JP3404522B2 - Hydroprocessing of heavy oil - Google Patents

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION As is well known, petroleum and coal-based heavy oils include high-molecular-weight and highly aromatic components called asphaltene, metal compounds such as vanadium and nickel, and compounds such as sulfur and nitrogen. It contains a lot of ingredients that are unfavorable to the quality. As a method for removing these components, a hydrotreating method in which a heavy oil and a catalyst are brought into contact with each other in a high-pressure hydrogen atmosphere has been widely used. The 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 hydrotreatment of heavy oil, which contains a large amount of oil. Many studies and patents have been made on the catalyst used in this slurry system. For example, a method using an oil-soluble iron compound, Mc using an oil-soluble molybdenum compound
ake process, Aurab using vanadium compound
on process, C using coal powder impregnated with iron sulfate
Excellent technologies such as the ANMET process and the SOC process using a combination of a transition metal compound and ultrafine powder have been proposed. Among these, particularly the method using hydrogen sulfide and an oil-soluble iron-based catalyst is an industrially very promising method in terms of cost and safety, and for example, many studies have been made as a catalyst for coal liquefaction reaction. . In this method, the oil-soluble iron-based catalyst reacts with hydrogen sulfide in the reaction system to form highly dispersed iron sulfide fine particles exhibiting a catalytic activity, and by the high catalytic activity of the iron sulfide fine particles, Hydroprocessing of heavy oil is performed. However, as mentioned in these studies, the fine particles of iron sulfide obtained by the reaction of this oil-soluble iron-based catalyst with hydrogen sulfide have a small particle size at the initial stage of the reaction and show high catalytic activity. Agglomeration and crystal growth of these fine particles with the progress of, the particle size increases,
There are problems that the initial catalytic activity cannot be obtained, and that the amount of the catalyst used must be increased in order to improve 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 the hydrotreating reaction, and a small amount of catalyst. Highly industrially advantageous hydrogenation of heavy oil that can efficiently hydrotreat undesired components such as asphaltene, vanadium, nickel and other metal compounds contained in heavy oil, and sulfur and nitrogen compounds contained in large amounts. Its purpose is to provide a processing method.

[0004]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, firstly,
In a method for hydrotreating heavy oil using an iron-based catalyst,
As an iron-based catalyst, ferric oxide and / or ferric hydroxide
The aqueous solution of the surfactant is added to the gel to condense the sol,
In oil obtained by extracting the formed precipitate with a hydrocarbon solvent
Characterized by using a dispersion type colloidal iron dispersion
A method for hydrotreating heavy oil is provided. Second, sulfide water
Odor of heavy oil using hydrogen and iron-based catalysts
As the iron-based catalyst, ferric oxide and / or ferric hydroxide.
Dilute sulfuric acid is added to diiron sol to condense the sol and generate
Obtained precipitate by extraction with a hydrocarbon solvent containing a surfactant.
To use a colloidal iron dispersion in oil
A featured heavy oil hydrotreating method is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a method for hydrotreating a heavy oil using a conventionally known hydrogen sulfide and an iron-based catalyst, which has not been heretofore known as a reaction catalyst of this kind. The feature is that the iron-like dispersion liquid is used. In the present invention, the oil-dispersed colloidal iron dispersion does not dissolve in a hydrocarbon solvent, but is stable and highly dispersed 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 the reaction system in the same manner as a conventionally known oil-soluble iron-based catalyst to produce iron sulfide (pyrotitite,
It has been confirmed by X-ray diffraction measurement that fine particles of Fe1-XS) are formed, but the particle size thereof is significantly smaller than that 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, and even if the reaction proceeds, aggregation / association or crystal growth of fine particles hardly occur, and the particle diameter thereof The change in is extremely small. As described above, the oil-dispersed colloidal iron dispersion liquid catalyst used in the present invention can reduce the particle size of iron sulfide fine particles exhibiting catalytic activity, and can control the increase of the particle size of these fine particles during the reaction. Therefore, 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 lasts for a long time, so that the asphaltene contained in the heavy oil is Undesirable components such as and metal compounds can be efficiently removed with a small amount of catalyst.

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

The first catalyst preferably used in the present invention is a ferric oxide and / or ferric hydroxide) sol to which an aqueous solution of a surfactant is added to coagulate the sol, and the resulting precipitate is carbonized. It is an oil-dispersed colloidal iron dispersion obtained by extraction with a hydrogen-based solvent.

In this case, the operation itself of condensing ferric oxide and / or ferric hydroxide sol with an aqueous solution of a surfactant and extracting it with a hydrocarbon-based solvent is itself described in academic literature, for example,
Kenjiro Meguro, Yasushi Kondo, Nihon Kagaku Magazine, Vol.76, Vol.6
Issue, pages 642-645 (1955).

The ferric oxide and / or ferric hydroxide sol used in this method may be prepared according to a conventionally known method. As such a preparation method, for example, boiling water is used to prepare a ferric salt. 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 sodium hydrogen carbonate solution.

As the surfactant used when the ferric oxide and / or ferric hydroxide sol is condensed, an anionic surfactant, a cationic surfactant, a nonionic surfactant,
Although any of the amphoteric surfactants can be used, the use of anionic surfactants is preferred. Examples of the anionic surfactant include alkylaryl sulfonic acid, alkylaryl sulfonic acid salt, alkyl sulfuric acid, alkyl sulfate, sulfosuccinic acid ester, sulfosuccinic acid ester salt, and the like, and alkylaryl sulfonic acid such as dodecylbenzene sulfonic acid. Is preferably used.

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

As the hydrocarbon solvent used for extracting the precipitate formed by the condensation of ferric oxide and / or ferric hydroxide sol, any hydrocarbon solvent can be used as long as it is compatible with heavy oil. Examples of such a solvent include a single solvent such as toluene, xylene, and decahydronaphthalene (also known as 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 ferric oxide and / ferric hydroxide sol to which dilute sulfuric acid is added to condense the sol, and the resulting precipitate is carbonized with a surfactant. 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 added is such that the number of moles of sulfuric acid contained therein is 0.01 times or more, preferably 0.05 times the number of moles of iron contained in the ferric oxide and / or ferric hydroxide sol. It is appropriate to make it twice or more. If the amount of dilute sulfuric acid added is too small, sufficient coagulation will not 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 the 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 solvent containing the surfactant used is such that the number of moles of the surfactant contained therein is the number of moles of iron contained in the ferric oxide and / or ferric hydroxide sol. It is appropriate that the amount is 0.05 times or more, preferably 0.1 times or more.

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

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

As the surfactant, the surfactant described in the first and the preparation methods 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 the surfactant. As such a hydrocarbon solvent, the solvent described in the paragraphs of the first and second preparation methods can be used as it is.

The amount of the hydrocarbon solvent containing the surfactant used is such that the number of moles of the surfactant contained therein is the number of moles of iron contained in the ferric oxide and / or ferric hydroxide sol. It is suitable to be 0.05 times or more, preferably 0.1 times or more.

To carry out the hydrotreatment of the heavy oil of the present invention,
For example, the dispersion catalyst obtained by the above-mentioned 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 adopted, but a fixed bed system or a suspension bed system may be used.

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

In the hydrotreating method of the present invention, reaction conditions such as reaction temperature, hydrogen pressure, hydrogen / heavy oil volume ratio, reaction time and the like are conventionally known hydrodesulfurization and hydrocracking of heavy oil. The usual reaction conditions used in 1. may be used 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 ˜2000 l / l, reaction time; 0-5 to 5 hours may be appropriately adopted.

[0029]

EXAMPLES Next, the present invention will be described in more detail by way of examples.

Example 1 [Preparation of Colloidal Iron Dispersion Catalyst in Oil Dispersion] (1) Ferric Nitrate Hydrate [Fe (NO3) 3.9H2O] 15.15 g (0.0
375 mol) in about 40 ml of pure water and put in a separating funnel. About 200 ml of pure water is put into a 300 ml Erlenmeyer flask and heated and boiled with an electric heater. While continuing boiling, the ferric nitrate aqueous solution is dropped at a rate of about 10 ml / min. After completion of the dropping, the Erlenmeyer flask is immersed in cold water to cool it to room temperature, and pure water is added to bring the total volume to 250 ml. As described above, a dark reddish brown and transparent ferric oxide sol having an 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. As a result, an aqueous solution of dodecylbenzenesulfonic acid having a concentration of 0.03 mol / l was prepared. (3) In a 200 ml beaker, ferric oxide sol 1 from (1) above
00 ml was added, and 50 ml of the dodecylbenzenesulfonic acid aqueous solution 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 concentrating the ferric oxide sol, add 25 ml of decalin
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 extraction was performed using a separating funnel. The iron concentration of this catalyst solution was 0.145 mol / l. [Hydrolysis of heavy oil] (5) Using the catalyst solution prepared as described above, Maya atmospheric residual oil (sulfur content 4.6 wt.%, Nitrogen content 0.57 wt.%, Heptane-insoluble asphaltene content 16.1) wt.%, vanadium content
A hydrogenation treatment of 420 ppm and nickel content of 82 ppm) was performed in the following manner. To an electromagnetic induction stirring type stainless steel autoclave with an internal volume of 100 ml, 6 ml of the catalyst solution obtained in (4) above and 22 g of Maya residual oil were added, and hydrogen gas containing 1.7 vol.% Hydrogen sulfide was charged at 10 MPa, and then from room temperature. The temperature was raised to 400 ° C. in about 1 hour, and the temperature was kept at 400 ° C. for 1 hour for reaction. During this time, the contents were stirred at a speed of 700 rpm. The reaction results are shown in A of Table 1.

