JPH0278441A - Catalyst for hydrogenation of hydrocarbon and production thereof - Google Patents

Abstract

PURPOSE:To make the heat treatment of a catalyst molded body unnecessary by molding a catalyst from a mixture of an Al oxide and/or hydroxide carrier with a group VI metal of the periodic table and amino-substd. mercaptan of hydrocarbon. CONSTITUTION:A soln. contg. at least one of water soluble compds. of groups VI and VIII metals of the periodic table and amino-substd. mercaptan of 1-15C hydrocarbon is prepd. A carrier material based on Al oxide and/or hydroxide is kneaded with the soln., molded and dried to produce a catalyst for hydrogenation of hydrocarbon. Otherwise the carrier material may be kneaded with a soln. of at least one of the water soluble compds., molded and impregnated with a soln. of the amino substd. mercaptan.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a catalyst for hydrotreating hydrocarbon oil and a method for producing the same.

[Conventional technology]

In so-called hydrogenation treatment, in which hydrocarbon oil is hydrogenated, desulfurized, denitrified, decomposed, etc. in the presence of hydrogen, inorganic oxide carriers such as alumina, silica-alumina, titania, etc.
A catalyst supporting at least one metal selected from group metals and group 8 metals as a hydrogenation active component is used,
Group 6 metals are Mo and W1 Group 8 metals are C.
O and N1 are commonly used.

These metals are usually supported in an oxide state and do not show activity in that state, so they must be activated by converting from an oxide state to a sulfide state in order to be subjected to a hydrogenation reaction. Pre-sulfurization is required.

Conventionally, this pre-sulfurization is generally carried out by filling a catalyst in a reactor for hydrogenating hydrocarbon oil, and then passing a sulfurizing agent together with hydrogen through the catalyst bed. The operating conditions for pre-sulfiding vary depending on the hydrotreating process and the sulfurizing agent used, but when hydrogen sulfide is used, it is contained in hydrogen at about 0.5 to 5 gfi%, the standard temperature per catalyst No. 11, 1000-3000 converted to pressure
The temperature is 180C (usually 250C or higher), and when carbon disulfide, n-butyl mercaptan, dimethyl sulfide, dimethyl disulfide, etc. are used, they are diluted with light hydrocarbon oil and used at a temperature of 250 to 250C. 3501
Z'1 pressure 20~100seg, liquid space velocity 0.5~2
hr"-' and a hydrogen/oil ratio of 200 to 1000 Nl/l.

After performing such a pre-sulfiding operation, the raw material oil to be actually treated is switched to, and the hydrotreating operation is started. The presulfiding operation determines the success or failure of the subsequent hydrotreating process, so appropriate selection of materials and careful operation are required. For example, when using a diluent, if the diluent contains olefins, the polymerization product will be poisoned by the catalyst, so it is necessary to use a hydrocarbon oil that does not contain olefins.

Also, when the catalytic metal reacts with hydrogen at high temperatures and is reduced, it becomes passivated, so to prevent this, it is necessary to use a large amount of sulfurizing agent, and the ratio of sulfurizing agent and hydrogen is important. Must be maintained properly. Furthermore, although such presulfurization is normally carried out over several days, this operation is temporary and is often not automated, requiring unusually complicated operations. , the burden on the operator is extremely heavy.

Therefore, it has been a challenge to omit pre-sulfurization or at least reduce the complexity of the operation.

Recently, a method has been proposed that can meet these demands.

In this method, a catalyst having the general formula R-
5(n)-R' (n is an integer of 3 to 20, RSR' is a hydrogen atom or an organic group having 1 to 150 carbon atoms per molecule) is impregnated with a polysulfide, and hydrogen gas The catalyst is heat-treated under a pressure of 65 to 275 C1o and 5 to 70 bar in the absence of
Publication No. 144).

According to this method, the polysulfide impregnated in the catalyst sulfurizes the active metal through heat treatment, so when pre-sulfiding is performed in the reactor, a sulfurizing agent and a diluent are not required, making the operation easier. Pre-sulfurization outside the reactor is also possible, in which case the pre-sulfurized catalyst can be loaded into the reactor and the hydrotreating operation can be started immediately.

The amount of polysulfide used above is the stoichiometric amount required to later sulfurize the entire active metal oxide (e.g. Coo, MoO) in the catalyst, diluted in a suitable organic solvent and impregnated. . However, since the above-mentioned polysulfide has a high viscosity, the viscosity tends to be high even when diluted with an organic solvent, and there is a problem that it becomes difficult to penetrate into the inside of the catalyst pores.

