CN114427029B - Heavy oil treatment method for realizing metal separation and recovery - Google Patents

Heavy oil treatment method for realizing metal separation and recovery Download PDF

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CN114427029B
CN114427029B CN202011187332.7A CN202011187332A CN114427029B CN 114427029 B CN114427029 B CN 114427029B CN 202011187332 A CN202011187332 A CN 202011187332A CN 114427029 B CN114427029 B CN 114427029B
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acid
oxygen
product
radical
leaching
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CN114427029A (en
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许可
陶梦莹
侯焕娣
董明
申海平
李吉广
赵飞
郭鑫
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/0438—Nitric acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0446—Leaching processes with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/34—Obtaining molybdenum

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to a heavy oil treatment method for realizing metal separation and recovery, which comprises the following steps: 1) Extracting and separating heavy oil containing Mo, ni and V to obtain extracted oil and metal residues; 2) Drying and crushing the metal residues, and roasting in a roasting device in the presence of oxygen-containing gas to obtain metal ash of MoO 3, niO and V 2O5; 3) Leaching the obtained metal ash by using an ammonia-ammonium salt solution to obtain Mo-containing leaching solution and V-and Ni-containing filter residues; 4) Extracting the Mo-containing leaching solution to obtain MoO 3 products; 5) Extracting the solid slag containing V and Ni to obtain a V 2O5 product and Ni-containing leaching solution; 6) And extracting the Ni-containing leaching solution to obtain a NiO product. The method has the advantages of good separation effect, simplified steps, less waste residue treatment amount and low cost.

Description

Heavy oil treatment method for realizing metal separation and recovery
Technical Field
The invention relates to a heavy oil treatment method for realizing metal separation and recovery.
Background
In recent years, with the increasing demand for petroleum and the increasing shrinkage of shallow easily-extracted light crude oil reserves, the proportion of heavy inferior crude oil with high sulfur, high metals and high carbon residue has been on the rise year by year trend in global crude oil supply. Meanwhile, with the increasing strictness of environmental protection regulations and the continuous upgrading of product quality standards, the heavy oil resource is required to be deeply processed, so that the resource utilization rate is increased, and the quality of oil products is further improved. The hydrogenation process, i.e. the process of the chemical reaction of the raw oil and the hydrogen under the action of the catalyst, has the advantages of high liquid yield, clean process and good product property. Therefore, the hydrogenation process is an effective way for realizing the efficient green conversion of heavy oil.
At present, some companies at home and abroad have made many researches on metal recovery and have obtained many industrial applications.
CN105274344a proposes a process for recovering molybdenum and vanadium from a spent petroleum catalyst. The method comprises the steps of empty firing and ball removing, ball milling, sodium carbonate roasting-water leaching, ammonium chloride vanadium precipitation and ion exchange enrichment of ammonium molybdate solution.
In the slurry bed heavy oil hydrogenation reaction system, a molybdenum-containing dead catalyst exists in hydrogenation tail oil containing other metals such as nickel, vanadium and the like. As shown in the above patent documents, the separation and recovery of molybdenum can be realized by adopting the processes of mixing and roasting alkali metal salts such as sodium carbonate, adding water for leaching, adding ammonium salt precipitant, adding acid for regulating the pH value of the solution, and the like. Although the processes can improve the recovery efficiency and the purity of molybdenum, the operation flow is complex, and the treatment amount of the follow-up waste residues is increased by introducing irrelevant recovered alkali metal ions.
Disclosure of Invention
The invention aims to provide a heavy oil treatment method for realizing metal separation and recovery, which has the advantages of good separation effect, simplified steps, less waste residue treatment amount and low cost.
In order to achieve the above object, the present invention provides a heavy oil treatment method for achieving metal separation and recovery, comprising:
1) Extracting and separating heavy oil containing Mo, ni and V to obtain extracted oil and metal residues;
2) Drying and crushing the metal residues, and roasting in a roasting device in the presence of oxygen-containing gas to obtain metal ash containing MoO 3, niO and V 2O5;
3) Delivering the obtained metal ash containing MoO 3, niO and V 2O5 into an ammonia-ammonium salt mixed solution for leaching to obtain Mo-containing leaching solution (leaching solution) and V and Ni-containing filter residues;
4) Adding acid into the obtained Mo-containing leaching solution to precipitate, and then washing, drying and roasting the obtained molybdic acid precipitate in sequence to obtain a MoO 3 product;
5) Acid leaching is carried out on the obtained filter residue containing V and Ni to obtain ammonium polyvanadate filter residue and Ni-containing leaching solution, the obtained ammonium polyvanadate filter residue is baked to be washed, dried and baked in sequence to obtain a V 2O5 product;
6) And extracting the Ni-containing leaching solution to obtain a NiO product.
Preferably, the extraction separation conditions in step 1) include:
The temperature is 40-220 ℃; and/or
The time is 0.1-5h; and/or
The extractant is at least one of benzene, toluene, xylene, straight-run diesel oil and catalytic cracking diesel oil; and/or
The mass ratio of the heavy oil to the extractant is 1-15:1.
Preferably, the comminution in step 2) is such that the metal residue has a particle size of 80-220 mesh.
Preferably, the firing conditions in step 2) include:
The temperature is 400-650 ℃; and/or
The time is 30-200min; and/or
The oxygen-containing gas is air and/or oxygen, preferably oxygen; and/or
The oxygen-containing gas stream is from 30 to 150mL/min relative to 1g of the metal residue, based on the volume of oxygen in the oxygen-containing gas.
Preferably, the leaching conditions of the ammonia-ammonium salt mixed solution obtained in the step 3) comprise: and/or
The weight ratio of the ammonia-ammonium salt mixed solution to the metal ash is 1-20; and/or
The ratio of the amount of NH 3·H2 O species in the mixed solution to the total amount of Mo and V species in the metallic ash is 0.1-5; and/or
The ammonium salt is at least one selected from ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate and ammonium acetate; and/or
The ratio of the amount of NH 4 + in the ammonium salt to the amount of V in the metal ash is 0.01-10; and/or
The temperature is 5-75 ℃; and/or
The time is 5-180min; and/or
The pH value of the leaching reaction system is 6.5-9.5.
