JP2001131561A - Method for hydrogenating heavy oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrially extremely advantageous method for hydrogenating a heavy oil, capable of suppressing crystal growth of iron sulfide fine particle in a hydrogenation treatment reaction and efficiently hydrogenating unfavorable components such as metal compounds of asphaltene, vanadium, nickel, etc., and sulfur and nitrogen compounds, etc., contained in a heavy oil with a small amount of a catalyst. SOLUTION: In this method for hydrogenating a heavy oil using hydrogen sulfide and an iron-based catalyst, a colloidal iron dispersion of dispersion in oil type is used as the iron-based catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an improved method for hydrotreating heavy oil using hydrogen sulfide and an iron-based catalyst.

[0002]

2. Description of the Related Art As is well known, petroleum and coal-based heavy oils include a high molecular weight and highly aromatic component called asphaltenes, metal compounds such as vanadium and nickel, and compounds such as sulfur and nitrogen. Contains many components that are not desirable for quality. As a method for removing these components, a hydrotreating method of contacting a heavy oil with a catalyst in a high-pressure hydrogen atmosphere has been widely used. This hydrotreating method is roughly classified into a fixed bed method or a suspension bed method using a granular catalyst, and a slurry method using a powdery catalyst or an oil-soluble metal compound catalyst and hydrogen sulfide. It is said that the slurry method is suitable for the hydrotreating of heavy oil with extremely large amounts of oil. Many studies and patents have been made on the catalyst used in this slurry method. For example, a method using an oil-soluble iron compound, Mc using an oil-soluble molybdenum compound
Oura process, Aurab using vanadium compound
On process, C using coal powder impregnated with iron sulfate
Excellent technologies such as an ANMET process and an SOC process using a combination of a transition metal compound and an ultrafine powder have been proposed. Among them, a method using hydrogen sulfide and an oil-soluble iron-based catalyst is an industrially extremely promising method in terms of price and safety, and many studies have been made as, for example, a catalyst for a coal liquefaction reaction. . In this method, an oil-soluble iron-based catalyst reacts with hydrogen sulfide in a reaction system to form highly dispersed iron sulfide fine particles exhibiting a catalytic activity, and the high catalytic activity of the iron sulfide fine particles forms Hydroprocessing of heavy oil is performed. However, as mentioned in these studies, the iron sulfide fine particles obtained by the reaction of this oil-soluble iron-based catalyst with hydrogen sulfide have a small particle diameter in the early stage of the reaction and exhibit high catalytic activity. Aggregation and crystal growth of these fine particles occur as the particle size increases, and the particle size increases.
There are problems such that the initial catalyst activity cannot be obtained, and that the amount of the catalyst must be increased in order to enhance the desired catalytic effect.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to overcome the above-mentioned problems of the prior art, and can suppress the crystal growth of iron sulfide fine particles during a hydrogenation reaction, and can use a small amount of catalyst. Hydrogenation of heavy oil which is industrially extremely advantageous, which can efficiently hydrotreat asphaltene, metal compounds such as vanadium and nickel, and undesired components such as sulfur and nitrogen compounds contained in heavy oil in an amount. Its purpose is to provide a processing method.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, first, in a method for hydrotreating heavy oil using hydrogen sulfide and an iron-based catalyst, the use of an in-oil-dispersed colloidal iron dispersion as the iron-based catalyst is described. A method for hydrotreating heavy oil is provided. Second, in the first method for hydrotreating heavy oil, an aqueous dispersion of a surfactant is added to ferric oxide and / or ferric hydroxide sol by dispersing a colloidal iron dispersion in oil. A method for hydrotreating heavy oil, characterized by being a dispersion obtained by coagulating the sol and extracting a generated precipitate with a hydrocarbon-based solvent. Third, in the first hydrotreating method, a colloidal iron-in-oil dispersion is formed by adding dilute sulfuric acid to ferric oxide and / or ferric hydroxide sol to condense the sol and form A method for hydrotreating heavy oil, characterized by being a dispersion obtained by extracting the precipitated precipitate with a hydrocarbon-based solvent containing a surfactant. Fourth, in the first hydrotreating method, the colloidal iron dispersion in oil is brought into contact with a ferric oxide and / or ferric hydroxide sol in a hydrocarbon solvent containing a surfactant. The present invention provides a method for hydrotreating heavy oil, which is a dispersion obtained by the above method.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a conventionally known method for hydrotreating heavy oil using hydrogen sulfide and an iron-based catalyst. It is characterized by using a state iron dispersion. In the present invention, the in-oil-dispersed colloidal iron dispersion is not dissolved in a hydrocarbon solvent, but takes a stable high dispersion state in the solvent, preferably a dispersion containing a surfactant. means.

