JP2002129171A - Decomposition method for heavy oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decomposition method for a heavy oil where the amount of precipitated carbon is small, the catalyst is hardly degraded, and the running cost is low. SOLUTION: This decomposition method uses an iron compound as a catalyst. The iron compound is obtained by heating an iron compound comprising at least one compound selected from the group consisting of iron hydroxide (FeOOH), triiron tetraoxide (Fe3O4), and diiron trioxide (Fe2O3) with steam or in an atmosphere containing steam.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for cracking heavy oil using a catalyst.

[0002]

2. Description of the Related Art Conventionally, in order to convert organic waste into useful organic matter, catalytic decomposition of organic waste using a zeolite catalyst has been performed (Japanese Patent Laid-Open No. 5-13803).
1).

[0003]

Problems to be Solved by the Invention Japanese Patent Laid-Open No. 5-138,0
The method 31 has the problems that the catalyst is deteriorated due to the deposition of carbon at the active site of the catalyst, and the production cost of the catalyst is high.

[0004] It is an object of the present invention to provide a method for decomposing heavy oil, which has a low carbon deposition amount, hardly deteriorates the catalyst, and has a low running cost.

[0005]

The heavy oil cracking method of the present invention is a method for cracking heavy oil using an iron compound as a catalyst to crack heavy oil. FeO
OH), triiron tetroxide (Fe ₃ O ₄ ) and diiron trioxide (Fe
Heavy oil, which is an iron compound obtained by selecting at least one iron compound from the group consisting of ₂ O ₃ ) and heating the iron compound in steam or an atmosphere containing steam. Disassembly method.

Preferred embodiments of the heavy oil cracking method of the present invention include the following. Unless inconsistent with one another, any of the following combinations are also included in the preferred embodiments of the present invention. (1) The selected iron compound is iron hydroxide (FeOOH)
It is. By subjecting FeOOH to steam heating treatment,
The water of crystallization in FeOOH evaporates, producing pores of 1 to 10 nm. A site showing catalytic activity appears in these pores.
At this time, part of the FeOOH changes to Fe ₃ O ₄ , Fe ₂ O _{3, and the} like. (2) Heat treatment is performed at 400 to 700 ° C. in steam or an atmosphere containing steam. By the treatment at 400 to 700 ° C., part of FeOOH is efficiently changed to Fe ₃ O ₄ and becomes magnetic, so that the magnetic force of the catalyst can be recovered. (3) Zirconium oxide (ZrO ₂ ) is supported or contained in the iron compound. (4) The catalyst carries or contains at least one member selected from the group consisting of zinc oxide, tin oxide, alkali metal oxides and alkaline earth metal oxides. With respect to zirconium oxide, zinc oxide and the like of the above (3) and (4), water is decomposed to generate active oxygen, active hydrogen, active hydroxyl group and the like, and these active species are described in the above (1) and (2). The iron compound moves to the pore surface active site to promote the decomposition of heavy oil. As a result, the rate of occurrence of carbon residues can be further reduced. That is, zirconium oxide, zinc oxide and the like work as a co-catalyst. (5) The catalyst comprises 100 parts by weight of the iron compound and 14 parts by weight or less of the zirconium oxide. More preferably,
When supported by the evaporation to dryness method described below, iron compound 1
00 parts by weight, zirconium oxide (ZrO ₂ )
It carries 1.6 to 7.7 parts by weight. Within this range, the generation of residues can be further reduced. (6) After mixing the heavy oil with the inert solvent, the resulting mixture is subjected to a heavy oil decomposition reaction. By diluting the heavy oil with the solvent, the carbon residue generation rate can be reduced as compared with the case where the heavy oil is not diluted. (7) The heavy oil cracking reaction is performed in steam or an atmosphere containing steam. In this case, iron hydroxide (FeOOH) and triiron tetroxide (F
e ₃ O ₄ ) and iron compound composed of at least one of diiron trioxide (Fe ₂ O ₃ ), and the heavy oil can be decomposed more effectively. (8) Heavy oil, inert solvent and iron hydroxide (FeOO)
H) is heated in steam or in an atmosphere containing steam to obtain a mixture of iron hydroxide (FeOOH), triiron tetroxide (Fe ₃ O ₄ ) and diiron trioxide (Fe ₂ O ₃ ). An iron compound composed of at least one or more is formed, and the iron compound is used as a catalyst. At this time, the iron compound is porous or fine particles. Even when iron hydroxide (FeOOH) is used substantially as a catalyst component, iron hydroxide (FeOOH), triiron tetroxide (Fe ₃ O ₄ ), and diiron trioxide ( An iron compound composed of at least one of Fe ₂ O ₃ ) is formed, and heavy oil can be decomposed more effectively. (9) The catalyst reaction product is separated into gas, light oil, uncracked heavy oil, solvent and water, and the separated solvent is circulated for use. Since the solvent is not decomposed by the catalyst, it can be recycled. (10) The heavy oil cracking method according to any one of claims 7 to 10, wherein a solvent selected from the group consisting of ketone, benzene, phenol, and a mixed solvent thereof is used as the inert solvent. The catalyst used in the present invention is inert with respect to these solvents and can be suitably used. (11) After the heavy oil cracking treatment, the catalyst is recovered by magnetic force. By doing so, the catalyst can be recycled and reused, and the implementation cost of the heavy oil cracking method can be reduced.

