JPS63302952A - Catalyst for conversion of hydrocarbon - Google Patents

Abstract

PURPOSE:To shorten the time required for initiating a reaction of a hydrocarbon converting catalyst by depositing an active metal component and an organosulfur compd. having >=100 deg.C b.p. and >=one active mercapto group in a molecule to an inactive heat resistant carrier. CONSTITUTION:After depositing a metal salt which functions as active seed by means of impregnation or kneading, etc. to an inactive heat resistant carrier, the carrier is dried and molded, and a metal oxide is deposited by calcining the molded carrier. Then, at least one kind of organosulfur compd. having >=100 deg.C b.p. and >=one active mercapto group in one molecule is deposited by spraying or impregnation to the carrier to obtain thus a hydrocarbon converting catalyst. Examples for said organosulfur compd. are octyl mercaptan, dodecyl mercaptan, diethylenether dithiol, isooctyl thioglycolate, etc.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to hydrotreating of hydrocracking or hydrodesulfurization of hydrocarbon feedstocks, furthermore, hydrogenation of hydrocarbon feedstocks,
It relates to catalysts for hydrocarbon conversion, including alkylation, isomerization, etc.

[Prior Art] Catalysts used for hydrotreating hydrodesulfurization, hydrocracking, etc. of hydrocarbon fractions are generally produced by supporting metal active components on a suitable carrier. Since calcination is usually performed as the final step, the metal active component is present in the catalyst in the form of an oxide with poor catalytic activity.

Therefore, when such a catalyst is used in a hydrocarbon conversion reaction, a so-called pre-sulfiding operation is required in advance to sulfurize and activate the metal active component in the catalyst.

As a pre-sulfiding method, a method is known in which a reactor is filled with a catalyst in which the metal active component is in the form of an oxide, and hydrogen sulfide gas and hydrogen gas are supplied to the reactor to sulfurize the metal active component of the catalyst. There is. Furthermore, a method has also been adopted in which a hydrocarbon oil such as light oil and hydrogen are supplied instead of hydrogen sulfide gas to pre-sulfurize the catalyst. In addition, sulfur compounds such as carbon disulfide, dimethyl sulfide (DMS), and dimethyl disulfide (DMDS) are also added to the hydrocarbon oil for presulfidation. Furthermore, JP-A No. 60-51547
As seen in the publication, a catalyst containing a metal active component is impregnated with a polysulfide of R-3(n)-R' (n=3 to 20), and then heated at a temperature of 200°C or less in a hydrogen stream. A method of activating (presulfiding) by heating has also been proposed.

[Problems to be Solved by the Invention] Among the conventional catalyst presulfurization methods described above, the method using hydrogen sulfide gas has the disadvantage that it is difficult to handle because this gas is toxic. . Furthermore, the method using hydrocarbon oil such as light oil and hydrogen requires a relatively long time for pre-sulfiding the catalyst and also requires a large amount of hydrocarbon oil.

In addition, since the catalyst must be maintained at a high temperature for a long period of time during pre-sulfurization, there is a concern that the original catalytic activity may be impaired. However, these problems can be solved by adding a sulfiding agent such as carbon disulfide, DMS, or DMDS to the hydrocarbon oil. However, these sulfiding agents are generally not only expensive, but also require equipment for storage and injection into the reactor.

Since the polysulfide proposed in JP-A-60-51547 has a high viscosity, it is necessary to dilute the polysulfide with an appropriate solvent to impregnate the catalyst.

The present invention aims to solve the various problems of the pre-sulfurization method using conventional catalysts as described above, and does not require a special pre-sulfurization process.In other words, the catalyst is packed in a reactor. When the temperature of the reactor is raised to the conversion reaction temperature of the hydrocarbon feedstock, the catalyst is sulfurized during the heating process, providing a catalyst that can carry out the hydrocarbon conversion reaction immediately after the temperature is raised to a predetermined temperature. do.

[Means for Solving the Problems] Therefore, the catalyst for hydrocarbon conversion according to the present invention has a metal active component in an inert heat-resistant carrier and at least one active mercapto group in one molecule, and has a boiling point is characterized by supporting an organic sulfur compound having a temperature of 100°C or higher.

[In the catalyst described in the Detailed Description of the Invention, the carrier component and the metal active component include A1□O1,5, which is commonly used in conventional hydrocarbon conversion catalysts.
A carrier component such as in2.5102-A120° and a metal active component selected from Groups 1B, VA, VIA, and 1 of the periodic table can all be used.

For example, as a catalyst for hydrotreating hydrocarbon fractions, a group VIA catalyst such as molybdenum, tungsten, etc. Generally, metals and/or Group Ⅰ metals such as iron, nickel, and cobalt are supported as oxides in an amount of 8 to 25% by weight based on the total weight of the catalyst, but the catalyst of the present invention also supports these carriers and Metal components can be used.