Preferably, the method comprises the steps of,
In step 4), the acid precipitation conditions include: the pH value of the sediment is 0-2; and/or
The temperature is 10-90 ℃; and/or
The time is 90-270min; and/or
The acidic precipitant is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid; and/or
The temperature of the calcination in step 4) is 300-550 ℃ and/or the time is 60-600min.
Preferably, the acid leaching conditions in step 5) comprise: leaching to pH 1-5, and/or temperature 10-50deg.C, and/or time 10-150min; and/or the acidic leaching agent is selected from hydrochloric acid, sulfur
One or more of an acid and nitric acid;
The temperature of the calcination in step 5) is 300-600 ℃ and/or the time is 60-600min.
Preferably, the step of the extraction process in step 6) includes:
a, mixing the leaching solution containing Ni obtained in the step 5) with a first alkaline substance to perform first precipitation treatment, and then performing solid-liquid separation to obtain a separation solution containing Ni;
b, mixing the Ni-containing separating liquid with a second alkaline matter, performing second precipitation treatment, and then performing solid-liquid separation to obtain Ni (OH) 2 precipitate;
and c, washing, drying and roasting the obtained Ni (OH) 2 precipitate in sequence to obtain the NiO product.
Preferably, in the step a, the conditions of the first precipitation treatment include: the first alkaline matter is selected from one or more of sodium carbonate and sodium hydroxide, the temperature is 5-90 ℃, the time is 1-300min, and the pH value of the leaching solution containing Ni during the first precipitation treatment is 3-8.
Preferably, in the step b, the conditions of the second precipitation treatment include: the second alkaline matter is selected from one or more of sodium carbonate and sodium hydroxide, the temperature is 5-90 ℃, the time is 1-300min, and the pH value of the separating liquid containing Ni is 8.5-12 when the second precipitation treatment is carried out; and/or
In the step c, the roasting temperature is 300-650 ℃ and the roasting time is 60-600min.
Preferably, the heavy oil contains 0.1 to 5wt% of Mo, 0.1 to 5wt% of Ni, 0.1 to 5wt% of V, 85 to 92 wt% of C and 5 to 12 wt% of H, based on the weight of the heavy oil.
Preferably, the heavy oil is selected from one or more of residuum and tail oil.
The invention has the following advantages:
1. The invention adopts a combination mode of solvent extraction, air roasting and ammonia/ammonium salt solution leaching to realize the selective separation and recovery of metals such as molybdenum, nickel, vanadium and the like from heavy oil. The yield and purity of molybdenum, nickel and vanadium are high, the product quality is stable, one-step separation of molybdenum and vanadium is realized, the process steps are simplified, the introduction of alkali metal ions is avoided, the subsequent waste residue treatment amount is reduced, and the method has important environmental protection value;
2. the molybdenum recovered from the heavy oil can be used as a synthetic raw material of a slurry bed heavy oil hydrogenation catalyst, and metals such as nickel, vanadium and the like in the heavy oil can also be recovered and used as other catalysts, so that the catalyst has great economic benefit.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is a schematic flow chart of one embodiment of the separation method of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As shown in fig. 1, the present invention provides a heavy oil treatment method for realizing metal separation and recovery, comprising:
1) Extracting and separating heavy oil containing Mo, ni and V to obtain extracted oil and metal residues;
2) Drying and crushing the metal residues, and roasting in a roasting device in the presence of oxygen-containing gas to obtain metal ash containing MoO 3, niO and V 2O5;
3) Feeding ammonia-ammonium salt mixed solution into the obtained metal ash containing MoO 3, niO and V 2O5 for leaching to obtain Mo-containing leaching solution and V and Ni-containing filter residues;
4) Adding acid into the obtained Mo-containing leaching solution to precipitate, and then washing, drying and roasting the obtained molybdic acid precipitate in sequence to obtain a MoO 3 product;
5) Adding acid to the obtained V-and Ni-containing filter residues for leaching to obtain ammonium polyvanadate filter residues and Ni-containing leaching solution, roasting the obtained ammonium polyvanadate filter residues in sequence, washing, drying and roasting to obtain a V 2O5 product;
6) And extracting the Ni-containing leaching solution to obtain a NiO product.
The invention adopts a combination mode of solvent extraction, air roasting and ammonia/ammonium salt solution leaching to realize the selective separation and recovery of Mo, ni and V from heavy oil. The metal yield and purity are high, the product quality is stable, the one-step separation of Mo and V is realized, the process steps are simplified, the introduction of sodium ions is avoided, and the subsequent waste residue treatment capacity is reduced.
According to a preferred embodiment of the present invention, the extraction separation conditions include: the temperature is 40-220 ℃; and/or the time is 0.1-5h, wherein the time can be adjusted according to the temperature to finish the extraction separation.
According to a preferred embodiment of the present invention, the extraction agent used for the extraction separation has a wide selection range, and is preferably at least one selected from benzene, toluene, xylene, straight-run diesel oil and catalytic cracking diesel oil.
According to a preferred embodiment of the invention, the mass ratio of heavy oil to extractant is 1-15:1.
According to the invention, the comminution in step 2) serves to reduce the particle size of the metal residue, which is advantageous for the calcination of the residue, for example, after comminution the residue has a particle size of 80-220 mesh.
According to the invention, the firing conditions in step 2) include: the temperature is 400-650 ℃, and/or the time is 30-200min, and the time can be specifically adjusted according to the temperature.
According to a preferred embodiment of the invention, the oxygen-containing gas is preferably air and/or oxygen, preferably oxygen.
According to a preferred embodiment of the invention, the oxygen-containing gas stream is 30-150mL/min relative to 1g of the metal residue, based on the volume of oxygen in the oxygen-containing gas. The oxygen-containing gas can be fed into the roasting device simultaneously with the heavy oil, or the heavy oil can be added into the roasting device at one time, and then the oxygen-containing gas is continuously or batchwise introduced.
According to the invention, the roasting device is well known to the person skilled in the art, for example a roasting furnace or the like.
According to the invention, the ammonia-ammonium salt mixed solution is leached to separate the ash containing MoO 3、V2O5 and NiO into an ammonium molybdate-containing leaching solution and ammonium polyvanadate and NiO-containing filter residues. The leaching conditions of the ammonia-ammonium salt mixed solution comprise: the weight ratio of the ammonia-ammonium salt mixed solution to the metal ash is 1-20.
According to the invention, it is preferred that the ratio of the amount of NH 3·H2 O species in the aqueous ammonia in the mixed solution to the total amount of Mo and V species in the metallic ash is 0.1-5.
According to the present invention, it is preferable that the ammonium salt is at least one selected from the group consisting of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate and ammonium acetate.
According to the invention, it is preferred that the ratio of the amount of NH 4 + species in the ammonium salt to the amount of V species in the metallic ash is 0.01-10; and/or the temperature is 5-75 ℃, and/or the time is 5-180min, and/or the pH value of the leaching reaction system is 6.5-9.5. The foregoing conditions may be satisfied individually or in combination.
According to the invention, step 3) and step 4) are used to convert the ammonium molybdate solution to a molybdic acid precipitate and to convert the ammonium molybdate precipitate to a MoO 3 product. The acid precipitation conditions include: the pH of the precipitate is 0-2, and/or the temperature is 10-90deg.C, and/or the time is 90-270min. According to the invention, the time can be adjusted depending on the temperature.
According to the invention, the acidic precipitant is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid. The roasting temperature is 300-550 ℃ and/or the roasting time is 60-600min. The calcination atmosphere may be an air atmosphere, and the content of MoO 3 in the MoO 3 product may be 90 wt% or more, preferably 95 wt% or more.
According to the invention, step 5) is used for separating ammonium polyvanadate solid and Ni-containing leaching solution from the solid slag containing ammonium polyvanadate and NiO, and pyrolyzing and converting the ammonium polyvanadate solid into a V 2O5 product. The acid leaching conditions include: leaching pH value is 1-5, and/or temperature is 10-50deg.C, and/or time is 10-150min.
The acidic leaching agent according to the present invention is for example selected from one or more of hydrochloric acid, sulfuric acid and nitric acid. The temperature of the calcination in step 5) is 300-600 ℃ and/or the time is 60-600min. The firing atmosphere may be an air atmosphere, and the content of V 2O5 in the V 2O5 product may be 90% by weight or more, preferably 95% by weight or more.
According to the invention, the extraction treatment in step 6) is used to convert the Ni-containing leaching solution into NiO product. As shown in fig. 1, the steps of the extraction process may include: a, mixing the leaching solution containing Ni obtained in the step 5) with a first alkaline substance to perform first precipitation treatment, and then performing solid-liquid separation to obtain a separation solution containing Ni; b, mixing the Ni-containing separating liquid with a second alkaline matter, performing second precipitation treatment, and then performing solid-liquid separation to obtain Ni (OH) 2 precipitate; and c, washing, drying and roasting the obtained Ni (OH) 2 precipitate in sequence to obtain the NiO product.
According to the present invention, the conditions for the first precipitation treatment in step a for removing impurities such as Fe and Al are not particularly limited, and for example, the conditions for the first precipitation treatment include: the first alkaline matter is selected from one or more of sodium carbonate and sodium hydroxide, the temperature is 5-90 ℃, the time is 1-300min, and the pH value of the leaching solution containing Ni during the first precipitation treatment is 3-8.
According to the invention, optionally, the second precipitation treatment in step b is used for producing Ni (OH) 2, the conditions of the second precipitation treatment comprising: the second alkaline matter is one or more of sodium carbonate and sodium hydroxide, the temperature is 5-90 ℃, the time is 1-300min, and the pH value of the separating liquid containing Ni is 8.5-12 when the second precipitation treatment is carried out.
Alternatively, the conditions for pyrolytically converting Ni (OH) 2 to NiO product in step c are not particularly limited, and the firing temperature is 300-650℃for 60-600min, for example. The firing atmosphere may be an air atmosphere. The NiO product may have a NiO content of 90 wt% or more, preferably 95 wt% or more.
Heavy oils are well known to those skilled in the art in accordance with the present invention, for example, having a Mo content of 0.1 to 5 wt.%, a Ni content of 0.1 to 5 wt.%, a V content of 0.1 to 5 wt.%, a C content of 85 to 92 wt.%, and a H content of 5 to 12 wt.%, based on the weight of the heavy oil. The heavy oil may be selected from one or more of residuum and tail oil, preferably heavy oil produced from hydro-thermal conversion of residuum, more preferably tail oil obtained from hydrogenation of Mo-containing catalyst and low quality heavy oil containing Ni, V metals.
According to the invention, preferably the method further comprises:
(I) Mixing the MoO 3 product obtained in the step (4), a solvent and a C1-C6 oxygen-containing organic acid, reacting at 20-150 ℃ to obtain a reaction mixture, and regulating the pH value of the reaction mixture to 2.5-5 to obtain a first product;
(II) mixing the first product with a C6-C18 oxygen-containing organic acid and reacting at 145-300 ℃, and separating and purifying the obtained product to obtain the organic oil-soluble molybdenum-containing compound.
According to the invention, preferably, in step (I), the weight ratio of the MoO 3 product to the solvent, calculated as molybdenum element, is 1: (1-20); the molar ratio of the MoO 3 product to the C1-C6 oxygen-containing organic acid calculated as molybdenum element is 1: (0.5-4).
According to the invention, preferably, in step (II), the molar ratio of said MoO 3 product to said C6-C18 oxygenated organic acid, calculated as molybdenum element, is 1: (1-10).
According to the invention, the reaction time in step (I) is preferably from 0.3 to 9 hours.
According to the invention, the reaction time in step (II) is preferably 1 to 12 hours.
According to the present invention, preferably, the solvent in step (I) is selected from water and/or an organic solvent; the organic solvent is selected from benzene, toluene, ethanol or petroleum ether.
According to the invention, preferably, the C1-C6 oxygenated organic acid is selected from formic acid, acetic acid, propionic acid, 2-methylbutyric acid, glycolic acid, isobutyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 2-hydroxysuccinic acid, 3-hydroxypropionic acid or citric acid.
According to the present invention, preferably, the C6-C18 oxygen-containing organic acid is selected from the group consisting of caproic acid, heptanoic acid, 2-propylheptanoic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, oleic acid, palmitic acid, stearic acid and naphthenic acid having 6 to 18 carbon atoms.
According to the invention, step (I) and/or step (II) are preferably carried out in an inert atmosphere.
The method according to the present invention, wherein the organic oil-soluble molybdenum-containing compound has a structure represented by formula (1):
Wherein a+b is 2, 3, 4, 5 or 6, m+n is 0, 1,2, 3, 4, 5 or 6, R 1 is a C1-C6 oxygen-containing organic acid radical, and R 2 is a C6-C18 oxygen-containing organic acid radical.
According to the method of the present invention, preferably, a is equal to b, and a+b is 2,4 or 6; m is equal to n, and m+n is 0, 2 or 4.
More preferably, the C1-C6 oxygen-containing organic acid radical is a monocarboxylate, a dicarboxylate or a polycarboxylate, preferably a dicarboxylate or a polycarboxylate, more preferably a formate, acetate, propionate, 2-methylbutyrate, glycolate, isobutyrate, valerate, oxalate, malonate, succinate, glutarate, 2-hydroxysuccinate, 3-hydroxypropiontricarboxylate or citrate.
More preferably, the C6-C18 oxygen-containing organic acid radical is a monocarboxylate, a dicarboxylate, a polycarboxylate, a thiocarboxylate, a sulfonate or a sulfinate, preferably a monocarboxylate, a dicarboxylate or a sulfonate, more preferably a caproate, a heptanoate, a 2-propylheptanoate, a octanoate, a 2-ethylhexanoate, a nonanoate, a decanoate, an oleate, a palmitate, a stearate or a naphthenate with a carbon number of 6-18.
More preferably, according to the method of the present invention, the organic oil-soluble molybdenum-containing compound contains 2 to 23% by weight of molybdenum metal element.
The organic oil-soluble molybdenum-containing compound synthesized by the method has excellent hydrogenation, coke inhibition and denitrification effects.
Other operations of the method of the present invention, such as filtration and drying, may employ operating conditions well known to those skilled in the art, and the present invention will not be described in detail.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
The RMX heavy oil used in the examples and comparative examples of the present invention is a heavy oil obtained by a residual oil hydro-thermal conversion process for developing a prolific upgraded oil in a petrochemical science institute, and the content of Mo, ni, V, C and H in the RMX heavy oil is 0.50 wt%, 0.23 wt%, 0.74 wt%, 87.18 wt% and 6.84 wt% respectively, based on the weight of the RMX heavy oil.
The yield of a metal of a product is the ratio of the weight of the metal in the product to the weight of the metal in the heavy oil feedstock.
In the examples and comparative examples of the present invention: the chemical reagent used is a product of national drug group chemical reagent limited company.
The metal content analysis was determined according to the ICP-other method on a PERKINELMER NEXION X inductively coupled plasma emission spectrometer.
Infrared spectra were tested on a Nicolet model 6700 fourier infrared spectrometer.
The relative molecular mass of the organomolybdenum compound was determined using mass spectrometry.
Example 1
(1) 300G of RMX tail oil is extracted for 1h at 120 ℃ by using 1200g of toluene, then an extraction phase and metal residues are obtained by filtering, and the toluene in the extraction phase is distilled off to obtain modified oil.
(2) The metal residue was dried at 140℃under 0.01MPa for 4 hours, and then the metal residue was crushed to 100 mesh in particle size by a crusher.
(3) The processes of steps (1) - (2) are repeated, 30g of accumulated metal residues (the mass fractions of Mo, ni and V are 5.2%, 1.6% and 4.8% respectively) are added into a roasting furnace, air roasting is carried out for 90min at the temperature of 550 ℃ and the air speed of 1500mL/min, flue gas is generated after roasting treatment, ash containing Mo, V and Ni is carried by combustion and enters a filter for gas-solid separation, so as to obtain flue gas and metal ash, the roasting furnace is cooled after roasting is finished, the metal ash containing Mo, V and Ni is back-blown by the filter to a collecting tower for collection, and the contents (calculated by oxide) of molybdenum, vanadium and nickel in the ash containing MoO 3, V 2O5 and NiO are respectively 41.3 wt%, 45.3 wt% and 10.7 wt%.
(4) Taking 20g of the ash containing Ni, mo and V obtained by roasting in the step (3), crushing the ash to 100 meshes, and leaching the ash for 60 minutes by using an ammonia-ammonium salt mixed solution at 25 ℃ and a pH value of 7.6, wherein the weight ratio of the ammonia-ammonium salt mixed solution to the ash containing the metal is 5, the ratio of the amount of NH 3·H2 O in ammonia water to the total amount of Mo and V in the ash is 1.2, and the ratio of the amount of NH 4 + in ammonium chloride to the amount of V in the ash is 3. At this time MoO 3 and V 2O5 react with ammonia to form ammonium salts, while NiO is unchanged. The ammonium salt of Mo is dissolved in water and filtered into leaching solution, while the aqueous solution of ammonium salt of V has small solubility, filtered into filter residue, and the filter residue containing Ni and V is washed with water and dried for later use.