In addition, the catalyst used for presulfidation is prepared by molding and drying alumina hydrate made from sodium aluminate as a raw material, baking it to turn aluminum into γ-alumina, and then impregnating it with an aqueous solution of a water-soluble compound of an active metal. , dried, then heat treated, active metal? The active metal is supported in the oxide form on a support made of γ-alumina by mixing alumina hydrate and an aqueous solution of a water-soluble compound of the active metal, forming it, drying, and firing it. It is made in a way that

[Problem to be solved by the invention]

The present invention can be produced more easily and inexpensively than the conventional methods described above, can be used for hydrotreating without requiring pre-sulfurization treatment, and can be directly subjected to hydrotreating without heat treatment. A catalyst for hydrotreating hydrogen;
An object of the present invention is to provide a manufacturing method 2 thereof.

[Means to solve the problem]

Means for solving the problems according to the present invention are as follows.

1 Aluminum oxide, hydrated oxide, or both? The carrier material as the main component and the metals of group 6 and 8 of the periodic table.
A catalyst for hydrotreating hydrocarbons, comprising a mixture of at least one water-soluble compound of group metals and an amino-substituted mercaptan of a hydrocarbon having 1 to 15 carbon atoms and hydrogen.

2. A carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component, a metal of group 6 of the periodic table, or a metal of group 8 of the periodic table.
A hydrocarbon characterized by kneading a solution of at least one water-soluble compound of group metal and an amino-substituted mercaptan of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, molding, and then drying. A method for producing a catalyst for hydrotreating.

3. A carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component, a metal of group 6 of the periodic table, metal of group 8 of the periodic table, etc.
An aqueous solution of at least one of the water-soluble compounds of group metals is kneaded, molded and once dried, and a solution of an amino-substituted mercaptan, a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, is added to the dried molded product. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises impregnating and then drying again.

4. A solution of an amino-substituted mercaptan, a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, is kneaded with a carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component, and then formed. Hydrocarbon hydrogenation, characterized in that the dried molded product is impregnated with an aqueous solution of at least one of water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table, and then dried again. Method for producing treatment catalyst.

5 A carrier material mainly composed of one or both of aluminum oxide and hydrated oxide, and a metal of group 6 of the periodic table, metal of group 8 of the periodic table.
A catalyst for hydrogenation of hydrocarbons, comprising a mixture of at least one water-soluble compound of group metal, phosphoric acid, and an amino-substituted mercaptan of a hydrocarbon having 1 to 15 carbon atoms and hydrogen. .

6. A carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component, a metal of group 6 of the periodic table, or a metal of group 8 of the periodic table.
A characteristic feature is that a solution of at least one water-soluble compound of a group metal, phosphoric acid, and an amino-substituted mercaptan of a hydrocarbon having 1 to 15 carbon atoms and hydrogen is kneaded, shaped, and then dried. A method for producing a catalyst for hydrotreating hydrocarbons.

7. A carrier material mainly composed of one or both of aluminum oxide and hydrated oxide, a metal of group 6 of the periodic table, metal of group 8 of the periodic table, etc.
An aqueous solution of at least one of the water-soluble compounds of group metals and phosphoric acid is kneaded, molded and once dried, and the dried molded product is coated with a hydrocarbon amino acid consisting of carbon and hydrogen having 1 to 15 carbon atoms. Can it be dried again after impregnation with a solution of substituted mercaptans? A method for producing a catalyst for hydrotreating hydrocarbons.

8. A carrier material mainly composed of one or both of aluminum oxides and hydrated oxides, and metals of group 6 of the periodic table and metals of group 8 of the periodic table.
An aqueous solution of at least one of the water-soluble compounds of group metals is kneaded, shaped and once dried, and the dried shaped product is treated with phosphoric acid and an amino-substituted hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating a catalyst with a mercaptan and then drying it again.

9 A carrier material mainly composed of one or both of an oxide and a hydrated oxide of aluminum, a metal of group 6 of the periodic table, a metal of group 8 of the periodic table, etc.
A solution of at least one water-soluble compound of group metal and an amino-substituted mercaptan of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms is kneaded, shaped and once dried,
A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating the dried molded product with an aqueous solution of phosphoric acid and then drying it again.

10 A carrier material containing one or both of aluminum oxide and hydrated oxide as a main component, phosphoric acid and carbon number 1
A solution of a hydrocarbon amino-substituted mercaptan consisting of ~15 carbons and hydrogen is kneaded, molded and once dried, and the dried molded product is injected with water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table. 1. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises impregnating with an aqueous solution of at least one of the above and then drying the catalyst again.

11 A solution of an amino-substituted mercaptan, a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, is kneaded and shaped into a carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component. The dried molded product is impregnated with a solution of phosphoric acid and at least one of water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table, and then dried again. A method for producing a catalyst for hydrotreating hydrocarbons.

12 Knead an aqueous solution of phosphoric acid into a carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component, mold the mixture, dry it once, and apply the formula 6 of the periodic table to the dried molded product.
It is characterized by being impregnated with a solution of at least one water-soluble compound of a group metal or a group 8 metal and an amino-substituted mercaptan of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, and then drying again. Method for producing a catalyst for hydrogenation of hydrocarbons 0 The carrier material containing aluminum oxide as a main component used in the present invention may be γ-alumina or boehmite obtained by heat treating aluminum hydrate. Use. Boehmite is a hydrated oxide of aluminum with the structural formula Alo (OH). Chemically speaking, boehmite gel is obtained by dehydrating a gel-like substance obtained by hydrolyzing sodium aluminate using a filter press. , spray-dried dehydrated boehmite gel is used. Boehmite also occurs naturally as boehmite, which includes S10, F
eO,? e O, MgO, C! Contains aO and the like as impurities. When boehmite is heated, it dehydrates and changes in the order of r-alumina → δ-alumina → θ-alumina, and 1
At temperatures above 000C, it becomes α-alumina (furundum). In this way, boehmite is an intermediate between aluminum hydroxide and aluminum oxide, so is it active? It may be used in combination with r-alumina, or only γ-alumina may be used as the carrier material.

Further, silica or titania 2 may be used in combination with these.

Water-soluble compounds of group 6 metals in the periodic table include ammonium molybdate and ammonium tungstate of molybdenum and tungsten, which are generally used as active metals in catalysts, and water-soluble compounds of group 8 metals that are generally used as active metals in catalysts. Cobalt, nickel, cobalt nitrate, cobalt carbonate, nickel nitrate, and nickel carbonate are used as active metals. Molybdenum trioxide and tungsten trioxide can be converted into ammonium molybdate and ammonium tungstate using ammonia gas, and used as an aqueous solution thereof.

The usage amount of the amino-substituted mercaptan, which is a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, is based on a group 6 metal of the periodic table,
Group 8 metals exhibit high activity in hydrogenation scales in sulfide forms (e.g. MoS%WSsC0FJsNiS
) is preferably 1 to 3 times the amount of sulfur required to form.

If the amount used is less than 1 equivalent, the activity will not be fully utilized, and if it exceeds 3 equivalents, the activity will no longer be improved, so the amount used in this ratio is sufficient.

In the above amino-7-substituted mercaptan, the moiety that acts as a sulfurizing agent for the active metal is the 18H group in the molecule of the amino-substituted mercaptan, so when the number of carbon atoms in the hydrocarbon group increases, the sulfurizing agent in the molecule acts as a sulfurizing agent. Since there are relatively fewer active parts, it is not only uneconomical, but also excess carbon and hydrogen. This is not preferable since it will be included in the catalyst. Therefore, 2-aminoethanethio-k (HN(!HC
! HSH) and 4-aminothiophenol (HNo HS
It is preferable to use an amino-substituted mercaptan having a small number of carbon atoms such as H), and it is preferable to use a mercaptan having at most 15 carbon atoms.

It is preferable that phosphoric acid is contained in the catalyst in an amount of about 3% in terms of PO.

Is the catalyst produced by the production method of the present invention a dry catalyst? The raw material is packed into a reaction tower and subjected to hydrotreating of hydrocarbon oil. The water used in the process of producing the catalyst may be removed by entering the reaction tower and then drying it.

(Function) In the catalyst of the present invention, 2-aminoethanethiol or 4-aminothiophenol having a 13H group, which acts as a sulfiding agent, is supported on a carrier material together with a water-soluble compound of an active metal, so that hydrocarbon In the process of increasing the humidity to the hydrodesulfurization reaction temperature of Tomari, the active metal is converted to sulfide, and it can be directly subjected to the hydrodesulfurization reaction of hydrocarbon oil without any special preliminary sulfurization treatment. , the catalyst of the present invention exhibits excellent activity.The reason is not clear, but 2-aminoethanethiol and 4-aminothiophenol form a soluble coordination compound (metal mercaptide) with a water-soluble active metal compound. This is thought to be due to the fact that it is supported on the carrier material in a highly dispersed state.

〔Example〕

In all of the following examples, the catalyst was extruded.
It was molded into a cylinder shape with a diameter of 1.5 mm and a length of 3 to 5 mm.

In addition, activity evaluation was determined by hydrodesulfurization reaction of Kuwait atmospheric gas oil.

The properties of the atmospheric gas oil used in the reaction were as follows.

Specific gravity (15/4C) 0.844 sulfur
(Weight %) 1.13 Nitrogen (Weight p'
9m) 162 Distillation properties (initial boiling point, C) 2
03.3 (50 volume % point, 2m') 299.0
(End point, C) 391.8 The reaction was carried out using a flow reactor under the following reaction conditions.

Catalyst amount 3 ml Raw material oil liquid hourly space velocity 2. Ohr-' Reaction pressure (hydrogen pressure) 30°2 Reaction temperature 330C Hydrogen/oil conversion 300 Nt/1 oil passage time
The oil treated for 8 hours was sampled every 2 hours, the sulfur content was measured, and the desulfurization rate was determined. The desulfurization rate shown in the following examples is the average value of the desulfurization rate determined from the sulfur content of the treated oil sampled at the 4th hour, 6th hour, and 8th hour.

Example 1 74.6 g of 2-aminoethanethiol was added to 3 oomt of a solution prepared from 37.0 g of molybdenum trioxide, 15.8 g of cobalt carbonate (CO content 49.1% by weight), ammonia gas and water. A solution of metal mercaptide was prepared.

272 g of this metal mercaptide solution and spray-dried boehmite-type alumina powder (AIO 73.5% by weight), l!
:Tr: After kneading was performed in a Ni-Goo to obtain a mixture of alumina and metal mercaptide, it was molded and shaped.

This molded body was dried at 1000C for 16 hours to obtain Catalyst 1.

The breaking strength of Catalyst 1 was 1.5 or more.

The metal content of catalyst 1 is molybdenum converted to MoO.
5% by weight, cobalt is 4it% in terms of Coo, and the amount of 2-aminoethanethiol used is
It was 1.5 times the theoretical amount of sulfur required to form oS s C+O3.

The desulfurization rate of this catalyst 1 was 81.8%.

Example 2 To 300rnt of a solution prepared from 37.0gs of tungsten trioxide, 15.8g of cobalt carbonate (CO content 49.1% by weight), ammonia gas and water, 52.1g of 2-aminoethanethiol was added to form a metal mercaptide. It was made into a solution.

This metal mercaptide solution and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a Neegu and kneaded to obtain a mixture of alumina and metal mercaptide, which was then molded.

This molded body was dried at 100C for 16 hours to obtain catalyst 2'f.

The breaking strength of Catalyst 2 was 1.5 or more.

The metal content of catalyst 2 is tungsten converted to WO.
5% by weight, cobalt is 4% by weight when converted to Coo, and the amount of 2-aminoethanethiol used is 1% when converted to the theoretical amount of sulfur necessary for W, C, to become WS and OoS, respectively. It was .5 times as large.

The desulfurization rate of this catalyst 2 was 81.5%.

Example 3 37.0 g of molybdenum trioxide, fval carbonate (c
.

300 ml of an aqueous solution was prepared from 15.8 g of FF (containing 149.1% by weight), ammonia gas and water.

This solution and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a kneader and kneaded to obtain a mixture of alumina and gold aqueous solution, which was then molded.

This molded body was dried at t100C for 16 hours.

Next c.: 2-aminoethanethiol 74.
6g? After impregnating the entire amount of the ethanol solution (120 ml), it was dried at 100'C for 16 hours to obtain Catalyst 3.

The breaking strength of catalyst 3 was 1.5φm or more.

The metal content of catalyst 3 is molybdenum converted to MoO.
Cobalt is 4% by weight in terms of coO, and before using 2-aminoethanethiol, MOLco is 1.5% in terms of the theoretical amount of sulfur required to become Mo52 and CoS, respectively. It was double that.

The desulfurization rate of this catalyst 3 was 81.5%.

Example 4 272 of the boehmite type alumina powder used in Example 1
g and 300 ml of an aqueous solution containing 121.1 g of 4-aminothiophenol were placed in a kneader and kneaded to obtain a mixture, which was then molded.

This molded body was dried at 100C for 16 hours.

The total amount of this dry molded product includes 37.0 g of molybdenum trioxide, 15.8 g of cobalt carbonate (Co content 49.1% by weight),
150 m/! of a solution prepared from ammonia gas and water! (
A catalyst 4 was obtained by impregnating the entire amount of PH7,5)f and drying at 100c for 16 hours.The procedure was repeated twice.

The breaking strength of Catalyst 4 was 1.5φ or more.

The metal content of catalyst 4 is 15% by weight of molybdenum in terms of MoO and 4Mftk% of cobalt in terms of Coo.
The amount of 4-aminothiophenol used is Mo, C
o was 1.5 times the theoretical amount of sulfur required to form MoS 5CoS.

The desulfurization rate of this catalyst 4 was 81.3%.

Example 5 38.5 g of molybdenum trioxide, cobalt carbonate (c.

300 g of a solution prepared from 12.5 g of 85 wt. % phosphoric acid and water
ml, 77.6 g of 2-aminoethanethiol was added to prepare a solution of metal mercaptide containing phosphoric acid.

This metal mercaptide solution and 673 g of dehydrated boehmite-type alumina gel (AIO 29.7% by weight) (7) were placed in a heated niegu to evaporate excess water.
A mixture of alumina and metal mercaptide was obtained by heating and kneading at a temperature of 100 mL, and then molded.

This molded body was dried at 100C for 16 hours to obtain catalyst 5.

The breaking strength of Catalyst 5 was 1.5 to 9Al1 or more.

The metal content of catalyst 5 is molybdenum converted to MoO.
5% by weight, cobalt is 4% by weight in terms of coo, phosphorus is 3% by weight in terms of po, and the amount of 2-aminoethanethiol used is MoSOO, respectively.
The theoretical amount of sulfur required to form CoS is 1.
It was 5 times more.

The desulfurization rate of this catalyst 5 was 81.8%.

Example 6 38.5 g of molybdenum trioxide, charcoal (((
! 0 content 49.1% by weight) 16.4 g, 85
A solution prepared from 12.5 g of phosphoric acid and water 30% by weight
77.6 g of 2-aminoethanethiol was added to 0 ml to prepare a solution of metal mercaptide containing phosphoric acid.

This metal mercaptide solution and 272 g of the boehmite-type alumina powder used in Example 1 were put into a kneader and kneaded to obtain a mixture of alumina and metal mercaptide, which was then molded.

This molded body was dried at 10oC for 16 hours and the catalyst 6? Obtained.

The breaking strength of catalyst 6 was 1.5 to - or more.

The metal content of catalyst 6 is molybdenum converted to MoO.
5% by weight, cobalt is 4% by weight in terms of cOo, phosphorus is 3% by weight in terms of P2O3, and the amount of 2-aminoethanethiol used is MoS.
It was 1.5 times the theoretical amount of sulfur required to reach % OoS.

The desulfurization rate of this catalyst 6 was 82.5%.

Example 7 38.5 g of molybdenum trioxide, cobal carbonate) (
(1!

Content 49.1% by weight) 16.4 g, 85% by weight
12.5 g of phosphoric acid and 3 oor of a solution prepared from hydrochloric acid
125.9 g of nl di,4-aminothiophenol was added to form a solution of metal mercaptide containing phosphoric acid.

This metal mercaptide solution and γ-alumina powder 20
A mixture of alumina and metal mercaptide 3 was obtained by putting 0 g into a kneader and performing two-dimensional molding.

This molded body was dried at 100C for 16 hours to obtain catalyst 7.

The breaking strength of Catalyst 7 was 1.5 to 9β fission or higher.

The metal content of catalyst 7 is molybdenum converted to MoO.
Cobalt is 4% by weight in terms of 000, phosphorus is 3% by weight in terms of PO, and the amount of 4-aminothiophenol used is Mo s C! o is MoS
The theoretical amount of sulfur required to form 5CoS is 1.
It was 5 times more.

The desulfurization rate of this catalyst 7 was 83.8%.

Example 8 Molybdenum trioxide 38.5 g, carbonate collar #) (C
.

300 g of a solution prepared from 16.4 g of phosphoric acid (49.1% by weight), 12.5 g of 85% by weight phosphoric acid and water
125.9 g of 4-aminothiophetool was added to m/ to prepare a solution of metal mercaptide containing phosphoric acid.

This metal mercaptide solution and 673 g of the boehmite-type alumina gel used in Example 5 were placed in a heated knead and heated at 95 C to evaporate excess water to obtain a mixture of alumina and metal mercaptide. After that, it was molded.

This molded body was dried at 100C for 16 hours to obtain catalyst 8.

The breaking strength of Catalyst 8 was 1,5 kg, 7 hyn or more.

The metal content of catalyst 8 is molybdenum is 15% by weight in terms of MOo, L cobalt is 4% by weight in terms of Coo, phosphorus is 3% by weight in terms of PO, and the amount of 4-aminothiophenol used is are MOlCO and MoS s
The theoretical poison of sulfur required to become CoS is 1.5
It was double that.

The desulfurization rate of this catalyst 8 was 82.6%.

Example 9 Molybdenum trioxide 38.5 g, cobal carbonate) (C
.

300 g of a solution prepared from 12.5 g of 85 wt. % phosphoric acid and water
ml was added with 125.9 g of 4-aminothiophenol to prepare a solution of metal mercaptide containing monophosphoric acid.

This metal mercaptide solution and 272 g of the boehmite-type alumina powder used in Example 1 were put into a kneader and kneaded to obtain a mixture of alumina and metal mercaptide, which was then molded.

This molded body was dried at 100C for 16 hours to obtain catalyst 9.

The breaking strength of Catalyst 9 was 1.5 forces or more.

The metal content of catalyst 9 is molybdenum converted to MoO.
5% by weight, cobalt is 4% by weight in terms of CoO, phosphorus is 3% by weight in terms of po, and the amount of 4-aminothiophenol used is Mo5Co, respectively.
In terms of the theoretical amount of sulfur required to become OO3, it is 1.
It was 5 times more.

The desulfurization rate of this catalyst 9 was 83.5%.

Example 1 300 ml of a solution prepared from 57.6 g of molybdenum trioxide, 20.9 g of nickel carbonate (N1 content 43.3% by weight), 30.4 g of 85% by weight phosphoric acid and water
2-aminoethanethiol IIQ, 1 g was added to
A solution of metal mercaptide containing phosphoric acid was prepared.

This metal mercaptide solution and 272 g of the boehmite-type alumina powder used in Example 1 were put into a kneader and kneaded to obtain a mixture of alumina, phosphoric acid, and metal mercaptide, which was then molded.

This molded body was dried at 100C for 16 hours to obtain catalyst 10.

The breaking strength of catalyst 10 was 1.51c9 Ats or more.

The metal content of catalyst 10 is molybdenum is 20% by weight in terms of MoO, nickel is 20% by weight in terms of NiO, phosphorus is 6.5% by weight in terms of PO, and the amount of 2-aminoethanethiol used. is MOlNl respectively MoS
, calculated as the theoretical amount of sulfur required to form NiS.
．． It was 5 times more.

The desulfurization rate of this catalyst 10 was 77.8%.

Example 11 38.5 g of molybdenum trioxide, Hval carbonate) (G.

content 49.1% by weight) 16-4 g N 12.5 g of 85% by weight phosphoric acid and 300 ml from water! An aqueous solution of was prepared.

This solution and 272 g of the boehmite-type alumina powder used in Example 1 were put into a nigu and kneaded to obtain a mixture of alumina, metal aqueous solution, and phosphoric acid.
Molded.

This molded body was dried at 100 U for 16 hours.

Next, the dried product was impregnated with 115 m/total amount of an ethanol solution containing 77.6 g of 2-aminoethanethiol.
After drying at r for 16 hours, catalyst 11 was obtained.

The breaking strength of catalyst 11 was 1.5 Ta)/km or more.

The metal content of catalyst 11 is molybdenum 15% by weight in terms of MOO, cobalt 4% by weight in terms of CoO, phosphorus 3% by weight in terms of po, and the amount of 2-aminoethanethiol used. are Mo5Co and MoS5 respectively.
The theoretical bond of sulfur required to become CoS is 1.5
It was double that.

The desulfurization rate of this catalyst 11 was 82.0%.

Example 12 Molybdenum trioxide 3s, s g % Charcoal H Cobalt (C
300 ml of a solution prepared from 16.4 g (O content 49.1% by weight), ammonia gas and water, and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a whole nigu and kneaded to form a mixture. After obtaining, it was molded.

This molded body was dried at 100C for 16 hours.

Next, 12.5 g of 85% by weight phosphoric acid and 2
The catalyst was impregnated with 120 ml of an ethanol solution containing 77.6 g of -aminoethanethiol and then dried at 100C for 16 hours to obtain catalyst 12.

The breaking strength of the catalyst 12 is 1.51=9. It was Al1 or more.

The metal content of catalyst 12 is molybdenum is 15% by weight in terms of MoO, cobalt is 4% by weight in terms of Coo, phosphorus is 3% by weight in terms of PO, and the amount of 2-aminoethanethiol used is are MOlCO and MoS, respectively.
C! In terms of the theoretical amount of sulfur required to become as, it is 1.
It was 5 times more.

The desulfurization rate of this catalyst 12 was 81.9%.

Example 13 Molybdenum trioxide 38.5 g % Charcoal e Cobalt (c
.

125.9 g of 4-aminothiophenol was added to 300 ml of a solution prepared from 16.4 g (content 49.1% by weight), ammonia gas, and water to obtain a solution of metal mercaptide.

This metal mercaptide solution and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a Neegu and kneaded to obtain a mixture, which was then molded.

This molded body was dried at ioo, C for 16 hours. Next, add 5 g of an aqueous solution containing 12.5 g of 85% by weight phosphoric acid to the dried product.
After impregnating a total amount of 0 ml, it was dried at 100 C for 16 hours to obtain catalyst 13.

The breaking strength of Catalyst 13 was 1.5 to 9/gILs or higher.

The metal content of the catalyst 13 is as follows: molybdenum is 15% by weight in terms of MoO, cobalt is 4% by weight in terms of COO,
The amount of phosphorus used is 3% by weight calculated as PO, and the amount of 4-aminothiophenol used is MoS 1.
The theoretical amount of sulfur required to form CoS is 1.5
It was double that.

The desulfurization rate of this catalyst 13 was 83.2%.

Example 14 272 of the boehmite type alumina powder used in Example 1
g, and 3 oomg of an aqueous solution containing 77.6 g of 2-aminoethanethiol and 12.5 g' of 85% by weight phosphoric acid were placed in a niegu and kneaded to form a mold.