The organic sulfur compound supported on the catalyst of the present invention is 1
It must have at least one active mercapto group in its molecule and have a boiling point of 100°C or higher. Specific examples of such organic sulfur compounds include alkyl mercaptans such as octyl mercaptan, dodecyl mercaptan, dimercaptopropane, and dimercaptobutane; polyalkylene ether polythiols such as diethylene ether dithiol and triethylene ether dithiol; isooctyl thio Glycolate, 2-ethylhexylmercaptopropionate, ethylene glycol dimercaptopropionate, butanediol dimercaptoacetate, trimethylolpropane tris-
Esters of monohydric to polyhydric alcohol and thiocarboxylic acid, exemplified by mercaptoacetate, pentaerythritol tetrakis-3-mercaptopropionate, etc.;
Examples include esters of mercapto alcohol and carboxylic acid such as mercaptoethyl acetate and dimercaptoethyl adipate; and thioethers such as diethylene thioether thiol.

The catalyst of the present invention is carried on a suitable inert heat-resistant carrier.

It is generally prepared by a procedure in which a suitable metal active component is loaded and fired, and then the organic sulfur compound of the present invention is loaded thereon.

Here, the steps from supporting the metal active component on the carrier to calcination are not substantially different from conventional catalyst preparation methods, and can be adopted in the present invention as well. For example, a method can be adopted in the present invention in which a metal salt to be an active species is supported on a carrier by means such as an impregnation method or a kneading method, and then this is dried, molded, and fired. The metal active component of is usually an oxide. Therefore, the catalyst of the present invention can also be prepared by supporting the above-mentioned sulfur compound on a conventional hydrocarbon conversion catalyst in which the metal active component is in the form of an oxide.

There are no particular restrictions on the method of supporting the organic sulfur compound, but the method for supporting the organic sulfur compound is as follows:
It is convenient and preferable to impregnate the seed or two or more types by any method such as a spray method or a dipping method. For impregnation, the organic sulfur compound can be used as it is, and there is no need to dilute it with a solvent. Also, after impregnation, no post-treatment such as heating is required. When the organic sulfur compound of the invention is used, the amount of sulfur required to maintain the desired sulfidity of the catalyst is sufficient to provide a sufficient amount of sulfur to completely penetrate into the pores of the catalyst.

By the way, it is in the catalyst for hydrocarbon conversion.

Even in the case of catalysts for hydrotreating hydrocarbon fractions that require a relatively high degree of sulfidation, the amount of sulfur required to obtain the degree of sulfidity that satisfies a given initial activity is based on all of the metal active components in the catalyst. It is sufficient to have at least about 70% of the stoichiometric amount to convert sulfide to sulfide. On the other hand, since hydrocarbon conversion catalysts generally have a large pore volume, it is possible to provide the above-mentioned amount of sulfur to the catalyst with a small amount of organic sulfur compound that can completely penetrate into the pores. be.

Therefore, the surface of the catalyst impregnated with the organic sulfur compound is not in a so-called "wet" state, so there is no need for special drying. Since it does not deteriorate at ambient temperature and the organic sulfur compound does not volatilize, it can be stored or transported normally.

[Function] In the conventional hydrocarbon catalytic conversion process, after filling a reactor with a catalyst and prior to supplying raw material hydrocarbon to it,
It is customary to sulfurize the catalyst by supplying a sulfurizing agent such as hydrogen sulfide gas or sulfur-containing hydrocarbon oil and hydrogen gas to a reactor, but when the catalyst of the present invention is used, this pre-sulfurization As in the case of a catalytic reaction process that uses a catalyst that does not require any steps, that is, does not require presulfidation, 1. If the catalyst of the present invention is charged into a reactor and then heated to a predetermined reaction temperature, During the temperature raising process, the sulfurization reaction progresses and the catalyst is sulfurized.9 Therefore, after the temperature of one reactor is raised, the raw material hydrocarbon can be immediately supplied to the reactor to start the desired reaction. In this case, the catalyst does not need to be completely sulfurized before the conversion reaction starts, and even if some unsulfurized portion remains, the unsulfurized portion will be sulfurized as the conversion reaction progresses.

Next, a specific example in which the catalyst of the present invention is applied to a hydrodesulfurization method will be described. After filling a reactor with the catalyst of the present invention, which is a conventional hydrodesulfurization catalyst supported with an organic sulfur compound, the temperature of the catalyst bed is raised to about 150 to 200°C while flowing an inert gas such as nitrogen through it. . Next, the supply gas is switched to hydrogen and the pressure is increased to a predetermined reaction pressure, and at the same time the temperature is increased to a constant reaction temperature of 15 to 15 b. In the process up to this point, the hydrodesulfurization catalyst in the reactor is presulfurized and activated. Thereafter, process parameters other than temperature and pressure, which are maintained at predetermined values, are set to predetermined values, and the raw hydrocarbon fraction is fed to the reactor to carry out the intended hydrodesulfurization treatment.

Note that the supply of the hydrocarbon fraction can also be started during the temperature raising process using hydrogen gas. The process parameters for hydrodesulfurization of typical hydrocarbon fractions are:
Temperature 300-450℃, hydrogen partial pressure 10-200kg/a
J, liquid space velocity 0.1 to 10 hr-1, water λ3/oil ratio 1
00-200ON rn'/KI2 etc. are generally adopted.