(5) Adding 65% nitric acid into the filtrate containing Mo to adjust the pH value of the filtrate to 0.6, reacting at 80 ℃ for 180min, and precipitating molybdenum in a form of ammonium polymolybdate as a precipitate. Washing the obtained ammonium polymolybdate precipitate with distilled water, drying, and roasting in air at 500 ℃ for 180min to obtain MoO 3 product, and drying and roasting to obtain MoO 3 product, wherein the yield of Mo is 96.2 wt%, and the weight fraction of MoO 3 in the MoO 3 product is 98.1%.
(6) And (3) adjusting the pH value of the filter residue containing V and Ni obtained by separation in the step (3) to 2.0 by using 65% by weight of nitric acid, and stirring and leaching for 120min at 25 ℃. At this time, niO reacts with nitric acid to generate nickel nitrate which is dissolved in water, the nickel nitrate is filtered and enters leaching solution, the obtained ammonium polyvanadate precipitate is added with 1 weight percent of dilute ammonia water for washing and then dried, and then the mixture is air-roasted for 120 minutes at 550 ℃ to obtain a V 2O5 product, and the calculated V yield is 97.5 weight percent, and the weight fraction of V 2O5 in the V 2O5 product is 98.7 percent.
(7) And (3) taking the Ni-containing leaching solution obtained by separation in the step (6), adjusting the pH value to 6.0 by using NaOH so as to enable Fe and Al in the leaching solution to be precipitated for 30min, and filtering the precipitate. The pH of the filtered Ni-containing filtrate was then adjusted to 9.0 with NaOH to precipitate Ni (OH) 2. The Ni (OH) 2 crystals were washed with distilled water and dried, and then air-calcined at 600℃for 120min to obtain a NiO product, which was calculated to give a Ni yield of 98.1% by weight and a NiO weight fraction of 98.4% in the NiO product.
Example 2
(1) As in example 1.
(2) As in example 1.
(3) The processes of steps (1) - (2) are repeated, 30g of accumulated metal residues (the mass fractions of Mo, ni and V are 5.2%, 1.6% and 4.8% respectively) are added into a roasting furnace, air roasting is carried out for 60min at 600 ℃ and 2300mL/min, flue gas is generated after roasting treatment, ash which burns with the Mo, V and Ni is carried into a filter, gas-solid separation is carried out, and flue gas and metal ash are obtained, the roasting furnace is cooled after roasting is finished, the metal ash containing the Mo, V and Ni is back-blown by the filter to a collecting tower for collection, and the contents (calculated as oxides) of molybdenum, vanadium and nickel in the ash containing MoO 3, V 2O5 and NiO are 42.2 wt%, 46.7 wt% and 11.2 wt% respectively.
(4) Taking 20g of the ash containing Ni, mo and V obtained by roasting in the step (3), crushing the ash to 100 meshes, and leaching the ash for 90 minutes by using an ammonia-ammonium salt mixed solution at 35 ℃ and a pH value of 8.2, wherein the weight ratio of the ammonia-ammonium salt mixed solution to the ash containing the metal is 5, the ratio of the amount of NH 3·H2 O in ammonia water to the total amount of Mo and V in the metal ash is 1, and the ratio of the amount of NH 4 + in ammonium chloride to the amount of V in the metal ash is 4. At this time MoO 3 and V 2O5 react with ammonia to form ammonium salts, while NiO is unchanged. The ammonium salt of Mo is dissolved in water and filtered into leaching solution, while the aqueous solution of ammonium salt of V has small solubility, filtered into filter residue, and the filter residue containing Ni and V is washed with water and dried for later use.
(5) Adding 65% nitric acid into the filtrate containing Mo to adjust the pH value of the filtrate to 0.4, reacting at 70 ℃ for 120min, and precipitating molybdenum in a form of ammonium polymolybdate as a precipitate. The obtained ammonium polymolybdate precipitate was washed with distilled water and dried, and then air-calcined at 550 ℃ for 120min to obtain a MoO 3 product, the Mo yield was 96.2 wt%, and the weight fraction of MoO 3 in the MoO 3 product was 98.1%.
(6) And (3) adjusting the pH value of the filter residue containing V and Ni obtained by separation in the step (3) to 1.5 by using 65% by weight of nitric acid, and stirring and leaching for 90min at 25 ℃. At this time, niO reacts with nitric acid to generate nickel nitrate which is dissolved in water, the nickel nitrate is filtered and enters leaching solution, the obtained ammonium polyvanadate precipitate is added with 1 weight percent of dilute ammonia water for washing and then dried, and then the mixture is air-roasted for 120 minutes at 600 ℃ to obtain a V 2O5 product, wherein the calculated V yield is 95.4 weight percent, and the weight fraction of V 2O5 in the V 2O5 product is 99.1 percent.
(7) As in example 1, a NiO product was obtained, and the Ni yield was calculated to be 98.7 wt%, with a NiO weight fraction of 95.7% in the NiO product.
Example 3
(1) As in example 1.
(2) As in example 1.
(3) The processes of steps (1) - (2) are repeated, 30g of accumulated metal residues (the mass fractions of Mo, ni and V are 5.2%, 1.6% and 4.8% respectively) are added into a roasting furnace, air roasting is carried out for 30min at the temperature of 650 ℃ and the air speed of 1500mL/min, flue gas is generated after roasting treatment, ash containing Mo, V and Ni is carried by combustion and enters a filter for gas-solid separation, so as to obtain flue gas and metal ash, the roasting furnace is cooled after roasting is finished, the metal ash containing Mo, V and Ni is back-blown by the filter to a collecting tower for collection, and the contents (calculated by oxide) of molybdenum, vanadium and nickel in the ash containing MoO 3, V 2O5 and NiO are respectively 41.2 wt%, 46.9 wt% and 12.2 wt%.
