 1, except that allophane slurry and silica alumina gel were mixed at 60% by weight and 30% by weight based on the weight after calcination. was designated as Example 2.

(2) Characteristics of catalyst The abrasion resistance of the above two examples was measured by the following method, and the specific surface area and pore distribution were also investigated.

#i4 Abrasion test: 45g of zeolite catalyst (USZ-205) used in fluid catalytic cracking (FCC method) was tested in an abrasion resistance measuring device.
It is shown as a relative value when the test value at that time is 1.0 after flowing for 42 hours at room temperature and at an air linear velocity of 287 ml/sec. The larger this value is, the better the abrasion resistance is.

Comparative Example 1: The carrier was composed of allophane treated only with water sieve and the silica alumina gel used in Example 1, and also supported henadium and nickel as in Example 1.

Comparison Example 2: Comparison in which the carrier is made of allophane frozen soil and silica alumina gel, and also supports henadium and nickel in the same manner as in Example 1. Example 3: Comparison of allophane treated only with water sieving Example 4 : FCC zeolite catalyst The above results are summarized in Table 1.

Table 1 (3) Hydrocracking of vacuum residue The Arabian heavy vacuum residue whose properties are shown in Table 2 was placed in an autoclave together with various catalysts and subjected to hydrocracking treatment. The conditions during the hydrogenolysis reaction were as follows.

Vacuum residual oil amount 80g, catalyst amount 10g, reaction temperature 450°
C1 reaction pressure 85 kg/cm2G, reaction time 1 hour.

Stirring speed: 500 rpm.

Table 2 The results obtained are summarized in Table 3. In addition, in Table 3, catalyst 3. When Catalyst 4 was used, coke production progressed rapidly and the reaction could only be completed for 30 minutes. therefore,
These catalysts3. The results in Table 3 for Catalyst 4 are data for a reaction time of 30 minutes.

Table 3 $3 - Water sieved allophane (corresponds to Comparative Example 3 in Table 2) t4 - FCC zeolite catalyst (corresponds to Comparative Example 4 in Table 2) t5: Total amount of products with a boiling point of 343°C or less . However, it also includes coke yield.

[Effects of the Invention] As is clear from the above explanation, the catalyst of the present invention has (1) excellent wear resistance (results shown in Table 1).

■Increasing the yield of kerosene and gas oil fractions in the hydrocracking reaction of heavy oil (Table 2), ■Lowering the coke yield (Table 2), ■Reducing hydrogen consumption (Table 2). (Table), (1) Reactions can proceed at relatively high temperatures, and (2) Since allophane is used as a raw material, catalyst costs can be reduced, making it highly useful in the petroleum refining field.

Procedural amendment June 6, 1981 Kazuo Wakasugi, Commissioner of the Patent Office 2 Name of the invention Method for processing heavy oil 3 Relationship with the person making the amendment Case Patent applicant name New Fuel Oil Development Technology Research Association 4. Agent address 〒10? 2-1O-85 Akasaka, Minato-ku, Tokyo, Daily publication of amendment orders Voluntary publication 6, Number of inventions increased by amendment None 7, Subject of amendment In each column of claims and detailed description of invention in the specification: ＼ 8. Contents of the amendment ■ The claims column is amended as shown in the attached sheet.

■1 The Detailed Description of the Invention column is amended as follows.

(1) "50-70" written in the bottom line of page 1 and line 10 of page 5 of the specification is corrected to "50-80".

(2) "30-50" written on page 4, line 3 of the specification cylinder and page 5, line 11 of the specification cylinder is corrected to "20-50".

(3) Change “30” written on page 5, line 12 of the specification cylinder to “20”
”.

(4) "70" written on page 5, line 13 of the specification is replaced by [80]
”.

(5) "60-80" written on page 5, line 19 of the specification is supplemented to "60-75".

(6) "40-20" written on page 5, line 20 of the specification cylinder is corrected to "40-25".

(7) “30% by weight” stated on page 10, line 17 of the specification section
is corrected to "40% by weight".

(8) "0.1% by weight" written in the fifth line from the bottom on page 14 of the specification is corrected to "1.0% by weight J."

Claim 1: A method for hydrotreating heavy oil, comprising a carrier comprising 50 to 50% by weight of allophane and 50 to 50% by weight of an inorganic heat-resistant binder, and vanadium and nickel supported on the carrier. A catalyst, in which the amount of vanadium and nickel supported is about 1 part by weight and 1 part by φ of the carrier, respectively.
~20 parts by weight, using a catalyst that is 0.5 to 10 parts by weight,
Reaction temperature 400-800°C9 Normal pressure-200kg/cm
A method for processing heavy oil, characterized by carrying out a hydrogenation reaction under the conditions of 2.

2. The total pore volume of the catalyst is 0.03~0.3cc/g, and the total volume of 40~1000 pores is Q, Q2cc/g or more, and the pore size is 1000~100OOA. Total volume is 0.1
The method for treating heavy oil according to claim 1, wherein the total volume of pores of cc/g or less and +000OA or more -L is 0.05 cc/g or less.

Procedural amendment May 7, 1985 Manabu Shiga, Commissioner of the Patent Office1, Indication of the case, Patent Application No. 104664 filed in 19822, Name of the invention, Heavy oil processing method 3, Person making the amendment Related Name of patent applicant New Fuel Oil Development Technology Research Association 4, Agent 5, Date of amendment order Voluntary 6, Subject of amendment Detailed explanation of the invention in the specification (1)
“Example 1゜2” written in the bottom row of page 1 of the specification is amended to “Examples 1, 2, and 3J.”

(2) "To the raw material allophane" stated in the bottom line of page 1 of the specification is corrected to "to the raw material allophane whose particle size distribution is shown in Table 1."

(3) "Wet type dispersion machine" stated in the bottom line θ of page 1 of the specification is corrected to "wet type crusher".

(4) Insert the following table following "... allophane slurry" stated on page 9, line 13 of the specification.

Table 1 (5) “...” stated in the second to first lines from the bottom of page 10 of the specification
...This was designated as Example 2. ” followed by Dinghai.

"Also, in the preparation stage of the mixed slurry, the raw material allophane having the same particle size distribution as shown in Table 1 was subjected to water bottle treatment to remove impurities, and this and silica sol were mixed to 70% by weight based on the weight after firing, and 30% % by weight, Aeon exchange water was added to the resulting mixture to form a uniform mixed slurry with a solid content concentration of 15% by weight, and this was pulverized using a wet pulverizer to obtain a particle size of 1O1ua or less. .From now on, Example 1
A catalyst was prepared in the same manner as in the case of the catalyst, and this was designated as Example 3. ” (6) Two types of r or more described in the second line of page 10 of the specification.”
be corrected to one or more of three types.

(7) [...
...It is shown as a relative value when the test value at that time is 1.0. " is corrected to "The relative value when the residual overlayer at that time is assumed to be 1.0 is shown as the test value for each example."

(8) "Table 1" stated in page 10, line 7 of the specification and page 15, line 3 of the specification is amended to "Table 2."

(9) Table number “Table 1” of Table 1 stated on page 12 of the specification
amend it to "Table 2" and amend the table as follows.

(10) "Table 2" written in the third line from the bottom of page 12 of the specification and in the fifth line of page 13 of the specification is amended to "Table 3."

(11) "Table 3" stated in the 1st, 2nd, and 4th to 5th lines of page 14 of the specification is amended to "Table 4."

(12) The table number "Table 3" in Table 3 described on page 14 of the specification is amended to "Table 4" and the table is amended as follows.

(13) "Table 2" stated in lines 5, 6, and 7 of page 15 of the specification is amended to "Table 4."

Claims (1)

[Claims] 1. In a method for hydrotreating heavy oil, 50 to 70% by weight of allophane and 30 to 50% by weight of an inorganic heat-resistant binder.
and vanadium and nickel supported on the carrier, wherein the supported amounts of vanadium and nickel are 1 to 20 parts by weight and 0.5 to 0.5 parts by weight, respectively, based on 100 parts by weight of the carrier. Using a catalyst that is 10 parts by weight, the reaction temperature is 400 to 600°C, normal pressure to 200 kg/c.
A heavy oil processing power method characterized by carrying out a hydrogenation reaction under conditions of m2. 2. The total pore volume of the catalyst is 0.03 to 0.3 cc/g
The total volume of pores between 40 and 1000 OOA is 0.02 cc/g or less.2, The total volume of pores between 1000 and 100 OOA is 0.1
2. The method for treating heavy oil according to claim 1, wherein the total volume of pores of cc/g or less and 10,000 Å or more is 0.05 cc/g or less.