KR20120124047A - Regenerated or remanufactured catalyst for hydortreating of heavy residue - Google Patents

Abstract

PURPOSE: A recycled or regenerated catalyst for a heavy crude oil hydrogenization process is provided to selectively remove vanadium elements from a used catalyst. CONSTITUTION: A recycled or regenerated catalyst for a heavy crude oil hydrogenization process includes active components and a carrier, and contains less than 1wt% of vanadium oxide measured by XRF. The active components are selected from the group consisting of molybdenum, tungsten, cobalt, nickel, and their oxide. The active components contains the molybdenum or the tungsten as a main catalyst, and the cobalt or the nickel as a co-catalyst.

Description

Regenerated or remanufactured catalyst for hydortreating of heavy residue}

The present invention relates to a regeneration or remanufacture catalyst for heavy oil hydrotreatment and a process for the preparation thereof. More specifically, after using heavy oil hydroprocessing catalysts such as residue hydrodesulfurization (RHDS) or denitrification catalysts, recovering valuable metals after recovering valuable metals or restoring the reduced catalytic activity of waste catalysts to be disposed of to 90% to 100%. The present invention relates to the regeneration or remanufacture of spent catalyst.

In petroleum refining, there are many processes for purifying various residues by hydrogenation. Desulfurization or denitrification processes such as, for example, naphtha, kerosene, or light oil; Desulfurization or denitrogenation process with heavy diesel oil; And desulfurization and denitrification of residue oil or heavy oil.

Especially, the catalyst used for the hydrogenation process of processing naphtha, kerosene, or light oil which has comparatively low boiling point and little metal impurity content, such as vanadium, has little degree of deterioration with use. In addition, these catalysts are deteriorated with use due to the accumulation of almost a small amount of carbonaceous material, which can be reused by removing them by combustion or the like. In addition, since the amount of carbonaceous on the catalyst is small also for the removal of carbonaceous, it is possible to obtain a reusable catalyst without requiring strict combustion control. In addition, even a catalyst once used may have a catalyst having a low degree of deterioration, and this can be reused as it is. These catalysts are again used for the treatment of naphtha, kerosene, or diesel without paying special attention.

In addition, although the hydrogenation catalyst of heavy gas oil and reduced pressure gas oil is reused by regeneration etc., the regeneration and use method thereof are also established. For example, in the heavy gasoline hydrocracking step, it is known that a hydrocracking catalyst and a hydrodenitrification catalyst for pretreatment can also be recycled and used by hydrogen activation or oxygen activation. Since the catalysts used in these hydrogenation treatments have almost no metal impurities in the treated raw material oil, there is little deposition of metal such as vanadium due to the raw materials even on the catalyst. In addition, it is easy to burn carbonaceous materials as well as deposits of carbonaceous materials, and the catalyst surface does not become very hot even when regenerated by combustion, and changes in the pore structure of the catalyst carrier and the supporting state of the active metal are small. Again, it could be used for the treatment of effluent oils such as heavy gas oil or reduced pressure gas oil (Stadies in Surface and Catalysis vol. 88 P199 (1994)).

However, in the hydrogenation of residue oil or heavy oil containing a higher boiling point or a residue which cannot be distilled, the raw material oil contains not only a high content of metal impurities but also a component which is easy to carbonize, such as an asphalt component. It contains a lot. Therefore, metal impurities or carbonaceous materials are included in a large amount on the used catalyst. In addition, qualitatively used catalysts, in which both metal and carbonaceous materials were accumulated, could not be simply burned and removed. (Catal. Today vol. 17 No. 4 P539 (1993), Catal. Rev. Sci. Eng. 33 (3 & 4) P281 (1991). For this reason, these spent catalysts were disposed of without being reused.

Heavy oil hydroprocessing catalysts, especially heavy oil desulfurization catalysts, are engaged not only in Korea but also in advanced nations, with the expansion and expansion of advanced facilities (heavy oil cracking processes) called the second oil field. Currently, Korea has a demand of 23,000 tons per year from four major refiners. These catalysts are all depended on imports, and the import price is currently about $ 20 / kg, which is more than about 500 billion won a year.

Such heavy oil desulfurization catalysts have a lifespan of 3-4 months for guard catalysts (mainly metals removed from heavy oil desulfurization shear), about 1 year for this catalyst, and are pulverized after use to recover only valuable metals or have low economic feasibility. It is the situation to bury in designated waste.

Generally, high temperature soda method, solvent extraction method, ion exchange method, and precipitation method are used for recovering valuable metals from spent petroleum desulfurization catalysts. Through the calcination process, valuable metals are recovered in the form of oxides. On the other hand, Korean Patent Laid-Open No. 2001-0022250 includes the steps of washing the waste catalyst using a solvent; Although a process for regenerating heavy oil hydrogenation including oxidizing a washed catalyst under an oxygen atmosphere to remove carbonaceous material, vanadium present in a spent catalyst cannot be selectively removed.

The present invention is to solve the above-mentioned problems of the prior art, an object of the present invention is a metal containing a sulfur component, carbonaceous component, vanadium oxide which is present in the waste catalyst hydrogenated heavy oil or residue oil to deactivate the activity It is to provide a regeneration or preparation catalyst for the hydrogenation of heavy oil or residue oil from which components have been efficiently removed.