This molded body F was dried at 100 rpm for 16 hours.

38.5 g of molybdenum trioxide was added to the entire dry molded body.
Fuvalt carbonate (Co content 49.1% by weight) 16.4
g.

Catalyst 14 was obtained by repeating twice the operation of impregnating the entire amount of 150ml of a solution prepared from ammonia gas and water and drying at 100C for 16 hours.

The breaking strength of catalyst 14 was 1.5ψ or more.

The metal content of the catalyst 14 is as follows: molybdenum is 15% by weight in terms of MOO, cobalt is 4% by weight in terms of CoO,
The amount of phosphorus is 3% by weight calculated as po, and the amount of 2-aminoethanethiol used is Mo.

The amount was 1.5 times the theoretical amount of sulfur required for each CO to become MoS 5OoS.

The desulfurization rate of this catalyst 14 was 81.8%.

Example 15 272 of the boehmite type alumina powder used in Example 1
g and 115 ml of an aqueous solution containing 77.6 g of 2-aminoethanethiol were placed in a Neegoo and kneaded to form a mold. This molded body was dried at 100C for 16 hours.

The entire view of this dry molded body shows 38.5 g of molybdenum trioxide.
Cobalt carbonate (co content 49.1% by weight) 16.4g
.

100 ml of a solution prepared from 12.5 g of 85% by weight phosphoric acid and water! After impregnating the entire amount, 16 at 100C
After drying for hours, catalyst 15 was obtained.

The crushing strength of catalyst 15 was 1.5 kg or more than As.

The metal content of the catalyst 15 is molybdenum is 15% by weight calculated as MOO34, and funocult is C! The amount of 2-aminoethanethiol used is converted to the theoretical amount of sulfur required for MOlGo to become MO3SCoS. It was 1.5 times.

The desulfurization rate of this catalyst 15 was 81.6%.

Example 16 272 of the boehmite type alumina powder used in Example 1
g and 30 g of an aqueous solution containing 12.5 g of 85w@% phosphoric acid.
A 0 ml sample was placed in a niigoo and kneaded to form a shape.

This molded body was dried at 100C for 16 hours.

38.5 g of molybdenum trioxide was added to the entire dry molded body.
Hupart carbonate (Co content @ 49.1% by weight) 16.4g
.

After impregnating the entire amount of metal mercaptide solution No. 250-me obtained by adding 77.6 g of 2-aminoethanethiol to a solution prepared from ammonia gas and water, 100C
After drying for 16 hours, catalyst 16 was obtained.

The breaking strength of catalyst 16 was 1.5ψ or more.

The metal content of the catalyst 16 is as follows: molybdenum is 15% by weight in terms of MoO, cobalt is 4% by weight in terms of 000,
Phosphorus is 31% in terms of PO, and the amount of 2-aminoethanethiol used is Mo and C.

was 1.5 times the theoretical amount of sulfur required to form Mo5SCO8.

The desulfurization rate of this catalyst 16 was 81.5%.

Conventional example (1) γ-alumina is used as a carrier and MoO is 15% by weight.
A commercially available catalyst (KF-742 manufactured by Nippon Ketchien Co., Ltd.) containing 4% of Coo.

This catalyst was subjected to the following pre-sulfurization treatment.

Sulfurized oil 3% by weight n-butyl mercaptan/Kuwaite normal pressure gas oil Catalyst amount 3 ml Raw material oil liquid hourly space velocity 2. Ohr-" Reaction pressure (hydrogen pressure) 30◆K2 Reaction temperature 316 tl' Hydrogen/oil ratio 300 Ml/1 oil passage time
g hr The activity of this pre-sulfurized catalyst was evaluated in the same manner as in the examples, and the desulfurization rate was 82.4%.

(2) Specific surface area 280 m'/g % Pore volume 0.
Molybdenum trioxide 19.2 g, Co content 49.1 to 100 g T-alumina molded carrier of 75 m/7 g.
Weight% cobalt carbonate 8.2g, 85% phosphoric acid 6
．． Impregnated with 80ml of impregnating solution prepared from 2g and water,
After drying at 10C for 16 hours, baking at 500C for 2 hours to obtain 15% by weight of MO0, 4% by weight of 0004, and 3% by weight of PO.
A containing catalyst was obtained.

This catalyst was subjected to pre-sulfurization in the same manner as (+1) above, and its activity was evaluated in the same manner as in the example. As a result, the desulfurization rate was 80.
It was 4%.

[Effect of the invention] The above conventional catalyst requires 8 hours for pre-sulfurization treatment, and the catalyst described in Japanese Patent Publication No. 61-11044 also requires at least 1 hour of calcination treatment after being impregnated with a sulfurizing agent. However, the catalyst of the present invention and the catalyst produced by the method for producing the same do not require presulfidation and can be used directly for hydrogenation treatment without the need for calcination, providing a more economical catalyst than conventional catalysts. Monkey.