The oil-dispersed colloidal iron dispersion catalyst used in the method of the present invention reacts with hydrogen sulfide in a reaction system in the same manner as a conventionally known oil-soluble iron-based catalyst to produce iron sulfide (pyroite,
Although Fe1-XS) fine particles are formed, it has been confirmed by X-ray diffraction measurement that the particle size is significantly smaller than when an oil-soluble iron-based catalyst is used. Further, the iron sulfide fine particles generated by the method of the present invention are different from those derived from conventionally known oil-soluble iron-based catalysts. Is extremely small. As described above, the in-oil-dispersed colloidal iron dispersion catalyst used in the present invention can reduce the particle size of the iron sulfide fine particles exhibiting catalytic activity, and can control the increase in the particle size of these fine particles during the reaction. According to the method for hydrotreating heavy oil of the present invention using such a dispersion as a catalyst, the catalytic activity is enhanced and the catalytic activity is maintained for a long time. Unwanted components such as metal and metal compounds can be efficiently removed with a small amount of catalyst.

As the catalyst composed of the above-mentioned colloidal iron dispersion in oil dispersion used in the present invention, those obtained by the following three preparation methods are preferably used.

[0008] The first catalyst preferably used in the present invention is to add an aqueous solution of a surfactant to a ferric oxide and / or ferric hydroxide sol to coagulate the sol and to carbonize the formed precipitate. It is a colloidal iron dispersion in oil obtained by extraction with a hydrogen-based solvent.

In this case, the operation of coagulating the sol of ferric oxide and / or ferric hydroxide with an aqueous solution of a surfactant and extracting the same with a hydrocarbon-based solvent is itself a scientific literature.
Kenjiro Meguro, Tamotsu Kondo, The Chemical Journal of Japan, Vol. 76, No. 6
No. 642-645 (1955).

The ferric oxide and / or ferric hydroxide sol used in the method may be prepared according to a conventionally known method. For example, such a preparation method includes, for example, adding a ferric salt to boiling water. Examples thereof include a method of dropping an aqueous solution and a method of partially neutralizing an aqueous solution of a ferric salt with an aqueous solution of sodium hydrogen carbonate.

Surfactants used for coagulating the ferric oxide and / or ferric hydroxide sol include anionic surfactants, cationic surfactants, nonionic surfactants,
While any of the amphoteric surfactants can be used, the use of an anionic surfactant is preferred. Examples of the anionic surfactant include an alkylarylsulfonic acid, an alkylarylsulfonic acid salt, an alkylsulfuric acid, an alkylsulfate, a sulfosuccinate, and a sulfosuccinate, and an alkylaryl sulfonic acid such as dodecylbenzenesulfonic acid. Is preferably used.

The amount of the aqueous surfactant solution is such that the number of moles of the surfactant contained in the aqueous solution is at least 0.01 times the number of moles of iron contained in the sol of ferric oxide and / or ferric hydroxide.
Preferably, it is suitably 0.05 times or more. If the number of moles of the surfactant is too small, not only does coagulation not sufficiently occur, but also it becomes difficult to perform the subsequent extraction with a hydrocarbon solvent.

The hydrocarbon solvent used for extracting the precipitate formed by the coagulation of the ferric oxide and / or ferric hydroxide sol may be any solvent that is compatible with heavy oil. Examples of such a solvent include a single solvent such as toluene, xylene, and decahydronaphthalene (also called decalin), and a mixed solvent (fuel oil) such as gasoline, kerosene, and light oil.

The second catalyst preferably used in the present invention is a method in which dilute sulfuric acid is added to a sol of ferric oxide and / or ferric hydroxide to coagulate the sol. It is an oil-dispersed colloidal iron dispersion obtained by extraction with a solution dissolved in a hydrogen-based solvent.

The ferric oxide and / or ferric hydroxide sol used here may be prepared by the method described in the first preparation method.

The amount of dilute sulfuric acid to be added is such that the number of moles of sulfuric acid contained therein is at least 0.01 times the number of moles of iron contained in the sol of ferric oxide and / or ferric hydroxide, preferably 0.05 times. It is appropriate that the number be twice or more. If the amount of the dilute sulfuric acid is too small, coagulation does not sufficiently occur.

As the surfactant, the surfactant described in the first preparation method can be used as it is.

The hydrocarbon solvent is not particularly limited as long as it is compatible with heavy oil and can dissolve a surfactant. As such a hydrocarbon solvent, the solvent described in the section of the first preparation method can be used as it is.

The amount of the hydrocarbon-based solvent containing the surfactant is such that the number of moles of the surfactant contained therein is less than the number of moles of iron contained in the ferric oxide and / or the ferric hydroxide sol. It is suitably at least 0.05 times, preferably at least 0.1 times.

The third catalyst preferably used in the present invention is a dispersion in oil obtained by contacting a ferric oxide and / or a ferric hydroxide sol with a hydrocarbon solvent containing a surfactant. A colloidal iron dispersion.

The ferric oxide and / or ferric hydroxide sol used here may be prepared by the methods described in the first and second preparation methods.

As the surfactant, the surfactants described in the first and second preparation methods can be used as they are.

The hydrocarbon solvent is not particularly limited as long as it is compatible with the heavy oil and can dissolve the surfactant. As such a hydrocarbon-based solvent, the solvents described in the first and second preparation methods can be used as they are.

The amount of the hydrocarbon-based solvent containing a surfactant is determined based on the number of moles of the surfactant contained therein and the number of moles of iron contained in the ferric oxide and / or ferric hydroxide sol. It is suitably at least 0.05 times, preferably at least 0.1 times.

To carry out the hydrotreating of the heavy oil of the present invention,
For example, the dispersion catalyst obtained by the above-described preparation method and hydrogen sulfide may be added to heavy oil and reacted in a hydrogen atmosphere. As a reaction system, a slurry bed system is usually employed, but a fixed bed system or a suspension bed system may be used.

As the heavy oil which is the raw material of the present invention, all conventionally known heavy oils derived from coal and petroleum which are to be subjected to hydrotreating methods such as hydrodesulfurization and hydrocracking are applied. . Examples of such heavy oils include atmospheric residual oil, vacuum residual oil, waste lubricating oil, and coal liquefied oil obtained by distilling crude oil. Further, as the hydrogen sulfide, not only hydrogen sulfide itself but also a compound which generates hydrogen sulfide in the reaction system, for example, a sulfur compound such as elemental sulfur and alkyl sulfide can be used. The concentration of hydrogen sulfide is not particularly limited, but it is appropriate that the concentration in hydrogen gas is about 0.5 to 5 vol%.

In the hydrotreating method of the present invention, the reaction conditions such as the reaction temperature, hydrogen pressure, hydrogen / heavy oil volume ratio, and reaction time are determined by the conventionally known hydrodesulfurization and hydrocracking of heavy oil. The usual reaction conditions used in the above may be employed as they are.

For example, reaction temperature: 200 to 500 ° C., hydrogen pressure: 5 to 20 MPa, hydrogen / heavy oil volume ratio: 500
Reaction conditions such as 適宜 2000 l / l, reaction time;

[0029]

Next, the present invention will be described in more detail with reference to examples.