Another object of the present invention is to provide a method for producing a regeneration catalyst for the hydrogenation of heavy oil or residue oil.

Still another object of the present invention is to provide a method for preparing a preparation catalyst for the hydrogenation of heavy oil or residue oil.

It is still another object of the present invention to provide a method for selectively removing vanadium elements from a spent catalyst containing vanadium elements.

It is still another object of the present invention to provide a process for the hydrogenation of heavy oil or residue oil using a regeneration or remanufacture catalyst for hydrogenation of heavy oil or residue oil.

It is still another object of the present invention to provide a hydrogenation method of heavy oil or residue oil which simultaneously uses a regeneration catalyst for hydrogenation of heavy oil or residue oil and a new catalyst.

The present invention comprises an active ingredient and a carrier,

The present invention relates to a regeneration or remanufacturing catalyst for hydrogenation of resid or heavy oil having a content of vanadium oxide of 1% by weight or less as measured by XRF.

The present invention also comprises a washing step of removing the residue or heavy oil from the waste catalyst by contacting the solvent with the waste catalyst for the hydroprocessing of the residue or heavy oil;

A heat treatment step of removing the carbon and sulfur dioxide by heat treating the washed catalyst; And

The present invention relates to a method for producing a regeneration catalyst for hydrogenation of resid or heavy oil comprising an acid treatment step of contacting a heat treated catalyst with an oxalic acid solution to remove metal impurities.

The present invention also comprises a washing step of removing the residue or heavy oil from the waste catalyst by contacting the solvent with the waste catalyst for the hydroprocessing of the residue or heavy oil;

A heat treatment step of removing the carbon and sulfur dioxide by heat treating the washed catalyst; And

An acid treatment step of contacting the heat treated catalyst with an acidic solution to remove metal impurities; And

It relates to a process for the preparation of a reprocessing catalyst for the hydrogenation of residue or heavy oil comprising the step of supporting an additional active ingredient in an acid treated catalyst.

The present invention also relates to a method for the selective removal of elemental vanadium comprising contacting a spent catalyst comprising elemental vanadium with an oxalic acid solution and impurities.

The present invention also provides a regeneration or remanufacturing catalyst comprising an active ingredient and a carrier, the content of vanadium oxide being 1 wt% or less as measured by XRF; And it relates to a process for the hydrogenation of heavy oil or residue oil comprising the step of contacting heavy oil or residue oil.

The present invention also relates to a process for hydroprocessing heavy oil or residue oil by contacting a layer containing a hydrotreatment catalyst with heavy oil or residue oil,

The hydroprocessing catalyst layer comprises an active ingredient and a carrier, and relates to a hydrogenation method of heavy oil or remnant oil comprising a regeneration or remanufacture catalyst and a new catalyst having a content of vanadium oxide of 1% by weight or less as measured by XRF.

The regenerated or remanufactured catalyst according to the present invention can be easily removed and reused by recovering more than 95% of its performance on a new catalyst basis. Can be reduced.

Figure 1 shows the results of the leaching reaction of the oxalic acid solution of molybdenum and vanadium as the main active component of the spent catalyst (the left side is MoO ₃ , the right side is V ₂ O ₅ ).
2 to 4 show the results of examining the leaching effects of MoO ₃ and V ₂ O ₅ when malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid were used (left side Is MoO ₃ and on the right is V ₂ O ₅ ).

The terms used in the present invention are as follows.

Heavy oil or resid oil means containing distillation residue components, such as a low pressure residual oil and a reduced pressure residual oil, and does not include what consists only of outflow oils, such as kerosene, light oil, and vacuum gas oil. Usually, heavy oil contains 1 weight% or more of sulfur components, 200 weight ppm or more of nitrogen components, 5 weight% or more of xanthan components, 5 ppm or more of vanadium, and 0.5 weight% or more of asphalt components. For example, crude oil, asphalt oil, pyrolysis oil, tar sand oil, or mixed oil containing them, etc. are mentioned besides the said atmospheric residual oil.

The new catalyst is preferably prepared as a hydrotreating catalyst such as desulfurization, demetallization, denitrification, decomposition, etc. of heavy oil, or may simultaneously have hydroprocessing activity such as desulfurization, demetalization, denitrification, decomposition, and the like. In general, a commercially available hydrodesulfurization catalyst, a hydrodesulfurization catalyst, and the like may be prepared, and a catalyst having a hydroprocessing function may be specially manufactured. These are not only used for the hydrogenation treatment as a catalyst but also once used for the hydrogenation treatment, but they are also used for a short period of time due to a problem in the apparatus and then used again as it is. That is, even if it is used temporarily, even if it does not carry out a special activation treatment, the catalyst which still has sufficient hydroprocessing activity considered from the beginning is also included.

The spent catalyst refers to a catalyst in which the new catalyst is once used for hydroprocessing such as heavy oil or residue oil, and as such, sufficient hydrogenation activity cannot be obtained. The dehydrogenation treatment is generally a desulfurization treatment, but may be a hydrogenation treatment such as demetallization, denitrogenation, dearomatization, and decomposition. Moreover, although heavy oil processing is common, the used catalyst may be regenerated for the hydrogenation of effluent oils, such as heavy diesel oil. The regeneration catalyst may be used for the hydrogenation of heavy oil. Generally, in heavy oil desulfurization catalysts, vanadium is deposited on the catalyst at least 10% from crude oil during desulfurization, at least 5% of carbon, which is a combustible material, and at least 10% is deposited on sulfur. Sulfur and carbon components deposited on the catalyst can be removed by an appropriate method, but vanadium is not easy to remove. Therefore, it is most important to selectively completely remove only the deposited vanadium without removing the metal active component of the catalyst.

The table below shows the typical composition of typical heavy oil spent catalysts in Table 1.

Kinds Mo V Ni Co Fe P S Al Moisture + Oil Waste catalyst
(weight%) 3 to 6 2-12 2 ~ 3 0.5 ~ 1 0.5 ~ 1 0.1 or less 8-12 honey. 5-12

Regeneration catalyst is to remove and activate the waste catalyst by the regeneration treatment process according to the present invention.

The remanufacturing catalyst is to carry an active ingredient in addition to the regeneration catalyst.

The present invention comprises an active ingredient and a carrier,

The present invention relates to a regeneration or remanufacturing catalyst for hydrogenation of resid or heavy oil having a content of vanadium oxide of 1% by weight or less as measured by XRF.

Active ingredients of the regeneration or remanufacturing catalyst according to the invention are known in the art and include, but are not limited to, for example, one or more selected from the group consisting of molybdenum, tungsten, cobalt, nickel and oxides thereof.

More specifically, the active ingredient may include molybdenum or tungsten as the main catalyst and cobalt or nickel as the cocatalyst.

The carrier is alumina; Alternatively, a carrier in which phosphorus, boron, silicon or oxides thereof are supported on alumina may be used, but is not limited thereto.

For example CoMo, NiMo, CoW, or NiW / γ-Al ₂ O ₃ depending on the combination.

Regeneration or remanufacturing catalyst according to the present invention is characterized in that the content of vanadium oxide measured by XRF is 1% by weight or less, sulfur trioxide content is 1% by weight or less. Specifically, the present invention selectively removes only a similar metal component or vanadium oxide, which is a poisonous substance of the active component, from the catalyst on which an active component such as molybdenum, tungsten, cobalt, and nickel oxide is carried, thereby maintaining the content at 1% by weight or less. However, the main catalyst components such as molybdenum or tungsten are characterized by containing at least 70%, preferably at least 80%, more preferably at least 90% relative to the new catalyst. The vanadium oxide content and sulfur trioxide content measured by the XRF may be, for example, 0.9 wt% or less, 0.8 wt% or less, 0.6 wt% or less, 0.5 wt% or less, 0.4 wt% or less, or 0.3 wt% or less. When the content of vanadium oxide and the content of sulfur trioxide are more than 1% by weight, respectively, the catalytic activity is low, which is not suitable for use as a regeneration or remanufacturing catalyst.

The regenerated or remanufactured catalyst according to the invention also has a BET specific surface area of at least 200 m 2 / g, for example at least 210 m 2 / g, at least 220 m 2 / g or at 230 to 300 m 2 / g. In the case of the spent catalyst, impurities are deposited in the pores so that the BET specific surface area is 100 m 2 / g or less, for example, 80 m 2 / g or less. However, the regenerated or remanufactured catalyst according to the present invention may exhibit activity similar to the new catalyst with a specific surface area of at least 80%, preferably at least 85%, more preferably at least 90%, compared to the new catalyst.

In addition, the regenerated or remanufactured catalyst according to the present invention has a vanadium element value of 50 ppm or less, for example, 40 ppm or less, 30 ppm or less, or 5 to 30 ppm when analyzing ICP elements. In the case of the waste catalyst, the element vanadium value of the catalyst poisoning component is 150 ppm or more, for example, 200 ppm or more, and the elemental value of the sulfur component is 800 ppm, for example, 1000 ppm or more. However, the regenerated or remanufactured catalyst according to the present invention has a low vanadium element value of 50 ppm and a sulfur element value of 100 ppm, for example, 80 ppm or less, and thus may exhibit excellent activity due to a low content of the catalyst poisoning substance.

The exact value of the vanadium or sulfur-based component of the regeneration or remanufacturing catalyst described above may be changed depending on the amount of vanadium or sulfur-based component remaining in the spent catalyst, and the amount of vanadium or sulfur-based component remaining in the spent catalyst may be Is changed depending on the amount of vanadium or sulfur-based components of the heavy oil or residue oil treated.

The regenerated or remanufactured catalyst of the present invention has a vanadium oxide content of 15% or less, for example, 10% or 8% or less, based on the waste catalyst, and a sulfur trioxide content measured by XRF. 10% or less, for example 5% or less, or 2% or less. In contrast, the regenerated or remanufactured catalysts of the present invention have a content of active components, such as nickel oxide, molybdenum oxide, or cobalt oxide, as measured by XRF of at least 80%, eg 90, based on the new catalyst. More than%, or more than 95%.

Therefore, in the regeneration or remanufacturing catalyst of the present invention, the amount of the active ingredient of the catalyst is similar to that of the new catalyst, but the poisonous substance compared to the waste catalyst has a significantly low amount of the vanadium-based compound, thereby showing excellent activity.

The regenerated or remanufactured catalyst according to the present invention has a compressive strength of at least 95% of the new catalyst. The regenerated or remanufactured catalyst according to the present invention has excellent mechanical strength even after processes such as heat treatment and acid treatment, so that the catalyst does not break even during the process of conveying and re-injecting the catalyst.

The hydrogenation treatment includes, but is not limited to, a hydrogenation desulfurization reaction or a hydrogenation denitration reaction.

The present invention also comprises a washing step of removing the residue or heavy oil from the waste catalyst by contacting the solvent with the waste catalyst for the hydroprocessing of the residue or heavy oil;

A heat treatment step of removing the carbon and sulfur dioxide by heat treating the washed catalyst; And

The present invention relates to a method for producing a regeneration catalyst for hydrogenation of resid or heavy oil comprising an acid treatment step of contacting a heat treated catalyst with an oxalic acid solution to remove metal impurities.

The solvent is not particularly limited as long as it is a solvent capable of washing heavy oil and the like, but hydrocarbons having 6 to 10 carbon atoms such as hexane or heptane can be used.

The heat treatment step is carried out in an oxygen atmosphere, for example, an air atmosphere, the preferred concentration of oxygen can be adjusted according to the type of waste catalyst, and the like is not particularly limited, but may be carried out under an oxygen concentration of 5 to 50% by weight, for example. have. In addition, the heat treatment step may be carried out under a water vapor of 0 to 70% concentration, preferably 5 to 60%, more preferably 10 to 50%.

The solution of the acid treatment step is an oxalic acid solution. The concentration of oxalic acid may vary depending on the type of spent catalyst, but may be used in an amount of 5 to 50% by weight. Oxalic acid selectively dissolves only the vanadium, the poisoning component of the catalyst, and does not dissolve active ingredients such as molybdenum, nickel or cobalt. Other carboxylic acids similar to oxalic acid do not selectively dissolve only vanadium.

The acid treatment step may be carried out at a temperature of 25 to 60 ℃, it may be carried out under an ultrasonic atmosphere if necessary.

The present invention also comprises a washing step of removing the residue or heavy oil from the waste catalyst by contacting the solvent with the waste catalyst for the hydroprocessing of the residue or heavy oil;

A heat treatment step of removing the carbon and sulfur dioxide by heat treating the washed catalyst; And

An acid treatment step of contacting the heat treated catalyst with an oxalic acid solution to remove metal impurities; And

It relates to a process for the preparation of a reprocessing catalyst for the hydrogenation of residue or heavy oil comprising the step of supporting an additional active ingredient in an acid treated catalyst.

Since the washing step, the heat treatment step and the acid treatment step are the same as the method for preparing the regenerated catalyst described above, the following will focus on the active ingredient supporting step.

The active ingredient comprises, for example, molybdenum, tungsten, cobalt, nickel and oxides thereof, as described above, and the supporting method is wet impregnated using active ingredient precursors known in the art and the drying and firing steps as necessary. You can proceed further.

The present invention also relates to an acidic solution comprising oxalic acid; And it relates to a method for the selective removal of the vanadium element comprising the step of contacting a spent catalyst containing the vanadium element as an impurity.

The vanadium element includes a vanadium oxide such as, for example, vanadium pentoxide. The concentration of oxalic acid is preferably 5 to 50% by weight, but is not limited thereto.

The step of contacting the acidic solution with the spent catalyst is preferably carried out at a slight heating, for example at a temperature of 25 to 60 ℃, it can be carried out under an ultrasonic atmosphere if necessary.

The invention also includes a process for the hydrogenation of heavy oil or residue oil, comprising the step of contacting a heavy oil or residue with a regeneration or remanufactured catalyst comprising an active ingredient and a carrier and having a vanadium oxide content of 1% by weight or less as measured by XRF. It is about.

Since the regeneration or remanufacturing catalyst is the same as described above, a description thereof will be omitted. The hydrogenation treatment includes, but is not limited to, a hydrogenation desulfurization reaction or a hydrogenation denitration reaction.

The present invention also relates to a process for hydroprocessing heavy oil or residue oil by contacting a layer containing a hydrotreatment catalyst with heavy oil or residue oil,

The hydroprocessing catalyst layer comprises an active ingredient and a carrier, and relates to a hydrogenation method of heavy oil or remnant oil comprising a regeneration or remanufacture catalyst and a new catalyst having a content of vanadium oxide of 1% by weight or less as measured by XRF.

Since the regeneration or remanufacturing catalyst is the same as described above, a description thereof will be omitted. In the layer containing the hydroprocessing catalyst, the regeneration or remanufacturing catalyst may be positioned at the front end side, and the new catalyst may be located at the rear end side such that heavy oil or residue oil first contacts the regeneration or remanufacturing catalyst. In another embodiment, the layer containing the hydrotreating catalyst may be alternately positioned with a regeneration or remanufacture catalyst and a new catalyst, and there may be two or more alternating layers.

The layer containing the hydrotreating catalyst may contain from 5 to 80% by volume of regeneration or remanufacture catalyst.

Hereinafter, the present invention will be described through specific examples, but the following examples are only means for explaining the present invention more specifically, and it will be fully understood by those skilled in the art that the present invention cannot be interpreted by limiting the claims. .

<Example 1 Waste Catalyst Acid Treatment Step Experiment with Oxalic Acid Solution>

In order to examine the leaching of oxalic acid solution of molybdenum and vanadium, the main active ingredient of spent catalyst, into oxalic acid solution in beaker, oxalic acid was dissolved in distilled water so that the concentration of oxalic acid solution was 5% ~ 15%. In a state in which 3 g of MoO ₃ and V ₂ O ₅ were added thereto, washing was performed for 15 minutes at 45 ° C. and ultrasonic strength of 40 kHz in an ultrasonic thermostat. The results are shown in FIG. FIG solution in the beaker into the MoO _3, as shown in 1 was a white powder to a cloudy cloudy state because the MoO ₃ melt sinking is observed on the bottom beaker, the beaker solution into the V ₂ O ₅ is a green foam occurs dioxane live The solution was finally dissolved in dark blue, and the higher the oxalic acid concentration, the shorter the time for blue.

<Comparative Example 1 Experiment of waste catalyst acid treatment step by other dicarboxylic acid>

The leaching effect of MoO ₃ and V ₂ O ₅ under the same conditions except that malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid were used instead of oxalic acid in Example 1 I looked at it. As shown in Table 2, in the case of adipic acid, glutaric acid, malonic acid, pimelic acid, and succinic acid, MoO ₃ was not dissolved, and the white powder was sinking to the bottom of the beaker in a cloudy state. V ₂ O ₅ was also not dissolved. Without showing the original yellow and can be confirmed through the result picture in Figures 2 to 4. On the other hand, substeric acid and azelaic acid were not dissolved in distilled water, so they were excluded from the dissolution test for MoO ₃ , V ₂ O ₅ .

Leaching of MoO ₃ , V ₂ O ₅ to Other Dicarboxylic Acids Organic acid type density(%) Distilled water MoO ₃ V ₂ O ₅ Adipic acid 5 O X X 10 X - - Glutaric acid 5 O X X 10 O X X 15 O X X Pimelic acid 10 O X X Malonic acid 5 O X X 10 O X X 15 O - X Suche mountain 5 O X X 10 O X X Subersan 5, 10, 15 X - - Azela 5, 10, 15 X - -

Example 2 CoMo / γ-Al ₂ O ₃ Regeneration and Reproduction

The waste catalyst drenched with heavy oil was washed with a sufficient amount of an organic solvent (such as n-heptane or n-hexane), and then dried in a drying furnace under a temperature condition of 100 to 120 ° C. through a natural drying process.

Thereafter, 40% of water vapor is contained and the catalyst is placed in the reaction firing tube while maintaining the temperature at 550 ° C. for 1 to 3 hours. At this time, an aspirator is installed at the rear end of the firing tube so By exiting the catalyst, the carbon deposited on the catalyst meets with oxygen in the air and is oxidized without sintering, where the active point of the catalyst is entangled, thereby completely removing the carbon deposited on the catalyst. At this time, the black spent catalyst becomes yellow or yellow with vanadium, a catalyst deactivation component, deposited on the surface of the catalyst while carbon is completely removed. In this process, aluminum sulfate formed on the surface of γ-Al ₂ O ₃ is decomposed to remove sulfur in the form of SO ₂ . (In this case, the concentration of water vapor can be changed from 0% to 70% by looking at the state of the catalyst, and the firing temperature can also be changed to 450 to 550 ° C. The temperature is raised to 5 to 10 ° C per minute from room temperature to 550 ° C.)

After oxalic acid is used to remove vanadium mainly deposited on the catalyst. When the high temperature dry state of the catalyst is directly contacted with the organic acid solution after completion of the heat treatment step, the catalyst may be damaged due to the strong heat of adsorption. The acid treatment step is carried out with the catalyst surface wet. In the acid treatment step, the oxalic acid concentration is 15%, and the temperature of the oxalic acid solution is maintained at 50 ° C., followed by 6 minutes of ultrasonic treatment at 40 kHz. (In this case, depending on the state of the catalyst, the concentration of oxalic acid may be changed to 2% to 60%, the temperature of the oxalic acid solution to 20 to 60 ° C, the frequency of ultrasonic 40kHz to 60kHz, and the ultrasonic treatment time to 5 to 30 minutes. After that, clean the oxalic acid on the catalyst with distilled water and dry it to complete the regeneration of the spent catalyst.

Subsequently, cobalt nitrate and hepta molybdate are impregnated with the initial wet impregnation to 0.3% based on CoO and Mo to 1% based on MO ₃ as necessary. At least 4 hours, dry firing at 550 ° C. for 2 hours, replenishing the lost Co and Mo to complete the preparation of the catalyst.

The regenerated and remanufactured catalysts were compared with the spent catalyst and the new catalyst, and are shown in Table 3.

Component analysis ingredient Waste catalyst Regeneration catalyst Remanufacturing Catalyst New catalyst XRF
(weight%) Al2O3 34.82 38.15 38.82 38.04 P2O5 - - - 0.93 SO3 1.24 0 0 - CaO 0.62 0.56 0.62 0.61 TiO2 0.62 0.11 0.62 0.62 V2O5 4.68 0.27 0.28 - Cr2O3 0.02 0 0.02 - Fe2O3 0.98 0.18 0.98 - Co2O3 5.37 5.34 6.37 5.89 Ni2O3 4.99 4.84 4.99 4.85 MoO3 46.56 50.35 47.2 48.27 WO3 0.11 0.19 0.11 0 ICP
Elemental analysis
(ppm) Co 50.79 43.31 44.21 50.82 Ni 55 55.72 54.84 55.73 Mo 15990 15742 16126 15822 Fe 61.25 60.14 58.32 20.14 S 956.9 59.15 51.87 nd V 203.8 17.25 16.14 nd Analysis item unit Waste catalyst Regeneration catalyst Remanufacturing Catalyst New catalyst BET
Specific surface area ㎡ / g 68.1916 262.5061 260.1764 276.1438 Compressive strength MPa 17.1745 16.2487 15.8412 17.1452

Desulfurization performance of the regenerated and remanufactured catalysts, spent catalysts and new catalysts was compared as follows.

The reactor used in the experiment was CATATEST UNIT, a fixed bed high pressure continuous flow reactor. The reactor has a maximum temperature of 550 ° C, a maximum pressure of 150 × 10Pa, and a liquid flow rate of 10 to 750 ml / hr. The liquid reactant is injected into the reactor quantitatively by a reciprocating micrometering pump, and hydrogen is 50m capillary. The capillary tube is injected into the reactor by means of a reducing pressure regulator. The flow rate of hydrogen is measured in a mass flow controller (MFC) attached to the front of the reactor and recorded in a recorder. The gas passing through the reactor is controlled by a back pressure regulator. The liquid and gas are passed through a condenser, separated by a high pressure separator and a low pressure separator, and then sampled.

The amount of outgoing gas is measured by a wet gas meter, and the amount of liquid is calculated by measuring the liquid flow rate in a high pressure separator and measuring the flow rate for a certain time by a solenoid valve.

The reactor temperature is controlled isothermally in the controller in four layers, and the control range is within 1K. The upper part of the reactor serves as a preheater, and the liquid reactant is vaporized in the preheater and injected into the catalyst bed.

The controller controls the temperature of the reactor, the liquid level of the high pressure separator, the liquid level of the reactants, and the like, and records the temperature of each layer of the reactor, the hydrogen inflow rate, the liquid level of the high pressure separator, and the liquid level of the low pressure separator.

The response variables were temperature, pressure, H2 / H.C. The molar ratio and contact time were determined and the range of reaction conditions was determined through preliminary experiments.

Reaction conditions and standard reaction conditions are shown in Table 4 below. In addition, all prepared catalysts were pre-treated after sulfiding the mixed gas (95% H 2 and 5% H 2 S) at 773 K in-situ in the reactor and then performing a reaction experiment. In addition, qualitative analysis of the reactants and products was carried out using G.C.mass (6890A, Hewlett Packard Co.) and quantitative analysis using G.C (6890A, Hewlett Packard Co.) with F.I.D. (flame ionization detector). The column used was an ultraperformance capillary column (50 × 0.32 ID, fused silica, 0.52mm crosslinked methylsilicon 19091A-115).

Reaction variation Operation ranges Standard condition 1. Catalysts
Loading weight
Particle size
0.5g
50 / 80,80 / 100,100 / 120mesh
0.5g
80/100 mesh 2. Reaction
Temperature
Pressure
Contact time (W / F)
H2 / HC mole ratio
DBT mol%
623-773 K
10 × 15 to 50 × 10Pa
0.01-0.04 gcat. hr / ml feed
10-100
0.5mol%
673K
30 × 10Pa
0.02 gcat. hr / ml feed
40
0.5mol%

The degree of reaction was expressed by conversion rate (X), reaction rate (γ) and selectivity (S). In addition, the position of the catalyst bed in the reactor must be determined in order to charge the catalyst in the reactor. The catalyst bed should be determined based on the location and volume where the temperature change is most safe and the diffusion of the reactants is easy. In this experiment, the catalyst layer was selected in the middle of the reactor with the smallest temperature control range.The catalyst and inert material were diluted with carborundum (SiC) at a ratio of 1: 5 and the volume of the catalyst layer was determined to be 15 cm 3, so The catalyst was charged in a range in which bypassing was suppressed. Catalyst charging was filled with quartz wool to prevent leakage of catalyst and inert charges at the inlet and outlet of the reactor, followed by 80 mesh carborundum. Insert the catalyst layer fixing ring thereon and put quartz fiber again, quantitatively fill the catalyst and carborundum, and after forming the catalyst layer, insert the quartz fiber and ring again, fill the carborundum on it, and fix it with glass fiber. Catalyst charging is complete. And the liquid reactant n-decane was transferred from the supply tank (supply tank) to the feed tank (supply pump) to the feed tank (control metering pump) was supplied to the reactor at the desired flow rate. At this time, the inflow rate was confirmed by 1ml quantitative glass tube. The hydrogen in the gaseous reactants is stored in a reservoir (10 ^² × 10 The desired pressure in the amount adjusted from Pa) is measured by an indicator, controlled by a pressure reducer, and then quantitatively introduced by the pressure difference by a capillary tube. Hydrogen entering the reactor is measured by a gas mass flow meter and recorded by a recorder. The gas flow meter was calibrated before the experiment. In this experiment, samples of the reaction product were analyzed after 2 hours after the reactant supply and the change of reaction conditions.

Reaction All catalysts were initially shown to have high activity, and were tested under normal conditions after the catalyst was stabilized. The results of the hydrodesulfurization of DBT under standard conditions of this experiment are shown in Table 5 below.

Item Waste catalyst Regenerative catalyst Remanufacturing Catalyst Sour catalyst DBT conversion rate
(conversion%) 41.2 82.2 84.9 85.2

Example 3 Regeneration and Reproduction of NiMo / γ-Al ₂ O ₃

The waste catalyst drenched with heavy oil was washed with a sufficient amount of an organic solvent (such as n-heptane or n-hexane), and then dried in a drying furnace under a temperature condition of 100 to 120 ° C. through a natural drying process.

Thereafter, 40% of water vapor is contained and the catalyst is placed in the reaction firing tube while maintaining the temperature at 550 ° C. for 1 to 3 hours. At this time, an aspirator is installed at the rear end of the firing tube so By exiting the catalyst, the carbon deposited on the catalyst meets with oxygen in the air and is oxidized without sintering, where the active point of the catalyst is entangled, thereby completely removing the carbon deposited on the catalyst. At this time, the black spent catalyst becomes yellow or yellow with vanadium, a catalyst deactivation component, deposited on the surface of the catalyst while carbon is completely removed. In this process, aluminum sulfate formed on the surface of γ-Al ₂ O ₃ is decomposed to remove sulfur in the form of SO ₂ . (In this case, the concentration of water vapor can be changed from 0% to 70% by looking at the state of the catalyst, and the firing temperature can also be changed to 450 to 550 ° C. The temperature is raised to 5 to 10 ° C per minute from room temperature to 550 ° C.)

After oxalic acid is used to remove vanadium mainly deposited on the catalyst. When the high temperature dry state of the catalyst is directly contacted with the organic acid solution after completion of the heat treatment step, the catalyst may be damaged due to the strong heat of adsorption. The acid treatment step is carried out with the catalyst surface wet. In the acid treatment step, the oxalic acid concentration is 15%, and the temperature of the oxalic acid solution is maintained at 50 ° C., followed by 6 minutes of ultrasonic treatment at 40 kHz. (In this case, depending on the state of the catalyst, the concentration of oxalic acid may be changed to 2% to 60%, the temperature of the oxalic acid solution to 20 to 60 ° C, the frequency of ultrasonic 40kHz to 60kHz, and the ultrasonic treatment time to 5 to 30 minutes. After that, clean the oxalic acid on the catalyst with distilled water and dry it to complete the regeneration of the spent catalyst.

Subsequently, cobalt nitrate and hepta molybdate are impregnated with the initial wet impregnation to 0.3% based on CoO and Mo to 1% based on MO ₃ as necessary. At least 4 hours, dry firing at 550 ° C. for 2 hours, replenishing the lost Co and Mo to complete the preparation of the catalyst.

The regenerated and remanufactured catalysts were compared with the spent catalyst and the new catalyst and their physical properties are shown in Table 6.

Component analysis ingredient Waste catalyst Regeneration catalyst Remanufacturing Catalyst New catalyst XRF
(weight%)
Al2O3 17.77 60.33 60.33 71.31 P2O5 13.29 12.13 9.55 SO3 31.28 0.74 0.74 0 CaO 0.49 0.67 0.68 0.79 V2O5 31.84 0.21 0.2 Cr2O3 0.14 Ni2O3 10.55 11.5 11.8 14.7 MoO3 7.93 13.26 14.12 16.88 ICP
Elemental analysis
(ppm)
Co nd nd nd nd Ni 2564 2659 2812 2728 Mo 20107 19927 20942 20176 Fe nd nd nd nd S 15293 2007 1982 1350 V 16681 24 28 nd Analysis item unit Waste catalyst Regeneration catalyst Remanufacturing Catalyst New catalyst BET
Specific surface area ㎡ / g 45.6587 239.8749 235.1498 254.1315 Compressive strength Mpa 21.0102 19.8412 17.5413 21.0184

Desulfurization performance of the regenerated and remanufactured catalysts, spent catalysts and new catalysts was compared as follows.

The reactor used in the experiment was CATATEST UNIT, a fixed bed high pressure continuous flow reactor. The reactor has a maximum temperature of 550 ° C, a maximum pressure of 150 × 10Pa, and a liquid flow rate of 10 to 750 ml / hr. The liquid reactant is injected into the reactor quantitatively by a reciprocating micrometering pump, and hydrogen is 50m capillary. The capillary tube is injected into the reactor by means of a reducing pressure regulator. The flow rate of hydrogen is measured in a mass flow controller (MFC) attached to the front of the reactor and recorded in a recorder. The gas passing through the reactor is controlled by a back pressure regulator. The liquid and gas are passed through a condenser, separated by a high pressure separator and a low pressure separator, and then sampled.

The amount of outgoing gas is measured by a wet gas meter, and the amount of liquid is calculated by measuring the liquid flow rate in a high pressure separator and measuring the flow rate for a certain time by a solenoid valve.

The reactor temperature is controlled isothermally in the controller in four layers, and the control range is within 1K. The upper part of the reactor serves as a preheater, and the liquid reactant is vaporized in the preheater and injected into the catalyst bed.

The controller controls the temperature of the reactor, the liquid level of the high pressure separator, the liquid level of the reactants, and the like, and records the temperature of each layer of the reactor, the hydrogen inflow rate, the liquid level of the high pressure separator, and the liquid level of the low pressure separator.

The response variables were temperature, pressure, H2 / H.C. The molar ratio and contact time were determined and the range of reaction conditions was determined through preliminary experiments.

Reaction conditions and standard reaction conditions are shown in Table 7 below. In addition, all prepared catalysts were pre-treated after sulfiding the mixed gas (95% H 2 and 5% H 2 S) at 773 K in-situ in the reactor and then performing a reaction experiment. In addition, qualitative analysis of the reactants and products was carried out using G.C.mass (6890A, Hewlett Packard Co.) and quantitative analysis using G.C (6890A, Hewlett Packard Co.) with F.I.D. (flame ionization detector). The column used was an ultraperformance capillary column (50 × 0.32 ID, fused silica, 0.52mm crosslinked methylsilicon 19091A-115).

Reaction variation Operation ranges Standard condition 1. Catalysts
Loading weight
Particle size
0.5g
50 / 80,80 / 100,100 / 120mesh
0.5g
80/100 mesh 2. Reaction
Temperature
Pressure
Contact time (W / F)
H2 / HC mole ratio
DBT mol%
623-773 K
10 × 15 to 50 × 10Pa
0.01-0.04 gcat. hr / ml feed
10-100
0.5mol%
673K
30 × 10Pa
0.02 gcat. hr / ml feed
40
0.5mol%

The degree of reaction was expressed by conversion rate (X), reaction rate (γ) and selectivity (S). In addition, the position of the catalyst bed in the reactor must be determined in order to charge the catalyst in the reactor. The catalyst bed should be determined based on the location and volume where the temperature change is most safe and the diffusion of the reactants is easy. In this experiment, the catalyst layer was selected in the middle of the reactor with the smallest temperature control range.The catalyst and inert material were diluted with carborundum (SiC) at a ratio of 1: 5 and the volume of the catalyst layer was determined to be 15 cm 3, so The catalyst was charged in a range in which bypassing was suppressed. Catalyst charging was filled with quartz wool to prevent leakage of catalyst and inert charges at the inlet and outlet of the reactor, followed by 80 mesh carborundum. Insert the ring for fixing the catalyst layer and put the quartz fiber again, and then quantitatively filled the catalyst and carborundum, and after forming the catalyst layer by inserting the quartz fiber and the ring again, filling the carborundum on it and fixing with glass fiber Catalyst charging is complete. And the liquid reactant n-decane was transferred from the supply tank (supply tank) to the feed tank (supply pump) to the feed tank (control metering pump) was supplied to the reactor at the desired flow rate.

At this time, the inflow rate was confirmed by 1ml quantitative glass tube. The hydrogen in the gaseous reactants is stored in a reservoir (10 ^² × 10 The desired pressure in the amount adjusted from Pa) is measured by an indicator, controlled by a pressure reducer, and then quantitatively introduced by the pressure difference by a capillary tube. Hydrogen entering the reactor is measured by a gas mass flow meter and recorded by a recorder. The gas flow meter was calibrated before the experiment. In this experiment, samples of the reaction product were analyzed after 2 hours after the reactant supply and the change of reaction conditions.

Reaction All catalysts were initially shown to have high activity, and were tested under normal conditions after the catalyst was stabilized. The results of the hydrodesulfurization of DBT under standard conditions of this experiment are shown in Table 8.

Item Waste catalyst Regenerative catalyst Remanufacturing Catalyst Sour catalyst DBT conversion rate
(conversion%) 35.7 80.7 82.3 82.9

Claims (10)

Comprising an active ingredient and a carrier,
Regeneration or remanufacturing catalyst for hydrogenation of resid or heavy oil having a vanadium oxide content of 1% by weight or less as measured by XRF.
The method of claim 1,
The active ingredient is a regeneration or remanufacture catalyst for the hydrogenation of resid or heavy oil, which is at least one selected from the group consisting of molybdenum, tungsten, cobalt, nickel and oxides thereof.
The method of claim 2,
The active ingredient comprises a molybdenum or tungsten as the main catalyst, a regeneration or remanufacture catalyst for the hydrogenation of the residue or heavy oil containing cobalt or nickel as the cocatalyst.
The method of claim 1,
The carrier is alumina; Or a regeneration or remanufacturing catalyst for hydrogenation of residue oil or heavy oil, which is a carrier carrying phosphorus, boron, silicon or oxides thereof in alumina.
The method of claim 1,
Regeneration or remanufacture catalyst for hydrogenation of residues or heavy oils having a sulfur trioxide content of 1% by weight or less as measured by XRF.
The method of claim 1,
Regeneration or remanufacturing catalyst for hydrogenation of resid or heavy oil having a BET specific surface area of at least 200 m 2 / g.
The method of claim 1,
Regeneration or remanufacture catalyst for hydrogenation of resid or heavy oil having vanadium element value of 50 ppm or less in ICP element analysis.
The method of claim 1,
Hydrogenation is a regeneration or remanufacture catalyst for hydrogenation of residue or heavy oil, which is hydrodesulfurization or hydrodesulfurization.
The method of claim 1,
Compressive strength is a regeneration or remanufactured catalyst for the hydrogenation of residue or heavy oils of at least 95% of the new catalyst.
The method of claim 1,
Regenerated or remanufactured catalysts have a vanadium oxide content of 15% or less based on spent catalysts and XRF content of active ingredients as measured by XRF of 80% or more based on new catalysts for the hydrogenation of residual or heavy oils. Regenerated or Remanufactured Catalysts.

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