The iron oxide catalyst for cracking heavy oil of the present invention is considered to function as a catalyst for the following reactions.

Embedded image In the above formula, R ₁ and R ₂ represent an organic group. In addition, active oxygen is generated by decomposition of water, and also functions as a catalyst for oxidation by the active oxygen.

Embedded image

Further, the iron oxide catalyst for cracking heavy oil of the present invention has an advantage that the recovery is easy because it contains an iron compound which is magnetic and can be recovered by magnetic force.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an iron oxide-based catalyst for decomposing heavy oil organic waste according to the present invention will be described. (1) Iron Oxide Catalyst for Heavy Oil Cracking The iron oxide catalyst for heavy oil cracking according to the present invention comprises iron hydroxide (FeOOH), iron tetroxide (Fe ₃ O ₄ ), and iron trioxide (Fe ₃ O ₃ ) can be obtained by heating one or more iron-based compounds in steam or an atmosphere containing steam. (2) Zirconium oxide-introduced iron oxide catalyst for heavy oil cracking The zirconium oxide-introduced iron oxide catalyst for heavy oil cracking according to the present invention includes iron hydroxide (FeOOH), triiron tetroxide (Fe
_An iron compound obtained from an iron-based compound comprising at least one of ₃ O ₄ ) and diiron trioxide (Fe ₂ O ₃ ); and zirconium oxide, zinc oxide, and tin oxide carried or contained in the iron compound. , Alkali metal oxides and alkaline earth metal oxides.

The iron compounds iron hydroxide (FeOOH), triiron tetroxide (Fe ₃ O ₄ ) and diiron trioxide (Fe ₂ O ₃ ) are starting materials for the production of the catalyst, and iron hydroxide (FeOOH) Forms triiron tetroxide (Fe ₃ O ₄ ) and diiron trioxide (Fe ₂ O ₃ ) by heating in a steam atmosphere. Also, the structure becomes porous. Triiron tetraoxide (Fe ₃ O ₄₎ and ferric oxide (Fe
₂ O ₃ ) are both catalyst constituents and serve as an oxidation-reduction catalyst while maintaining the following reaction equilibrium.

Embedded image Iron hydroxide (FeOOH), as long as each of the above roles is fulfilled
The ratio of the triiron tetraoxide (Fe ₃ O ₄₎ and ferric oxide (Fe ₂ O ₃₎ is not particularly limited. Further, similarly to general catalysts, when the specific surface area increases due to porosity or fine particles, the catalytic activity increases.

When zirconium oxide is carried or contained in the iron compound, zirconium oxide is carried and contained in the iron-based compound. In this case, heating is performed in the following manner in steam or in an atmosphere containing steam. . (A) Heat treatment of an iron-based compound, and then supporting zirconium oxide, and further heating. (B) heat-treating the iron-based compound, and then supporting zirconium oxide, without further heating; (C) The zirconium oxide is supported without heating the iron-based compound, and then heated. (D) zirconium oxide is supported on the iron-based compound without heat treatment, and the heavy oil decomposition reaction is carried out in a steam or an atmosphere containing steam without heating thereafter, and the zirconium oxide-carrying iron is supported. The heat treatment of the system compound is performed. Although any of the above (a) to (d) can be adopted,
(C) is preferred, and (a) is particularly preferred.

When zirconium oxide is contained in the iron-based compound, generally, the iron-based compound and zirconium oxide are mixed and coprecipitated, and then heat treatment is performed. Zirconium oxide, zinc oxide, tin oxide, alkali metal oxide,
The alkaline earth metal oxide promotes the positive reaction (i) of (i). The reaction image is as shown below

Embedded image

The iron oxide-based catalyst introduced with zirconium oxide or the like for cracking heavy oil according to the present invention generally has a temperature of 30.
The pressure is from 0 to 600 ° C. and the pressure is from normal pressure to 25 MPa or more (supercritical range).

(3) Method for Producing Zirconium Oxide and Other Iron Oxide Catalysts for Heavy Oil Cracking The method for producing the iron oxide catalyst for heavy oil cracking according to the present invention comprises iron hydroxide (FeOOH), triiron tetroxide (Fe ₃ O ₄ ) and at least one iron-based compound selected from the group consisting of diiron trioxide (Fe ₂ O ₃ ), and heating the iron-based compound in steam or an atmosphere containing steam. Is obtained. As the iron-based compound, iron hydroxide (FeOOH) can be used, and the iron hydroxide is heated in steam or in an atmosphere containing steam to form an iron compound, and then zirconium oxide or the like is added to the iron compound. It can be carried or contained. In this case, the iron oxide catalyst can also be obtained by coprecipitating a salt such as zirconium and an iron salt.

(3-1) A step of heating iron hydroxide (FeOOH) in steam or an atmosphere containing steam to form an iron compound. Iron hydroxide is charged into a reaction tube made of, for example, quartz, and the steam pressure is set to, for example, 1 atm (normal pressure), and the temperature is set to, for example, 350 ° C.
In the temperature range of ~ 700 ° C, iron hydroxide (FeOO
H), triiron tetroxide (Fe ₃ O ₄ ) and diiron trioxide (Fe
Heat treatment is performed for a time sufficient to form at least one type of iron compound of ₂ O ₃ ), for example, a steam treatment time of 1 hour to form an iron compound. Examples of the atmosphere containing steam include superheated steam, saturated steam, and combustion exhaust gas. When zirconium oxide or the like is not supported or contained, the iron compound is used in the heavy oil cracking method of the present invention.

(2-2) Step of supporting zirconium oxide and the like on the formed iron compound To support zirconium oxide and the like on the formed iron compound, the iron compound is suspended in water while the suspension is suspended. In the suspension,
For example, zirconium hydroxide is generated and supported on an iron compound, and then dried and fired to carry zirconium oxide on the iron compound. The supporting method of zinc oxide, tin oxide, alkali metal oxide and alkaline earth metal oxide is basically the same as that of zirconium oxide. Incorporation of zinc oxide or the like is carried out by coprecipitating a salt of a metal to be contained and an iron salt. Examples of the alkali metal oxide include Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs.
₂ O, Fr ₂ O, especially Li ₂ O, Na ₂ O and K
₂ O is preferred. As alkaline earth metal oxides, B
There are eO, MgO, CaO, SrO, BaO, and RaO, with BeO, MgO, and CaO being particularly preferred.

(Embodiments) The present invention will be described below in detail based on specific embodiments 1 to 6. In the examples,
An iron oxide-based catalyst not supporting zirconium oxide (manufactured only in the following step 1) and a zirconium oxide-supported iron oxide-based catalyst were prepared as follows. (1) Preparation of an iron oxide catalyst not supporting zirconium oxide and an iron oxide catalyst supporting zirconium oxide Charge the FeOOH powder into a quartz reaction tube and place it in steam at 350 ° C.
Heat treatment was performed at -700 ° C for 1 hour. 2. 20 ml / g of ion-exchanged water was added to the obtained iron compound and stirred for 2 hours to obtain a suspension of the iron compound. 3. While stirring, 0.1 mol / l of ZrOCl ₂
A predetermined amount of the aqueous solution was added. After completion of the dropwise addition, the mixture was further stirred for 1 hour and left for 24 hours. 4. The reaction suspension was dried at 110 ° C. for 12 hours and the water was completely evaporated. 5. After removing the precipitated excess Zr compound by peeling off the solid iron oxide-based catalyst, the powder was pulverized. After the pulverized powder was formed, it was pulverized again and classified. 6. The classified powder (particle size: 0.2 to 0.4 mm) was charged into a quartz reaction tube and heat-treated in steam at 350 to 700 ° C for 1 hour to obtain a zirconium oxide-supported iron oxide catalyst.

Example 1 The change in magnetic properties of a zirconium oxide-supported iron oxide-based catalyst at the steam treatment temperature under steam was tested under the following conditions. The results are shown in Table 1 and FIG. Catalyst used: zirconium oxide-supported iron oxide-based catalyst (zirconium oxide: iron compound = 7.7: 100) Steam treatment temperature: 350 to 700 ° C. Magnetic measurement test: The amount recovered with a permanent magnet was visually evaluated. X-ray diffraction: Performed by powder X-ray diffraction method (ordinary method).

[0019]

[Table 1]

From the results shown in Table 1 and FIG. 1, when the steam treatment temperature was 350 ° C., the magnetism of the catalyst was weak and the magnetic recovery was difficult, but when the steam treatment temperature was 400 to 700 ° C., the catalyst recovered the magnetic force. Possible magnetism was provided. Also, X
From the results of the line diffraction, it was found that the steam treatment temperature was 400 ° C. and 50 ° C.
At 0 ° C. to 700 ° C., Fe ₃ O ₄ having magnetism was detected. Therefore, a catalyst that can be magnetically recovered by performing steam treatment at 400 ° C. to 700 ° C. is obtained.

Example 2 Comparison of Zirconium Oxide Loading Method The following objects to be decomposed were decomposed under the following conditions. The results are shown in FIG. Decomposition target: 10% normal pressure residual oil, 90% benzene Mixture supply amount: 0.78 g / h Reaction temperature: 500 ° C Catalyst amount / Decomposition target supply amount: 1.0 g / (g · h) Zirconium oxide supported Method: evaporation to dryness method (method of Example 1) Filtration method (see below)

<Supporting Zirconium Oxide by Filtration Method> FeOOH powder is charged into a quartz reaction tube,
The mixture was treated at 50 to 500 ° C. for 1 hour to obtain an iron oxide catalyst. 2. The obtained iron oxide catalyst was heated in a vacuum at 200 ° C. for 1 hour. 3. ZrOC in vacuum against heat-treated iron oxide catalyst
l ₂ The aqueous solution was dropped at 10 g per 1 g of the oxidizing iron oxide-based catalyst. 4. After dropping, the resulting suspension was stirred for 1 hour,
Left for hours. 5. After filtration, drying was performed at 110 ° C. for 12 hours, and water was evaporated. 6. The obtained powder was press-molded and then pulverized and decomposed (powder particle size: 0.2 to 0.4 mm). 7. The obtained iron oxide catalyst was treated in steam at 500 ° C. for 1 hour. The catalyst loaded with zirconium oxide by filtration is
Even in the case of zirconium oxide: iron oxide = 1.7: 100, the same resolution as that of zirconium oxide: iron oxide = 7.7: 100 was exhibited by the catalyst supporting zirconium oxide by the evaporation to dryness method.

Example 3 With respect to an iron oxide catalyst (zirconium oxide: iron oxide = 0: 100), only the residual oil at normal pressure was used as a decomposition target, the reaction temperature was 500 ° C., and the amount of catalyst / the supply amount of decomposition target substance 1 When the catalytic cracking reaction was carried out in a steam atmosphere at a rate of 0.5 g / (g / h), 92.5%
Becomes gas, gasoline, kerosene, heavy oil of C19 or higher,
7.5% of carbon residue of the supplied atmospheric residue was generated.

Example 4 An iron oxide-based catalyst (zirconium oxide: iron oxide = 0: 100) was mixed with 50 wt.
% And benzene 50 wt% as a decomposition target, a reaction temperature of 500 ° C., a catalyst amount / amount of the decomposition target supply 1.0 g / (g / h), and a catalytic decomposition reaction was performed in a steam atmosphere. 93.6% of the supplied atmospheric residual oil was gas, gasoline, kerosene and heavy oil of C19 or higher, and 6.4% of the supplied atmospheric residual oil had carbon residues.

Experimental Example 5 Iron oxide catalyst (zirconium oxide: iron oxide = 0: 100), iron oxide catalyst supported on zirconium oxide (zirconium oxide: iron oxide = 7.7: 10)
About 0), 10 wt% of normal pressure residual oil and 90 w of benzene
t% of the mixture was subjected to a catalytic reaction in a steam atmosphere at a reaction temperature of 500 ° C., an amount of catalyst / amount of the substance to be decomposed 1 g / (g / h). Did not occur. Example 6 Iron oxide-based catalyst (zirconium oxide: iron oxide =
0: 100), zirconium oxide-supported iron oxide catalyst (zirconium oxide: iron oxide = 2.0, 4.3, 7.7, 1)
3.7: 100), the reaction temperature was 400 ° C., the amount of catalyst / the amount of the substance to be decomposed was 1 g / (g / h), and acetone, butanone, phenol and benzene were supplied in a steam atmosphere to carry out the catalytic reaction. Was. In both cases, it was found that acetone, butanone, phenol and benzene were not decomposed and could be reused after recovery.

[Brief description of the drawings]

FIG. 1 shows a test of the change in magnetic properties of a zirconium oxide-supported iron oxide-based catalyst at the steaming temperature when the iron oxide catalyst is steamed under the following conditions. The results are shown in Table 1 and FIG.

FIG. 2 shows the results of a comparative experiment performed using a catalyst in which zirconium oxide is supported on an iron oxide-based catalyst by an evaporation to dryness method and a filtration method.

Continuing from the front page (72) Inventor Nobuhiro Sato 2-56, Suda-cho, Mizuho-ku, Nagoya, Aichi Prefecture Inside Nihon Insulator Co., Ltd. (72) Inventor Shuichi Yoshida 2-56, Suda-cho, Mizuho-ku, Nagoya, Aichi Japan Insulator Co., Ltd. F term (reference) 4G069 AA03 AA08 AA09 BB04A BB04B BC51A BC51B BC66A BC66B CC05 FA08 FC04 FC07 4H029 BA11 BB05 BB06 BB07 BB10 BC02 BC03 BC04 BD01 BD17 CA00 DA00

Claims (12)

[Claims] 1. A method for decomposing heavy oil using an iron compound as a catalyst, wherein the iron compound is composed of iron hydroxide (FeOOH), triiron tetroxide (Fe ₃ O ₄ ). And iron obtained by heating at least one iron-based compound from the group consisting of diiron trioxide (Fe ₂ O ₃ ) and heating the iron-based compound in steam or an atmosphere containing steam. A method for cracking heavy oil, which is a compound. 2. The heavy oil cracking method according to claim 1, wherein the selected iron-based compound is iron hydroxide (FeOOH). 3. The heavy oil cracking method according to claim 1, wherein the heat treatment in the steam or the atmosphere containing the steam is performed at 400 to 700 ° C. 4. The method according to claim 1, wherein the iron compound is zirconium oxide (Zr).
O ₂₎ is supported or contained, heavy oil cracking process according to any one of claims 1 to 3. 5. The catalyst according to claim 1, wherein the catalyst carries or contains at least one member selected from the group consisting of zinc oxide, tin oxide, alkali metal oxides and alkaline earth metal oxides. Heavy oil decomposition method. 6. The catalyst according to claim 4, wherein the catalyst comprises 100 parts by weight of the iron compound and 14 parts by weight or less of the zirconium oxide.
Or the heavy oil cracking method according to 5. 7. The heavy oil cracking method according to claim 1, wherein after the heavy oil is mixed with an inert solvent, the obtained mixture is subjected to a cracking reaction of the heavy oil. 8. The heavy oil cracking method according to claim 7, wherein the heavy oil cracking reaction is performed in steam or in an atmosphere containing steam. 9. A heavy oil, an inert solvent and iron hydroxide (Fe
OOH) is heated in steam or in an atmosphere containing steam to obtain a mixture of iron hydroxide (FeOOH), triiron tetroxide (Fe ₃ O ₄ ), and diiron trioxide (Fe ₂ O ₃ ). The heavy oil cracking method according to any one of claims 1 to 6, wherein an iron compound composed of at least one or more is formed and the iron compound is used as a catalyst. 10. The heavy fuel according to claim 7, wherein the catalyst reaction product is separated into gas, light oil, uncracked heavy oil, solvent and water, and the separated solvent is circulated for use. Oil decomposition method. 11. The heavy oil cracking method according to claim 7, wherein a solvent selected from the group consisting of ketone, benzene, phenol and a mixed solvent thereof is used as the inert solvent. 12. The heavy oil cracking method according to claim 1, wherein the catalyst is recovered by magnetic force after the heavy oil cracking treatment.