Example 1 [Preparation of Catalyst for Dispersion of Colloidal Iron Dispersion in Oil] (1) Ferric nitrate hydrate [Fe (NO3) 3.9H2O] 15.15 g (0.0
375 mol) in about 40 ml of pure water and put into a separating funnel. About 200 ml of pure water is put into a 300 ml Erlenmeyer flask, heated and boiled with an electric heater, and the above aqueous ferric nitrate solution is dropped at a rate of about 10 ml / min while continuing to boil. After completion of the dropwise addition, the Erlenmeyer flask is immersed in cold water and cooled to room temperature, and pure water is added to make the total volume 250 ml. As described above, a ferric oxide sol having a dark red-brown and transparent iron concentration of 0.15 mol / l was prepared. (2) Separately, 0.98 g (0.003 mol) of dodecylbenzenesulfonic acid (soft type) is dissolved in pure water to make the total volume 100 ml. Thus, an aqueous solution of dodecylbenzenesulfonic acid having a concentration of 0.03 mol / l was prepared. (3) Ferric oxide sol 1 of (1) above in a 200 ml beaker
Then, 50 ml of the aqueous solution of dodecylbenzenesulfonic acid of the above (2) was added thereto to coagulate the ferric oxide sol. In this example, the number of moles of dodecylbenzenesulfonic acid added is 0.1 times the number of moles of iron. (4) After coagulating the ferric oxide sol, 25 ml of decalin was added.
In addition, the mixture was gently stirred with a stirrer for about 5 minutes. By this operation, the ferric oxide colloid was extracted and dispersed in decalin. Separation of the decalin phase (dispersion type catalyst solution) and the aqueous phase after the extraction was performed using a separating funnel. The iron concentration of this catalyst solution was 0.145 mol / l. [Hydrogenation treatment of heavy oil] (5) Using the catalyst solution prepared as described above, Maya atmospheric residue (sulfur content 4.6 wt.%, Nitrogen content 0.57 wt.%, Heptane-insoluble asphaltene content 16.1) wt.%, vanadium content
Hydrogenation treatment of 420 ppm and nickel content of 82 ppm) was performed in the following manner. 6 ml of the catalyst solution obtained in the above (4) and 22 g of Maya residual oil were added to an electromagnetic induction stirring type stainless steel autoclave having an internal volume of 100 ml, and hydrogen gas containing 1.7 vol. The temperature was raised to 400 ° C. in about 1 hour, and the reaction was carried out at 400 ° C. for 1 hour. During this time, the contents were stirred at a speed of 700 rpm. The reaction results are shown in Table 1A.

Example 2 [Preparation of Catalyst for Dispersion in Colloidal Iron Dispersion in Oil] (1) A ferric oxide sol having an iron concentration of 0.15 mol / l was prepared in the same manner as in Example 1. (2) Separately, dilute sulfuric acid having a concentration of 0.03 mol / l was prepared. (3) Separately, 4.90 g of dodecylbenzenesulfonic acid
Was dissolved in decalin to make the total volume 100 ml. Thus, a decalin dodecylbenzenesulfonate solution having a concentration of 0.15 mol / l was prepared. (4) Ferric oxide sol 1 of (1) above in a 200 ml beaker
Then, 50 ml of the diluted sulfuric acid of the above (2) was added dropwise to the mixture to coagulate the ferric oxide sol. In this example, the number of moles of sulfuric acid added is 0.1 times the number of moles of iron. (5) After the ferric oxide sol was condensed, 25 ml of the above-mentioned solution (3) of decalin dodecylbenzenesulfonate was added, followed by gentle stirring with a stirrer for about 5 minutes. With this operation,
The ferric oxide colloid was extracted and dispersed in the decalin solution. In this example, the number of moles of the added dodecylbenzenesulfonic acid is 0.25 times the number of moles of iron. Separation of the decalin phase (catalyst liquid) and the aqueous phase after the extraction was performed using a separating funnel. The iron concentration of this catalyst solution was 0.19 mol / l. [Hydrogenation treatment of heavy oil] (6) Catalyst solution 5 ml, decalin 1 prepared as above
ml and 22 g of Maya atmospheric pressure residual oil were added to the autoclave, and hydrogenation was carried out in the same manner as in Example 1. Table 1 shows the reaction results.
B.

Example 3 [Preparation of Catalyst for Dispersion of Colloidal Iron Dispersion in Oil] (1) A ferric oxide sol having an iron concentration of 0.15 mol / l was prepared in the same manner as in Example 1. (2) Separately, dodecylbenzenesulfonic acid 4.90
g was dissolved in decalin to make the total volume 100 ml. Thus, a decalin dodecylbenzenesulfonate solution having a concentration of 0.15 mol / l was prepared. (3) Ferric oxide sol 1 of (1) above in a 200 ml beaker
20 ml of the above solution (2) of decalin dodecylbenzenesulfonate was added thereto, and the mixture was gently stirred with a stirrer for about 5 minutes. By this operation, the ferric oxide colloid was extracted and dispersed in the decalin solution. In this example, the number of moles of the added dodecylbenzenesulfonic acid is
It was 0.2 times the number of moles of iron. Separation of the decalin phase (catalyst liquid) and the aqueous phase after the extraction was performed using a separating funnel. The iron concentration of this catalyst solution was 0.185 mol / l. [Hydrogenation treatment of heavy oil] (4) 5 ml of catalyst solution prepared as above, decalin 1
ml and 22 g of Maya atmospheric pressure residual oil were added to the autoclave, and hydrogenation was carried out in the same manner as in Example 1. Table 1 shows the reaction results.
C.

Comparative Example 1 For comparison with the reaction results of Examples 1 to 3, a reaction was carried out using iron (III) 2-ethylhexanoate (also known as iron octylate), which is an oil-soluble iron compound. In this reaction, a mineral spirits solution of iron octylate (iron concentration of 6 wt.%
3.34 g (3.7 ml), 2.3 ml of decalin and 22 g of Mayan atmospheric residue were added to the autoclave, and hydrogenation was carried out in the same manner as in Example 1. The reaction results are shown in Table 1D.

[0034]

[Table 1]

As can be seen from the results in Table 1, when the catalyst in the oil-dispersed colloidal iron dispersion prepared by the method of the present invention is used, good results can be obtained in asphaltene decomposition rate and vanadium removal rate. That is, in Experiment Nos. A, B, and C, which are examples of the present invention, the amount of addition of iron as a catalyst component was about 50 mg, which was about 1/4 of Experiment No. D using an oil-soluble iron compound. Nevertheless, the asphaltene decomposition rate exceeds experiment number D. Regarding the vanadium removal rate, Experiment No. A is almost the same as Experiment No. D. Further, the production rate of coke (toluene-insoluble matter), which is an undesirable product, is lower in the production rate of the method of the present invention than in Experiment No. D, which is advantageous.

[0036]

The catalyst comprising the colloidal iron dispersion in oil dispersion used in the present invention can reduce the particle size of the iron sulfide fine particles exhibiting catalytic activity, and can increase the particle size of these fine particles during the reaction. According to the method for hydrotreating heavy oil of the present invention using such an iron-dispersed iron compound as a catalyst, the catalytic activity is enhanced and the catalytic activity is maintained for a long time. In addition, undesired components such as asphaltenes and metal compounds contained in heavy oil can be efficiently removed with a small amount of catalyst.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiki Sato 16-3 Onogawa, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Teruo Kondo 16-3, Onogawa, Tsukuba, Ibaraki Pref. F-term in Environmental Technology Research Institute (reference) 4G069 AA02 AA08 BA21C BA37 BB04A BB04B BB09A BB09B BB10C BB19A BB19B BC66A BC66B BD01A BD01B BD08A BD08B CC02 CC05 DA03 FA01 FB80 FC02 FC03 4H029 CA00 DA00

Claims (4)

[Claims] 1. A method for hydrotreating heavy oil using hydrogen sulfide and an iron-based catalyst, characterized in that a colloidal iron dispersion in oil is used as the iron-based catalyst. Hydrotreating method. 2. An aqueous dispersion of a colloidal iron dispersion in oil is added to a sol of ferric oxide and / or ferric hydroxide by adding an aqueous solution of a surfactant to coagulate the sol. 2. The method for hydrotreating heavy oil according to claim 1, wherein the dispersion is a dispersion obtained by extraction with a system solvent. 3. A colloidal iron dispersion in an oil-dispersed state, wherein diluted sulfuric acid is added to a ferric oxide and / or ferric hydroxide sol to coagulate the sol, and the resulting precipitate contains a surfactant. The method for hydrotreating heavy oil according to claim 1, wherein the dispersion is a dispersion obtained by extraction with a hydrocarbon solvent. 4. The colloidal iron dispersion in oil dispersion is a dispersion obtained by contacting a ferric oxide and / or ferric hydroxide sol with a hydrocarbon solvent containing a surfactant. The method for hydrotreating heavy oil according to claim 1, wherein: