Hydroconversion catalyst, process for its preparation and use

Abstract

The application discloses a kind of hydroconversion catalyst and its preparation method and application, belong to catalytic technology field.The preparation method is dissolved in water with metal inorganic salt and forms solution, with lye adjusting the pH value of the solution is acidic, add waste oil, heated to 80-120 DEG C under stirring and react 0.5-3h;Resting delamination, take upper organic phase, after washing with extractant spin-evaporated desolventizer, after drying, obtain the catalyst.The catalyst is used as coal / heavy inferior oil hydroconversion, catalytic activity is high, cost is low, dispersibility is high, reduces process operating cost;Catalyst raw material source is extensive, cost is low;At the same time, solve the utilization problem of catering waste oil, both reduce environmental pollution and can change waste into treasure, and maximumly realize the use value of catering waste oil.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, and particularly relates to a hydrogenation conversion catalyst, its preparation method, and its application. Background Technology

[0002] Clean and efficient utilization of coal and heavy, low-grade oil resources to convert them into oil products and chemicals is an effective means to compensate for insufficient petroleum resources, accelerate economic development, and reduce environmental pollution, and is also an important guarantee for energy security. Catalysts are the core technology in the coal / heavy, low-grade oil hydroconversion process. They can effectively reduce reaction severity, improve the utilization rate of activated hydrogen and the quality of liquid products, improve product quality, increase coal conversion rate, and enhance the economics of the hydrocracking process. This is currently a research hotspot in coal / heavy, low-grade oil hydroconversion. There are three types of catalysts used in coal / heavy, low-grade oil hydroconversion: solid powder catalysts, water-soluble catalysts, and oil-soluble catalysts. Solid powder catalysts have significant drawbacks: firstly, the tail oil contains a large number of solid particles, which are difficult to utilize and treat; secondly, they have low dispersibility and short lifespan. Water-soluble catalysts have complex dispersion processes, low hydrogenation activity, and low coal conversion rates. Compared with water-soluble catalysts, oil-soluble catalysts have simpler dispersion processes, higher hydrogenation activity, and a significant coking suppression effect. Therefore, developing easier-to-prepare oil-soluble catalysts has become a widely concerned topic.

[0003] For coal / heavy low-grade oil, highly dispersible catalysts can enhance the interaction between the catalyst and the coal / heavy low-grade oil, achieving optimal hydrogenation effect. Chinese patent CN113492008A discloses a composite oil-soluble catalyst for a coal tar slurry bed hydrogenation process. The patent uses oil as raw material to obtain a composite oil-soluble catalyst containing at least two metals. The preparation method includes the following steps: (1) oil and alkali are loaded into a reaction vessel in proportion for saponification reaction, and the mixture is boiled and refluxed for 0.5 to 2 hours under stirring; (2) metal inorganic salt and solvent are added, and a displacement reaction is carried out under stirring, and the reaction is carried out at a temperature of 65 to 95°C for 1 to 3 hours; (3) the mixture is cooled and allowed to stand to separate into layers, the upper organic phase is separated, and the solvent is evaporated to obtain the composite oil-soluble catalyst. The catalyst prepared by this patent has good solubility and dispersion performance in coal tar, high catalytic activity, and high yield of light oil. However, its preparation steps are complicated. Saponification reaction is required first, and then the metal in the alkali solution and the metal in the metal inorganic salt are subjected to a displacement reaction. Chinese Patent CN111841630A discloses a nickel-based oil-soluble catalyst for co-refining of coal / heavy oil. The active component of the catalyst is nickel, and the weight content of nickel in the catalyst is 6% to 20%. The preparation method includes the following steps: (1) Dissolve the fatty acid required for the reaction in ethanol and mix it thoroughly with alkaline solution, and add solvent. The reaction temperature is 60 to 95°C and the reaction time is 2 to 5 hours; (2) Prepare a nickel salt aqueous solution and add it dropwise to the reaction system, controlling the dropping rate to 1 to 10 ml / min. The reaction temperature is 60 to 95°C. After the dropping is completed, continue the reaction for 2 to 5 hours; (3) After the reaction is completed, quickly separate the liquids, discard the aqueous phase, add an appropriate amount of toluene or xylene to the oil phase, wash it, remove the solvent by rotary evaporation, and dry it to obtain the nickel-based oil-soluble catalyst for fatty acids. The catalyst prepared by this invention has good oil solubility, and it is in full contact with the coal / heavy oil system and hydrogen during the reaction. It has high catalytic hydrogenation activity and coke suppression activity, and the coal conversion rate is high. However, the preparation process of this catalyst is complicated, and the raw material fatty acids are relatively expensive.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a hydroconversion catalyst, its preparation method, and its application. Utilizing widely available and inexpensive waste cooking oil as raw material, the catalyst is prepared in one step and used as a catalyst for the hydroconversion of coal / heavy, low-quality oil. It exhibits high catalytic activity, low cost, and high dispersibility, thereby reducing process operating costs.

[0006] To achieve the above objectives, the present invention adopts the following specific technical solutions.

[0007] The present invention provides a method for preparing a hydroconversion catalyst, which involves dissolving a metal inorganic salt in water to form a solution, adjusting the pH of the solution to acidity with an alkaline solution, adding waste oil, heating to 80-120℃ with stirring for 0.5-3 hours, cooling and allowing the mixture to stand to separate into layers, taking the upper organic phase, washing with an extractant, removing the solvent by rotary evaporation, and drying to obtain the catalyst.

[0008] Furthermore, the mass ratio of the metal inorganic salt to water is 1:10-25; the mass ratio of the metal inorganic salt to waste oil is 0.5-5:10.

[0009] Preferably, the water is distilled water or deionized water.

[0010] Furthermore, the metal in the inorganic metal salt includes one or more of Fe, Ni, Mo, Co, or W.

[0011] Preferably, the inorganic salt is one or more of nitrate, hydrochloride, molybdate, or tungstate.

[0012] Furthermore, the waste oil includes waste cooking oil. The waste cooking oil includes vegetable oil and / or animal oil.

[0013] Furthermore, the vegetable oil comprises unsaturated fatty acids, and the animal oil comprises saturated fatty acids.

[0014] Furthermore, the vegetable oil includes oleic acid and linoleic acid, and the animal oil includes stearic acid and palmitic acid.

[0015] Preferably, the vegetable oil includes one or more of the following: jatropha oil, cottonseed oil, palm oil, tung oil, coconut oil, walnut oil, camellia seed oil, soybean oil, peanut oil, walnut oil, peony seed oil, corn oil, rapeseed oil, sesame oil, sunflower seed oil, or rice bran oil; and the animal oil includes one or more of the following: beef tallow, mutton tallow, lard, or chicken tallow.

[0016] Furthermore, the alkaline solution adjusts the pH of the solution to 3.5-6.5. In this application, the inorganic metal salt is essentially strongly acidic. The addition of alkaline solution is to adjust the acidity so that the inorganic metal salt solution reaches a level essentially the same as that of the waste oil, thereby facilitating uniform dispersion and stable reaction of the metal in the waste oil.

[0017] Preferably, the alkali includes one or more of sodium hydroxide, potassium hydroxide, or organic ammonia.

[0018] More preferably, the alkaline solution is added by first adding an organic ammonia solution to adjust the pH value to not less than 3.5, letting it stand for 1-2 hours, and then adding sodium hydroxide or potassium hydroxide to continue adjusting the pH value to 3.5-6.5.

[0019] Preferably, the extractant comprises one or more of n-heptane, toluene, xylene, n-hexane, or petroleum ether.

[0020] The present invention also provides a hydroconversion catalyst, which is prepared by the above-described preparation method.

[0021] The present invention also provides an application of the hydroconversion catalyst described above in the hydroconversion of coal and / or heavy inferior oil.

[0022] In this invention, the raw materials for the catalyst are widely available and inexpensive; at the same time, it solves the problem of utilizing waste cooking oil, which not only reduces environmental pollution but also turns waste into treasure, and maximizes the utilization value of waste cooking oil.

[0023] The catalyst is prepared by a one-step method, and the preparation process is simple and easy to operate. The catalyst exhibits good solubility and dispersion in coal / heavy, low-grade oil, high intrinsic activity, and good stability. During the hydrogenation reaction of coal / heavy, low-grade oil, it can further promote the conversion of coal / heavy, low-grade oil, improving coal conversion rate and oil yield. Detailed Implementation

[0024] The embodiments of the present invention will be described in detail below with reference to specific examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified, specific conditions in the examples are performed under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used without a specified manufacturer are all commercially available conventional products. Furthermore, the proportions or contents of components not specified in the present invention can be any proportions or contents, and are not limited to mass ratios, concentration ratios, molar ratios, or volume ratios.

[0025] The effective product for converting coal and heavy, low-quality oil into petroleum products is usually hexane-soluble matter. Therefore, in the examples, the test results are calculated based on the yield of hexane-soluble matter.

[0026] Example 1

[0027] A method for preparing an oil-soluble Ni / Mo composite catalyst: 22.53 g of nickel nitrate and 24.17 g of ammonium molybdate are dissolved in 935 g of distilled water to form a solution. The pH of the solution is adjusted to 5.5 with 1 mol / L sodium hydroxide aqueous solution. 117 g of kitchen waste soybean oil is added, and the mixture is heated to 105 °C and stirred for 3 h. After cooling and allowing to stand for separation, the upper organic phase is separated using a separatory funnel. The organic phase is washed with n-heptane, and this washing process is repeated 3 times. After removing n-heptane by rotary evaporation, the mixture is dried in a vacuum drying oven at 75 °C for 24 h to obtain an oil-soluble Ni / Mo composite catalyst, wherein the molar ratio of Ni to Mo is 1:1.

[0028] A mixture of Shangwan coal sample (dry, ash-free), the prepared oil-soluble Ni / Mo composite catalyst, sulfur, and tetrahydronaphthalene was added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal sample to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Ni+Mo was 2:1; and the amount of oil-soluble Ni / Mo composite catalyst (based on the mass of active metal Ni+Mo) added was 1 wt% of the Shangwan coal sample. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of the hexane-soluble product was 76.08 wt.%.

[0029] The Tarim River residue oil, the prepared oil-soluble Ni / Mo composite catalyst, sulfur, and tetrahydronaphthalene were mixed and added to a 100 mL high-pressure reactor. The mass ratio of Tarim River residue oil to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Ni+Mo was 2:1; and the amount of oil-soluble Ni / Mo composite catalyst (based on the mass of active metal Ni+Mo) added was 1 wt% of the Tarim River residue oil. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450°C at a rate of 10°C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of hexane-soluble product was 91.80 wt.%.

[0030] A mixture of Shangwan coal sample (dry, ash-free), the prepared oil-soluble Ni / Mo composite catalyst, sulfur, Tarim River residue oil, and tetrahydronaphthalene was added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal sample, tetrahydronaphthalene, and Tarim River residue oil was 1:1:1; the molar ratio of sulfur to Ni+Mo was 2:1; and the amount of oil-soluble Ni / Mo composite catalyst (based on the mass of active metal Ni+Mo) added was 1 wt% of the total mass of Shangwan coal sample and Tarim River residue oil. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of hexane-soluble product was 72.5 wt.%.

[0031] Example 2

[0032] A method for preparing an oil-soluble Fe / Ni / Mo composite catalyst: 13.00 g of ferric chloride, 14.64 g of nickel nitrate, and 15.71 g of ammonium molybdate were dissolved in 870 g of distilled water. The pH of the solution was adjusted to 5.5 with 1 mol / L sodium hydroxide aqueous solution. 108 g of kitchen waste palm oil was added, and the mixture was heated to 105 °C and stirred for 3 h. After cooling and allowing it to stand for separation, the upper organic phase was separated using a separatory funnel. Toluene was added to the organic phase for washing, and this washing process was repeated 3 times. After removing the toluene by rotary evaporation, the mixture was dried in a vacuum drying oven at 75 °C for 24 h to obtain the oil-soluble Fe / Ni / Mo composite catalyst, wherein the molar ratio of Fe, Ni, and Mo is 1:1:1.

[0033] A mixture of Shangwan coal sample (dry, ash-free), the prepared oil-soluble Fe / Ni / Mo composite catalyst, sulfur, and tetrahydronaphthalene was added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal sample to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Fe+Ni+Mo was 2:1; and the amount of oil-soluble Fe / Ni / Mo composite catalyst (based on the mass of active metals Fe+Ni+Mo) added was 1 wt% of the Shangwan coal sample. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of the hexane-soluble product was 74.98 wt.%.

[0034] Example 3

[0035] A method for preparing an oil-soluble Fe / Mo composite catalyst: 20.00 g of ferric chloride and 24.17 g of ammonium molybdate are dissolved in 880 g of deionized water. The pH of the solution is adjusted to 6.5 with 1 mol / L potassium hydroxide aqueous solution. 110 g of waste jatropha oil is added, and the mixture is heated to 95 °C and stirred for 1 h. After cooling and allowing to stand for separation, the upper organic phase is separated using a separatory funnel. The organic phase is washed three times with petroleum ether, and then the petroleum ether is removed by rotary evaporation. After drying in a vacuum drying oven at 75 °C for 24 h, an oil-soluble Fe / Mo composite catalyst is obtained, wherein the molar ratio of Fe to Mo is 1:1.

[0036] A mixture of Shangwan coal sample (dry, ash-free), the prepared oil-soluble Fe / Mo composite catalyst, sulfur, and tetrahydronaphthalene was added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal sample to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Fe+Mo was 2:1; and the amount of oil-soluble Fe / Mo composite catalyst (based on the mass of active metals Fe+Mo) added was 1 wt% of the Shangwan coal sample. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of the hexane-soluble product was 74.18 wt.%.

[0037] Example 4

[0038] A method for preparing an oil-soluble Fe / Ni composite catalyst: 20.00 g of ferric chloride and 22.53 g of nickel nitrate were dissolved in 850 g of distilled water. The pH of the solution was adjusted to 5.5 with 1 mol / L sodium hydroxide aqueous solution. 106 g of waste tallow oil was added, and the mixture was heated to 120 °C. After stirring for 0.5 h, the mixture was cooled and allowed to stand to separate into layers. The upper organic phase was separated using a separatory funnel. The organic phase was washed three times with n-heptane, and the n-heptane was removed by rotary evaporation. The mixture was then dried in a vacuum drying oven at 75 °C for 24 h to obtain the oil-soluble Fe / Ni composite catalyst, wherein the molar ratio of Fe to Ni was 1:1.

[0039] An oil-soluble Fe / Ni composite catalyst prepared from Shangwan coal samples (dry ash-free basis), sulfur, and tetrahydronaphthalene were mixed and added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal samples to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Fe+Ni was 2:1; and the amount of oil-soluble Fe / Ni composite catalyst (based on the mass of active metal Fe+Ni) added was 1 wt% of the Shangwan coal samples. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of the hexane-soluble product was 72.05 wt.%.

[0040] Example 5

[0041] A method for preparing an oil-soluble Fe / Co composite catalyst: 20.00 g of ferric chloride and 22.56 g of cobalt nitrate were dissolved in 850 g of distilled water. The pH of the solution was adjusted to 6 with 1 mol / L sodium hydroxide aqueous solution. 106 g of kitchen waste peanut oil was added, and the mixture was heated to 105 °C. After stirring for 3 h, the mixture was cooled and allowed to stand for separation. The upper organic phase was separated using a separatory funnel. The organic phase was washed three times with n-heptane, and the n-heptane was removed by rotary evaporation. The mixture was then dried in a vacuum drying oven at 75 °C for 24 h to obtain the oil-soluble Fe / Co composite catalyst, wherein the molar ratio of Fe to Co was 1:1.

[0042] A mixture of Shangwan coal sample (dry, ash-free), the prepared oil-soluble Fe / Co composite catalyst, sulfur, and tetrahydronaphthalene was added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal sample to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Fe+Co was 2:1; and the amount of oil-soluble Fe / Co composite catalyst (based on the mass of active metal Fe+Co) added was 1 wt% of the Shangwan coal sample. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of the hexane-soluble product was 70.86 wt.%.

[0043] Example 6

[0044] A method for preparing an oil-soluble Fe-based catalyst involves dissolving 40.00 g of ferric chloride in 800 g of distilled water, adjusting the pH of the solution to 5.5 with a 1 mol / L sodium hydroxide aqueous solution, adding 100 g of kitchen waste corn oil, heating to 105 °C, stirring for 3 h, cooling and allowing to stand for separation, separating the upper organic phase using a separatory funnel, washing the organic phase three times with n-heptane, removing the n-heptane by rotary evaporation, and drying in a vacuum drying oven at 75 °C for 24 h to obtain the oil-soluble Fe-based catalyst.

[0045] A mixture of Shangwan coal sample (dry, ash-free), the prepared oil-soluble Fe-based catalyst, sulfur, and tetrahydronaphthalene was added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal sample to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Fe was 2:1; and the amount of oil-soluble Fe-based catalyst (based on the mass of active metal Fe) added was 1 wt% of the Shangwan coal sample. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of the hexane-soluble product was 66.36 wt.%.

[0046] Example 7

[0047] A method for preparing an oil-soluble Ni / Mo composite catalyst differs from Example 1 in that: before adjusting the pH of the solution to 5.5 with a 1 mol / L sodium hydroxide aqueous solution, the pH of the solution is first adjusted to 3.5 with a 500 mg / L quaternary ammonium salt.

[0048] A mixture of Shangwan coal sample (dry, ash-free), the prepared oil-soluble Ni / Mo composite catalyst, sulfur, and tetrahydronaphthalene was added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal sample to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Ni+Mo was 2:1; and the amount of oil-soluble Ni / Mo composite catalyst (based on the mass of active metal Ni+Mo) added was 1 wt% of the Shangwan coal sample. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of the hexane-soluble product was 78.12 wt.%.

[0049] The Tarim River residue oil, the prepared oil-soluble Ni / Mo composite catalyst, sulfur, and tetrahydronaphthalene were mixed and added to a 100 mL high-pressure reactor. The mass ratio of Tarim River residue oil to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Ni+Mo was 2:1; and the amount of oil-soluble Ni / Mo composite catalyst (based on the mass of active metal Ni+Mo) added was 1 wt% of the Tarim River residue oil. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450°C at a rate of 10°C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of n-hexane-soluble product was 92.24 wt.%.

[0050] A mixture of Shangwan coal sample (dry, ash-free), the prepared oil-soluble Ni / Mo composite catalyst, sulfur, Tarim River residue oil, and tetrahydronaphthalene was added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal sample, tetrahydronaphthalene, and Tarim River residue oil was 1:1:1; the molar ratio of sulfur to Ni+Mo was 2:1; and the amount of oil-soluble Ni / Mo composite catalyst (based on the mass of active metal Ni+Mo) added was 1 wt% of the total mass of Shangwan coal sample and Tarim River residue oil. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of n-hexane-soluble product was 73.43 wt.%.

[0051] It can be seen that the catalyst in this embodiment shows a more significant advantage than that in Example 1 when used in the hydroconversion catalytic reaction of coal and heavy inferior oil, respectively.

[0052] Comparative Example 1

[0053] A mixture of Shangwan coal sample (dry, ash-free), molybdenum isooctanoate catalyst from Shanghai Aladdin Biochemical Technology Co., Ltd., sulfur, and tetrahydronaphthalene was added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal sample to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Mo was 2:1; and the amount of molybdenum isooctanoate catalyst (based on the mass of active metal Mo) added was 1 wt% of the Shangwan coal sample. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of hexane-soluble product was 64.05 wt.%.

[0054] Comparative Example 2

[0055] A mixture of Shangwan coal sample (dry, ash-free), Shenhua ultrafine hydrated iron oxide (FeOOH) catalyst, sulfur, and tetrahydronaphthalene was added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal sample to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Fe was 2:1; and the amount of FeOOH catalyst (based on the mass of active metal Fe) added was 1 wt% of the Shangwan coal sample. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of hexane-soluble product was 58.07 wt.%.

[0056] Comparative Example 3

[0057] A mixture of Shangwan coal sample (dry, ash-free), ferric oxide catalyst from Tianjin Beilian Fine Chemicals Development Co., Ltd., sulfur, and tetrahydronaphthalene was added to a 100 mL high-pressure reactor. The mass ratio of Shangwan coal sample to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Fe was 2:1; and the amount of ferric oxide catalyst (based on the mass of active metal Fe) added was 1 wt% of the Shangwan coal sample. The reactor was purged three times with nitrogen at 3 MPa, then three times with hydrogen at 3 MPa. Hydrogen was then introduced to bring the pressure to 7 MPa. The temperature was raised from room temperature to 450 °C at a rate of 10 °C / min, held at this temperature for 1 hour, and then rapidly cooled using a blower. The results showed that the yield of hexane-soluble product was 57.19 wt.%.

[0058] It is evident that the catalyst of this invention has a significantly improved catalytic effect compared to currently commercially available catalysts.

[0059] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention. In addition, those skilled in the art can understand that although some embodiments here include certain features included in other embodiments but not other features, the combination of features of different embodiments means that they are within the scope of the present invention and form different embodiments. For example, in the above claims, any one of the claimed embodiments can be used in any combination. The information disclosed in this background section is only intended to deepen the understanding of the overall background technology of the present invention, and should not be regarded as an admission or in any form implying that the information constitutes prior art known to those skilled in the art.

Claims

1. A process for the preparation of a hydroconversion catalyst, characterized in that, The metal inorganic salt is dissolved in water to form a solution, the pH value of the solution is adjusted to be acidic by using a lye, waste oil is added, and the solution is heated to 80-120 DEG C under stirring for 0.5-3 h; after standing and layering, the upper organic phase is taken, washed by adding an extractant, and then desolventized by rotary evaporation, and the catalyst is obtained after drying; The metal in the metal inorganic salt includes one or more of Fe, Ni, Mo, Co or W; The waste oil includes catering waste oil; the catering waste oil includes one or more of plant oil and / or animal oil; The plant oil includes one or more of Jatropha oil, cottonseed oil, palm oil, tung oil, coconut oil, walnut oil, oil-tea camellia seed oil, soybean oil, peanut oil, peony seed oil, corn oil, rapeseed oil, sesame oil, sunflower seed oil or rice bran oil; the animal oil includes one or more of beef tallow, mutton tallow, lard or chicken oil; The adjusting of the pH value of the solution by using a lye includes: first adding an organic ammonia solution, adjusting the pH value to be not less than 3.5, standing for 1-2 h, and then adding sodium hydroxide or potassium hydroxide, and continuously adjusting the pH value to be 5.5-6.

5.

2. The production method according to claim 1, characterized by, The inorganic salt is one or more of nitrate, hydrochloride, molybdate or tungstate.

3. The preparation method according to claim 1, characterized in that, The mass ratio of the metal inorganic salt to water is 1:10-25; The water is distilled water or deionized water.

4. The method of claim 1, wherein, The mass ratio of the metal inorganic salt to waste oil is 0.5-5:

10.

5. The preparation method according to claim 1, characterized in that, The extractant includes one or more of n-heptane, toluene, dimethylbenzene, n-hexane or petroleum ether.

6. A hydroconversion catalyst characterized in that, The catalyst is prepared by the preparation method in any one of claims 1-5.

7. Use of the hydroconversion catalyst in claim 6 in the hydroconversion of coal and / or heavy and poor quality oil.