(4) Taking 20g of the ash containing Ni, mo and V obtained by roasting in the step (3), crushing the ash to 100 meshes, and leaching the ash for 120min by using an ammonia-ammonium salt mixed solution at 55 ℃ and a pH value of 7.0, wherein the weight ratio of the ammonia-ammonium salt mixed solution to the ash containing the metal is 4, the ratio of the amount of NH 3·H2 O in ammonia water to the total amount of Mo and V in the ash is 1.2, and the ratio of the amount of NH 4 + in ammonium chloride to the amount of V in the ash is 6. At this time MoO 3 and V 2O5 react with ammonia to form ammonium salts, while NiO is unchanged. The ammonium salt of Mo is dissolved in water and filtered into leaching solution, while the aqueous solution of ammonium salt of V has small solubility, filtered into filter residue, and the filter residue containing Ni and V is washed with water and dried for later use.
(5) As in example 1, a MoO 3 product was obtained, the yield of Mo was 94.7% by weight and the weight fraction of MoO 3 in the MoO 3 product was 98.3%.
(6) As in example 1, V 2O5 was obtained, calculated to give a V yield of 97.2% by weight and a V 2O5 weight fraction in the V 2O5 product of 98.5%.
(7) As in example 1, a NiO product was obtained, and the Ni yield was calculated to be 96.5% by weight, and the weight fraction of NiO in the NiO product was 98.1%.
Example 4
(1) As in example 1.
(2) As in example 1.
(3) The procedure of steps (1) - (2) was repeated, and 30g (mass fractions of Mo, ni and V are 5.2%, 1.6% and 4.8%, respectively) of the metal residue was accumulated. Adding into a roasting furnace, and roasting for 180min at 450 ℃ and a gas speed of 3000 mL/min. The ash content containing Mo, V and Ni is carried by flue gas generated by roasting treatment and enters a filter for gas-solid separation to obtain flue gas and metal ash. And cooling the roasting furnace after roasting is finished, and back-blowing metal ash containing Mo, V and Ni into a collecting tower by a filter to collect. The ash containing MoO 3 and V 2O5 and NiO was analyzed for molybdenum, vanadium and nickel content (calculated as oxides) of 33.1 wt%, 36.2 wt% and 8.6 wt%, respectively.
(4) As in example 1.
(5) As in example 1, moO 3 was obtained in a yield of 93.9 wt% and MoO 3 was 97.7 wt% in the MoO 3 product.
(6) The product of V 2O5 was obtained as in example 1, calculated to give a V yield of 95.1% by weight and a V 2O5 weight fraction of 98.6% in the product of V 2O5.
(7) As in example 1, a NiO product was obtained, and the Ni yield was calculated to be 95.2% by weight, and the weight fraction of NiO in the NiO product was 98.4%.
Example 5
Substantially the same as in steps (1) - (7) of example 1, except that in step (4), the ammonia-ammonium salt mixed solution was leached at 45 ℃ and pH 8.5 for 90min, wherein the weight ratio of the ammonia-ammonium salt mixed solution to the metal ash content was 6, the ratio of the amount of NH 3·H2 O substance in the ammonia water to the total amount of Mo and V substance in the metal ash was 1.5, and the ratio of the amount of NH 4 + substance in the ammonium chloride to the amount of V substance in the metal ash was 2.
The Mo yield was calculated to be 93.7 wt% for the Mo 3 product and 95.8 wt% for the Mo 3 in the Mo 3 product. The V 2O5 product was obtained in a yield of 93.2 wt% and the V 2O5 weight fraction in the V 2O5 product was 99.1%. The Ni yield was calculated to be 97.1 wt% for the NiO product, which was 97.5 wt% for NiO.
Comparative example 1
(1) As in example 1.
(2) As in example 1.
(3) The procedure of steps (1) - (2) was repeated, and 30g (mass fractions of Mo, ni and V are 5.2%, 1.6% and 4.8%, respectively) of the accumulated metal residue was mixed with 8.3g of sodium carbonate. The mixed powder was air-calcined at 600 c for 120min. (Mo and V react with sodium carbonate during calcination to form sodium molybdate and sodium carbonate which are soluble in water, whereas NiO does not react with sodium carbonate and is insoluble in water)
(4) And (3) leaching the roasting product obtained in the step (3) with 35g of water at 90 ℃ for 90min, dissolving sodium salts of V and Mo in water at the moment, filtering, entering leaching solution, washing filter residues containing Ni with water, and drying for later use.
(5) Hydrochloric acid with the weight percentage of 37% is added into leaching solution containing V and Mo to adjust the pH value of the leaching solution to 8.2, 6.1g of ammonium chloride is added, the precipitation temperature is 50 ℃, and the precipitation time is 30min. The precipitate was washed by filtration and dried and calcined to give a V 2O5 product with a yield of 95.2 wt% and a V 2O5 product with a V 2O5 weight fraction of 93.6%. Adding 37% hydrochloric acid into the filtrate containing Mo to adjust the pH value of the filtrate to 0.8, reacting for 30min, and precipitating molybdenum in the form of molybdic acid precipitate. And (3) filtering and washing the molybdic acid precipitate, and drying and roasting to obtain a MoO 3 product, wherein the yield of Mo is 92.5 weight percent, and the weight fraction of MoO 3 in the MoO 3 product is 93.7 percent.
(6) Taking the Ni-containing filter residue obtained in the separation in the step (5), and adding 16.2g of 5% hydrochloric acid solution by weight. After heating the mixture to 90 ℃, stirring and leaching for 30min. Cooling, adjusting pH to 6.0 with NaOH to precipitate Fe and Al in the leaching solution for 30min, and filtering. The pH of the filtered Ni-containing filtrate was then adjusted to 9.0 with NaOH to precipitate Ni (OH) 2. The Ni (OH) 2 crystals were washed with distilled water and dried, and then air-calcined at 600℃for 120min to obtain a NiO product, calculated to give a Ni yield of 97.6 wt%, and the weight fraction of NiO in the NiO product was 98.1%.
As can be seen from comparing examples 1-5 with comparative example 1, the present invention directly adopts ammonia-ammonium salt to impregnate and separate Mo and V, simplifies the steps of separating Mo and V by basic roasting-water impregnation and then ammonium salt precipitation in comparative example, can efficiently separate molybdenum, nickel and vanadium, has high yield and purity of molybdenum, nickel and vanadium, stable product quality, simplifies the process steps, avoids the introduction of alkali metal ions, reduces the subsequent waste residue treatment amount, and has important environmental protection value.
Example 6
(I) The molybdenum trioxide recovered in example 1 was dispersed in a solvent (a mixed solution of water and ethanol, weight ratio of water to ethanol: 1:1) in a flask, the weight ratio of molybdenum trioxide to solvent being 1:20. inert gas purging, adding succinic acid at the temperature of 100 ℃ for reaction for 8 hours, wherein the molar ratio of the succinic acid to molybdenum trioxide (calculated by molybdenum element) is 3:1, a step of; after the reaction, the pH value of the solution is adjusted to 4.5 by using dilute ammonia water to obtain a first product.
(II) adding preheated nonanoic acid to the solution in a molar ratio of molybdenum trioxide (calculated as molybdenum element) to nonanoic acid of 1:4.5, mixing, preheating the pelargonic acid at 100 ℃, reacting for 3 hours at 245 ℃ after the mixing, and separating the solvent after the reaction is finished to obtain the organic oil-soluble molybdenum-containing compound.
The structure of the organic molybdenum compound is tested by adopting infrared spectrum, and the infrared spectrum is adopted ：γ＝2962cm-1、1708cm-1、1534cm-1、1462cm-1、1423cm-1、1289cm-1、986cm-1、780cm-1、731cm-1.
As is clear from the infrared spectrum data, an absorption peak ascribed to Mo-O-Mo appears near 690-790cm -1, 2961cm -1,1462cm-1 is an antisymmetric stretching vibration peak and an antisymmetric deformation vibration peak of the C-H bond of CH 3 on the organic acid alkyl group, 1534cm -1、1462cm-1 is an antisymmetric stretching vibration peak and a symmetrical stretching vibration peak of the coordinated carboxyl group, respectively, which indicates that the organic oil-soluble molybdenum-containing compound has a structure shown in formula (1).
Example 7
An organomolybdenum compound was produced in the same manner as in example 6 except that the pH of the reaction mixture was adjusted to 0.5 in step (I). And after the reaction is finished, separating the reaction product to remove the solvent phase, washing the oil phase with water, and distilling under reduced pressure to remove light components to obtain the organic molybdenum compound.
Infrared spectrum ：γ＝2956cm-1,1708cm-1,1509cm-1,1421cm-1,1297cm-1,1118cm-1,983cm-1,684cm-1.
The infrared spectrum analysis shows that the 690cm -1-790cm-1 has no absorption peak of Mo-O-Mo, which indicates that the organic molybdenum compound does not have the structure shown in the formula (1).
The organic oil-soluble molybdenum-containing compound with the structure shown in the formula (1) synthesized by the method has excellent hydrogenation, coke inhibition and denitrification effects.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (25)

1. A heavy oil treatment method for realizing metal separation and recovery, characterized in that the method comprises the following steps:
1) Extracting and separating heavy oil containing Mo, ni and V to obtain extracted oil and metal residues;
2) Drying and crushing the metal residues, and roasting in a roasting device in the presence of oxygen-containing gas to obtain metal ash containing MoO 3, niO and V 2O5, wherein the roasting conditions comprise: the temperature is 400-650 ℃;
3) Delivering the obtained metal ash containing MoO 3, niO and V 2O5 into an ammonia-ammonium salt mixed solution for leaching to obtain Mo-containing leaching solution and V and Ni-containing filter residues; the leaching conditions of the ammonia-ammonium salt mixed solution comprise: the weight ratio of the ammonia-ammonium salt mixed solution to the metal ash is 1-20; the ratio of the amount of NH 3·H2 O species in the mixed solution to the total amount of Mo and V species in the metallic ash is 0.1-5; the ratio of the amount of NH 4 + in the ammonium salt to the amount of V in the metal ash is 0.01-10; the temperature is 5-75 ℃; the time is 5-180min; the pH value of the leaching reaction system is 6.5-9.5;
4) Adding acid into the obtained Mo-containing leaching solution to precipitate, and then washing, drying and roasting the obtained molybdic acid precipitate in sequence to obtain a MoO 3 product;
5) Acid leaching is carried out on the obtained filter residue containing V and Ni to obtain ammonium polyvanadate filter residue and Ni-containing leaching solution, the obtained ammonium polyvanadate filter residue is baked to be washed, dried and baked in sequence to obtain a V 2O5 product;
6) Extracting the Ni-containing leaching solution to obtain a NiO product;
The method further comprises the steps of:
(I) Mixing the MoO 3 product obtained in the step 4), a solvent and a C1-C6 oxygen-containing organic acid, reacting at 20-150 ℃ to obtain a reaction mixture, and regulating the pH value of the reaction mixture to 2.5-5 to obtain a first product;
(II) mixing the first product with a C6-C18 oxygen-containing organic acid and reacting at 145-300 ℃, and separating and purifying the obtained product to obtain an organic oil-soluble molybdenum-containing compound;
The organic oil-soluble molybdenum-containing compound has a structure shown in a formula (1):
(1),
Wherein a+b is 2, 3, 4, 5 or 6, m+n is 0, 1,2, 3, 4, 5 or 6, R 1 is a C1-C6 oxygen-containing organic acid radical, and R 2 is a C6-C18 oxygen-containing organic acid radical.
2. The method of claim 1, wherein the extractive separation conditions in step 1) comprise:
The temperature is 40-220 ℃; and/or
The time is 0.1-5h; and/or
The extractant is at least one of benzene, toluene, xylene, straight-run diesel oil and catalytic cracking diesel oil; and/or
The mass ratio of the heavy oil to the extractant is 1-15:1.
3. A process according to claim 1 or 2, wherein the comminution in step 2) is such that the metal residue has a particle size of 80-220 mesh.