Example 2 [Preparation of colloidal iron dispersion liquid catalyst in oil dispersion] (1) In the same manner as in Example 1, a ferric oxide sol having an iron concentration of 0.15 mol / l was prepared. (2) Separately from this, dilute sulfuric acid having a concentration of 0.03 mol / l was prepared. (3) Separately, 4.90 g of dodecylbenzene sulfonic acid
Was dissolved in decalin to bring the total volume to 100 ml. Thus, a dodecylbenzenesulfonic acid decalin solution having a concentration of 0.15 mol / l was prepared. (4) In a 200 ml beaker, ferric oxide sol 1 from (1) above
00 ml was added, and 50 ml of the dilute sulfuric acid of the above (2) was added dropwise thereto 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 dodecylbenzenesulfonic acid decalin solution of (3) above was added and gently stirred with a stirrer for about 5 minutes. By this operation,
Ferric oxide colloid was extracted and dispersed in the decalin solution. In this example, the number of moles of dodecylbenzenesulfonic acid added is 0.25 times the number of moles of iron. Separation of the decalin phase (catalyst solution) and the aqueous phase after extraction was performed using a separating funnel. The iron concentration of this catalyst solution was 0.19 mol / l. [Hydrolysis of heavy oil] (6) 5 ml of catalyst solution prepared as above, decalin 1
ml and Maya normal pressure residual oil 22 g were added to the autoclave and hydrogenated in the same manner as in Example 1. The reaction results are shown in Table 1.
Shown in B.

Example 3 [Preparation of colloidal iron dispersion catalyst dispersed in oil] (1) In the same manner as in Example 1, a ferric oxide sol having an iron concentration of 0.15 mol / l was prepared. (2) Separately, dodecylbenzene sulfonic acid 4.90
g was dissolved in decalin to bring the total volume to 100 ml. Thus, a dodecylbenzenesulfonic acid decalin solution having a concentration of 0.15 mol / l was prepared. (3) In a 200 ml beaker, ferric oxide sol 1 from (1) above
00 ml was added, 20 ml of the dodecylbenzenesulfonic acid decalin solution of (2) above was added, 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 dodecylbenzenesulfonic acid added is
It was 0.2 times the number of moles of iron. Separation of the decalin phase (catalyst solution) and the aqueous phase after extraction was performed using a separating funnel. The iron concentration of this catalyst solution was 0.185 mol / l. [Hydrolysis of heavy oil] (4) 5 ml of catalyst solution prepared as above, 1 decalin
ml and Maya normal pressure residual oil 22 g were added to the autoclave and hydrogenated in the same manner as in Example 1. The reaction results are shown in Table 1.
Shown in C.

Comparative Example 1 In order to compare 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, iron octylate mineral spirits solution (iron concentration 6 wt.%
Was added), decalin 2.3 ml and Maya atmospheric residual oil 22 g were added to the autoclave and hydrogenated in the same manner as in Example 1. The reaction results are shown in D of Table 1.

[0034]

[Table 1]

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

[0036]

INDUSTRIAL APPLICABILITY The catalyst composed of an oil-dispersed colloidal iron dispersion liquid used in the present invention can reduce the particle size of iron sulfide fine particles exhibiting catalytic activity, and further increase the particle size of these fine particles during the reaction. Since it can be controlled, according to the heavy oil hydrotreating method of the present invention using such an oil-dispersed iron-based compound as a catalyst, the catalytic activity is enhanced and the catalytic activity lasts for a long time. It is possible to efficiently remove undesirable components such as asphaltene and metal compounds contained in heavy oil with a small amount of catalyst.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Teruo Kondo 16-3 Onogawa, Tsukuba City, Ibaraki Prefectural Institute of Industrial Science (56) Reference JP-A-6-346064 (JP, A) JP-A 6-205968 (JP, A) JP 58-108294 (JP, A) JP 61-143490 (JP, A) JP 58-79092 (JP, A) JP 59-75986 (JP, A) JP-A-9-77503 (JP, A) JP-B-39-24632 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C10G 45/04-45/12 C10G 49 / 12 C10G 1/00 C10G 1/06

Claims (2)

(57) [Claims] 1. Hydrogen for heavy oil using hydrogen sulfide and an iron-based catalyst
In the chemical treatment method, the iron-based catalyst is ferric oxide or
And / or ferric hydroxide sol with an aqueous solution of surfactant added
The sol is condensed to form a precipitate, which is then converted into a hydrocarbon solvent.
Use an oil-dispersed colloidal iron dispersion obtained by extraction with
A method for hydrotreating heavy oil, characterized by being used. 2. Hydrogen of heavy oil using hydrogen sulfide and iron-based catalyst
In the chemical treatment method, the iron-based catalyst is ferric oxide or
And / or ferric hydroxide sol by adding dilute sulfuric acid to the sol.
Hydrocarbon system containing a surfactant that condenses and precipitates
Oil-dispersed colloidal iron dispersion obtained by extraction with a solvent
A method for hydrotreating heavy oil, comprising: