JPH04265157A - Hydrogenation refining catalyst and its production - Google Patents

Abstract

PURPOSE:To provide a hydrogenation refining catalyst enabling efficient desulfurization, denitrification and hydrogenation of petroleum fraction by hydrogenation refining. CONSTITUTION:A silica-alumina carrier contg. 2-35wt.% silica is prepd. and 0.1-1.1wt.% PdO, 2.0-6.0wt.% CoO and 10-20wt.% MoO3 are supported on the carrier to obtain a hydrogenation refining catalyst. This catalyst has high catalytic performance to desulfurization, denitrification and hydrogenation and attains >=115 relative desulfurization activity and >=115 relative denitrification activity to light oil.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a hydrorefining catalyst used in hydrorefining hydrocarbons, particularly for efficiently desulfurizing, denitrifying, and hydrogenating hydrocarbons such as petroleum fractions. The present invention relates to a hydrorefining catalyst and a method for producing the same.

0002

[Prior Art] For example, petroleum fractions ranging from naphtha to vacuum gas oil contain impurities such as sulfur and nitrogen derived from crude oil, so these impurities must be removed by hydrorefining treatment. is being carried out.

[0003] In hydrorefining treatment, for example, naphtha is poured together with hydrogen into a reaction vessel provided with a catalyst layer of a hydrorefining catalyst in which a catalytic metal is supported on a carrier, and hydrogen is added to the hydrocarbons in the naphtha. sulfur by H2S and nitrogen by NH
3, and at the same time converts unsaturated hydrocarbons such as aromatics and olefins into saturated hydrocarbons.

0004

[Problems to be Solved by the Invention] Conventionally, as the above-mentioned hydrorefining catalyst, alumina, silica-alumina is used as a carrier, and VII such as Fe, Co, Ni, etc. is used as a catalytic metal.
Catalysts that support Group I metals, Group VIB metals such as Mo, and W are known, but none have high catalytic activity for all of desulfurization, denitrification, and hydrogenation. Nitrogen and hydrogenation could not be carried out well.

Furthermore, attempts have been made to develop hydrorefining catalysts using group VIII noble metals such as Pt and Pd, but none have yet been produced that exhibit high catalytic activity in all of desulfurization, denitrification, and hydrogenation.

In view of the current situation, the present inventor has conducted intensive research to develop a hydrorefining catalyst that can efficiently desulfurize, denitrify, and hydrogenate petroleum fractions through hydrorefining treatment. When the catalyst metals were Pd and Co, which are group VIII metals, and Mo, which is a group VIB metal, Pd-C was used.
It was found that a ternary system of o-Mo should be used.

The present invention has been made based on the above findings, and an object of the present invention is to provide a hydrogenation process that enables efficient desulfurization, denitrification, hydrogenation, etc. of petroleum fractions through hydrorefining treatment. An object of the present invention is to provide a purified catalyst. Another object of the present invention is to provide a method for producing a hydrorefining catalyst having the above characteristics.

[0008]

[Means for Solving the Problems] The above objects are achieved by the hydrorefining catalyst and the method for producing the same according to the present invention. In summary, the present invention provides a silica-alumina support containing 2 to 35 wt% of silica and 0.1 to 1.1 wt. of PdO.
%, CoO 2.0-6.0wt%, MoO3 10
This is a hydrorefining catalyst characterized by supporting ~20 wt%. Furthermore, although the present invention does not limit the method of supporting the catalyst metal, the method for producing the hydrorefining catalyst of the present invention is preferably carried out in an ammine complex salt solution in which a Pd compound and a Co compound are dissolved in an aqueous ammonia solution. A silica-alumina support material is immersed to support the Pd and Co by an ion exchange method, and then the support material is air-dried and calcined, and then immersed in an aqueous solution of a Mo compound to add Mo to the support material. is further supported, and then air-dried and fired again. According to another aspect of the present invention, the carrier material is first immersed in an aqueous solution of a compound of Mo to support Mo, and then the carrier material is air-dried and calcined, and then a compound of Pd and a compound of Co are added to the carrier material. The carrier material is immersed in an ammine complex salt solution dissolved in an aqueous ammonia solution to support Pd and Co, and then air-dried and fired again, or the carrier material is coated with a Pd compound, a Co compound, and a Mo compound in ammonia. It is also possible to make the carrier material support Pd, Co, and Mo at once by immersing it in an ammine complex salt solution dissolved in an aqueous solution, and then air drying and firing.

[0009]

EXAMPLES The present invention will be explained in detail below.

[0010] In the hydrorefining catalyst of the present invention, the catalytic metal is P.
Pd-Co- in the form of oxides of dO, CoO, MoO3
It is composed of a ternary Mo system, has excellent desulfurization, denitrification, and hydrogenation efficiency, and can hydrorefinize hydrocarbons such as petroleum fractions at low temperature, low pressure, and high liquid space velocity. It is something. Hydrocarbons to be subjected to hydrorefining treatment using the catalyst of the present invention are not limited, but petroleum fractions, particularly petroleum fractions from naphtha to vacuum gas oil, are suitable.

[0011] The Pd-Co-Mo ternary catalyst of the present invention has high activity for desulfurization, denitrification, and hydrogenation, and depending on the hydrocarbon to be hydrorefined, it can be used for atmospheric gas oil In the case of catalytic performance, the relative desulfurization activity is 115 or more, and the relative denitrification activity is 115 or more.

In the hydrorefining catalyst of the present invention, a silica-alumina carrier is used as the carrier. When silica is added to alumina, the specific surface area of the carrier increases, solid acidity is imparted, and the desulfurization reaction accompanying the carbon-sulfur bond cleavage occurs.
This is because denitrification reactions accompanying carbon-nitrogen bond cleavage can be increased. This silica affects the sulfur poisoning resistance and hydrocarbon decomposition activity of the catalyst, and the silica content is 2w.
If it is less than t%, the resistance to sulfur poisoning of the catalyst will decrease and the hydrogenation activity will decrease, while if it exceeds 35wt%, it will impart strong decomposition activity to the catalyst, making it difficult to hydrogenate aromatic and unsaturated hydrocarbons. This is not preferable and also causes the problem that the viscosity of petroleum fractions etc. decreases. Therefore, the silica content in the silica-alumina support is 2 to 35 wt%, preferably 5 to 30 wt%.
%, more preferably 10 to 25 wt%.

[0013] A small amount of refractory inorganic oxide, such as magnesia, zirconia, titania, hafnia, boria, natural or crystalline zeolite, and diatomaceous earth, may be added to the silica-alumina carrier, for example, in a range of 10 wt% or less. can.

Catalytic metal Pd (palladium) in the catalyst, C
The contents of O (cobalt) and Mo (molybdenum) are 0.1 to 1.1 wt % for PdO and 2.0 wt % for CoO as oxides.
The range of MoO3 is preferably 0 to 6.0 wt% and 10 to 20 wt%. The content of PdO in the catalyst is 0.1wt%
At less than Can not. On the other hand, the content of PdO is 1.1
If it exceeds wt%, undesirable reactions such as hydrogenolysis are likely to occur, and there is also the disadvantage that the cost of the catalyst increases. The same applies to CoO, when the CoO content in the catalyst is 2.
If it is less than 0wt%, the hydrogenation activity of the catalyst is small, and 6.0w
If it exceeds t%, the hydrogenation activity will similarly decrease. Furthermore, if the content of MoO3 in the catalyst is less than 10 wt%, desulfurization and
High desulfurization and denitrification efficiency cannot be expected due to Mo, which has high denitrification activity, and sulfur and nitrogen cannot be removed with high efficiency even if Pd and Co have desulfurization and denitrification effects. On the contrary, MoO
When the content of 3 exceeds 20 wt%, the supported Mo
is not preferable because it aggregates and does not work effectively. Therefore, the content of catalytic metal in the catalyst is 0.1 to 1.1 wt PdO.
%, CoO 2.0-6.0wt%, MoO3 10
The range of ~20 wt% is good, preferably PdO is 0.2
~0.7wt%, CoO 3.0~5.0wt%, Mo
O3 is 12 to 18 wt%.

[0015] 3 of Pd-Co-Mo with such content
With the base catalyst, desulfurization and denitrification activities higher than expected from Pd-Mo and Co-Mo catalysts can be obtained, and the hydrorefining treatment removes sulfur, nitrogen, and halogens from hydrocarbons such as petroleum fractions. can be removed with high efficiency, and unsaturated hydrocarbons such as aromatics and olefins can be converted into saturated hydrocarbons with high efficiency.

[0016] The above catalyst metal can be supported on a silica-alumina support by simultaneously precipitating them from a colloidal aqueous solution containing silica and alumina, or by impregnating silica with an aqueous solution containing an aluminum compound. However, this can be easily accomplished by immersing a silica-alumina support material in an aqueous solution containing a catalytic metal compound. Suitable compounds for the metal catalyst Pd include palladium chloride, palladium chloride, and the like. Suitable compounds for Co include cobaltous nitrate, cobaltous sulfate, cobaltous fluoride, etc., and suitable compounds for Mo include ammonium molybdate, ammonium paramolybdate, molybdic acid, etc. .

Compounds of these catalytic metals are prepared by dissolving a compound of the VIII metals Pd and Co in an ammonia aqueous solution to form an ammine complex salt of Pd and Co, and then preparing a silica
M of group VIB metal is supported on an alumina support material and then
Supporting the compound of Pd, Co, on the carrier material
, preferred from the viewpoints of highly dispersed Mo support, catalytic performance, and ease of production, and provides the highest catalytic activity. However, Mo is first supported on the carrier material, and then Pd and C are supported.
It is also possible to support Pd, Co and Mo on the carrier material at once.

Therefore, in the preferred method for producing a hydrorefining catalyst of the present invention, ammine complex salts of Pd and Co are produced by dissolving a Pd compound and a Co compound in an ammonia aqueous solution, and silica is added to the ammine complex salt solution. - An alumina-based carrier material is immersed to support Pd and Co by ion exchange method, and then the carrier material is air-dried and calcined, and then immersed in a solution of a Mo compound to support Mo on the carrier material.
is further supported, and then air-dried and fired again. PdO and CoO are formed by firing the silica-alumina support material supporting Pd and Co, and then MoO3 is formed by firing the support material supporting Mo.
is formed, and PdO and CoO are formed on the silica-alumina support.
A Pd-Co-Mo ternary hydrotreating catalyst supporting MoO3 is obtained.

According to another aspect of the production method of the present invention, the carrier material is first immersed in an aqueous solution of a Mo compound.
Then, the carrier material is air-dried and calcined, and then immersed in an ammine complex salt solution in which a Pd compound and a Co compound are dissolved in an aqueous ammonia solution to coat the carrier material with P.
d and Co, and then air-dried and fired again, or the support material is coated with a compound of Pd, a compound of Co, and a compound of Mo.
Pd, Co, and Mo are supported on the carrier material at once by immersing the compound in an ammine complex salt solution dissolved in an ammonia aqueous solution, followed by air drying and firing.

[0020] The Pd-Co-Mo3 of the present invention as described above
According to the original hydrorefining catalyst, it can be used in the hydrorefining treatment of hydrocarbons such as petroleum fractions to remove impurities such as sulfur and nitrogen from hydrocarbons and to remove unsaturated hydrocarbons such as aromatics and olefins. can be converted into saturated hydrocarbons with high efficiency, and the conditions for the hydrorefining treatment can be low temperature, low pressure, and high liquid hourly space velocity.

Next, the present invention will be further explained based on specific examples.

Example 1 A silica-alumina support material was immersed in an ammine complex salt solution of Pd and Co to support Pd and Co. After air drying and firing, the support material was immersed in an aqueous solution of Mo to support Mo. 1.0 wt% of PdO, 3.5 wt% of CoO, and MoO3 as catalytic metals on a silica-alumina support with a silica content of 10 wt%, which was produced by supporting, air-drying, and firing.
Using a hydrorefining catalyst supported with 14.0 wt%, naphtha was used as the feedstock, the reaction temperature was 330°C, and the reaction pressure was 32.
The hydrorefining treatment was carried out under the reaction conditions of kg/cm2 G, liquid hourly space velocity of 0.97 V/H/V, and hydrogen to feedstock flow rate ratio of 600 SCF/B, and the relative desulfurization activity and relative denitrification activity at that time were investigated. .

The properties of the raw material naphtha used are as follows. Specific gravity: 0.8531 Sulfur content: 1.0 wt% Nitrogen content: 170 ppm The relative desulfurization activity of the catalyst was evaluated by determining the reaction rate coefficient K1.7 of the desulfurization reaction based on the following equation. K1.7 = (S-0.7-S0-0.7) x LHS
V However, S: Sulfur amount (wt) after hydrorefining treatment of feedstock oil
%), S0: Sulfur content (w) of feedstock oil before hydrorefining treatment
t%) Relative denitrification activity was evaluated by determining the reaction rate coefficient K1.0 of the denitrification reaction based on the following equation.

[0024] K1.0 = lnN0 /N×LHSV However, N: Nitrogen amount after hydrorefining treatment of feedstock oil (ppm)
, N0: Nitrogen content (ppm) of raw oil before hydrorefining treatment
).

Example 2 In Example 1, the catalytic metal content of the hydrorefining catalyst was changed to 1.0 wt% of PdO, 2.0 wt% of CoO, and 2.0 wt% of MoO3.
The catalyst manufacturing method and hydrorefining treatment conditions were the same as in Example 1 except that the amount was 14.0 wt%. Similarly, the relative desulfurization activity and relative denitrification activity of the catalyst for hydrorefining treatment were investigated.

Example 3 In Example 1, the catalytic metal content of the hydrorefining catalyst was changed to 1.0 wt% of PdO, 6.0 wt% of CoO, and 6.0 wt% of MoO3.
The catalyst manufacturing method and hydrorefining treatment conditions were the same as in Example 1 except that the amount was 14.0 wt%. Similarly, the relative desulfurization activity and relative denitrification activity of the catalyst for hydrorefining treatment were investigated.

Example 4 The order in which the catalyst metals were supported was different from that in Example 1, and the support material was first immersed in an aqueous solution of Mo to support Mo, air-dried and fired, and then Pd and Co were supported. A carrier material is immersed in an ammine complex salt solution to support PdO and CoO,
PdO1.0wt%, CoO produced by air drying and firing
Hydrotreating was carried out in the same manner as in Example 1, except that a hydrorefining catalyst supporting 3.5 wt% and 14.0 wt% of MoO3 was used, and the relative desulfurization activity and relative denitrification activity at that time were investigated. Ta.

Example 5 An ammine complex salt solution of Pd, Co, and Mo was prepared, and a silica-alumina support material was immersed in the solution to prepare Pd, Co, and Mo.
PdO1.0wt%, CoO3.5wt%, MoO3 produced by supporting Co and Mo at once, air drying, and firing.
Hydrotreating was carried out in the same manner as in Example 1, except that a hydrotreating catalyst supported at 14.0 wt% was used, and the relative desulfurization activity and relative denitrification activity at that time were examined.

Comparative Example 1 In Example 1, the catalytic metal content of the hydrorefining catalyst was changed to 0.05 wt% of PdO, 0.03 wt% of CoO, and 0.03 wt% of Mo.
The catalyst manufacturing method and hydrorefining treatment conditions were the same as in Example 1 except that O3 was 14.0 wt%. Similarly, the relative desulfurization activity and relative denitrification activity of the catalyst for hydrorefining treatment were investigated.

Comparative Example 2 In Example 1, the catalytic metal content of the hydrorefining catalyst was changed to 1.0 wt% of PdO, 8.0 wt% of CoO, and 8.0 wt% of MoO3.
The catalyst manufacturing method and hydrorefining treatment conditions were the same as in Example 1 except that the amount was 14.0 wt%. Similarly, the relative desulfurization activity and relative denitrification activity of the catalyst for hydrorefining treatment were investigated.

Comparative Example 3 In Example 1, the catalytic metal content of the hydrogenation catalyst was changed to 1.0 wt% PdO, MoO
3 The catalyst manufacturing method and hydrorefining treatment conditions were the same as in Example 1 except that the amount was 14.0 wt%. Similarly, the relative desulfurization activity and relative denitrification activity of the catalyst for hydrorefining treatment were investigated.

Comparative Example 4 In Example 1, the catalytic metal content of the hydrorefining catalyst was changed to 3.5 wt% CoO, M
The catalyst manufacturing method and hydrorefining treatment conditions were the same as in Example 1 except that oO3 was 14.0 wt%. Similarly, the relative desulfurization activity and relative denitrification activity of the catalyst for hydrorefining treatment were investigated.

Comparative Example 5 In Example 1, Pd and Co as catalyst metals were replaced with Pd and Co.
t, and the content of the catalytic metal of the hydrorefining catalyst is Pt.
The catalyst manufacturing method and hydrorefining treatment conditions were the same as in Example 1, except that O1.0 wt% and MoO3 14.0 wt%.
I did the same. Similarly, the relative desulfurization activity and relative denitrification activity of the catalyst for hydrorefining treatment were investigated.

Comparative Example 6 In Example 1, F was used instead of Pd and Co as catalyst metals.
Fe
The catalyst manufacturing method and hydrorefining treatment conditions were the same as in Example 1 except that 2 O3 was 1.0 wt% and MoO3 was 14.0 wt%. Similarly, the relative desulfurization activity and relative denitrification activity of the catalyst for hydrorefining treatment were investigated.

Comparative Example 7 In Example 1, Ni was used instead of Co as the catalyst metal, and the content of the catalyst metal in the hydrorefining catalyst was changed to PdO1.
0wt%, NiO3.5wt%, MoO314.0wt
A catalyst was produced in the same manner as in Example 1, except that the
A hydrorefining treatment was performed, and the relative desulfurization activity and relative denitrification activity at that time were investigated.

Table 1 shows the results of Examples 1 to 5 and Comparative Examples 1 to 7.

[0037]

[Table 1]

As shown in Table 1, in Examples 1 to 5, 0.1 to 1.1% of the catalytic metal was added to the silica-alumina support.
PdO in the range of wt%, 2.0-6.0 wt% Co
Since a hydrorefining catalyst supported with O, 10 to 20 wt% MoO3 is used, the relative activity of desulfurization and denitrification of the catalyst against atmospheric gas oil as feedstock is high, and the hydrocarbons in atmospheric gas oil are effectively removed. It is possible to desulfurize, denitrify, and convert unsaturated hydrocarbons to saturated hydrocarbons.

On the other hand, in Comparative Examples 1 to 3, PdO, CoO, and MoO3 are supported as catalyst metals, but the content of any of the catalyst metals is outside the scope of the present invention. None of them had high relative activities for desulfurization and denitrification, and the catalytic activity was poor in any of the items. Also, in Comparative Examples 4 to 7, some of the catalyst metals used in the present invention were missing or other metals were used instead, so the catalyst performance was similarly poor in either desulfurization or denitrification. Inferior.

[0040]

Effects of the Invention As explained above, the hydrorefining catalyst of the present invention comprises a silica-alumina support containing 2 to 35 wt% of silica, 0.1 to 1.1 wt% of PdO, and Co.
2.0-6.0wt% O, 10-20w MoO3
Since it is supported at t%, by using it in hydrorefining treatment, desulfurization, denitrification, hydrogenation, etc. of petroleum fractions etc. can be carried out efficiently. Further, according to the production method of the present invention, ammine complex salts of Pd and Co are produced from a Pd compound and a Co compound, and a silica-alumina carrier material is immersed in the ammine complex solution, and then Pd is added to the ammine complex salt.
and Co are supported by an ion exchange method, and then the carrier material is air-dried and calcined, and then immersed in an aqueous solution of Mo compound to further support Mo on the carrier material, and then air-dried and calcined again to perform the above hydrogenation. Since a purified catalyst is obtained, the catalyst can be manufactured easily and its catalytic performance can be exhibited well.

Claims (4)

[Claims] Claim 1: 0.1 to 1.1 wt% of PdO is added to a silica-alumina support containing 2 to 35 wt% of silica.
, CoO 2.0-6.0wt%, MoO3 10-2
A hydrorefining catalyst characterized in that it is supported at 0 wt%. 2. A silica-alumina support material is immersed in an ammine complex salt solution in which a Pd compound and a Co compound are dissolved in an ammonia aqueous solution.
o is supported by an ion exchange method, and then the carrier material is air-dried and calcined, and then immersed in an aqueous solution of a compound of Mo to further support Mo on the carrier material, and then air-dried and calcined again. A method for producing a chemical refining catalyst. 3. The carrier material of claim 2 is first immersed in an aqueous solution of a Mo compound to support Mo, and then the carrier material is air-dried and fired, and then a Pd compound and a Co compound are added to an ammonia aqueous solution. A method for producing a hydrorefining catalyst, which comprises immersing it in a solution of a dissolved ammine complex salt to support Pd and Co on a carrier material, and then air-drying and calcining it again. 4. The carrier material of claim 2 is a compound of Pd,
Pd was added to the carrier material by immersing a Co compound and a Mo compound in an ammine complex salt solution in which a Co compound and a Mo compound were dissolved in an aqueous ammonia solution.
, Co and Mo are supported at once, and then air-dried and calcined.