4. The method according to claim 1 or 2, wherein the firing conditions in step 2) comprise:
the time is 30-200min; and/or
The oxygen-containing gas is air and/or oxygen; and/or
The oxygen-containing gas stream is from 30 to 150mL/min relative to 1g of the metal residue, based on the volume of oxygen in the oxygen-containing gas.
5. The method of claim 4, wherein the firing conditions in step 2) include: the oxygen-containing gas is oxygen.
6. The method according to claim 1 or 2, wherein the ammonia-ammonium salt mixed solution leaching conditions in step 3) comprise:
the ammonium salt is at least one selected from the group consisting of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate and ammonium acetate.
7. The method according to claim 1 or 2, wherein, in step 4),
The acid precipitation conditions include: the pH value of the sediment is 0-2; and/or the temperature is 10-90 ℃; and/or the time is 90-270min; and/or the acidic precipitant is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid; and/or
The roasting conditions include: the temperature is 300-550 ℃; and/or for 60-600min.
8. The method according to claim 1 or 2, wherein, in step 5),
The acid leaching conditions include: leaching to a pH value of 1-5; and/or the temperature is 10-50 ℃; and/or the time is 10-150min; and/or the acidic leaching agent is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid; and/or
The roasting conditions include: the temperature is 300-600 ℃; and/or for 60-600min.
9. The method according to claim 1 or 2, wherein in step 6), the step of extracting process comprises:
a, mixing the leaching solution containing Ni obtained in the step 5) with a first alkaline substance to perform first precipitation treatment, and then performing solid-liquid separation to obtain a separation solution containing Ni;
b, mixing the Ni-containing separating liquid with a second alkaline matter, performing second precipitation treatment, and then performing solid-liquid separation to obtain Ni (OH) 2 precipitate;
And c, washing, drying and roasting the obtained Ni (OH) 2 precipitate in sequence to obtain the NiO product.
10. The method of claim 9, wherein,
In the step a, the conditions of the first precipitation treatment include: the first alkaline matter is selected from one or more of sodium carbonate and sodium hydroxide, the temperature is 5-90 ℃, the time is 1-300min, and the pH value of the leaching solution containing Ni is 3-8 when the first precipitation treatment is carried out; and/or
In step b, the conditions of the second precipitation treatment include: the second alkaline matter is selected from one or more of sodium carbonate and sodium hydroxide, the temperature is 5-90 ℃, the time is 1-300min, and the pH value of the separating liquid containing Ni is 8.5-12 when the second precipitation treatment is carried out; and/or
In the step c, the roasting temperature is 300-650 ℃ and the roasting time is 60-600min.
11. The method according to claim 1 or 2, wherein the heavy oil has Mo content of 0.1 to 5wt%, ni content of 0.1 to 5wt%, V content of 0.1 to 5wt%, C content of 85 to 92 wt%, and H content of 5 to 12 wt%, based on the weight of the heavy oil.
12. The method of claim 1 or 2, wherein the heavy oil is selected from one or more of a residuum and a tail oil.
13. The method according to claim 1 or 2, wherein,
In the step (I), the weight ratio of the MoO 3 product to the solvent calculated by molybdenum element is 1: (1-20); the molar ratio of the MoO 3 product to the C1-C6 oxygen-containing organic acid is 1 based on molybdenum element: (0.5-4).
14. The method according to claim 1 or 2, wherein,
In the step (II), the molar ratio of the MoO 3 product to the C6-C18 oxygen-containing organic acid calculated as molybdenum element is 1: (1-10).
15. The method according to claim 1 or 2, wherein,
The reaction time in step (I) is 0.3 to 9 hours.
16. The method according to claim 1 or 2, wherein,
The reaction time in step (II) is1 to 12 hours.
17. The method according to claim 1 or 2, wherein,
The solvent in step (I) is selected from water and/or an organic solvent; the organic solvent is selected from benzene, toluene, ethanol or petroleum ether.
18. The method according to claim 1 or 2, wherein,
The C1-C6 oxygen-containing organic acid is selected from formic acid, acetic acid, propionic acid, 2-methyl butyric acid, glycolic acid, isobutyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 2-hydroxysuccinic acid, 3-hydroxy tricarboxylic acid or citric acid.
19. The method according to claim 1 or 2, wherein,
The C6-C18 oxygen-containing organic acid is selected from caproic acid, heptanoic acid, 2-propyl heptanoic acid, caprylic acid, 2-ethylhexanoic acid, nonanoic acid, capric acid, oleic acid, palmitic acid, stearic acid or naphthenic acid with 6-18 carbon atoms.
20. The method according to claim 1 or 2, wherein,
Step (I) and/or step (II) are carried out in an inert atmosphere.
21. The method according to claim 1 or 2, wherein,
In the formula (1), a and b are equal, and a+b is 2,4 or 6; m is equal to n, and m+n is 0, 2 or 4.
22. The method according to claim 1 or 2, wherein,
The C1-C6 oxygen-containing organic acid radical is monocarboxylate radical or multicarboxylate radical.
23. The method of claim 22, wherein,
The C1-C6 oxygen-containing organic acid radical is formate, acetate, propionate, 2-methylbutyrate, hydroxy acetate, isobutyrate, valerate, oxalate, malonate, succinate, glutarate, 2-hydroxy succinate, 3-hydroxy tricarballylate or citrate.
24. The method according to claim 1 or 2, wherein,
The C6-C18 oxygen-containing organic acid radical is monocarboxylate, multicarboxylate, thiocarboxylate, sulfonate or sulfinate.
25. The method of claim 24, wherein,
The C6-C18 oxygen-containing organic acid radical is a caproate radical, a heptanoate radical, a 2-propyl heptanoate radical, a caprylate radical, a 2-ethylhexyl acid radical, a nonate radical, a caprate radical, an oleate radical, a soft fatty acid radical, a stearate radical or a naphthenate radical with 6-18 carbon atoms.
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