The catalyst for hydrocarbon conversion of the present invention uses a sulfide catalyst such as the above-mentioned hydrodesulfurization method of hydrocarbon fractions, hydrocracking method of hydrocarbons, hydrogenation method, alkylation method, isomerization method, etc. It can also be used for reactions.

[Example] Example I AI, O, Mob, 10.0wt%, Co02.0
A hydrodesulfurization catalyst on which NiO1, O% and lt% were supported was prepared by a conventional method.

Approximately 720+ aQ of trimethylolpropane tris-mercaptoprobionate was taken, and 1 kg of the above catalyst was immersed in it. Slow stirring was continued until the sulfur compound sufficiently penetrated into the pores of the catalyst, all of the sulfur compound was impregnated into the catalyst particles, and the catalyst surface was no longer "wet." The amount of sulfur supported on the catalyst thus obtained was 10.8 wt% as S. This catalyst will be referred to as catalyst A.

Example 2 2-ethylhexyl-3-mercaptopropionate and diethylenethioether dithiol (SH-C,) were added to the same hydrodesulfurization catalyst as in Example 1 in the same manner as in Example 1.
I, -3-C, 11, -5H) and dodecyl mercaptan, respectively. These are designated as catalysts B, C and D. The amount of sulfur supported as S was 11.3 wt% for catalyst B, 21.4 vt% for catalyst C, and 11.8 tit% for catalyst.

Example 3 A hydrodesulfurization reaction test for each of catalysts A, B, C, and D was carried out in the following manner.

A high-pressure reactor with an inner diameter of 19 mm and a length of 1.8 m was filled with the catalyst, and the temperature was raised to 200° C. while flowing nitrogen gas. After that, nitrogen gas was switched to hydrogen gas, and 150kg/aJ
The hydrogen gas and feedstock oil were each pressurized to 70%
ON ry? The reaction temperature was increased to a predetermined reaction temperature at a temperature increase rate of 20° C./hr while supplying the reactor at a rate of 1.0 KI2/hr and 1.0 KI2/hr.

After reaching the predetermined reaction temperature, LH3V Q, 2hr-
”, hydrogen/oil ratio 70ONrn'/KQ, hydrogen partial pressure 150
The reaction test was conducted while maintaining the steady condition of kg/cd.

The properties of the atmospheric distillation residue oil used as the raw material oil are shown below.

Specific gravity (15/4℃) 0.960 Viscosity (50℃)
4, 53cst sulfur 2.2
83 wt% Nitrogen 2220 ppm Asphaltene 2.1 wt% Conradson carbon 9.9 wt% Metal (Ni + V) 70 ppm + Example 4 After filling the same reactor as Example 3 with catalyst A and raising the temperature to 180 ° C. while flowing nitrogen gas. , nitrogen gas was switched to hydrogen gas, and the pressure was increased to 150 kg/cd. Next, while supplying hydrogen gas to the reactor at a rate of 70 ONrn'/hr, the temperature was raised to a predetermined reaction temperature at a rate of 20° C./hr. Thereafter, under the same steady conditions as in Example 3, a hydrodesulfurization reaction test was conducted using the same feedstock oil as in Example 3.

Comparative Example The hydrodesulfurization catalyst prepared in Example 1 was charged into the same reactor as in Example 3 without supporting a sulfur compound, and the temperature was raised to 180°C while flowing nitrogen gas. The gas was switched to hydrogen gas and the pressure was increased to 150 kg/aJ. After that, add hydrogen gas and diesel oil to 40O each.
2 while flowing at N rn'/hr, 1.0 KQ/hr.
The temperature was raised to 80°C at a rate of 30°C/hour. then 2
The catalyst was presulfurized by maintaining the temperature at 80° C. for 48 hours.

After the sulfurization was completed, the gas oil was switched to the feedstock oil used in Example 3, and the hydrodesulfurization reaction test was conducted under the same conditions as Example 3 by increasing the temperature to the predetermined reaction temperature at a rate of 30°C/hour. did.

Table 1 shows the experimental results of Examples 3 and 4 and Comparative Example.

(Left below) As is clear from the results shown in Table 1, the hydrodesulfurization catalyst of the present invention is equivalent to or superior to the hydrodesulfurization catalyst presulfurized by the conventional method, even without performing a presulfurization operation. Demonstrates catalytic performance.

[Effects of the Invention] The catalyst of the present invention can sulfurize and activate the catalyst during the temperature raising process of the catalyst bed when starting a normal catalytic conversion reaction. There is no need to provide a special sulfurization process. Therefore, it is possible to shorten the time until the start of one reaction, and furthermore, there is no need for a sulfiding agent such as light oil for sulfurization, so if the catalyst of the present invention is used, the cost required for hydrocarbon conversion can be significantly reduced. You can get benefits such as:

Claims (1)

[Claims] 1. An inert heat-resistant carrier containing a metal active component and at least one active mercapto group in one molecule, with a boiling point of 100°C
A catalyst for hydrocarbon conversion characterized by supporting an organic sulfur compound as described above.