KR20160138413A - Method for regenerating and utilizing heavy-oil desulfurization catalyst - Google Patents

Abstract

The method for regeneration of heavy oil desulfurization catalyst of the present invention comprises the steps of extracting a heavy oil desulfurization catalyst charged in one heavy oil desulfurization apparatus and having a metal permissible amount MPr1 of less than 0, represented by the following formula (1) A step of regenerating the desulfurization catalyst, and a step of charging the regenerated heavy oil desulfurization catalyst into at least one different heavy oil desulfurization apparatus.
· MPr1 = (PV / 2Vv) × {8 × 10 5 × (PD) 1.3} × (Sp / Vp) - (VA1 + VA2)
Here, PV is the pore volume at the time of the new catalyst, Vv is the volume when 1 mass% of vanadium is deposited on 1 kg of the new catalyst, and it is the volume when it is regarded as vanadium sulfide. PD is the average pore diameter Vp is the average volume of one grain at the time of fresh catalyst, VA1 is the amount of vanadium accumulation (% by mass) accumulated in the original apparatus, and VA2 is the average outer surface area of one grain at the time of fresh catalyst, Is the vanadium accumulation amount in the case of using the catalyst regenerated in the catalyst.

Description

[0001] METHOD FOR REGENERATING AND UTILIZING HEAVY-OIL DESULFURIZATION CATALYST [0002]

The present invention relates to a regeneration utilization method of a heavy oil desulfurization catalyst used for a hydrodesulfurization treatment of heavy oil.

BACKGROUND ART [0002] In petroleum refining, there are many processes for refining various kinds of oil fractions by hydrogenation purification treatment, and various catalysts for the purification have been developed. Examples of such a catalyst include a desulfurization denitration catalyst such as naphtha, kerosene and light oil, a heavy diesel desulfurization denitration catalyst, a decomposition catalyst, and a desulfurization denitration catalyst such as residual oil and heavy oil. Among them, the catalyst used in the hydrogenation refining treatment of naphtha, kerosene, light oil or the like, which has a relatively low boiling point and has almost no metal impurity content such as vanadium, has a small degree of deterioration by use.

Naphtha, kerosene, diesel, and the like are not deteriorated by metal impurities such as vanadium, and deterioration of the catalyst is caused by accumulation of a small amount of carbonaceous material. Thus, when carbon was removed from the catalyst by combustion, the catalyst could be reused. Also, with respect to the removal of carbonaceous material, since the amount of carbonaceous matter on the catalyst was small, the catalyst could be regenerated without strict combustion control. In addition, the degree of deterioration was small in the used catalyst, and such a catalyst could be reused as it is without regeneration treatment.

BACKGROUND ART In recent years, hydrogen reforming catalysts such as heavy oil and reduced pressure light oil have been regenerated and reused, and the regeneration method and reuse method of the catalyst have been established. For example, the hydrocracking catalyst used in the heavy oil light hydrocracking process, and the hydrogenated denitrogen catalyst used for the pretreatment thereof, are regenerated and reused by hydrogen activation or oxygen activation. Since the catalyst used for the hydrogenation purification treatment of these distillate oil is used for a raw material oil having a small amount of metal impurities, deposition of a metal such as vanadium on a catalyst is small. In addition, the carbonaceous material deposited on the catalyst is small, and the carbonaceous material deposited on the catalyst is liable to burn. Therefore, since the surface of the catalyst does not become as high as that at the time of regeneration by combustion, the change of the pore structure of the catalyst and the supported state of the active metal by the regeneration treatment is small and the catalyst is used again for the treatment of effluent oil such as heavy gas oil and reduced pressure gas oil (See Non-Patent Document 1).

However, heavy oil containing oil having a higher boiling point or oil not capable of distillation contains a large amount of components easily susceptible to carbonization, such as asphaltene fraction, and metal impurities, and a large amount of Carbonaceous materials and metal particles are deposited. Since the carbonaceous material can not simply be removed from the spent catalyst in which the carbonaceous and metal fractions are stored at the same time, the carbonaceous material must be removed at a high combustion temperature. Therefore, the change of the pore structure of the catalyst and the supported state of the active metal by the regeneration treatment became large, and the function of the catalyst after the carbonaceous substance was removed remarkably decreased (see Non-Patent Document 2 and Non-Patent Document 3). In view of this, the catalyst used in the hydrogenation purification treatment of heavy oil was disposed of without being reused.

However, in order to reduce waste and reduce the cost of the catalyst, it is very important to regenerate and reuse the catalyst used in the hydrogenation purification treatment of heavy oil. As a recycling method of the regenerated catalyst, for example, a regeneration method of a heavy oil hydrotreating catalyst described in Patent Document 1 and a hydrodesulfurization method of heavy oil described in Patent Document 2 are known. According to the regeneration method of the heavy oil hydrotreating catalyst described in Patent Document 1, the catalyst deactivated by the use in the heavy oil hydrotreating treatment process is regenerated, and the catalyst is regenerated from the pore volume, pore diameter, vanadium accumulation amount and outer surface area per volume Can be used again for the hydrogenation treatment of the heavy oil. Further, according to the hydrodesulfurization method of the heavy oil described in Patent Document 2, the catalyst which has been inactivated by the use in the hydrogenation treatment process such as heavy oil and is not used can be regenerated and effectively utilized.

Japanese Patent No. 3708381 Japanese Patent No. 3527635

 Studies in Surface and Catalysis, vol. 88, P199 (1994)  Catal. Today, vol. 17, No. 4, P539 (1993)  Catal. Rev. Sci. Eng., 33 (3 & 4), P281 (1991)

However, in the regeneration method of the heavy oil hydrotreating catalyst described in Patent Document 1, the physical properties of the used catalyst as a raw material of the regenerated catalyst depend on the raw material and the operating conditions, and thus have a great influence on regeneration. It is not necessarily usable as a regenerated catalyst. In addition, the method of hydrodesulfurization of heavy oil described in Patent Document 2 merely suggests a regeneration method of one apparatus only once, and is not a continuous and stable regeneration method. Therefore, it is an object of the present invention to provide a regeneration utilization method of heavy oil desulfurization catalyst, which can more effectively reuse spent catalyst.

As a result of intensive studies, the inventors of the present invention have found that even when using a catalyst that has been inactivated and used in heavy oil hydrogenation refining process and which can not be regenerated conventionally, the metal permissible amount calculated from the pore volume, pore diameter, vanadium accumulation amount, It is possible to utilize the regenerated catalyst as much as possible stably in many apparatuses by judging and applying the use of the regenerated catalyst in other apparatuses, thereby completing the present invention. That is, the present invention is as follows.

[1] A process for producing a heavy oil desulfurization catalyst, comprising the steps of: extracting an heavy oil desulfurization catalyst charged in one heavy oil desulfurization apparatus and having a metal allowable amount MPr1 of less than 0 expressed by the following formula (1) Wherein the at least one heavy oil desulfurization catalyst is charged to at least one different heavy oil desulfurization apparatus.

· MPr1 = (PV / 2Vv) × {8 × 10 5 × (PD) 1.3} × (Sp / Vp) - (VA1 + VA2) ··· (1)

In the formula (1), each symbol represents the following.

PV: Pore volume at the time of the new catalyst (m ³ / kg)

Vv: Volume when vanadium was deposited on 1 kg of the new catalyst as 3.8 vol% when considered as vanadium sulfide = 3.8 10 ^-6 (m ³ / kg)

PD: Average pore diameter at the time of the new catalyst (m)

Sp: Average external surface area (m ² ) of one grain at the time of the new catalyst

Vp: Average volume of one grain in the new catalyst (m ³ )

VA1: Amount of vanadium accumulated in the original apparatus (mass%) (based on new catalyst)

VA2: Amount of vanadium deposited (mass%) (based on fresh catalyst) when the catalyst regenerated in the same apparatus was used

[2] In the step of charging the regenerated heavy oil desulfurization catalyst to at least one different heavy oil desulfurization apparatus, the regenerated heavy oil desulfurization catalyst may be a reforming catalyst for reforming the heavy fuel oil so that the metal permissible amount MPr2 expressed by the following formula (2) The method for regeneration of heavy oil desulfurization catalyst according to [1], wherein the heavy oil desulfurization catalyst is charged into a heavy oil desulfurization apparatus.

· MPr2 = (PV / 2Vv) × {8 × 10 5 × (PD) 1.3} × (Sp / Vp) - (VA1 + VB1) ··· (2)

In the formula (2), each symbol represents the following.

PV: Pore volume at the time of the new catalyst (m ³ / kg)

Vv: Volume when vanadium was deposited on 1 kg of the new catalyst as 3.8 vol% when considered as vanadium sulfide = 3.8 10 ^-6 (m ³ / kg)

PD: Average pore diameter at the time of the new catalyst (m)

Sp: Average external surface area (m ² ) of one grain at the time of the new catalyst

Vp: Average volume of one grain in the new catalyst (m ³ )

VA1: Amount of vanadium accumulated in the original apparatus (mass%) (based on new catalyst)

VB1: Amount of vanadium deposited (mass%) (based on fresh catalyst) accumulated when a catalyst regenerated in a new apparatus is used

[3] The regeneration utilization method of heavy oil desulfurization catalyst according to [2], wherein the metal permissible amount MPr2 expressed by the formula (2) is in the range of 1 to 5.

According to the present invention, it is possible to provide a regeneration utilization method of a heavy oil desulfurization catalyst which can more effectively reuse the spent catalyst.

1 is a schematic view for explaining a downflow type fixed bed reactor used in an embodiment of the present invention.

The regeneration utilization method of the heavy oil desulfurization catalyst in the present invention includes a step of extracting the heavy oil desulfurization catalyst, a step of regenerating the heavy oil desulfurization catalyst, and a step of charging the heavy oil desulfurization apparatus. Hereinafter, the regeneration utilization method of the heavy oil desulfurization catalyst of the present invention will be described in detail.

[Step of extracting the heavy oil desulfurization catalyst]

The step of extracting the heavy oil desulfurization catalyst according to the present invention is a step of extracting the heavy oil desulfurization catalyst which is filled in one heavy oil desulfurization apparatus and whose metal allowable amount MPr1 expressed by the following formula (1) is less than zero.

· MPr1 = (PV / 2Vv) × {8 × 10 5 × (PD) 1.3} × (Sp / Vp) - (VA1 + VA2) ··· (1)

In the formula (1), each symbol represents the following.

PV: Pore volume at the time of the new catalyst (m ³ / kg)

Vv: Volume when vanadium was deposited on 1 kg of the new catalyst as 3.8 vol% when considered as vanadium sulfide = 3.8 10 ^-6 (m ³ / kg)

PD: Average pore diameter at the time of the new catalyst (m)

Sp: Average external surface area (m ² ) of one grain at the time of the new catalyst

Vp: Average volume of one grain in the new catalyst (m ³ )

VA1: Amount of vanadium accumulated in the original apparatus (mass%) (based on new catalyst)

VA2: Amount of vanadium deposited (mass%) (based on fresh catalyst) when the catalyst regenerated in the same apparatus was used

(Heavy oil desulfurization device)

The heavy oil desulfurization apparatus of the present invention performs desulfurization, denitrification, deoxidization, and hydrocondylation and decomposition of hydrocarbon with heavy oil by a hydrogenation refining process. Further, the heavy oil desulfurization apparatus can perform not only hydrogenation purification such as desulfurization and denitrification but also demetallization and hydrogenolysis of asphaltene. In view of this point, the heavy oil desulfurization apparatus is used not only for the purpose of desulfurization of heavy oil but also in combination with a residual up-grading process such as residual flow catalytic cracking (RFCC), caulking and solvent depletion. The product heavy oil obtained by the heavy oil desulfurization apparatus is used, for example, as RFCC raw material, coker raw material and low sulfur product heavy oil.

Next, the hydrogenation purification treatment performed in the heavy oil desulfurization apparatus will be described. The hydrogenation purification treatment conducted in the heavy oil desulfurization apparatus is not particularly limited as long as the heavy oil can be desulfurized. However, the hydrogenation purification treatment to be carried out in the heavy oil desulfurization apparatus will be explained by taking the hydrogenation purification treatment by the fixed bed reactor as an example. The heavy oil to be a raw material for the hydrogenation refining treatment includes residues such as an atmospheric residue and a reduced-pressure residue. However, the heavy oil does not include only the effluent oil such as kerosene, light oil and reduced pressure light oil. For example, the heavy oil includes 1 mass% or more of sulfur, 200 mass ppm or more of nitrogen, 5 mass% or more of residual coal, 5 ppm or more of vanadium, and 0.5 mass% or more of asphaltene. Examples of the heavy oil include crude oil other than normal pressure residues, asphalt oil, pyrolysis oil, tar sand oil, and mixed oil thereof. The heavy oil to be the raw material for the hydrogenation refining treatment is not particularly limited as long as it is the same as the above, but an atmospheric residue, a decompressed residue, a reduced residue or a mixed oil of an asphalt oil and a decomposed light oil is suitably used as a raw material for the hydrogenation purification treatment.

The reaction temperature for the hydrogenation refining treatment is preferably 300 to 450 캜, more preferably 350 to 420 캜, and still more preferably 370 to 410 캜. The hydrogen partial pressure of the hydrogenation purification treatment is preferably 7.0 to 25.0 MPa, and more preferably 10.0 to 18.0 MPa. The liquid space velocity of the hydrogenation process is purified, preferably 0.01~10h ^-1, and more preferably in the 0.1~5h ^-1, more preferably 0.1~1h ^-1. Hydrogen / feed oil ratio of the hydrogenation process is purified, preferably 500~2,500Nm ³ / kl, and more preferably 700~2,000Nm ³ / kl. On the other hand, the adjustment of the sulfur content of the produced oil and the metal content (vanadium, nickel, etc.) obtained by the hydrogenation refining treatment can be carried out, for example, by appropriately adjusting the reaction temperature in the hydrogenation purification treatment.

(Heavy oil desulfurization catalyst)

The heavy oil desulfurization catalyst in the present invention is a catalyst which is used at least once for the hydrogenation refining treatment of heavy oil, in which a catalyst usually used for desulfurization of heavy oil (including a sulfurized catalyst) is used at least once. Normally, carbon and vanadium are adhered to the catalyst by use. The heavy oil desulfurization catalyst is not particularly limited as long as it is used for the hydrogenation purification treatment of heavy oil. For example, an alumina catalyst carrying molybdenum on an alumina support is used as a heavy oil desulfurization catalyst. In this case, cobalt or nickel is used as a cocatalyst.

The alumina carrier may contain at least one of phosphorus, silicon and boron. The content in the heavy oil desulfurization catalyst in at least one of phosphorus, silicon and boron in terms of oxides is preferably 30.0 mass% or less, more preferably 0.1 to 10.0 mass%, still more preferably 0.2 To 5.0% by mass. However, the content of at least one of phosphorus, silicon and boron in the catalyst is preferably at least one kind selected from the group consisting of phosphorus, silicon and boron, which is oxidized at a temperature of 400 DEG C or higher, The content is expressed in mass%.

The content of molybdenum in the heavy oil desulfurization catalyst is preferably 0.1 to 25.0 mass%, and more preferably 0.2 to 8.0 mass%. The content of cobalt or nickel in the heavy oil desulfurization catalyst is preferably 0.1 to 10.0 mass%, more preferably 0.2 to 8.0 mass%. On the other hand, the metal content in the heavy oil desulfurization catalyst is defined as the mass of the oxide of the metal to be measured, expressed as mass%, by oxidation treatment at a temperature of 400 占 폚 or higher and no loss due to heating.

Since heavy oil contains a large amount of asphaltene and vanadium, carbon fuel and vanadium are deposited in the heavy oil desulfurization catalyst used for the hydrogenation purification treatment of heavy oil. The carbon content covers the catalyst surface of the heavy oil desulfurization catalyst and lowers the catalytic activity of the heavy oil desulfurization catalyst. However, by the regeneration treatment such as the solvent extraction and the oxidation combustion treatment, the carbon content deposited on the heavy oil desulfurization catalyst can be removed, and the catalytic activity of the heavy oil desulfurization catalyst can be increased. The content of the carbon content in the used heavy oil desulfurization catalyst before the regeneration treatment is preferably from 10 to 70 mass%, more preferably from 0.2 to 8.0 mass%. If the content of the carbon content in the heavy oil desulfurization catalyst is more than 70% by mass, the activity of the catalyst is not sufficiently increased even if the regeneration treatment is carried out, or the regeneration treatment at a high temperature is required to increase the activity of the catalyst. There is a case. On the other hand, the content of the carbon content in the heavy oil desulfurization catalyst is defined as the mass of the carbon content in the target catalyst in terms of mass%, with reference to the oxidation of the carbon content at 400 ° C or higher and no loss by heating.

The content of vanadium in the used heavy-fuel desulfurization catalyst before the regeneration treatment is preferably 35 mass% or less, and more preferably 20 mass% or less. If the content of vanadium is larger than 35 mass%, the activity of the catalyst is not sufficiently increased even if the catalyst is subjected to the regeneration treatment, or it is necessary to regenerate the catalyst at a high temperature in order to increase the activity of the catalyst. . Vanadium deposited on the heavy oil desulfurization catalyst can not usually be removed by the regeneration treatment.

The content of vanadium in the used catalyst hardly changes between before and after the regeneration treatment. Therefore, on the basis of the metal permissible amount MPr1 calculated using the content of vanadium in the used catalyst, it is possible to identify a catalyst that can not be used even if it is regenerated with a usable catalyst before the regeneration treatment. Since it is wasteful to regenerate the catalyst that can not be used even when regenerated, it is preferable to selectively remove the catalyst which can not be used even before the regeneration treatment, from the spent catalyst.

The catalyst used for the hydrogenation refining process and the catalyst subjected to the oxidation treatment, particularly the combustion treatment, for the regeneration treatment are different from each other in the case where the pore structure of the catalyst and the supported state of the active metal are changed by the heating of the catalyst during the treatment, . As an index for evaluating these, there is a specific surface area and pore volume of the catalyst. The specific surface area and the pore volume of the catalyst are gradually reduced by the hydrogenation purification treatment and the adhesion of the impurities, and are also likely to be reduced by the regeneration treatment. The specific surface area and pore volume of the heavy oil desulfurization catalyst that has been used are preferably 70% or more of the specific surface area and pore volume of the fresh catalyst, respectively. The specific surface area of the heavy oil desulfurization catalyst that has been used is preferably 60 to 220 m ² / g, and more preferably 100 to ²⁰⁰ m ² / g. The pore volume of the heavy oil desulfurization catalyst that has been used is preferably 0.3 to 1.2 cc / g, and more preferably 0.4 to 0.8 cc / g.

On the other hand, the fresh catalyst is a catalyst which is produced as a catalyst and has never been used for hydrogenation purification treatment. The new catalyst also includes a catalyst which is once used for the hydrogenation purification treatment but is discontinued for a short period of time due to troubles on the apparatus and used again and used as it is. That is, even if the catalyst is temporarily used, a catalyst capable of being used as it is, even if it is subjected to a specific catalytic reaction, or has sufficient hydrogenation activity as originally assumed from the beginning without performing a regeneration process such as screening, . The new catalyst may be a commercially available catalyst or a specially prepared catalyst. The fresh catalyst may be a catalyst obtained by carrying out a sulfurization treatment as a pretreatment for use in a hydrogenation treatment.

(Metal allowance)

The metal permissible amount MPr1 in the above equation (1) is an index for judging whether or not the catalyst regenerated from the heavy oil desulfurization apparatus can be used for a predetermined period in the same heavy oil desulfurization apparatus. As the metal permissible amount MPr1 is larger than 0, deposition of a large amount of vanadium can be allowed, so that the catalyst can be used for a predetermined period in the same heavy oil desulfurization apparatus with sufficient margin. On the other hand, when MPr1 is less than 0 (i.e., negative value), the activity of the regenerated catalyst due to the deposition of vanadium is insufficient for use in the heavy oil desulfurization apparatus before the period of use of the catalyst reaches a predetermined period It becomes. Therefore, by using the metal permissible amount MPr1, it is possible to select heavy oil desulfurization catalyst having no activity that can be used in the heavy oil desulfurization apparatus from the heavy oil desulfurization catalyst deactivated by vanadium deposition on the catalyst, A heavy oil desulfurization catalyst which can not be used in the heavy oil desulfurization apparatus can be specified. In the present invention, the catalyst whose metal allowable amount MPr1 is less than 0 is judged as a catalyst to be withdrawn from the heavy oil desulfurization apparatus. Hereinafter, Formula (1) will be described in detail.

The metal permissible amount MPr1 of the above formula (1) is an index of the amount of vanadium accumulation which can be further allowed until the catalyst is deactivated by the deposition of vanadium and its service life is reached. The smaller this value is, the more vanadium deposition can not be allowed. In the present invention, the MPr1 of the catalyst withdrawn from the heavy oil desulfurization apparatus is less than zero. On the other hand, the value of MPr1 of the commercially available catalyst is usually 50 or less even when the amount of vanadium accumulation (VA1 + VA2) is 0% (new catalyst), 20 to 35 for desmethyl catalyst and 10 to 25 for desulfurization catalyst.

The first term in the above formula (1) represents the permissible vanadium deposition amount in the new catalyst and is determined by the initial physical properties such as the pore volume of the fresh catalyst and does not change by the use and regeneration treatment of the catalyst. PV is the pore volume at the time of the new catalyst. Vv is a volume of vanadium when the vanadium is regarded as vanadium sulfide when the vanadium is deposited on 1 kg of the fresh catalyst and is a constant of 3.8 x 10 ^-6 (m ³ / kg). On the other hand, in ordinary hydrogenation refining treatment, it is considered that vanadium is deposited as vanadium sulfide. PD is the average pore diameter at the time of the new catalyst. Constant 8 × 10 ⁵ × (PD) ^1.3 is the diffusion depth of vanadium into the pores of the catalyst obtained from the analysis results of various catalysts studied. The diffusion depth is usually proportional to (diffusion coefficient / reaction rate constant) ^-0.5 , and the diffusion coefficient is considered to be proportional to the catalyst pore diameter (see Chapter 5 of the revised Chemical Engineering Manual, Chapter 27). However, according to the studies of the present inventors, it has been found that the present catalyst is proportional to ^1.3 (catalyst pore diameter PD) as described above.

Sp is the outer surface area of one grain at the time of new catalyst, and is actually a value as an average value. Vp is the volume of one grain at the time of the new catalyst, and is an average value similarly to Sp. (Sp / Vp) is the outer surface area per volume of the individual catalyst as an average, and is specified by the shape at the time of producing the new catalyst.

The VA1 of claim 2 is used for a predetermined period of time in a heavy oil desulfurization apparatus (hereinafter, this heavy oil desulfurization apparatus is referred to as "A apparatus" in order to distinguish the new catalyst from at least one other heavy oil desulfurization apparatus described later) (Mass%)) of the vanadium accumulation amount accumulated at the time when the catalyst is accumulated. VA2 is an actual value or a predicted value of the vanadium accumulation amount (new catalyst standard (mass%)) accumulated when the regenerated catalyst regenerating the fresh catalyst used in the apparatus A is used for a required period in the apparatus A. When VA1 is less than 0.5% by mass, deposition of vanadium in the catalyst is small, and the used catalyst can be reused without regeneration. Therefore, the used catalyst to be subjected to the regeneration treatment preferably has a VA1 of 1.0% by mass or more. On the other hand, VA1 and VA2 are expressed as the accumulation amount of vanadium deposited on the catalyst, but vanadium contained in the catalyst does not necessarily have to be deposited on the catalyst. For example, the amount of vanadium entering the pores of the catalyst, entering the catalyst, or reacting with the catalyst component, etc., is included in the accumulation amount of vanadium. The values of VA1 and VA2 of the used catalyst are usually 0 to 70 mass%. In the upstream portion of the reaction zone of the apparatus A, the values of VA1 and VA2 are as high as 30 to 70 mass%.

[Process for regenerating the heavy oil desulfurization catalyst]

In the step of regenerating the heavy oil desulfurization catalyst in the present invention, the recovered heavy oil desulfurization catalyst is regenerated. The regeneration treatment performed in the step of regenerating the heavy oil desulfurization catalyst can be carried out, for example, by removing oil and the like by solvent washing, removing carbon powder, sulfur and nitrogen components by oxidation treatment, Removal of the catalyst in a normal shape by removing the catalyst, and the like. The oxidation treatment is preferably performed outside the reactor.

In a preferable regeneration treatment of a used catalyst having a large amount of carbon particles, the used catalyst is first washed with a solvent. Preferred solvents include, for example, toluene, acetone, alcohol, and naphtha, petroleum such as kerosene and light oil. In this cleaning treatment, for example, while the catalyst is in the hydrogenation purification treatment reactor, the light oil is circulated to clean the catalyst, and then a gas such as nitrogen gas at about 50 to 300 ° C is circulated to dry the catalyst. Alternatively, the diesel may be circulated to be cleaned and then taken out as it is. In order to prevent the generation of heat and spontaneous ignition, the catalyst may be damped with light oil and dried when necessary. There is also a method of removing the crushing, differentiation (pulverization) catalyst, scale and the like of the mass from the used catalyst extracted from the reactor, washing it with light oil and further washing with naphtha to make the catalyst easy to dry. When the amount of the used catalyst is small, the method of cleaning the catalyst with toluene is suitable for completely removing the oil from the catalyst.

In order to recover the catalytic activity of the catalyst from which oil and impurities have been removed by washing, it is necessary to further remove the carbon powder deposited on the catalyst by oxidation treatment. The oxidation treatment is generally performed by a combustion treatment in which the atmospheric temperature and the oxygen concentration are controlled. If the atmospheric temperature is excessively high or the oxygen concentration is too high, the surface of the catalyst becomes hot and the crystal form and the supported state of the supported metal are changed, or the pores of the support are decreased, and the catalytic activity is sometimes lowered. If the atmospheric temperature is excessively low or the oxygen concentration is too low, the removal of the carbon content by combustion may be insufficient and the catalytic activity may not be sufficiently recovered in some cases. The atmospheric temperature of the combustion treatment is preferably 200 to 800 deg. C, and more preferably 300 to 600 deg.

It is preferable to control the oxygen concentration in the combustion process in accordance with the combustion method, in particular, the state of contact between the combustion gas and the catalyst. For example, the oxygen concentration in the combustion treatment is preferably 1 to 21% by volume. The surface temperature of the catalyst is controlled by adjusting the atmospheric temperature, the oxygen concentration and the flow rate of the atmospheric gas in the combustion process, and the change in the crystal structure of the metal such as molybdenum in the catalyst during the combustion process and the change Or to prevent the reduction of the specific surface area and the pore volume of the catalyst.

It is preferable to remove the catalyst or the like differentiated from the burned catalyst and use only the catalyst of the normal shape as the regeneration catalyst. If the differentiated catalyst remains in the catalyst, clogging and drift may occur in the catalyst bed in the reactor, or the pressure loss of the fluid in the reactor may become large, so that normal operation of the reactor may not be continued.

[Process to charge the heavy oil desulfurization apparatus]

In the step of charging the heavy oil desulfurization apparatus of the present invention, the regenerated heavy oil desulfurization catalyst is charged into at least one different heavy oil desulfurization apparatus. As a result, in the heavy oil desulfurization apparatus that has discharged the heavy oil desulfurization catalyst in the process of extracting the heavy oil desulfurization catalyst, the spent catalyst that can not be reused can be reused and the spent catalyst can be more effectively reused.

The heavy oil desulfurization apparatus for filling the regenerated heavy oil desulfurization catalyst is not particularly limited as long as it is a heavy oil desulfurization apparatus different from the heavy oil desulfurization apparatus in which the heavy oil desulfurization catalyst is extracted in the step of extracting the heavy oil desulfurization catalyst. Further, the heavy oil desulfurization apparatus for charging the regenerated heavy oil desulfurization catalyst may be one or two or more. The heavy oil desulfurization apparatus in the step of charging the heavy oil desulfurization apparatus is the heavy oil desulfurization apparatus similar to that described in the step of extracting the heavy oil desulfurization catalyst, so that the description of the heavy oil desulfurization apparatus is omitted.

In the present invention, the regenerated heavy oil desulfurization catalyst may be charged to the heavy oil desulfurization apparatus in which the metal allowable amount MPr2 expressed by the following formula (2) is 0 or more. As a result, it is desirable to appropriately select another heavy oil desulfurization apparatus capable of reusing the used catalyst.

· MPr2 = (PV / 2Vv) × {8 × 10 5 × (PD) 1.3} × (Sp / Vp) - (VA1 + VB1) ··· (2)

In the formula (2), each symbol represents the following.

PV: Pore volume at the time of the new catalyst (m ³ / kg)

Vv: Volume when vanadium was deposited on 1 kg of the new catalyst as 3.8 vol% when considered as vanadium sulfide = 3.8 10 ^-6 (m ³ / kg)

PD: Average pore diameter at the time of the new catalyst (m)

Sp: Average external surface area (m ² ) of one grain at the time of the new catalyst

Vp: Average volume of one grain in the new catalyst (m ³ )

VA1: Amount of vanadium accumulated in the original apparatus (mass%) (based on new catalyst)

VB1: Amount of vanadium deposited (mass%) (based on fresh catalyst) accumulated when a catalyst regenerated in a new apparatus is used

The metal permissible amount MPr2 of the above formula (2) can be obtained by using the heavy oil desulfurization apparatus (apparatus A) It is an indicator for judging whether or not it is usable. As the metal permissible amount MPr2 is larger than 0, the catalyst can be used for a predetermined period in the B apparatus with margin. On the other hand, when MPr2 is less than 0, the activity of the regenerated catalyst is insufficient for use in the B apparatus due to deposition of vanadium before the period of use of the catalyst reaches a predetermined period. However, in the case of VA2 > VB1, even if it can not be used in the A device, there is a possibility that the device becomes usable in the B device. It is possible to quantitatively judge this by using the index of the metal allowable amount MPr2. The metal permissible amount MPr2 in the B apparatus is 0 or more, preferably 1 or more and 5 or less, and more preferably 3 or more and 5 or less. The expression (2) is the same as the above (1) except that VA1 + VA2 is changed to VA1 + VB1, and therefore the description of the expression (2) is omitted. VB1 is an actual value or a predicted value of the vanadium accumulation amount (new catalyst standard mass%) accumulated when the new catalyst is used in the B apparatus for a predetermined period.

Since the metal allowable amount MPr1 of the above formula (1) is less than 0, the used catalyst can not be used in the apparatus A. However, since the metal allowable amount MPr2 of the above formula (2) is 0 or more, the used catalyst can be used in the apparatus B. As described above, it is possible to appropriately select an apparatus which can use the used catalyst which can not be used in the apparatus A based on the metal allowable amount MPr2 of the catalyst. VA1 can be defined as a cumulative vanadium accumulation amount after multiple regeneration and use, and MPr2 can also be used for judging whether or not the catalyst can be used after regenerating and using it plural times. On the other hand, the catalyst extracted from the apparatus A and regenerated does not necessarily have to be used in one apparatus B, and can be used in a plurality of apparatuses when the condition represented by MPr2 is satisfied.

Example

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited at all by these examples.

[Characteristics of Raw Heavy Oil]

The raw material heavy oil used in each of the examples and comparative examples was evaluated as follows. Atmospheric pressure residues were used for raw fuel oil.

(density)

The density of the atmospheric pressure residue at 15 캜 was measured in accordance with JIS K 2249.

(Kinematic viscosity)

And the kinematic viscosity at normal pressure at 50 캜 was measured according to JIS K 2283.

(Content of xanthan powder)

The content of residual carbon monoxide remaining in normal pressure was measured according to JIS K 2270.

(Asphaltene content)

The content of asphaltene fraction of atmospheric pressure was measured according to IP 143.

(Content of sulfur)

According to JIS K 2541, the content of sulfur residue at atmospheric pressure was measured.

(Content of nitrogen content)

And the content of nitrogen content of atmospheric pressure residual oil was measured according to JIS K 2609.

(Content of vanadium)

The content of vanadium in the residual atmospheric pressure was measured according to the Petroleum Institute Act JPI-5S-10-79.

(Content of nickel)

The content of atmospheric pressure nickel was measured according to the Petroleum Institute Act JPI-5S-11-79.

(Distillation property)

The distillation property of the atmospheric residual solution was measured according to JIS K 2254.

[Characteristics of catalyst]

The catalysts used in each of the Examples and Comparative Examples were evaluated as follows.

For the elemental analysis of vanadium and the like, calcination was conducted at 650 ° C for 1 hour. Molybdenum and vanadium were dissolved as an ash in the acid, and then subjected to inductively coupled plasma luminescence absorption spectrometry, and cobalt and nickel were mixed with ash and lithium tetraborate Was made into beads by high frequency superheating and analyzed by fluorescent X-ray analysis. The carbon content is also 15% (the carbon content in the catalyst is expressed as% by mass of carbon in the target catalyst, based on the oxidation of the target catalyst at 400 ° C or higher until it is no longer reduced) Or less, preferably 10% or less. The carbon content is often about 10 to 70% at the stage of use, but the carbon content can be removed from the catalyst phase by the regeneration treatment to reduce the content thereof. If the carbon content is excessively high, it covers the catalyst surface to lower the catalytic activity, but if the carbon content is reduced by the regeneration treatment, the activity can be restored. On the other hand, for the analysis of carbon and sulfur, the crushed samples were analyzed by a C-S coincidence analyzer. The average length of the catalyst was averaged by measuring the length in the direction perpendicular to the cross section of the particles of 10 particles arbitrarily extracted with a vernier caliper. The average outer surface area and average volume of one grain were calculated from the shape of the grain cross-sectional area and the average length.

[Characteristics of Generated Significance]

In each of the examples and the comparative examples, the product oil obtained from the raw material heavy oil by the hydrogenation refining treatment was evaluated in the same manner as the evaluation of the properties of the raw material heavy oil. The evaluation method of the significance of the production is the same as the evaluation method of the property of the raw material heavy oil described above, so that the description of the method of evaluation of the property of production is omitted.

[Production of the new catalyst used in each of the examples and comparative examples]

630 g of molybdenum oxide and 150 g of basic nickel carbonate in terms of NiO were dissolved in deionized water using 180 g of malic acid to prepare an impregnation solution of 2000 milliliters. A 4,000 g four-leaf alumina carrier (specific surface area 230 m ² / g, average pore size 120 angstrom, pore volume 0.69 ml / g) was prepared so as to have a water content of the impregnation solution suitable for the absorption amount of the following carrier This impregnation solution was impregnated for 15 minutes. The alumina support impregnated with the impregnation solution was dried at 120 ° C. for 3 hours and calcined at 500 ° C. for 5 hours to obtain a new catalyst 1.

[Production of regenerated catalyst used in each of the examples and comparative examples]

(Example 1)

- Hydrogenation refining treatment with new catalyst -

As shown in Fig. 1, the downflow type fixed bed reactor was divided into four beds (four equal parts on a volume basis), a commercially available datalite catalyst on the most upstream side bed (hereinafter referred to as "first bed" (Second to fourth beds) were charged with fresh catalyst 1. Table 1 below shows the physical properties and metal permissible amount of the fresh catalyst 1. After the usual preliminary sulfuration treatment, the reaction temperature was adjusted so that the sulfur was kept constant (0.3 mass% or less) under the reaction condition 1 shown in the following Table 3, using the atmospheric pressure residue 1 shown in the following Table 2 And the hydrogenation purification treatment was carried out for 330 days. The reaction temperature at 330 days was 396 ° C. The properties of the product oil 1 obtained from the atmospheric residue 1 by the hydrogenation purification treatment are shown in Table 4 below.

- Playback processing -

After the catalyst 1 in the reactor was washed with light oil and dried and cooled while flowing nitrogen gas, the used catalyst was taken out from the second to fourth beds of the reactor and mixed well to obtain the used catalyst 1 . On the other hand, the physical properties and the metal tolerance of the used catalyst 1 are shown in Table 1 below. Thereafter, the massive water and the fine powder were removed from the used catalyst 1 by a sieve. Approximately 300 g of the used catalyst 1 from which the massive water and the debris were removed was heated at a heating temperature of 300 DEG C while supplying 100% nitrogen gas at a flow rate of 100 cc / min using a rotary firing furnace (rotational speed: 5 rpm) For 1 hour. Thereafter, the mixed gas of 50% nitrogen gas and 50% air was supplied at a flow rate of 100 cc / min while being fired at a firing temperature of 450 캜 for 3 hours. After the fired used catalyst 1 was cooled, And the separated product were removed from the spent catalyst 1 to obtain a regenerated catalyst 1. The physical properties and the metal tolerance of the regenerated catalyst 1 are shown in Table 1 below. On the other hand, the value of VA2 is the value of V2 of Comparative Example 1 described later.

- Hydrogenation purification treatment by regenerated catalyst -

The downflow type fixed-bed reactor was divided into four beds (four equal parts based on volume), and a regeneration catalyst 1 was charged in the first bed with a commercially available delegate catalyst and the second to fourth beds directly under the same. After the usual preliminary sulphurization treatment, the reaction mixture was subjected to the reaction at a reaction temperature of not higher than 0.3% by mass in the reaction condition 2 shown in the following Table 3, using the atmospheric pressure residue 2 shown in the following Table 2, The hydrogenation purification treatment was carried out for 330 days. The reaction temperature on day 330 was 398 ° C. The properties of the product oil 2A obtained from the atmospheric pressure residue 2 by the hydrogenation purification treatment are shown in Table 4 below. On the other hand, the downflow type fixed bed reactor is the same as that used for the hydrogenation purification treatment by the fresh catalyst, but by using the atmospheric pressure residue 2 having a vanadium content lower than that of the normal pressure residue 1 as raw material heavy oil, .

- Playback processing -

The used regenerated catalyst 1 was regenerated in the same manner as the regeneration process of the used catalyst 1 to obtain the regenerated catalyst 2A. The physical properties and the metal tolerance of the regenerated catalyst 2A are shown in Table 1 below.

(Comparative Example 1)

- Hydrogenation refining treatment with new catalyst -

Hydrogenation purification treatment was carried out under the reaction condition 1 shown in the following Table 3 by using the atmospheric pressure residue 1 and the fresh catalyst 1 shown in the following Table 2 in the same manner as in Example 1.

- Playback processing -

In the same manner as in Example 1, the used catalyst 1 was regenerated to obtain a regenerated catalyst 1.

- Hydrogenation purification treatment by regenerated catalyst -

The downflow type fixed-bed reactor was divided into four beds (four equal parts based on volume), and a regeneration catalyst 1 was charged in the first bed with a commercially available delegate catalyst and the second to fourth beds directly under the same. After the usual preliminary sulfidation treatment, the reaction mixture was subjected to a preliminary sulfidation treatment using the atmospheric pressure residue 1 shown in the following Table 2 under the reaction condition 1 shown in the following Table 3 so that the sulfur content became constant (0.3 mass% or less) The hydrogenation purification treatment was carried out for 330 days. The reaction temperature at 330 days was 408 ° C. The properties of the product oil 2B obtained from the atmospheric residue 1 by the hydrogenation purification treatment are shown in Table 4 below.

- Playback processing -

The used regenerated catalyst 1 was regenerated in the same manner as the regeneration process of the used catalyst 1 to obtain the regenerated catalyst 2B. The physical properties and the metal tolerance of the regenerated catalyst 2B are shown in Table 1 below.

From the results of Example 1 and Comparative Example 1, it can be seen that the used catalyst can be used for another predetermined period of time by using it in another apparatus in which the value of MPr2 is 0 or more even when the value of MPr1 is less than 0 . On the other hand, the ratio of the sulfur content of the product oil 2A of the example 1 is larger than the sulfur content of the product oil 2B of the comparative example 1, but the target value of the produced sulfur oil is high in a device with a low load on the catalyst, There is no problem in using the used catalyst of No. 1. On the other hand, in the used catalyst of Comparative Example 1, the apparatus having a high load on the catalyst is assumed, and the target value of the sulfur content of the produced sulfur is low, so that the property of the product oil 2B of Comparative Example 1 is insufficient.

1: first bed
2: second bed
3: third bed
4: fourth bed

Claims (3)

Removing a heavy oil desulfurization catalyst which is charged in one heavy oil desulfurization apparatus and whose metal allowable amount MPr1 expressed by the following formula (1) is less than 0;
Recovering the recovered heavy oil desulfurization catalyst;
Further comprising the step of charging the regenerated heavy oil desulfurization catalyst to at least one different heavy oil desulfurization apparatus.
· MPr1 = (PV / 2Vv) × {8 × 10 5 × (PD) 1.3} × (Sp / Vp) - (VA1 + VA2) ··· (1)
In the formula (1), each symbol represents the following.
PV: Pore volume at the time of the new catalyst (m ³ / kg)
Vv: Volume when vanadium was deposited on 1 kg of the new catalyst as 3.8 vol% when considered as vanadium sulfide = 3.8 10 ^-6 (m ³ / kg)
PD: Average pore diameter at the time of the new catalyst (m)
Sp: Average external surface area (m ² ) of one grain at the time of the new catalyst
Vp: Average volume of one grain in the new catalyst (m ³ )
VA1: Amount of vanadium accumulated in the original apparatus (mass%) (based on new catalyst)
VA2: Amount of vanadium deposited (mass%) (based on fresh catalyst) when the catalyst regenerated in the same apparatus was used The method according to claim 1,
In the step of charging the regenerated heavy oil desulfurization catalyst into at least one different heavy oil desulfurization apparatus,
Wherein the regenerated heavy oil desulfurization catalyst is charged into a different heavy oil desulfurization apparatus such that the metal permissible amount MPr2 expressed by the following formula (2) is 0 or more.
· MPr2 = (PV / 2Vv) × {8 × 10 5 × (PD) 1.3} × (Sp / Vp) - (VA1 + VB1) ··· (2)
In the formula (2), each symbol represents the following.
PV: Pore volume at the time of the new catalyst (m ³ / kg)
Vv: Volume when vanadium was deposited on 1 kg of the new catalyst as 3.8 vol% when considered as vanadium sulfide = 3.8 10 ^-6 (m ³ / kg)
PD: Average pore diameter at the time of the new catalyst (m)
Sp: Average external surface area (m ² ) of one grain at the time of the new catalyst
Vp: Average volume of one grain in the new catalyst (m ³ )
VA1: Amount of vanadium accumulated in the original apparatus (mass%) (based on new catalyst)
VB1: Amount of vanadium deposited (mass%) (based on fresh catalyst) accumulated when a catalyst regenerated in a new apparatus is used 3. The method of claim 2,
Wherein the metal permissible amount MPr2 represented by the formula (2) is 1 or more and 5 or less.

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