JPS594492B2 - Processing method for magnesium silicate waste catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering valuable metals contained in a catalyst containing magnesium silicate from a waste catalyst obtained from a hydrotreating process of heavy hydrocarbon oil.

The present inventor had previously proposed a catalyst containing sepiolite (magnesium silicate) as a main component as a catalyst for hydrotreating heavy hydrocarbon oil.

This type of catalyst is used for hydrorefining treatment of heavy hydrocarbon oil,
It can be used as a catalyst for various hydroprocessing processes such as hydrodemetallization treatment and hydrothermal cracking treatment, but it has a significantly extended catalyst life compared to conventional alumina and silica-alumina catalysts. , and has the characteristic of adsorbing large amounts of vanadium and nickel components from hydrocarbon oil before being deactivated.

The present invention utilizes the characteristics of such a magnesium silicate catalyst to utilize this catalyst as a catalyst for hydrotreating heavy hydrocarbon oils containing metals, and to treat valuable metals in heavy hydrocarbon oils. This was done in order to efficiently recover valuable metals such as vanadium and nickel deposited on the catalyst from the resulting waste catalyst.

Conventionally, methods for recovering valuable metals such as vanadium, molybdenum, and nickel from desulfurization catalysts are known.

For example, Japanese Patent Publication No. 52-5436 proposes an NaC1 roasting method, Japanese Patent Application Laid-Open No. 102595-1987 proposes a Na2S04 roasting method, and Japanese Patent Publication No. 47-21387 proposes a NaCl roasting method. proposed an ammonia water extraction method.

However, all of these conventional methods target waste catalysts using alumina or silica-alumina as carriers, and the methods that target the magnesium silicate-based catalyst of the present invention differ in the component composition of the applied waste catalyst. There are significant differences, especially in the amounts of vanadium and nickel deposited on the catalyst, with the alumina and silica-alumina supported catalysts covered by conventional methods compared to the magnesium silicate supported catalysts according to the present invention. This is a low amount of /3 or less.

Furthermore, the chemical reactivity of alumina and silica alumina targeted by the conventional method is different from that of magnesium silicate, which is the target of the present invention, and even when the conventional method is applied to this waste magnesium silicate catalyst, good results are not obtained. I won't give it.

In any case, a suitable treatment method is required to recover valuable metals from spent magnesium silicate and cate catalysts, but no effective method has been proposed so far.

The present invention is a method for recovering valuable metals that is effectively applied to magnesium silicate-based waste catalysts, which is a valuable metal recovery method that can be effectively applied to magnesium silicate-based waste catalysts that have deposits of valuable metals obtained from a heavy hydrocarbon oil hydrotreating process. First, use 300 ml of catalyst.
After oxidizing and roasting at a temperature of ℃ or higher to burn and remove the sulfur and carbon contained therein, the obtained oxidized and roasted product is mixed with NaCl or/and Na 2 S 04 at an atomic ratio of Na/ In addition at a rate such that V is 1.0 or more,
The process consists of firing at a temperature of 700 to 1300°C to convert the vanadium contained therein into sodium vanadate salt, and then eluting the vanadium from the fired product using water or a weakly alkaline aqueous solution. .

The term "hydroprocessing of heavy hydrocarbon oil" as used in the present invention is to be interpreted broadly, and includes refining processes such as hydrorefining (hydrodesulfurization) and hydrodemetallization, as well as water treatment for the purpose of lightening. In addition, the term "catalyst containing magnesium silicate as a main component" as used in the present invention means a catalyst system containing magnesium silicate as a catalytically active component or a catalyst carrier component.

As the magnesium silicate, synthetic or natural sepiolite is preferably used.

In the case of sepiolite catalysts, in addition to sepiolite itself, modified sepiolite whose composition or skeletal structure has been partially changed in order to improve performance is included.

Examples of modified sepiolite include a fired product of sepiolite, a demagnesized product of sepiolite, a kneaded product of sepiolite, and a metal catalyst component supported on sepiolite or the modified sepiolite.

In the method of the present invention, first, the waste catalyst extracted from the heavy oil hydrotreating process is subjected to oxidation roasting treatment.

In this case, the main metal components of the spent catalyst are Mg, Si, V,
Although it is Ni, when Mo or Co is used as a catalytically active component, these metal components are also included.

Among these metal components, (1) and Ni components are deposited on the catalyst from the hydrocarbon oil during use of the catalyst.

Of course, if these metals are present in the 4-fresh catalyst, some of them are from this beginning, but most of them are derived from the hydrocarbon oil.

The spent catalyst also contains carbon and sulfur, which were deposited on the catalyst during hydrocarbon processing.

The composition of the spent catalyst varies depending on the catalyst preparation method and the treatment conditions for heavy hydrocarbon oil, but when used for a long time in the hydrodemetalization treatment of heavy oil, it exhibits the following composition.

The oxidation roasting temperature of the waste catalyst is 300°C or higher, preferably 4°C or higher.
The temperature is 00°C or higher, and carbon and sulfur in the catalyst are burned and removed by this treatment.

As mentioned above, the spent catalyst in the present invention contains extremely large amounts of metals and sulfur, but the oxidation roasting temperature is 300
If the temperature is lower than °C, these will react and produce sulfate, which is not preferable.

Therefore, in the present invention, a roasting temperature of 300° C. or higher, preferably 400° C. or higher is adopted so that sulfate is not generated or even if it is generated, it is thermally decomposed.

However, there is an upper limit to the roasting temperature in this case;
It is necessary to maintain the temperature below 00°C, preferably below 800°C.

This roasting temperature has a large effect on the elution rate of vanadate in the subsequent vanadate elution step, and when the roasting temperature exceeds 900°C, the vanadate elution rate deteriorates significantly.

Although the reason why the vanadate elution rate deteriorates significantly when the roasting temperature reaches a high temperature of about 900°C has not been clearly elucidated, the waste catalyst in the present invention
When roasted at around 0°C, it will sinter significantly and the apparent volume of the waste catalyst will rapidly decrease, and molten vanadium pentoxide will react with magnesia and be converted to poorly water-soluble magnesium vanadate. Considering this fact, in the high-temperature roasting process, the yagnesia or magnesium silicate contained in the waste catalyst reacts with the vanadium pentoxide produced by the oxidative roasting to produce more stable and less water-soluble magnesium vanadate. At the same time, as a result of sintering or the reaction of magnesia and silicic acid contained in the waste catalyst to convert into stable magnesium silicate such as pyroxene, the porosity of the roasted product is significantly impaired and the silicic acid is It is presumed that this is due to activation.

The oxidation roasting process can be carried out using fixed bed, moving bed, rotary kiln,
It can be carried out in a fluidized bed or any other conventional method.

Air is usually used as the oxidizing agent, but oxygen, a mixed gas of oxygen and air, or a mixture of these gases diluted with a gas such as steam or nitrogen can also be used.

The oxidation products obtained in this oxidation roasting step are mainly carbon dioxide gas and sulfur dioxide, but among these, sulfur dioxide is converted into sulfuric acid by a known method and then used as a treatment agent in the subsequent treatment step of the present invention. Alternatively, the sulfur dioxide may be recovered by being absorbed into the magnesium hydroxide slurry produced as a by-product in a subsequent step.

Next, the oxidized roasted product of the waste catalyst obtained as described above is heated at a temperature of 700°C or higher, preferably 800°C or higher by adding sodium chloride (NaCI) or/and sodium sulfate (Na25O4). To roast.

In order to perform this roasting efficiently, the roasted waste catalyst must be NaC.
1 or/and Na 2 S 04 , thoroughly mixed, and then roasted as is or after molding to an appropriate particle size.

The amount of NaCl or Na 2804 or a mixture of both varies greatly depending on the properties of the waste catalyst, especially the vanadium content. is selected so that it is 1 or more.

In order to increase the vanadium elution rate in the subsequent vanadium elution process and to efficiently separate and recover other metals in the subsequent metal recovery process, Na/V
The ratio is preferably maintained within the range of 1.5 to 4.0.

The waste catalyst roasted product is treated with NaCl or/and Na25O,
When roasting in the presence of , the roasting temperature is extremely critical, and it is usually necessary to select a temperature of 700°C or higher, preferably 800°C or higher.

Roasting is possible even at temperatures below 700°C, but in this case Mg, Ni, and Si are removed in the subsequent acid or alkali treatment process.
When recovering these metal components, an extremely fine muddy residue that is difficult to filter is generated, making it extremely difficult to separate and recover these metal components.

In addition, in the case of such low temperature roasting of 700°C or less, it is difficult to elute vanadium from the roasted product, the recovery rate is low, and the residual component contains a considerable amount of vanadium. As a result, when separating and recovering M g tSi or Ni from the residual components,
A small amount of vanadium becomes mixed into these components, and it becomes necessary to separate the vanadium from these components again.

In the present invention, the extremely large influence or effect of the oxidation roasting temperature on the vanadium elution rate and the properties of the residue after vanadium elution, as described above, is different from that seen in similar treatment steps for ordinary alumina-based waste catalysts. , and the effects of oxidative roasting in the present invention are considered to be fundamentally different from those in the case of an alumina-based catalyst.

That is, in the case of the magnesium silicate-based waste catalyst of the present invention, if it is oxidized and roasted at a high temperature of 700°C or higher or 800°C or higher, the magnesia and silica or magnesium silicate contained in the waste catalyst will be stabilized, and the subsequent stage It is recognized that when acid or alkali is applied in the process, it becomes less likely to become muddy.

As an example of such a stabilized magnesium silicate, for example, pyroxene is known, but as mentioned above, in the present invention, when the waste catalyst is oxidized and roasted at a high temperature of 900°C or higher, at least magnesia and silica are used. It has been confirmed that some of it transforms into pyroxene.

In addition, high-temperature roasting of the waste catalyst in the presence of sodium salt must be carried out at a temperature of 700°C or higher, preferably 800°C or higher, but roasting at a high temperature of over 1300°C will cause the roasted product to This is not preferable because it partially melts, resulting in extremely poor reactivity, making it extremely difficult to recover components such as Mg, Si, and Ni in subsequent steps.

For these reasons, the roasting temperature of the waste catalyst in the presence of sodium salt in the present invention is preferably selected in the range of 700 to 1300°C, preferably 800 to 950°C.

The roasting process at this stage can be carried out in a conventional fixed bed, fluidized bed, rotary kiln, or moving bed type roasting furnace.

In this roasting step in the presence of sodium salt, the following reaction occurs, and it is thought that easily water-soluble sodium salt of vanadate is produced.

○ Roasting in the presence of NaCl ○ Roasting in the presence of Na2SO4 The roasting in the present invention is preferably carried out while circulating steam, air, oxygen, or moist air.
In the case of roasting in the presence of Na2SO4, as understood from the above reaction formula, such gas flow is not particularly required.

Next, the roasted product obtained from the second stage roasting step in the presence of a sodium salt is subjected to an elution or leaching treatment using water or a weakly alkaline aqueous solution.

According to this elution treatment step, the vanadium content in the roasted product is converted into vanadate sodium salt, which is very easily eluted as described above, so that components such as Ni, Mg, and Si are not dissolved. Only the vanadium component can be selectively eluted.

Although the roasted product from the first roasting step, which is the raw material for processing in this case, may be used as it is, it is advantageous to grind it to an appropriate size in order to improve vanadium elution efficiency.

As the treatment agent for vanadium elution, in addition to pure water, a weakly alkaline aqueous solution containing a small amount of alkaline substances such as ammonia, caustic soda, and sodium carbonate is used.

Moreover, as this treatment agent, an alkaline waste liquid obtained after separating the vanadium component from the solution in which the vanadate salt has been eluted can also be used.

The elution conditions are not critical and may be normal pressure or room temperature conditions, but in order to further increase the elution rate, a temperature of 100° C. or higher and F conditions may also be employed.

Note that the spent catalyst in the present invention may contain molybdenum as a catalytic activity or component, but in this case molybdenum behaves similarly to vanadium and is eluted together with vanadium in this elution process. The eluate obtained in this case contains vanadate and unreacted NaCl.
Or, in addition to Na2SO4, a small amount of soluble molybdate is mixed in.

The separation of each metal from the eluate can be carried out according to a conventionally known method.
Vanadate and molybdate are selectively extracted by adding grade amine, and ammonium sulfate is added to the extract to adjust the pH to 8i, thereby selectively precipitating vanadium from the solution as ammonium metavanadate. can be separated.

In addition, NaC1 after separating the tertiary amici extract
The extraction residue containing NaCl or Na2SO4 can be reused as a treatment agent for the solution in the vanadate elution process, and can also be used as a treatment agent for the solution in the vanadate elution step.
It can also be used as a SO4 source.

The remaining components obtained in the elution treatment process of the roasted material described above are:
Considered as a high-quality nickel ore containing mainly Ni, Si and Mg, nickel can be produced from it according to conventional geological methods, or the residual component may contain a small amount of vanadium. In this case, the vanadium contained therein can be transferred to an easily water-soluble salt by adding NaCl or/and Na 2 S 04 and roasting again, and then the vanadium elution treatment can be performed again.

Furthermore, this residual component can be used in the first or second roasting process to raise the melting point of the roasted product and prevent damage to the furnace material.

In other words, in the case of a waste catalyst containing a large amount of vanadium, V2O5 and vanadate with a low melting point are produced in the second stage roasting process, but these products are generally made of refractory bricks used as fl. However, this can be prevented by adding the above-mentioned residue component.

In addition to being used historically as described above, the residual components can be subjected to various chemical treatments to separate and recover the valuable components contained therein.

For example, NaOH, Na2CO3 or N
a By carrying out a leaching treatment using an aqueous solution containing either one of HCOa or a mixture of two or more thereof, the silicon contained therein is selectively eluted into the aqueous solution as a readily water-soluble silicate; It can be separated from the poorly water-soluble residue mainly containing dimagnesium and nickel.

If the waste catalyst contains aluminum, the aluminum content will be eluted along with the silicon content in this leaching step, but in this case, by selecting the leaching conditions and method, it is also possible to separate and leach only the silicon content.

The processing conditions in this leaching step vary depending on the type of processing agent used for leaching the silicon content and the properties of the residue containing silicon content, which is the processing raw material, and cannot be unambiguously determined, but usually the temperature is above room temperature. temperature is adopted, and the concentration of the treatment agent consisting of the sodium salt in the aqueous solution is 5% or more,
Preferably it is 10 or more.

In any case, the processing conditions are appropriately selected depending on the properties of the waste catalyst, the roasting conditions, the type of processing agent, etc.

The silicate solution obtained from this silicic acid content elution step may be used as it is as an adsorbent raw material, but H2SO, H
By adding an acid such as Cl or a salt thereof, the pH can be maintained at 9 or less, and silicic acid or silica gel can be precipitated and separated.

In this case, the solution after separating the silicic acid or silica gel mainly contains Na2SO4 or NaCl, which is recycled to the second roasting process and used in the roasting process. It can be used as a source of NaCl or Na 2 S04.

In this way, Na 2 S 04 and NaC produced as by-products
When reusing silicic acid or silica gel in the roasting process, the silicic acid or silica gel precipitate may be mixed with any desired quality so as to obtain the desired quality. It can be done by method.

When this silicic acid or silica gel precipitation separation step is incorporated into the treatment process of the present invention, it is particularly advantageous to use a sepiolite-based waste catalyst obtained from a hydrodemetallization step of residual oil as the target waste catalyst.

In other words, the maximum amount of metal deposited on a Seviolite-based hydrodemetallization catalyst is almost constant regardless of the oil type under normal hydrotreating conditions, and the amount of vanadium deposited on the catalyst is proportional to its silicon content. The atomic ratio V/Si is 1.5 to 2.5 (average value of the catalyst layer).

On the other hand, NaCl or Na2SO produced as a by-product in this precipitation step
The ratio of sodium to silica in 4 is the atomic ratio Na/
Si is in the range of about 3 to 6.

On the other hand, the amount of NaCl or Na2804 required in the second roasting step is approximately proportional to the vanadium content, and the atomic ratio Na/V is usually in the range of 1.5 to 4.0.

From these facts, the atomic ratio N in the second roasting process
a/S i ranges from 2 to 10.

Therefore, when treating sepiolite-based waste catalysts, the sodium salt by-produced in the silicic acid or silica gel precipitation step can be recycled to the second roasting step. Almost the entire amount of sodium salt required in the baking process can be supplied in just the right amount.
This is extremely convenient for continuous operation of the process.

In addition, the silicic acid content contained in the residue from the third stage elution treatment step was leached and separated using an alkali (
The residue components after the fourth step) mainly contain nickel and magnesium, but according to the research of the present inventor, the nickel contained in this residue is due to the fact that the residue is baked at a high temperature in the previous roasting step. However, it is recognized that it can be leached with aqueous solutions of ammonium salts such as aqueous ammonia, ammonium chloride, and ammonium sulfate.

In this case, leaching of nickel with an aqueous ammonium salt solution is possible at room temperature and under normal pressure, but in order to speed up the leaching rate of nickel and increase the extraction rate, use a pressurized container such as an autoclave to Preferably, it is carried out at a temperature of 200° C. and under pressure.

When the leaching treatment is performed in this manner, only the nickel component is selectively eluted from the residue as a nickel ammonia complex, so the leaching solution can be used as a raw material for high-purity nickel.

In addition, the residue after eluting nickel contains magnesium, which can be further purified using conventionally known methods to convert it into high-purity magnesia, or it can be used as it is for use in heavy oil combustion furnaces. It can be used as magnesium hydroxide.

In addition, when carrying out the waste catalyst treatment method of the present invention, mainly Ni, Mg, S after the vanadium salt elution treatment in the third step.
It is also possible to add a strong acid such as sulfuric acid, hydrochloric acid, or nitric acid to the residue containing i to make Ni and Mg easily soluble in water, and then transfer the resulting solution into a solution to obtain a residue mainly consisting of silicic acid.

A feature of this process is that silicic acid contained in a relatively large amount can be easily separated and recovered as a residue by adding a relatively small amount of acid.

In this elution step, it is preferable to treat the residue with sulfuric acid at a high temperature in order to increase the extraction rate of Ni and Mg from the residue, but a high extraction rate can also be obtained even if the residue is treated with hydrochloric acid or nitric acid at a relatively low temperature. Sometimes.

The acid concentration in the aqueous solution used as the treatment agent is usually 5 parts or more, but depending on the properties of the residue, a high concentration of 50 parts or more may be used.

The solution containing magnesium and nickel salts obtained by this elution process is heated and concentrated by adding ammonia with ethanol, or/and ammonium sulfate is added and heated to concentrate, so that the dissolved nickel is replaced by nickel sulfate, which has a low solubility in water. It can be separated by crystallization as ammonium.

This nickel ammonium sulfate can be purified into a nickel salt containing almost no magnesium by repeating crystallization.

In addition, the mother liquor obtained in this case is an aqueous magnesium salt solution containing a small amount of nickel, and to this solution, an alkali such as NaOH, NaHCO3, Na2CO3 is added to precipitate and separate the metals as hydroxides. The resulting mother liquor can also be used as a source of sodium salt for use in the second roasting step.

Next, the process diagrams of the preferred embodiment of the present invention described above are shown in FIGS. 1 and 2, but these process steps are only basic and are not limited thereto. , various modifications are possible.

Next, the present invention will be explained in more detail with reference to Examples.

It should be noted that all values shown in the examples are based on weight unless otherwise specified.

Example 1 Sepiolite containing about 64% of SiO2 and about 28% of MgO (most of the rest is water) was thoroughly kneaded in the presence of water and then formed into granules, and nickel and molybdenum were added to the resulting carrier. 0.6% and 1.7% respectively as oxides
The catalyst was prepared by supporting.

Using this catalyst, vanadium 290IP, nickel 9Q
Vacuum residue oil containing P, 8Pfl iron, and 3.85% sulfur was heated to a hydrogen pressure of 140 9/cI! , reaction temperature 380-425
Hydrogenation was carried out under the conditions of ℃.

The produced oil contains 10-25 layers of vanadium and 15-25 layers of nickel.
The composition of the resulting oil, which contained 1.2 to 1.6 parts of sulfur, was kept approximately constant by gradually increasing the reaction temperature.

After approximately 5,500 hours of treatment, the demetallization activity of the catalyst decreased and the composition of the produced oil could no longer be maintained due to the temperature increase, so the reaction was stopped and the spent catalyst was extracted.

The properties of this spent catalyst were as follows. This waste catalyst 20
g was calcined at 600° C. for about 1 hour using a naturally vented roasting furnace to remove carbon and sulfur.

The weight of the obtained oxidized roasted product was about 129.

Next, N a 2 S 0410& was added to this roasted product, and it was finely ground to a particle size smaller than 20 mesh.
The mixture was baked in the roasting furnace at 0° C. for about 2 hours.

The thus obtained baked product was sufficiently leached with water at about 80°C, and the residue was separated by filtration.

When the vanadium content in the filtrate was analyzed and the recovery rate of vanadium was determined, the recovery rate was approximately 96%.

Next, the residue obtained by this leaching treatment was further thoroughly washed with warm water, and then leached at 50° C. using a 20% NaOH aqueous solution, and the silicon content was recovered as sodium silicate.

After repeated washing sufficiently until almost no silicon content was leached out, the silicon content in the silicon leachate was analyzed, and the silicon recovery rate was approximately 84%.

50% diluted sulfuric acid was added little by little to this silicon-containing leachate to precipitate silicic acid.

The obtained silicic acid precipitate was heated at about 50°C, aged, filtered, thoroughly washed with dilute ammonium sulfate aqueous solution, and dried at about 120°C to obtain a porous silica gel of about 3.09. Ta.

Sulfuric acid was added to the filtrate after the silicic acid precipitation separation to neutralize it to about 7.0% O to obtain a Na2804 solution containing a small amount of silicic acid, vanadium, and aluminum.

This solution contains approximately 7.0% Na2SO4. F (as anhydride), which is the same as the N a 2 shown above.
Since it could be recycled to the roasting process using S 04 , substantially no waste water containing valuable components such as vanadium and silicic acid was produced.

On the other hand, the residue containing nickel and magnesium after filtering off the silicic acid is treated with NaOH leaching to remove the silicic acid adhering to it, and then treated with 10% ammonia.
Dispersed in an aqueous solution containing 35% (NH4)2Co,
The mixture was heated to about 100° C. and stirred in an autoclave to extract the nickel.

After performing this treatment for about 3 hours, it was filtered and the nickel contained in the filtrate was analyzed, and the recovery rate was 88.
He was in charge.

The obtained residue is magnesium hydroxide containing small amounts of iron and silicon, which can be used as a raw material for magnesium, and can also be used as is as a low-melting point vanadium compound produced during combustion in a heavy oil combustion furnace. It is also suitable as magnesium hydroxide to be blown in to prevent damage to furnace materials caused by carbon dioxide, and can also be used as an SO2 trapping material.

Example 2 Spent catalyst 20 having the same composition as that used in Example 1
After oxidizing and roasting g at 600℃ for 1 hour, NaC11
0.9 was added thereto, and the mixture was pulverized to a particle size smaller than 20 mesh, and the pulverized product was roasted in the atmosphere at a temperature of 850° C. for about 2 hours.

The roasted product was sufficiently leached with water at about 50°C, and the residue was filtered.

When the vanadium content in the filtrate was analyzed, the vanadium recovery rate was approximately 91%.

Approximately 5.0 ml of NaCl is added to the filtered residue. ! Add 9 to 9
After roasting at 00°C for about 2 hours and leaching with water, the total recovery rate of vanadium including the first leaching amount reached approximately 100 parts.

Example 3 In Example 2, an excess of 20% diluted sulfuric acid was added to the residue obtained by extracting and separating the vanadium containing vanadium by approximately 100%.
The treatment was carried out at 0°C for about 3 hours.

When the obtained treated product was separated by filtration, the residue consisted of silicic acid containing almost no Ni and Mg, and magnesium and nickel were extracted in the obtained filtrate at a ratio of approximately 100 parts.

Furthermore, since the residue obtained in this step was a smooth sand-like substance, it was extremely easy to filter and wash it.

[Brief explanation of the drawing]

1 and 2 are basic process diagrams of the method of the present invention.

Claims (1)

[Claims] 1. In a catalyst mainly composed of magnesium silicate, the waste catalyst containing vanadium obtained from the hydrogenation process of heavy hydrocarbon oil is oxidized and roasted at a temperature of 300°C or higher, and then For the obtained oxidized roasted product, Na
C1 or/and Na2SO4 with an atomic ratio Na/V of 1.0
In addition, the vanadium contained therein is converted into a water-soluble vanadate by firing at a temperature of 700 to 1300°C, and then this vanadate is selectively eluted and separated. A method for treating waste catalyst. 2 Oxidation roasting temperature is 300 to 900°C, preferably 40°C
The method according to claim 1, wherein the temperature is 0 to 800°C. 3. The method according to claim 1 or 2, wherein the roasting temperature in the presence of NaCl and/or Na2SO4 is 800 to 950°C. 4 In a catalyst whose main component is magnesium silicate, the waste catalyst containing vanadium obtained from the hydrogenation process of heavy hydrocarbon oil was oxidized and roasted at a temperature of 300°C or higher. For the baked product, Na
C1 or/and Na2SO4 with an atomic ratio Na/V of 1.0
After addition, the vanadium contained therein is converted to water-soluble vanadate by baking at a temperature of 700 to 1300°C, and then this vanadate is selectively eluted and separated. , by applying an alkaline aqueous solution to the resulting residue after vanadate elution, the silicon contained therein is eluted as a soluble silicate, and the poorly water-soluble residue containing magnesium and nickel is separated. A method for treating a waste catalyst characterized by: 5 Alkaline aqueous solution is Na OH= Na 2 C
The method according to claim 4, which contains either Os or NaHCO3, or two or more thereof. 6 In a catalyst mainly composed of magnesium silicate, the waste catalyst containing vanadium obtained from the hydrogenation process of heavy hydrocarbon oil is oxidized and roasted at a temperature of 300 ° C. or higher, and then the obtained oxidized and roasted For the product, Na
C1 or/and Na 2804 with an atomic ratio Na/V of 1.
The vanadium contained therein was converted into a water-soluble vanadate by adding the vanadium to a water-soluble vanadate by baking at a temperature of 700 to 1300°C, and then the vanadate was selectively eluted and separated. After that, an alkaline aqueous solution is applied to the residue obtained after elution of the vanadate to elute the silicon contained therein as a soluble silicate, and to separate the poorly water-soluble residue containing magnesium and nickel. The method is further characterized in that an aqueous solution containing ammonia or/and an ammonium salt is applied to the poorly water-soluble residue containing magnesium and nickel to elute the nickel component as a water-soluble ammonia complex, and at the same time, the residue containing magnesium is separated. How to dispose of waste catalyst. T In a patent featuring magnesium silicate, the waste catalyst containing vanadium obtained from the hydrotreating process of heavy hydrocarbon oil is oxidatively roasted at a temperature of 300°C or higher, and then the resulting oxidatively roasted For the product, Na
C1 or/and Na 280. When the atomic ratio Na/V is 1.
0 or more, and by baking at a temperature of 700 to 1300°C, the vanadium contained therein is converted to water-soluble nohanadate, and then this vanadate is selectively eluted and separated. , applying an alkaline aqueous solution to the resulting residue after eluting the vanadate to elute the silicon contained therein as a soluble silicate, and separating the poorly water-soluble residue containing magnesium and nickel; Furthermore, sulfuric acid or/and hydrochloric acid or an ammonium salt thereof is added to the water-soluble silicate aqueous solution separated from the residue after vanadate elution to pH 9.
Adjust as follows to precipitate silicic acid and obtain a solution containing sodium sulfate or/and sodium chloride, and use this solution as a source of NaCl or/and Na 2 S 04 in the preceding second roasting step. A method for treating a waste catalyst characterized by: 8 In a catalyst whose main component is magnesium silicate, the waste catalyst containing vanadium obtained from the hydrogenation process of heavy hydrocarbon oil is oxidized and roasted at a temperature of 300°C or higher, and then the resulting oxidized and roasted For the baked product, N
aC1 or/and Na 2 S 04 in atomic ratio Na/
Add so that V is 1.0 or more, 700 to 1300℃
The vanadium contained therein is converted into water-soluble nohanadate by firing at a temperature of , and a method for treating a used catalyst, which comprises adding an acid to a residue containing a Si content to elute the nickel and magnesium content, and obtaining a residue consisting of silicic acid. 9 In a catalyst whose main component is magnesium silicate, the waste catalyst containing vanadium obtained from the hydrogenation process of heavy hydrocarbon oil is oxidized and roasted at a temperature of 300 ° C. or higher, and then the obtained oxidized roasted For the product, Na
C1 or/and Na2SO4 with an atomic ratio Na/V of 1.0
After addition, the vanadium contained therein is converted to water-soluble vanadate by baking at a temperature of 700 to 1300°C, and then this vanadate is selectively eluted and separated. An acid is added to the resulting residue containing Ni, Mg, and Si after elution of the vanadate to elute the nickel and magnesium components, and a residue consisting of silicic acid is obtained, which is separated from the residue consisting of silicic acid. By adding ammonium sulfate or/and ammonia to a solution containing magnesium and nickel,
The processing power of waste catalysts is also characterized by the generation of precipitates containing nickel.