Applicant: Sumitomo Metal Mining Co., Ltd. , -8 ,of ゝ--7

Claims (1)

[Scope of Claims] 1. A carrier material containing either or both of an oxide and a hydrated oxide of aluminum as a main component, and a metal of group 6 of the periodic table, metal of group 8 of the periodic table.
A catalyst for hydrotreating hydrocarbons, comprising a mixture of at least one water-soluble compound of group metals and an amino-substituted mercaptan of a hydrocarbon having 1 to 15 carbon atoms and hydrogen. 2. A carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component, a metal of group 6 of the periodic table, or a metal of group 8 of the periodic table.
A hydrocarbon characterized by kneading a solution of at least one water-soluble compound of group metal and an amino-substituted mercaptan of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, molding, and then drying. A method for producing a catalyst for hydrotreating. 3. A carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component, a metal of group 6 of the periodic table, metal of group 8 of the periodic table, etc.
An aqueous solution of at least one of the water-soluble compounds of group metals is kneaded, shaped and once dried, and a solution of an amino-substituted mercaptan, a hydrocarbon consisting of carbon having 1 to 15 carbon atoms and hydrogen, is added to the dried shaped product. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises impregnating and then drying again. 4. A solution of an amino-substituted mercaptan, a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, is kneaded and formed into a carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component. Hydrocarbon hydrogenation, characterized in that the dried molded product is impregnated with an aqueous solution of at least one of water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table, and then dried again. Method for producing treatment catalyst. 5 A carrier material mainly composed of one or both of aluminum oxide and hydrated oxide, and a metal of group 6 of the periodic table, metal of group 8 of the periodic table.
A catalyst for hydrogenation of hydrocarbons, comprising a mixture of at least one water-soluble compound of group metal, phosphoric acid, and an amino-substituted mercaptan of a hydrocarbon having 1 to 15 carbon atoms and hydrogen. . 6. A carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component, a metal of group 6 of the periodic table, or a metal of group 8 of the periodic table.
A solution of at least one water-soluble compound of group metal, phosphoric acid, and an amino-substituted mercaptan of a hydrocarbon having 1 to 15 carbon atoms and hydrogen is kneaded, shaped, and then dried. A method for producing a catalyst for hydrotreating hydrocarbons. 7. A carrier material mainly composed of one or both of aluminum oxide and hydrated oxide, a metal of group 6 of the periodic table, metal of group 8 of the periodic table, etc.
An aqueous solution of at least one of the water-soluble compounds of group metals and phosphoric acid is kneaded, molded and once dried, and the dried molded product is coated with a hydrocarbon amino acid consisting of carbon and hydrogen having 1 to 15 carbon atoms. 1. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises impregnating with a solution of substituted mercaptan and then drying again. 8. A carrier material mainly composed of one or both of aluminum oxides and hydrated oxides, and metals of group 6 of the periodic table and metals of group 8 of the periodic table.
An aqueous solution of at least one of the water-soluble compounds of group metals is kneaded, shaped and once dried, and the dried shaped product is treated with phosphoric acid and an amino-substituted hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating a catalyst with a mercaptan and then drying it again. 9 A carrier material mainly composed of one or both of an oxide and a hydrated oxide of aluminum, a metal of group 6 of the periodic table, a metal of group 8 of the periodic table, etc.
A solution of at least one water-soluble compound of group metal and an amino-substituted mercaptan of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms is kneaded, shaped and once dried,
A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating the dried molded product with an aqueous solution of phosphoric acid and then drying it again. 10 A carrier material containing either or both of aluminum oxide and hydrated oxide as a main component, phosphoric acid, and a carbon atom having 1 to 1 carbon atoms.
A solution of amino-substituted mercaptan, a hydrocarbon consisting of 15 carbons and hydrogen, is kneaded, molded and once dried, and the dried molded product is injected with water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table. 1. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises impregnating with an aqueous solution of at least one type of catalyst and then drying the catalyst again. 11 A solution of an amino-substituted mercaptan, a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, is kneaded and shaped into a carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component. The dried molded product is impregnated with an aqueous solution of phosphoric acid and at least one of water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table, and then dried again. A method for producing a catalyst for hydrotreating hydrocarbons. 12 An aqueous solution of phosphoric acid is kneaded into a carrier material containing either or both of an oxide of aluminum and a hydrated oxide as a main component, and the molded product is once dried. , impregnated with a solution of at least one water-soluble compound of a Group 8 metal and an amino-substituted mercaptan of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, and then drying again. A method for producing a catalyst for hydrotreating hydrocarbons.